HighBeam Research

Title: The wet gas sulphuric acid plant: Part 2; Following the discussion in Part 1 of the gas cleaning section of the wet gas sulphuric acid plant, Leonard J. Friedman and Samantha J. Friedman of Acid Engineering & Consulting continue with a review of the unit operations in the contact section, discussing various equipment designs, materials and the handling of gas stream variables and impurities.(Acid Plant Design) Date: 7/1/2004; Publication: Sulphur; Author: Friedman, Samantha J. The aim of this paper is to provide a basic understanding of the design and operating considerations of a wet gas (metallurgical or spent acid regeneration) sulphuric acid plant. A better understanding of the factors that affect equipment design, materials, operation, and the effect of variables should lead to a successful sulphuric acid plant project. In Part 1 we discussed the gas cleaning section. In this concluding part we turn our attention to the contact section. Contact section In the contact section of the wet gas sulphuric acid plant, cleaned S[O.sub.2] gas is dried, converted to S[O.sub.3] and then absorbed in water contained in 98% sulphuric acid to form sulphuric acid. Flow through the system is shown on Fig. 1 and described below. Gas flow The wet, cleaned gas from the purification system enters the drying tower, where it is dried to a dew point of -40[degrees]C to prevent acid condensation corrosion of downstream equipment. In the drying tower, the gas is contacted with a circulating stream of 93% sulphuric acid that absorbs the water from the gas. Dry S[O.sub.2] gas leaves the tower and passes through an entrainment separator before entering the main blower. The blower provides the suction to draw the gas through the gas cleaning system and drying tower and provides the pressure to force it through the remainder of the plant. The blower discharges to a series of gas to gas heat exchangers that heat the gas to the catalyst ignition temperature of about 420[degrees]C using heat from the converter's S[O.sub.2] to S[O.sub.3] oxidation reaction. The heated gas flows to the converter where the S[O.sub.2] is oxidised to S[O.sub.3] over a vanadium pentoxide catalyst. The converter contains four catalyst layers with cooling between each bed. Cooling is

provided to increase overall conversion, as shown in Fig. 2. The first catalyst bed operating line (line 1) is shown with gas temperature (heat of reaction) increasing with conversion and approaching the equilibrium line. The gas is indirectly cooled (line 2) and enters the second bed, where conversion increases (line 3). The two basic types of converter arrangements are: single absorption, where the gas passes through four converter catalyst beds followed by S[O.sub.3] absorption (about 98% conversion of S[O.sub.2]); and double absorption, where the gas is withdrawn after two or three passes over the catalyst, S[O.sub.3] is removed by absorption in sulphuric acid, and the gas is returned to the converter for final conversion in the remaining one or two beds. Double absorption plants operate at a conversion efficiency of greater than 99.7%. Gas from the converter is cooled in gas to gas heat exchangers before entering the absorption tower where the S[O.sub.3] is absorbed in water contained in a circulating stream of 98% sulphuric acid. Gas from the absorption tower, with 98% (single absorption) or 99.7% (double absorption) of the incoming S[O.sub.2] removed as sulphuric acid, is discharged to the atmosphere via a stack. Acid system In the drying tower, 93% sulphuric acid entering the tower at 43[degrees]C absorbs water from the gas. As the acid passes through the tower, it is heated by the heat of condensation of water and dilution of the acid. Acid leaves the tower and flows to a pump tank, where it is pumped through a shell-and-tube acid cooler before being returned to the tower. The 98% acid from the absorber acid system is added to the pump tank to maintain the drying acid concentration at 93%. A portion of the drying acid is transferred to the absorber acid system via an S[O.sub.2] stripper to control absorber acid strength. Product 93% acid is withdrawn from the stripper, cooled in an acid cooler, and sent to product storage. Sulphur trioxide is removed from the gas in the absorber system by contacting the gas with a circulating stream of 98% sulphuric acid. The absorber acid enters the tower at 80[degrees]C and is heated by sensible heat in cooling the gas and the heat of condensation of S[O.sub.3]. The acid leaves the tower and enters a pump tank where it is pumped through an acid cooler and returned to the tower. Water in the S[O.sub.2] gas, which enters the contact section of the plant from the gas cleaning system and is removed in the drying tower, is added as 93% acid to the absorber acid system to combine with the S[O.sub.3] removed from the gas, forming sulphuric acid.

Effect of variables There are three variables that affect the sizing, cost, and operation of the contact section of the plant. They are gas volume, S[O.sub.2] gas concentration, and the amount of water in the entering gas. Gas volume The majority of equipment in the contact section of the plant is sized based on the volume of gas to be handled. This includes acid towers, gas to gas heat exchangers, and converter and gas ducts. These represent the bulk of the cost of the contact section of the plant. The remaining equipment (gas to gas heat exchanger, acid circulation and cooling) are sized based on acid production and S[O.sub.2] gas strength. S[O.sub.2] gas strength The S[O.sub.2] gas strength is critical to the design, equipment sizing, and operation of the contact section of the plant. The upper operating limit for S[O.sub.2] concentration in a conventional type plant to prevent overheating the catalyst in the first bed (loss of vanadium/activity) is 12% S[O.sub.2] at an [O.sub.2]/S[O.sub.2] ratio greater than 0.8, and as high as 14% S[O.sub.2] with an [O.sub.2]/S[O.sub.2] ratio of greater than one. A high strength design (patented by L. J. Friedman in the mid 1970s) developed to handle gases from oxygen flash smelting and regenerative scrubbing systems operates at 20-22% equivalent S[O.sub.2] to the converter. The lower limit of S[O.sub.2] concentration, without the addition of external heat, is 3-3.5% for a single absorption plant and 3.5-4% for a double absorption plant (3.5% is based on a co-current venturi type interstage absorber). This lower limit is based on the available heat recoverable from the converter oxidation reaction needed to heat the cold incoming S[O.sub.2] gas to converter catalyst ignition temperature, defined as the autothermal S[O.sub.2] level. Plants can be operated at S[O.sub.2] strengths below the autothermal level with the addition of heat, usually provided by fossil fuel in indirect preheaters. Gas to gas heat exchanger sizing and cost vary with the S[O.sub.2] gas strength and flow. As S[O.sub.2] strength decreases, the size and cost of the exchangers increase, especially at levels below 5-6%. For a fixed smelting or acid production rate sending a fixed amount of S[O.sub.2] to the sulphuric acid plant, the S[O.sub.2] strength and gas volume are obviously related. As the S[O.sub.2] strength increases, the

gas volume decreases along with the size and cost of the plant. Figure 3 shows the relationship of gas cleaning, contact section, and total plant capital cost as a function of gas strength for a plant processing a fixed quantity of S[O.sub.2]. Water balance All of the water that enters the contact section of the plant leaves as product acid. Therefore, the amount of water permitted in the gas entering the drying tower is limited by the product acid strengths produced by the plant (Fig. 4). A properly designed plant would reduce this value further by requiring a minimum of 10% of the water added as liquid to the acid system for acid strength control. As S[O.sub.2] gas strength decreases, water balance considerations become critical. At some point, acid strength cannot be maintained with conventional gas cooling, and expensive gas cleaning system gas cooling is required using refrigerated gas coolers or pre-drierconcentrator systems. If too much water enters the contact section of the plant, acid strength in the drying and absorber systems cannot be maintained. The diluted acid will cause extensive corrosion damage to the acid system equipment (pumps, coolers, piping, tower internals, and instruments). Some of the problems associated with gas volume, S[O.sub.2] strength, and water balance are illustrated in the following examples. In one plant handling gas from Pierce Smith copper converters, the acid plant design was based on 200% air ingress at the converter hoods (considered a conservative number), resulting in an S[O.sub.2] strength at the acid plant of 4-8% (averaging 6%) with gas cooling comfortably able to produce 93% product acid (Fig 5). After about six months operation, converter air ingress increased to 400-500%, reducing S[O.sub.2] gas strength to 2-4% (averaging 3%). The acid plant designed to accept a fixed volume of gas could not handle all the addition gas, and a portion was bypassed direct to the stack. S[O.sub.2] gas strength was below the autothermal level requiring continuous operation of the fossil fuel fired preheater to maintain the plant in heat balance, thus increasing operating costs. Water balance could not be maintained, and the smelter purchased 98% sulphuric acid for addition to the plant to remove the excess water as 93% acid. Another plant had similar problems, but added an expensive predrierconcentration system to solve the water balance problem as well as extensive modifications to the plant to increase gas handling capacity. The proper solution was to correct the air ingress problem at the converter; water cooled hoods should reduce air ingress to less than 100%.

Equipment/system design Gas heat exchangers Gas to gas heat exchangers use the heat of the converter S[O.sub.2] to S[O.sub.3] oxidation reaction to preheat incoming cold S[O.sub.2] gas to catalyst ignition temperature and, in double absorption plants, to cool and reheat the gas entering and leaving the interstage absorption system. The exchangers also provide the cooling between catalyst beds for high conversion efficiency. In plants with high S[O.sub.2] strengths, excess heat is available from the converter system and is used to preheat air, heat boiler feed water, and/or superheat steam. Thirty years ago, gas-gas exchangers were designed as shell and tube segmented baffle full bundle units with a heat transfer coefficient of 10-20 kg.cal/[m.sup.2].[degrees]C.hr. Low heat transfer coefficients and high gas pressure drops of this design led to the development of alternative designs commonly used today. These include shell-and-tube single-pass cross flow exchangers, multi-pass cross flow exchangers using baffles with no tubes in the baffle window, and disc and doughnut exchangers with no tubes in the baffle window (disc and doughnut cross flow). Each of these designs operates at comparable pressure drops with heat transfer coefficients three times that of the old full bundle design. Cold heat exchangers are normally constructed of carbon steel. Hot units (heat exchanger between the first and second catalyst bed, and the exchanger between the second and third bed) are constructed of 1 1/4Cr-1/2 Mo Alonised tubes for high temperature strength and scale resistance or of 304 series stainless steel, with the choice dependent on economics. Essentially all new acid plants are using stainless steel for hot exchangers. These large units require careful design, including considerable over surface for fouling, and incorporating tube support and detuning baffles to prevent vibration. Gas flow through cold exchangers, where acid condensation is possible, is arranged with the S[O.sub.3] gas flowing down through the tubes to force condensed acid out of the tube bundle and into the bottom head of the exchanger. Hot exchangers are also arranged with the S[O.sub.3] gas in the tubes to avoid the need for temperature and scale protection of the shell. Converter system Catalyst Sulphuric acid oxidation catalysts of essentially the same basic formulation have been in use for over 70 years. The catalyst contains 6-9 wt% vanadium pentoxide as the active component with potassium

and sodium sulphates as promoters, supported on a diatomaceous earth (silica) carrier. Catalyst ignition temperature is a function of the vanadium and sodium/potassium sulphate content, and is about 410[degrees]C. The upper temperature limit for continuous operation is about 640[degrees]C to prevent loss of vanadium and reduced activity. For many years, catalysts were in the form of extruded pellets 6 mm in diameter by 10-mm long. Clean pellet catalyst beds operate at relatively a high pressure drop, about 800-1200 mm water total for the four beds. The catalyst is also a good filter of dust particles, especially at operating temperature when the material is sticky. Dust is held in a shallow layer at the top of the bed, increasing bed pressure drop about 800 mm over a one year operating period, reducing plant gas handling capacity and requiring screening to remove the dust. All new sulphuric acid plants and most existing plants use ring catalysts. All catalyst manufacturers (Topsoe, Monsanto and BASF) now produce ring catalysts, with operating and screening experience showing about equal performance. Topsoe, BASF and more recently Monsanto later developed a ribbed ring shaped catalyst to further reduce pressure drop. The ribbed ring is the standard catalyst used today. Converter design Sulphuric acid converters are vertical cylindrical vessels equipped with internals to support four separate layers of catalyst. Until recently, the vessels were constructed of a carbon steel shell (metalised with aluminum in hot areas for scale resistance) with either cast iron posts or steel beams supporting cast iron or stainless steel grids for the catalyst. Units of this design have been in operation for over 50 years and have operated successfully with minimal maintenance. Currently, all acid plant designers are offering a stainless steel converter design (304 series). Stainless steel converters use a stainless steel shell, hemispherical domes, posts, and beams to support stainless steel catalyst trays. There is a significant number of stainless steel converter installations, and the design is considered satisfactory. The main problem occurs at high temperature (>540[degrees]C), when stainless steel forms a scale that flakes off when the metal is allowed to cool (pinging converters). In plants with frequent shutdowns the scale causes increased pressure drop in the catalyst bed and more frequent catalyst screenings. One should be cautious to ensure the converter shell design pressure is above the main blower shut off pressure, and the catalyst trays (first

bed) are designed conservatively above expected dirty gas pressure drop. Many of these converters are designed for the normal operating pressure and pressure drop to reduce metal thickness and cost. In one case, a damper inadvertently closed downstream of the converter, putting the blower in a surge condition. This increased the system pressure to blower shut off pressure, causing extensive damage to the converter. Acid system Each acid tower system (drying, interstage absorber, final absorber) is composed of a gas-liquid contacting tower, acid/surge volume collection, either in a pump tank or a reservoir in the base of the tower, circulating pump, acid cooler, and acid entrainment/mist removal device. Acid towers An efficient liquid-gas contacting device is required to remove water from the gas in the drying tower and to absorb S[O.sub.3] from the gas in the absorption towers. The conventional acid tower is a steel tower lined with Pecora mastic, 10 mil Teflon sheet, and acid brick. Two layers of acid brick are used in the bottom section of the tower up to the packing support, and one layer of acid brick for the remainder of the straight side. The tower bottom is a dished head with a bottom acid outlet. The packing is supported on a ceramic dome to transfer the load to the tower shell and avoid brick arches or piers. Drying towers are packed with 2500 mm to 3500 mm of 3-inch ceramic intalox saddles, topped with 600 mm of 2-inch saddles to aid in acid distribution and reduce acid entrainment. Absorption towers have 3050 mm to 3650 mm of 3-inch packing. The preferred acid distributor is a trough and spout type (usually cast iron) with a minimum of ten acid feed points per square meter of tower cross-section and the acid discharging from the spouts 100 mm below the top of the packing. This design is well proven, highly efficient, and flexible. Recent difficulty in obtaining quality castings for trough and spout distributors, as well as cost, has led some designers to offer pipe distributors, which are usually buried in the 2-inch packing. This is an old design that lost favour about 30 years ago due to problems of poor distribution and tower performance resulting from distributor holes plugging and/ or corroding, and from leaks in flanges (all below 300600mm of packing). Current pipe distributors are offered with Teflon outlets and Lewmet nozzles, and can be constructed of a stainless alloy (approximate composition: 17Cr, 17Ni, 4Si), marketed by Chemetics as Saramet and Edmeston of Sweden as Sandvik SX. However, many of the problems of pipe distributors still remain. Currently, stainless steel (SX, Saramet,

and 310 Stainless) trough and spout distributors are offered by all acid plant suppliers (except Lurgi who use their cast iron pipe distributor). An alternative tower packing support uses acid brick arches spaced about 2-2.5 m apart, supporting Aludur ceramic beams and ceramic grid blocks. This design is acceptable at equal cost to the dome design, and has been used for many years. In the last 15 years acid towers and pump tanks constructed of unlined Saramet, SX, 310 stainless and Hastelloy C-276 have gone into operation at various acid plants. Saramet and Sandvik SX alloy have also been used for acid pipe distributors, piping, and acid coolers. There have been numerous problems and failures of unlined metal towers attributed to S[O.sub.3]/oleum attacking the silicon in absorption towers, and dilute acid attack (corrosion) in drying towers. Analysis indicates areas of the tower metal wall that are not adequately wetted by the acid are corroded by low acid concentration in dry towers and by S[O.sub.3]/oleum in absorption towers. Alternative tower designs include the Lurgi venturi tower and the Monsanto HE tower. The Lurgi venturi tower uses a two stage, horizontal and vertical venturi for acid-gas contacting, followed by a packed and irrigated separator tower. In weak gas metallurgical plants, the Lurgi venturi has been used as an interstage absorber without acid irrigation on the separator, where the co-current gas and acid flow leave more heat in the exit gas. This reduces the interstage heat exchanger cost and allows the plant to be autothermal at a lower S[O.sub.2] concentration. The design is well proven in acid plants around the world for over 25 years. Marginal economics and reduced operating flexibility have caused limited installations in North America. The Monsanto HE tower has been on the market for about 20 years. The design is based on work performed by the Fractionation Research Institute (FRI) indicating that increased packing mass transfer efficiency can be obtained with increased liquid distribution. The HE tower currently uses a 310 stainless steel trough and spout distributor incorporating 4-5 times the number of acid feed points per square meter of cross-section, and 3-inch packing depth reduced to about 2150 mm in the drying tower and to 2450 mm in the absorption towers. No 2-inch packing is used. Tower design velocity (tower diameter) is the same as the conventional tower, but is less flexible and more sensitive. The reduced packing depth requires optimum acid distribution to maintain efficiency. A number of design changes have been made. Hastelloy screens have been replaced by Lewmet screens to prevent plugging of the small distributor spout holes with brick chips, packing chips and/or sulphate; 310 Stainless or Sandvik SX trough distributors are used following corrosion failure (casting defects) in the original cast iron pipe distributor; and reentrainment separators have been added to improve

the quality and efficiency of Monsanto CS series entrainment-mist eliminator candles. Acid pump tanks Acid pump tanks provide acid surge volume for the vertical acid pumps and sufficient volume to hold the acid contained in the system (tower, piping, cooler) on pump shutdown. Pump tank design has developed over the years from a vertical cylindrical, flat-bottom, brick-lined tank usually 2290-mm high to a number of alternative designs. These alternative designs include using a dish bottom to avoid the brick expansion problems of a flat bottom; horizontal cylindrical brick-lined tanks to avoid corrosion of the unlined flat steel tank roof; and eliminating the tank altogether by locating the tower at grade and using the base of the tower for the required acid surge reservoir, with external vertical pump with or without a pump boot. Each of the alternative designs is acceptable, with the horizontal lined tank and reservoir in the base of a tower at grade the most preferred and most widely accepted today. Recently, a number of plants have installed unlined horizontal cylindrical tanks constructed of Saramet or SX. Some of the unlined metal pump tanks in service have had corrosion problems (failures) due to areas of dilute acid, usually from incomplete mixing of dilute acid or dilution water. In one plant the dilution pipe developed a hole resulting in a layer of dilute acid on top of the acid in the tank, corroding a one-metre high section of the tank wall. Acid pumps Acid pumps are traditionally vertical pumps to avoid suction valves, seals, and packing. Many acid plants around the world use Chas. S. Lewis vertical pumps constructed of their proprietary process iron and Lewmet high nickel alloy. Pump operating life between required maintenance is a function of acid concentration and temperature, and is about two to three years with 98% acid at 115[degrees]C. Acid coolers Acid coolers have progressed from parallel banks of stacked "S"shaped cast iron sections to stainless steel shell and tube or plate exchangers, with and without anodic protection. Chemetics has marketed annodically protected stainless steel shell and tube acid coolers for about 30 years, with numerous installations around the world. About 20 years ago, Monsanto introduced its version of the acid cooler. About 15 years ago, Edmeston installed a non-anodically protected shell-and-tube acid cooler using Sandvik SX alloy at the Boliden Rohnskar smelter in Sweden. Boliden is also using the Sandvik SX alloy for an acid distributor and acid piping.

Alternative acid cooler designs, used mainly in Europe with mixed success, include Hastelloy plate exchangers with and without anodic protection, Teflon shell-and-tube exchangers, and cast iron tube air coolers. Entrainment separators/mist eliminators Acid entrainment separators are used in the top of the drying tower to remove acid droplets from the gas to prevent corrosion of the main blower and gas heat exchangers. Typical entrainment separators collect by particle impingement, and use a 12.5-mm thick woven Teflon pad or a candle with compressed fibreglass in a stainless steel wire frame. The majority of installations in recent years have used the candle type, but problems with solids plugging have caused difficulty in many plants. Mist eliminators are required in the absorption towers to remove acid entrainment and sub-micron acid mist. Two types of units are used: dual pad or candle impingement devices, and candle type Brownian movement devices. The dual pad incorporates a high-density woven pad to agglomerate mist particles to large droplets, and a low-density woven Teflon pad as an entrainment separator for the large droplets. Candle type entrainment separators are composed of compressed fibreglass in a stainless steel frame collect large particles by impingement. Candle mist eliminators of compressed fibreglass using Brownian movement as the collecting method can be designed for efficiencies of greater than 99% for particles less than one micron. Impingement type mist eliminator efficiency is gas velocity sensitive, with collection efficiency decreasing with decreasing velocity of gas flow. The units have been used successfully in all types of acid plants (including metallurgical acid plants with varying gas flow) for about 30 years and are low in cost. For plants producing oleum, which generates a large quantity of submicron particles, and plants wanting a more efficient mist removal device, high efficiency candle units are used. The candles are constructed of 50-mm to 75-mm thick compressed fiberglass supported in a stainless steel wire frame. Collection is by Brownian movement of particles at laminar gas velocity (low velocity). One advantage of this type of candle unit is collection efficiency increases as gas flow-velocity is reduced. High efficiency candles cost about five times that of impingement type devices. Care should be used in selecting the candle type as efficiency can vary for sub micron particles depending on the fiberglass bed thickness and density. For example, the normal specification for high efficiency candle type mist eliminators is 100% for particles greater than one micron and 99.5% for particles less than one micron. Acid heat recovery

For about 20 years, the major emphasis in sulphuric acid plant development has been directed at recovering heat at usable levels from the acid system. Anodically protected shell-and-tube acid coolers have been used for about 25 years for preheating boiler feed water to 95[degrees]C and for producing hot water for process heating. Boliden is using acid heat as the heat source in their seawater absorptionstripping S[O.sub.2] concentration system. Recent work is aimed at recovering acid heat as low-pressure steam (50-100 psig). To recover acid heat directly as steam, acid temperatures must be increased from 110-120[degrees]C to about 200-250[degrees]C, which requires new construction materials for acid system components. All major acid plant designers are actively working in this area. Chemetics' efforts reportedly involve using annodically protected Saramet. Lurgi has installed one heat recovery system in Europe. Monsanto has installed many systems in the last 20 years using 310 stainless steel in a narrow acid concentration range of 99-99.8% strength. Conclusion The last 20 years have been an unusual period for accelerated development in sulphuric acid plant technology. The depressed state of new sulphuric acid plant construction has forced engineering contractors to reduce their staff, letting go of many experienced people. In many cases, design changes and process developments are being implemented by relatively inexperienced people who lack the years of design and operating experience needed to minimise errors and reduce the learning curve to acceptable levels. Life was much simpler in the 1970s, when a fairly reliable and welloperating plant could be obtained by calling one or more acid plant contractors and leaving the design to them. This is not true today, where owner operating and engineering personnel must be intimately involved in all areas of the acid plant design and equipment and materials selection to avoid one of a kind and/or high risk designs that may be detrimental to acid production, the smelter's sulphur emission reduction programme, or put the smelter's operation in jeopardy. For any new or major acid plant modification project, especially in the current environment, Acid Engineering & Consulting, Inc. strongly recommends project development, analysis, and execution by a team composed of the owner's operating, engineering, and materials personnel augmented with consultants who have extensive sulphuric acid plant design and operating experience. The combined knowledge and experience of the team and a team approach to project development and execution assures a highly

reliable, well-operating, and low-maintenance acid plant at the lowest capital cost. COPYRIGHT 2004 CRU Publishing Ltd. This material is published under license from the publisher through the Gale Group, Farmington Hills, Michigan. All inquiries regarding rights should be directed to the Gale Group.

Title: Meeting acid quality requirements. (removal of mercury content)(Sulphur 98: Special Conference Issue) Date: 9/1/1998; Publication: Sulphur; Author: Connock, Lisa
In order to meet product acid quality requirements the sulphuric acid produced as a byproduct of metallurgical and smelting operations must be treated to remove the mercury content, typically to less than 0.5 ppm. Lisa Connock reports on the most popular techniques used to achieve these levels as well as a new technique which removes the mercury from the product acid rather than metallurgical gas entering the acid plant. Many sulphide ores contain varying amounts of mercury which is volatilized during metallurgical roasting and smelting operations. The mercury occurs in the sulphur dioxide gas partly as elemental mercury and partly in a chemically bound form. In a normal wet gas cleaning system, where metallurgical process gases are purified and cooled before passing through wet electrostatic precipitators, the elemental mercury vapours present in the process gases are only separated to a relatively small extent. Therefore, mercury easily enters the following stages where it is absorbed by sulphuric acid and results in a contaminated product which does not meet product acid quality requirements. Acid containing less than 1 ppm is a standard requirement, while less than 0.5 ppm is mandatory for sulphuric acid designated for food processing or animal feed production and fertilizer manufacture.[1] In fact, low mercury acid (e.g. containing 0.1 ppm Hg) often attracts a premium over typical merchant grade product containing up to 0.5 ppm mercury.[2] The most popular gas purification techniques for mercury removal are the Boliden Norzink process (34 plants worldwide) and the Thiosulphate

process (4 plants worldwide).[3] Both of these processes treat the smelter gas before it enters the sulphuric acid plant. A further option is to remove the mercury from the product acid using the relatively new Molecular Recognition Technology developed by IBC Advanced Technologies, which uses specially designed ligands to remove the mercury.[4] Process descriptions, performance and operating data, and process economics for alternative mercury removal techniques are given below. Boliden Contech of Helsingborg, Sweden offers three gas cleaning technologies for mercury removal: the Boliden Norzink process, the Thiosulphate process and selenium filter technology. The Thiosulphate process is used in conjunction with sulphuric acid production and yields an acid with a typical mercury content of 0.1-0.3 ppm. The Boliden Norzink process is a gas cleaning process and as such is used both for sulphuric acid production and for cleaning of gases prior to emission to the atmosphere. The process typically removes mercury to a level of between 0.5 and 1 ppm but can be improved to 0.2 ppm by cooling the gas to 20-25 [degrees] C and using very efficient wet electrostatic precipitators. Boliden's selenium filter can be used for mercury removal from dry or water vapour-saturated gases of any origin, provided they contain mercury in the elemental, gaseous form, e.g. off-gases from metallurgical processes and flue gases from waste incineration. Selenium filters achieve very low residual levels of mercury in the purified gas (0.025 mg/[Nm.sup.3] normal guarantee). Boliden Norzink mercury removal process Prior to mercury removal treatment by the Boliden Norzink process [ILLUSTRATION FOR FIGURE 1 OMITTED], gas must be cleaned in wet electrostatic precipitators until visibly clear. The S[O.sub.3] mist must be [less than]20 mg/[Nm.sup.3] as S[O.sub.3] and the dust should be reduced to [less than]1 mg/[Nm.sup.3]. The gas temperature at the entrance to the mercury scrubber should not exceed 40 [degrees] C. The scrubber (reaction tower) is installed in the plant directly after the last wet electrostatic precipitator stage. The gas scrubbing process is based upon the very fast and complete reaction that takes place when metallic mercury vapour comes into contact with mercuric chloride complex ions dissolved in a water solution in a gas scrubber: H[g.sup.0] + Hg[[(Cl).sub.n].sup.2-n] [right arrow] [Hg.sub.2][Cl.sub.2] + (n-2) [Cl.sup.-] (2 [less than or equal to] n [less than or equal to] 4)

During this reaction mercurous chloride (calomel) is precipitated as an insoluble compound suspended in the liquid phase. In order to separate the precipitated calomel, part of the solution, which would otherwise circulate over the reaction scrubber, is passed to a small thickener where it settles to the bottom as a heavy sludge. The clarified overflow solution is returned to the circulation circuit, while the heavy calomel sludge is passed to a second thickener, together with a certain volume of solution which must be bled from the primary scrubber circuit. The solution can be chemically treated by addition of appropriate chemicals to the secondary thickener/bleed treatment unit to provide a problemfree effluent. A small volume of excess calomel is removed for further processing. Calomel can be stored, disposed of or further refined into chemicals or converted into mercury metal, according to the user's preference. The rest of the calomel is passed to the chlorination vessel, where it is oxidized by the addition of chlorine gas to mercuric chloride: [Hg.sub.2][Cl.sub.2] + [Cl.sub.2] [right arrow] 2Hg[Cl.sub.2] The reaction takes place in standard chlorination equipment by contacting the chlorine gas in a vacuum ejector system. The strong mercury chloride solution from the chlorination stage is transferred to a small feed tank, from which it is closed into the scrubber reaction system to compensate for the consumption of mercuric ions. The scrubber is designed so that the mercury content of the gas leaving the scrubber will have been reduced to typically 0.05-0.10 mg/ [Nm.sup.3]. Sample performance and operating data are given in Table 1. Thiosulphate process In the Thiosulphate process [ILLUSTRATION FOR FIGURE 2 OMITTED], mercury-contaminated gas is treated in two consecutive drying towers. In the first drying tower the major part of [TABULAR DATA FOR TABLE 1 OMITTED] [TABULAR DATA FOR TABLE 2 OMITTED] the water content and a minor part of the mercury content is absorbed in circulating 78% sulphuric acid (absorption acid). In this predrying stage it is essential to control the acid strength and the acid temperature (40 [degrees] C) at the inlet to the predryer. At a normal product acid concentration of about 95 [degrees] C it is difficult to remove mercury to a low residual level because the oxidising power of the strong acid affects the mercury precipitation

mechanisms. However, if the acid concentration is reduced to around 80% it is easier to precipitate the mercury. In the (post)drying stage, the gas arrives at the second dryer with most of its original elemental mercury content and some residual water content. Circulating 99% sulphuric acid absorbs the water and mercury vapours. Cooling is not normally necessary in this stage. The high concentration of acid is maintained by adding make-up S[O.sub.3] gas to the interconnected small absorption (oxidation) tower. The amount of sulphur trioxide needed is nearly equivalent to the amount of water absorbed by the dryer. The purified gas enters the sulphuric acid contact plant, where sulphuric acid containing well below 0.5 g/ton Hg, typically 0.1-0.3 ppm Hg ([less than]0.5 g/ton Hg) is produced. After the two-stage drying process all mercury will be contained in the drying acids. The mercury-contaminated acid bleed from the drying towers is pumped to a reactor tank where it is diluted with water to about 80%, cooled and contacted with a solution of sodium thiosulphate solution. A precipitate of insoluble mercury sulphide and free sulphur is formed by different mechanisms. The removal of mercury in the 80% acid with thiosulphate is mainly based on the following reaction: [H.sub.2]S[O.sub.4] + [Na.sub.2][S.sub.2][O.sub.3] [right arrow] S + S[O.sub.2] + [Na.sub.2]S[O.sub.4] + [H.sub.2]O Sulphur is formed in a fine colloidal form with a large active surface for the absorption of mercury. At higher acid concentrations, i.e. 85% or more, the oxidising power of the strong acid oxidises the elemental sulphur to sulphur dioxide with the result that mercury removal efficiency is impaired. [TABULAR DATA FOR TABLE 3 OMITTED] Celite is also added to the reactor to facilitate the subsequent filtration. The resulting purified weak sulphuric acid is recycled to the contact acid plant where it is used as makeup water in the existing absorption system. The solids separated from the acid are collected in a container for disposal or recycle. Selenium filter technology The selenium filter is normally the last step in a gas cleaning process and the gas entering it should have a relatively low dust content, not higher than 10 mg/[m.sup.3].

The selenium filter mass consists of a support material, mainly silica, which is coated with the active substance, selenium, by a special process. The porous structure and granular size of the support material maintains a low pressure drop over the filter. Mercury in the gas reacts with the selenium to form mercury selenide (HgSe). Owing to the high stability, extremely low solubility in water and very low vapour pressure of mercury selenide, the spent selenium filter mass is non-combustible and will not leak mercury due to vaporization or leaching, thus making it suitable for disposal. The standard filter unit consists of a cylindrical shelf fitted with inlet and outlet connectors. The gas is forced radially through a cylindrical layer of the filer mass. Standard units are available in a wide range of sizes. The optimum residence time for the gas inside the filter normally varies from 2 to 9 seconds depending upon the mercury concentration. Capital and operating cost comparisons Capital cost comparisons for Boliden mercury removal technologies are given in Table 2. The Thiosulphate process is generally more expensive to install than the Boliden Norzink process, unless there is a predrying tower already in the acid plant. The relative cost of selenium filters compared to the Boliden Norzink and Thiosulphate methods increases with capacity. The reason for this is that selenium filters, for practical reasons, are not normally built for capacities higher than about 40,000 [Nm.sup.3]/h. Parallel units become necessary for higher volumes. The Boliden Norzink and Thiosulphate methods, however, can be built for much higher throughputs in one line. Therefore, the selenium filters are most economical for gas volumes of up to 30,000 [Nm.sup.3]/h containing up to 1-2 mg/[Nm.sup.3] of mercury. Operating costs for the Boliden Norzink and Thiosulphate process are given in Table 3. No data is given for selenium filters as the selenium filter mass normally lasts five years or more before it needs to be exchanged. Molecular Recognition Technology Molecular Recognition Technology (MRT), developed by IBC Advanced Technologies, Inc., American Fork, Utah, is a highly efficient separation technology which uses a series of fixed bed columns packed with SuperLig[R] materials (specially designed ligands, chemically bonded to solid supports, such as silica gel), to selectively separate specific individual metal species from mining/metallurgical effluent streams. The columns can be built in skid mounted modular form and can be fully automated for continuous operation. In contrast to conventional chelation chemistries (such as ion exchange) which often distinguish among ions based only on a single

parameter (i.e. charge, solubility, size), MRT utilizes "host-guest" chemistry to selectively bind with ions based on multiple parameters such as size, co-ordination chemistry and geometry. Tailored organic molecules, "hosts", selectively bind with target molecules, "guests", in a lock-and-key fashion. The host molecules are bound to a solid substrate and are used to remove the target guest molecules from a passing industrial stream. A simple chemical process removes the guest molecules leaving the hosts ready for reuse. Three of the original researchers in host-guest chemistry won the 1987 Nobel Prize in Chemistry. When applied for the removal of trace mercury from metallurgical sulphuric acid, the MRT process can be used alone for bulk removal of mercury from streams containing up to 150 ppm mercury, where no other mercury removal system exists, or in "polishing" applications where bulk mercury removal facilities already exist. With the MRT system mercury levels of less than 0.1 ppm can be obtained in the output stream in the "polishing" mode, based on input levels of 0.3-3 ppm mercury. MRT process description The concentrated sulphuric acid stream, which may require prefiltration, at ambient temperature, and at corrected oxidation-reduction potential (ORP) of 600-900 mV vs Ag/AgCl (using S[O.sub.2] or 30% [H.sub.2][O.sub.2]), is fed through the fixed bed columns at 30 bed volumes per hour. The ORP in the indicated range ensures that the mercury is in the +2 oxidation state, so it is removed most efficiently and so the SuperLig[R] material is not harmed by any ligand oxidation. The mercury is loaded onto the SuperLig[R] in the columns which are in lead/trail configuration. The MRT skid usually consists of several columns operating in series. The acid enters the lead column and flows downward through the bed of SuperLig[R] material. The SuperLig[R] material removes the bulk of the mercury in the acid. The acid flows out of the bottom of the lead column and enters the top of the next column and continues in this manner through the remaining columns. The columns downstream of the lead column perform the polishing function to ensure that the mercury levels in the product acid are reduced below 0.1 ppm. The purified acid stream passes through the system and is ready for market as low mercury acid product. The columns are operated in cyclic mode. Each column in turn operates as the lead column. When the lead column is fully loaded it is taken out of service and the second column in the series becomes the lead column. The standby column containing fresh SuperLig[R] becomes the final polishing column. This mode of operation ensures that the lead column is fully loaded utilizing the full SuperLig[R] capacity.

The newest column is always at the end which ensures the maximum polishing capacity to achieve the desired low mercury levels in the product acid. The performance of the system is monitored by taking regular acid samples and analysing for mercury. As the mercury concentration leaving the lead column approaches the feed mercury concentration, the SuperLig[R] is becoming fully loaded and will need to be taken out of service. Process options The MRT system offers the option of multi-cycle use by stripping of the ligand with a choice of various eluents, which regenerates the ligand, or one time use only, depending upon the specific application and needs of the end user. Multi-cycle use Figure 3 shows the process flow sheet for multi-cycle use with thiourea eluent. Once fully loaded with mercury, the lead column is drained and washed with ambient 55% sulphuric acid, then drained and washed with ambient water. This two-stage wash and drainage is required to minimize the heat of mixing of water with concentrated sulphuric acid in the eluent and feed respectively. The discharge from the lead column is either recycled or discharged to effluent. The SuperLig[R] in the lead column is eluted with recycled and filtered eluate from the previous cycle followed by fresh filtered ambient acidic thiourea (eluent). The initial volume containing the vast majority of the bound mercury is discharged from the lead column and passed on to the mercury recovery circuit. The rest is held in the eluate recycle tanks for the next elution. After elution another two-stage wash and drainage is required to prepare the lead column as the trail column for the next cycle, to minimize eluant cross contamination to the new lead column and to minimize heat of mixing effects. The second two-stage wash and drain consists of ambient water followed by ambient 55% sulphuric acid. There are two options for mercury recovery: Option 1: The solution discharged to the mercury recovery circuit is simply hydrolysed with the addition of base such as NaOH, raising the pH to greater than 9, and collection of the Hg (II) as HgS solid, which can be filtered and recovered. The thiourea products can be oxidized to carbon dioxide and nitrogen by using hydrogen peroxide or other oxidizing conditions.

Option 2: It is also possible to electrowin to produce metallic mercury of marketable quality. In this process, the ambient mercury-rich eluate fraction is collected in an agitated surge tank. The pH is raised to above 2 (to neutralize the 0.1M [H.sub.2]S[O.sub.4] and the thiourea) by the controlled addition of 50% NaOH. The conditioned eluate is then pumped to the batch operated EW cells via cartridge filters. During electrowinning mercury liquid is formed at the cathode. Current efficiencies of 30-60% can be expected, depending upon the final mercury concentration in the spent electrolyte. Power consumption is estimated at 1 kWh/kg mercury produced. The mercury settles to the bottom of the cell and is drawn off as pure mercury metal product which can be packaged and sold. The thiourea decomposes to sulphur and urea. The mercury-lean electrolyte contains 10-50 ppm mercury and is pumped to waste water treatment. One option to be further tested is to minimize thiourea decomposition and attempt to recycle part of the electrolyte stream as fresh eluant make-up. One time use only polishing system The one time use only option shown in Fig. 4 is most efficient in polishing applications. The SuperLig[R], once fully loaded with mercury, is removed from the column and either disposed of directly in the internal plant operations (e.g. by recycling back to the smelter and collecting with the primary mercury recovery system) or sent to outside third parties where the product can be safely disposed of under environmentally sound conditions. Results of mercury extraction with MRT Figure 5 demonstrates typical cycle data for removal of mercury from concentrated sulphuric acid. The solution at an input mercury concentration of 450 ppb was flowed through the single column system for 10 full loading and elution cycles. Before each loading cycle, the mercury was eluted using 0.5M thiourea and 0.1M [H.sub.2]S[O.sub.4] and washed with distilled, deionized water and reagent grade [H.sub.2]S[O.sub.4]. The oxidation reduction potential was maintained at 600-900 mV vs Ag/AgCl. The mercury content in the effluent solution averaged less than 50 ppb. The results also confirmed that the stability of the SuperLig[R] was maintained through at least ten cycles. Commercial tests, consisting of multi-columns in series, at several major European base metal smelting/refining complexes have successfully demonstrated the MRT polishing process, including both single use and multi-cycle re-use of the SuperLig[R]. Consistent

mercury levels in sulphuric acid output solution of less than 0.1 ppm have been achieved based on mercury content in feed ranging from 110 ppm. Pilot units operating at flow rate of 30-60 bed volumes per hour have achieved mercury output levels of 0.05 ppm, based on input feed concentrations of 0.6-0.7 ppm, in single cycle use application. References 1. Daum K. H. and Sneyd, R. J.: "Gas purification for metallurgical sulphuric acid plants". Sulphur 93, Hamburg (April 1993). 2. "Quantity vs quality", Sulphur No. 231, pp. 21-24 (Mar-Apr 1994). 3. Private correspondence with Boliden Contech. 4. Dale, J. B. and Izatt, N.E.: "The use of Molecular Recognition Technology (MRT) for treatment of mining and metallurgical effluent solution. COPYRIGHT 1998 CRU Publishing Ltd. This material is published under license from the publisher through the Gale Group, Farmington Hills, Michigan. All inquiries regarding rights should be directed to the Gale Group.

Title: Improvements in gas cleaning systems for cold-gas sulphuric acid plants. (Sulphuric Acid Technology) Date: 7/1/1989; Publication: Sulphur;
Progress in the quest for efficiency, energy economy, effluent control Improvements in gas cleaning systems for cold-gas sulphuric acid plants Elemental sulphur used in sulphur-burning sulphuric acid plants is usually of such high purity that the combustion gases can be passed directly as feed gas to the conversion stages with no preliminary cleaning treatment. In stark contrast, [SO.sub.2]-containing off-gases resulting from the thermal treatment of sulphide ores, waste sulphates or waste sulphuric acid are heavily contaminated with dust and with chemical impurities, which may not only impair the operation of the sulphuric acid plant but also appear as unacceptable constituents in the product acid. To remove them to high standards of purity necessitates treatment in a massive, elaborate and costly gas purification system. The ideal combination of simplicity and cheapness with high efficiency, low energy consumption and zero pollution is about as elusive as the philosopher's stone; nevertheless, there have been a number of quiet improvements in the various parts of gas

cleaning systems over the years, and some of the latest designs are beginning to shake off the old clumsy image and to offer the prospect of definite improvements in the economics of sulphuric acid production from off-gases. In the operation of a sulphuric acid plant a very pure feed gas is an important prerequisite. This is necessary not only to ensure that the product will be of an acceptable purity but also in the interests of efficient and safe operation of the plant. Feed gases produced as offgases from other processes rather than from the combustion of elemental sulphur almost always contain a heavy loading of impurities of various kinds, and that is, indeed, one of the adverse economic factors common to all of them. Clearly the range of impurities and their concentration depends on how and from what input material the off-gas has been produced. Metallurgical operations (pyrites and non-ferrous ore roasting) usually produce the greatest diversity and the greatest loadings, and it is that type of plant which is contemplated in the rest of this article. Outline of a metallurgical gas cleaning system Impurities from such sources fall into four broad categories: dusts, fumes, volatiles and gaseous impurities. Dusts are discharged as such from the roaster. The loading and particle size range depend on the type of furnace and the nature of the ore being processed. A fluidizedbed roaster processing flotation pyrites (very fine pyrites separated from certain copper sulphide ores by flotation), for example, is likely to emit a higher proportion of fine dust than an old-fashioned multiplehearth roaster processing coarse-grained pyrites. Fumes are aerosols of ultra-fine solid particles of materials, especially lead and zinc compounds, which are vaporized at the very high temperature in the roaster but resolidify in the exhaust gas at relatively high temperatures (300-400 [degrees] C) as it cools. They range in size between about 0.01 and 2 m. Volatiles remain in the vapour phase to lower temperatures; they include compounds of arsenic, selenium and mercury, and sulphuric acid. Gaseous impurities include hydrogen chloride, hydrogen fluoride, carbon dioxide and small quantities of carbon monoxide. The latter two are not harmful in the concentrations at which they normally occur. In the first process step of the sulphuric acid plant, sulphur dioxide is oxidized to sulphur trioxide as it passes through a solid catalyst. Any dust or ash present in the feed gas will be filtered out in the first catalyst bed, occluding the voids through which the gas passes and in which the all-important contact between the gas and the catalytic surface takes place. As the dust accumulates, the resistance to gas flow increases, to compensate for which more power must be used in the main blower, while the efficiency of the catalyst falls off somewhat. Eventually the pressure drop becomes unacceptable and the plant

must be shut down to permit screening of the first-bed catalyst. This has to be undertaken as a necessary maintenance operation from time to time during the service life of any sulphuric acid plant, but (for obvious reasons) as infrequently as possible. So it is necessary to exclude entrained solids from the feed gas to a very high standard. Arsenic, selenium and mercury compounds will pass in the vapour phase through all the catalytic stages of the plant and will be absorbed into the product acid. They are all toxic, and only very low concentrations are permissible in product acid, especially that destined for use in the food or pharmaceutical industries. Arsenic additionally damages the catalyst, while mercury compounds can build up in heat exchangers, reducing efficiency and even causing failures. For those reasons, and on account of technological problems in post-treating high-concentration sulphuric acid, it is usual practice to remove them from the feed gas before it enters the sulphuric acid plant. Hydrogen chloride and hydrogen fluoride damage the silica-supported vanadium pentoxide catalyst by chemical attack. They also become absorbed in the product acid and cause corrosion in the acid circuits. Since they are vapours, they must be removed from the feed gas by wet scrubbing. Under the conditions in the scrubbing process, the small concentration of sulphur trioxide always present in the feed gas will react with water to form sulphuric acid, which condenses as an aerosol of exceedingly fine liquid particles known as acid mist. This effect is much exacerbated if fume has not previously been removed from the gas, since it acts as a nucleating agent for the mist particles. Mist will create havoc in contact with any metal surfaces later in the plant, and it must be rigorously excluded, but on account of the exceedingly fine size of the particles this is very difficult and requires especially effective measures. The gas cleaning system must therefore perform a number of discrete operations under differing conditions. In order, these are dust and fume removal, wet scrubbing, mist elimination and mercury removal (if required). As will be explained below, it is also necessary to cool the gas between the scrubbing section and the final mist eliminators. For technical reasons, all parts of the system must function at high efficiency but, for economic reasons, all must cause the bare minimum of pressure drop. It is the balance between these opposing criteria -- for the price of efficiency is nearly always pressure drop -- that determines the type and design of the individual stages of the gas cleaning system. Nevertheless, there is still scope for variation in design philosophy, at least in some parts of the system. Recently, also, new environmental regulations have necessitated changes in the way liquid effluents from the wet stages are handled in some systems.

Dust and fume removal Conventional gas cleaning systems remove as much as possible of the solids and fume from the gas stream in a dry state. Pressure drop considerations rule out the use of mechanical impingement devices such as fabric filters for collecting dust from the sizeable volumes of gas involved. With few exceptions, the coarser dust particles are collected in dry cyclones, which may typically reduce the dust content of the gas from 50-150 g/[Nm.sup.3] to 10-15 g/[Nm.sup.3] for a pressure drop of 5-10 mbar. The raw gas is first cooled, if necessary, to 250-400 [degrees] C. This is low enough for fume components to resolidify from the vapour phase but far enough above the dewpoint of corrosive constituents to obviate the need for special materials of construction. To remove the remaining fines, the only device efficient enough at an acceptably low pressure drop is an electrostatic precipitator. The gas passes through a corona (silent) discharge between banks of electrodes, which are alternately grounded and maintained at a negative potential of 10-80 kV. Electrons streaming from the charged electrodes collide with neutral gas molecules, converting them to negative ions, and these in turn attach themselves to dust particles, which are consequently drawn towards the grounded (collector) electrodes, where they are discharged. To attain the charge intensity needed to produce a corona discharge at the lowest possible potential, the charged electrode needs to have a very small surface area, whereas the collector electrodes should have a large surface area to ensure the most efficient possible capture of the charged dust particles. For that reason dry precipitators normally comprise a series of parallel collector plates, vertically mounted so that the discharged dust can fall from them by gravity into discharge hoppers beneath, with rows of discharge wires, which may be fluted or barbed to enhance the corona effect, suspended in frames in the spaces between them. Mechanically operated hammers are provided to dislodge accumulated dust from the collector electrodes. The gas flows horizontally through the precipitator.[1,2] Electrostatic precipitators are extremely efficient (99%+) at minimal pressure drop (about 1 mbar), but they are of necessity very large on account of the need to keep gas velocities below the level at which the already precipitated dust will be re-entrained to any significant extent. Their initial cost is therefore high. Electricity consumption is about 1.52.5 kWh per 1,000 [Nm.sup.3]. Quenching, scrubbing and cooling It is necessary next to remove any dust which may have passed through the precipitator as well as sub-micron fume, volatiles and gaseous impurities. For that purpose the gas has to be cooled and then scrubbed. Scrubbing will saturate the gas with moisture, and since it

will be most efficient if the gas is already in that condition, it has long been the practice to cool the gas by quenching with aqueous scrubbing liquor in a void spray tower. Under the essentially adiabatic conditions, the gas is cooled by evaporation of water from the scrubbing liquor until the temperature reaches saturation point, normally somewhere between 50 [degrees] and 80 [degrees] C. The gas then passes into the scrubber. In early plants this was always a tower scrubber, either packed or with tray internals of some kind. Many plants have been built with the saturator and a tray scrubber integrated in a single tower; this type of device is known as a Peabody or Swemco tower. In recent years towers have been replaced increasingly by other kinds of gas-liquid contact device. In the quench/scrubber section, most of the volatile impurities such as arsenic and selenium compounds condense and dissolve in the scrubbing liquor. Gaseous impurities such as hydrogen chloride and hydrogen fluoride are also largely absorbed. The small proportion of sulphur trioxide in the gas reacts with the water vapour, and sulphuric acid condenses, mostly as a fog of sub-micron particles known as acid mist, though some dissolves in the scrubbing liquor. The wash liquor in the scrubbing system is cooled, for two reasons. First, it enhances the scrubbing efficiency for the most volatile impurities, hydrogen chloride and hydrogen fluoride. Secondly, the moisture content of the saturated feed gas at the temperature at which it leaves the quench tower is too high to maintain a high product concentration in the subsequent sulphuric acid plant, especially if the feed gas is lean off-gas from a smelting operation: not enough sulphur trioxide would be produced in the sulphuric acid plant to use up the water absorbed in the drying tower. Therefore further cooling is required to condense out the surplus moisture. The lower value represents the lowest product concentration that can be handled in a normal contact sulphuric acid plant without recourse to special materials of construction. Because the scrubbing liquor is recirculated, its sulphuric acid concentration and impurities content will build up unless a bleed stream is withdrawn and replaced with water or more dilute liquor from elsewhere. How large a portion of the circulation has to be bled, and consequently the sulphuric acid concentration of the scrubbing liquor, are determined by the maximum permissible vapour pressure over the solution of the gaseous impurities such as hydrogen chloride and hydrogen fluoride, which depends on their concentration in the solution and on the temperature. Where the feed gas contains unusually high concentrations of hydrogen fluoride, a siliceous material may be dispersed into the wash acid, or the gas may even be passed through a supplementary scrubbing tower filled with siliceous material, to react with the hydrogen fluoride to form fluosilicic acid, which has a much lower vapour pressure. In general, the wash acid contains between 5%

and 60% [H.sub.2SO.sub.4]. The advantage of maintaining the higher concentration is that acid of this strength can be purified and utilized or, if circumstances permit, upgraded by addition to the absorption circuit of the acid plant. Since sulphur dioxide is soluble to an appreciable extent in dilute sulphuric acid, the wash acid is circulated through a stripping column swept by the incoming air which is needed to adjust the oxygen content of the feed gas to the desired [O.sub.2]/[SO.sub.2] ratio. The wash acid circulating in the wet stages of the gas cleaning plant is very corrosive, and lead was for long the traditional acid-resistant material of construction. It is still used to some extent but, on account of its cost and the scarcity of skilled lead solderers, its place has largely been taken today by plastics. Today most saturation/scrubbing equipment is constructed with a carbon steel shell protected from acid attack by a plastic liner, which is itself protected from hot gases and erosion by acid-resistant bricks. An additional layer of carbon brick may be needed to protect the acid bricks from fluorine attack. Over the past 20 years, a cheaper, more compact alternative to conventional scrubber systems -- the Venturi contactor -- has been proved in an increasing number of installations and has, indeed, become virtually the industry standard. The gas passes downwards through a constriction into which the scrubbing liquor is injected in the same direction from spray nozzles arranged around its periphery. Because of the intensity of the gas-liquid contact in this type of scrubber, it is possible to dispense with the quencher-saturator, although conservatively designed installations may still include it. For a given pressure drop, a Venturi scrubber can achieve greater efficiency at a lower liquid circulation rate than a spray tower operating at the same pressure drop. And because the gas and liquid are admitted in cocurrent, the gas-side pressure drop can be reduced or eliminated altogether by using a higher liquid circulation rate.[4] Operating at a pressure drop of 12.5 mbar, a Venturi scrubber is about 75% efficient at removing sub-micron lead or zinc oxide fume.[5] Lurgi GmbH has a two-stage scrubber design incorporating a downdraught Venturi saturator as its first stage. It has been used in a number of non-ferrous metal smelters, steel works and waste incineration plants. After passing through the Venturi contactor the gas is collected into a short funnel-shaped duct, emerging radially through the gap between its lower end and the annular rim of a horizontal circular deflector. Scrubbing liquor is introduced into this zone through a single, central, large-aperture nozzle. The clearance between the bottom of the duct and the deflector is adjustable according to the gas volume, ensuring that the velocity of impingement between the gas and the scrubbing liquor is maintained at its optimum under the varying conditions that are so characteristic of non-ferrous smelting operations. As the gas emerges through the gap, guide vanes impart a

cyclonic motion to it. This throws liquid droplets and wet dust against the inside surface of the scrubber casing, where they coalesce and run into the sump. A separate cooler is needed after a Venturi scrubber to reduce the moisture content of the gas and to increase the solubility of hydrogen halides. This may be a conventional tower cooler, as used in current Swemco designs, or -- provided the sulphur dioxide concentration in the gas is about 6% or more -- it is possible to use graphite ("Karbate") shell-and-tube coolers in place of tower coolers. (At lower sulphur dioxide concentrations the surface area requirement is too high.) These coolers are mounted vertically so that the moisture condensing from the gas drains down the tube walls. A small amount of condensate is recirculated as irrigation liquor to prevent fouling if abnormal amounts of dust are carried over. Since the concentration of dissolved material in the liquid film is continuously declining along the length of the tube as moisture condenses into it, hydrogen fluoride and hydrogen chloride still present in the gas are efficiently absorbed in the liquid film. Lurgi has an indirect counter-current shell-and-tube cooler design known, from the cross-sectional shape of the tube walls, as a "star cooler".[5] The tubes, which are made of extruded lead, have fins on the interior (gas-side) surface to improve heat transfer. The total surface area on the gas side, and therefore its efficiency as an absorber for gaseous impurities, is in fact as high as that of a packed tower/acid cooler system of equivalent cost. Pressure drop in a cooler of this type designed to lower the gas temperature from 60 [degrees] to 40 [degrees] C is about 15 mbar. In a new 2,200-t/d sulphuric acid plant which Chemetics International Co., of Canada, is building for Noranda at a smelter in Quebec, quench cooling is used for initial cooling of the very hot gas from the smelter. This means that the heat and moisture loading are much higher downstream, and the saturation temperature in the gas washing system is about 80 [degrees] C. This is too high for lead, and the sudden moisture collapse which would result from cooling the unusually moist gas would rule out the use of graphite. Therefore Chemetics is installing a two-stage shell-and-tube cooler system in high-alloy stainless steel, the hotter of the two coolers being made of UNS N10276 (Hastelloy 276) and the colder of UNS 531254 (Avesta 254-SMO). These coolers have been designed with large-diameter tubes to eliminate the possibility of plugging and are symmetrical so that they can be reversed after a number of years in operation to extend their service life.[7] Mist elimination On account of its low particle size, acid mist is notoriously difficult to remove from a gas stream. It passes readily through all kinds of scrubber and would pass through the sulphuric acid plant drying tower,

to cause havoc in the heat exchangers which raise the temperature of the feed gas up to the [SO.sub.2]/[SO.sub.3] conversion temperature. It must therefore be very thoroughly removed from the gas as the last stage of the gas cleaning process: in general, the efficiency has to be greater than 99% and the gas must be optically clear. The difficulty arises from the extremely small size of the mist particles. About 40% of the acid mist particles in washed sulphur dioxide feed gas are 1 [micro]m or less in diameter.[8] The simplest form of separation device, an impingement filter such as a fibre pad filter, only works effectively if there is a big difference in momentum between the entrained particles and the gas molecules, so that they collide with the fibres of the filter medium while the gas molecules pass easily round them. At a particle size below about 1 [micro]m, the difference in momentum is becoming rather small, and such a fine-mesh filter is needed to produce a good separation that it presents a considerable resistance to the flow of gas.[8] Once again, therefore, electrostatic precipitators are used on account of their high efficiency at low pressure drop. On account of electrostatic effects, wet precipitators operate more efficiently at low mist loadings than they do at high ones; therefore it is common practice to have two precipitators, or two sets of parallel precipitators, in series. Sometimes the first set is placed upstream of the gas cooler. Wet electrostatic precipitators are nowadays of a markedly different design from dry precipitators. Collector electrodes are not plates, as in dry precipitators and in earlier designs of wet precipitator, but vertical ducts, typically about 0.25 m across. Their length is determined by the relation between the gas velocity and the migration rate of the charged mist particles and is typically 5-6 metres. The discharge electrodes run along their central axes. Both must be resistant to corrosion by the precipitated acid. Formerly lead was almost always used, as a structural material or as a lining for steel components, but it has been replaced progressively by plastics (for collector electrodes) and highalloy stainless steels. These are more durable and permit a far greater degree of prefabrication. Plastics are, of course, electrical insulators and have hydrophobic surfaces, and in order to ensure that the inside surface of the ducts will be coated with a continuous film of conductive liquid, the plastics are specially treated. As in dry precipitators, the object is to produce a corona discharge to charge the mist particles so that they will be repelled towards the grounded collector electrodes. Corona discharges form most easily round points or along sharp edges, and to obtain a satisfactory corona discharge at a potential unlikely to cause sparking, discharge electrodes are usually made as thin circular wires, or barbed or longitudinally ribbed wires or rods. It is also clearly important to ensure that the structure is sufficiently robust to maintain the designed

minimum clearance between the discharge and collector electrodes at all times, otherwise there is a danger of sparking. This is a factor of importance, for example, in the design of precipitators with plastic collector electrodes, which may distort in service if inadequately supported. From the point of view of theoretical efficiency, the ideal collector electrode is a tube of circular cross-section, since that is the only shape in which it is possible to establish a perfectly uniform electric field. Like the tubes in a heat exchanger, these are usually anchored in tubesheets at their ends (rigidly at at least one). Unlike a heat exchanger, however, there is no need for space between the tubes, but this cannot be avoided with cylindrical tubes; a precipitator with circular tubes therefore occupies a larger site area than one of the same capacity with square-section tubes, which fit together snugly. Square tubes can also be bonded or welded together to make a completely rigid structure, eliminating all risk of distortion under normal service conditions. Square-section collector electrodes also have a larger surface area than the largest cylindrical electrodes that will fit into the same plan area; however, the electric field is decidedly non-uniform, and the operating potential must be limited to a value which will not produce sparking between the discharge electrode and the middle of each face of the collector, which is well below the ideal potential across the longer distance between the discharge electrode and the corners of the collector electrode. As a compromise, some current precipitator designs have polygonal tubes. In the Hugo Petersen precipitator,[9] which is constructed of leadlined steel, the tubes are octagonal. With a special design of discharge electrode, the electric field distribution closely approaches that in a circular tube. This precipitator is entirely prefabricated, obviating the need for lead solderers in the field. In 1980 Lurgi introduced a design based on a honeycomb structure of extruded hexagonal PVC tubes, bonded together with glass fibre-reinforced polyester (FRP). This design is in successful operation in at least 25 units and is replacing the company's earlier design based on circular tubes. During the middle of the present decade, Boliden Mineral AB developed a tubular design, now manufactured and marketed by Edifo AB, to replace an earlier square-tubed precipitator series at one of its smelters in Sweden.[10] On account of the severe winter temperatures and the outdoor siting of the precipitators, stainless steel was chosen as the electrode material in preference to both lead and plastics. After a certain amount of experimentation with different discharge electrodes, a square rigid rod carrying a series of sharp needles welded to each face was found to give the best results. Another feature of this precipitator is that the insulators for the support frame of the discharge electrodes are not kept dry by continuous ventilation by heated air, as in many other designs, but are housed in a sealed box and heated

electrically. In a further development of the concept, the functions of precipitator and cooler have been integrated in a single unit, in which cooling water circulates between the collector electrodes. In some circumstances, it has been stated, single precipitator-cooler units can replace the need for a second set of conventional precipitators. Although a small-gauge electrode is needed to produce a good corona discharge, a wide-gauge, non-discharging electrode is more efficient at repelling the charged particles towards the collector electrode. The American company Beltran Inc. markets a two-stage precipitator design in which the first stage is optimized for particle charging and the second for particle collection.[11] For applications with sulphuric acid not exceeding 50% concentration it is normally fabricated in plastics (FRP). The residence time in the charging zone is considerably less than in the single-stage type of precipitator, and as no corona current is flowing in the collection zone, the overall power consumption is stated to be less than one third that of a single-stage precipitator of the same efficiency. Mercury removal Mercury occurs as an impurity in a number of commercial non-ferrous ores, most notably in zinc sulphides, the roasting of which is one source of [SO.sub.2]-containing off-gases used in sulphuric acid manufacture. During roasting, it is liberated in elemental form as its vapour, which is only partially removed in the normal gas cleaning train; the remainder finds its way into the product acid. With increased awareness of the toxic hazard of mercury, the industry now has specifications for maximum mercury levels in sulphuric acid for most purposes, and in some metallurgical acid plants these would be infringed without special treatment. Though it is possible to remove mercury from sulphuric acid by chemical treatment, it is generally preferred to remove it from the roaster gas. Most of the development work has been undertaken in Scandinavia, and of the various procedures investigated one, the Boliden-Norzink process, which is licensed to Lurgi, is most usually practised. This process is incorporated as the last stage in the gas cleaning system, downstream of the wet precipitators. The roaster gas is washed in a packed tower by a liquor comprising a solution of mercuric chloride, [Hg.sub.2Cl.sub.2]. This is separated from a sidestream in a thickener. To compensate for the depletion of the mercuric chloride in the scrubber circuit, a portion of the thickened slurry is subjected to oxidation with chlorine, which regenerates mercuric chloride, and is returned to the circuit. A mist eliminator in the top of the scrubbing tower prevents entrained droplets of scrubbing liquor from being carried over to the sulphuric acid plant. The process, which is in operation in a number of units, is highly efficient: the product acid

mercury level in acid produced from a zinc concentrate containing 350 ppm Hg is 0.3 ppm or less, which indicates an overall mercury removal efficiency greater than 99.9%.[12] Unconventional gas cleaning systems The conventional gas cleaning train as described above is clearly a quite complex and expensive installation. It also produces acidic liquid effluents containing some harmful and unpleasant substances. Apart from the developments in the individual stages, some of which have been mentioned above, improvements have been directed mainly at simplifying and cheapening the whole gas cleaning system and at eliminating effluent discharges. Conditions in some of the contemporary metallurgical installations have also presented some challenges in the design and materials specification of gas cleaning systems. Chemetics has a licence for the EDV (ElectroDynamic Venturi) gas cleaning system developed in France by LAB SA. The gas passes sequentially through two cross-flow scrubbing towers, downwards through the first and upwards through the second. Wash acid is introduced through a series of specially designed spray nozzles disposed down the central axis of the scrubber. Each produces a flat double conical spray pattern extending across the entire cross-section of the spray tower. The intense contact between the gas and the liquid cools and saturates the gas, thoroughly wets all particulate material, and arrests the coarser particles. Atop the second scrubber is a Venturi, and the adiabatic expansion which it causes cools the gas and promotes condensation to form on the fine particles. Above the scrubber is a high-intensity spray which entraps most of the remaining particulates. Finally, the gas passes through a an "electro-filtering Venturi module", designed to take the place of conventional wet precipitators. Further condensation takes place in the throat of another Venturi, and then the gas passes through a corona discharge issuing from the point of a negative electrode immediately above a spray nozzle. Particles and mist in the gas become charged negatively, while a positive charge is induced in the droplets from the spray nozzle. The attraction between the oppositely charged particles and spray enhances the scrubbing effect. Though successful at removing dust, heavy metals and halides, Chemetics' first EDV system, installed at a 770-t/d sulphuric acid plant for Vieille Montagne in Belgium in 1985, was unable to meet acid mist guarantees on a consistent basis. A single stage of wet precipitators had to be installed downstream, which solved the problem. Further development is in progress to eliminate the need for that in future. The three-stage gas cleaning system based on froth scrubbing technology, developed by E. I. Du Pont de Nemours & Co., that Monsanto EnviroChem Systems Inc. has installed as a replacement for a traditional gas

cleaning system at American Cyanamid's spent sulphuric acid regeneration plant at Hannibal, MO. It is now Monsanto's preferred gas cleaning technology for spent acid regeneration and metallurgical sulphuric acid installations. Hot gas at about 315 [degrees] C enters a reverse-jet scrubber, which quenches and saturates it and removes solid particulate. After passing through a separator, the gas passes through a "froth column" and a final reverse-jet scrubber, which cools the gas, condenses and collects acid mist, and removes any remaining solid particulate. All parts of the system are made of FRP, with the exception of the hot gas duct, which is brick lined. The portion of the first reverse jet scrubber above the spray zone is protected from thermal damage by irrigation with wash acid. An emergency water system is provided to maintain a water flow as long as required in the event of a failure in the wash acid circulation system. The turbulence induced in the scrubber by the contrary motion of the gas and the liquid jet produces a volume of froth containing large, rapidly resonating, non-atomized liquid volumes which present a large effective surface area to the gas. The froth zone and scrubbing efficiency can be maintained at high turn-down rates. The liquid is not atomized to any significant extent. Pressure drop is about 10 mbar. The froth column is a flooded baffle tray column in which the gas and liquid flows are arranged to create frothing conditions. It is stated to be 50% more efficient at cooling and scrubbing than conventional designs operating at the same pressure drop, and can be designed for flow rates and temperatures that minimize the formation of acid mist. Because the primary reverse jet scrubber is so efficient at removing particulate material, the scrubbing liquor in the froth column/final reverse jet circuit contains very little solids and can be cooled in a plate cooler. The installation is compact enough to be shop fabricated. The reverse jet scrubbers have only one or two large, wide spray nozzles, which are unlikely to become choked. Overall pressure drop is about half that of a spray tower/Venturi/gas cooler system. And mist levels in the cleaned gas are apparently so low that no wet precipitators are deemed necessary; certainly, none has been provided at the Hannibal plant. Effluent management In common with many other industries, sulphuric acid manufacturers have come under increased pressure in recent years to minimize the environmental impact of their operations, not just from gaseous emissions but also from liquid effluents. The Ralph M. Parsons Co., for example, recently undertook a contract to modify a gas cleaning system, which formerly used sea water as the scrubbing liquor and discharged it after stripping to recover sulphur dioxide, to a

recirculating system with indirect cooling by sea water. The new installation included bleed water treatment comprising neutralization followed by precipitation of heavy metals and separation of solids.[13] In its Total Recovery Concept, Hugo Petersen has avoided the waste of sulphuric acid values involved in neutralizing and discharging bleed liquor.[9] The following outline description is representative only: in practice, each plant would be custom-designed to suit the conditions of the individual site. Whatever the sulphur dioxide/moisture content of the gas, the sulphuric acid concentration of the wash liquor in the scrubbing circuit is maintained at 50-60%. To ensure good absorption of hydrogen halides, the acid concentration in the subsequent cooling stage must be kept down to 2-3%, so a separation device is installed in the gas line after the scrubber to knock out entrained scrubber acid. The cooled acid passes through a two-stage wet precipitator installation using the octagonal-tubed design described earlier. Drainage from the precipitators is introduced as make-up into the scrubbing liquor circuit. The moderately concentrated acid in the scrubbing tower circuit, containing almost all the solids (largely metal sulphates in both dissolved and insoluble form) is filtered and the solids are recycled to the roaster. Special treatment is needed to deal with impurities such as arsenic and selenium, which report only in the roaster gas and do not occur in the slag or cinder. The acid filtrate is further treated to precipitate the dissolved metals as sulphides, which are also recycled to the roaster, along with mercury values removed in the mercury recovery system (if included). The acid is then introduced to the acid plant absorber system in place of process water. The standard of purification is therefore governed by the product acid specification. The weak acid from the cooler circuit has to be neutralized and disposed of, but it amounts to only 10% of the effluent from a normal plant. It is neutralized in two stages, in the first of which most of the dissolved metals are precipitated as hydroxides, which are separated and returned to the roaster. In the second stage the sulphate values are precipitated, usually as calcium sulphate. This can sometimes be disposed of into a metallurgical process, the calcium values ending up in the slag, but when this option is not available it can be discharged safely on account of its low heavy metals content. The liquid remaining after neutralization is pure enough to be discharged without ill effect. References [1]"EGR Dust Collection". Lurgi Express Information S 1272/2.78. [2]"Horizontal Precipitators". Lurgi GmbH publication No. T 170 e (Sep 1982). [3]Sander, U. H. F., Rothe, U., and Kola, R.: "Sulphuric Acid". In "Sulphur, Sulphur Dioxide and Sulphuric Acid" (ed. More). British Sulphur (1984), p. 288. [4]Friedman, L. J.: "The sulfuric acid plant: Recent advances review and analysis". In "Sulphur 88": Preprints for British Sulphur's 13th International Conference, Vienna

(Nov 1988), pp. 429-452. [5]"Scrubbing and Cooling System in Sulphuric Acid Plants". Lurgi Express Information No. T 1270/7.83. [6]Black, B. (Swemco Ltd): Private communication (Jun 1989). [7]Bhaga, D.: Private communication (Jun 1989). [8]Daum, K.-H., and Schmitt, H.-D.: "Recent developments in gas cleaning systems for coldgas sulphuric acid plants". Presented at "Sulphur 85": British Sulphur's 9th International Conference, London (Nov 1985). [9]Daum, K.-H.: Private communication (Jun 1989). [10]Johansson, H., and Hedman, L.: "Wet electrostatic precipitator in stainless steel for sulphuric acid process -- experiences and improvements". In "Sulphur 88", pp. 137149. [11]Beltran, M.R., and Surati, H.: "Use of two-stage electrostatic precipitators in metallurgical roasting and sulphuric acid applications". In "Making the Most of Sulphuric Acid": Proceedings of British Sulphur's 5th International Conference, London (Nov 1981). [12]Steintveit, G.: "The Boliden-Norzink mercury removal process for purification of roaster gases". Norzink A/S, Odda, Norway. [13]Haydon, B. C.: Private communication (Jun 1989). COPYRIGHT 1989 CRU Publishing Ltd. This material is published under license from the publisher through the Gale Group, Farmington Hills, Michigan. All inquiries regarding rights should be directed to the Gale Group.

Title: Getting the details right.(Sulphuric Acid Technology) Date: 7/1/1995; Publication: Sulphur; In a technology as mature as that of sulphuric acid production, radical change is unusual and seemingly unnecessary. But improvements of detail are still important and worth while. Next year marks the 250th anniversary of the first recorded industrial production of sulphuric acid, when a Dr Roebuck pushed an iron cart containing a flaming mixture of "brimstone" (elemental sulphur) and nitre into a square chamber lined with lead and - somewhat hastily, one imagines - closed the door. The condensate later collected from inside the lead chamber consisted mainly of sulphuric acid. From such a humble beginning grew a mighty, world-wide industry producing millions of tonnes of sulphuric acid every year. The main technological developments which made that possible were, first, the development of a continuous rather than batch-operated process scheme for the lead chamber process and then, much more significantly, the advent of the contact process, which uses a heterogeneous catalyst instead of nitrogen oxides to oxidize sulphur dioxide to sulphur trioxide. The first patent for a contact process, using platinum as the catalyst, was awarded to one Phillips, of Bristol, England, in 1831, though it was

not until later in the century, with the growth in demand for highconcentration sulphuric acid for dyes and explosives production, that serious attempts were made to develop it. The new process offered the prospect of making sulphuric acid of a purity and concentration not attainable with any lead chamber process, and it cut out the nitrogen oxides which, even in the environmentally care-free days of the industrial revolution, must have been seen as an offensive nuisance. Once vanadium pentoxide had been identified as the best basis for the catalyst, the contact process became one of the most efficient processes in the entire chemical industry, and apart from just one substantial improvement the introduction of intermediate absorption in the 1960s - it is, in principle, very little different today from what it was in the 1920s. That is not to say that contact sulphuric acid plant technology today is not massively more sophisticated than in the early days. Research and development effort which, in other, less fortunate areas of the chemical industry, might have been expended in the quest for a better alternative to a barely satisfactory process has, in the case of the sulphuric acid industry, gone into refining, polishing and generally perfecting an already highly satisfactory process to fulfil contemporary economic, energetic, environmental and efficiency criteria, and adapting it for new areas of application. The last comprehensive review of the complete process was Monsanto's HRS process, in which the drying tower was omitted and the intermediate absorber and its associated heat exchangers - an inherent source of thermal inefficiency and a possible seat of corrosion in the conventional double-absorption process - were replaced by a hot condensation system operating at a higher-than-normal acid concentration (99+%) and temperature (up to 220 [degrees] C) to allow maximum recovery of useful heat from the acid. In principle, the concept was not new, as hot condensation was already well known in "wet gas" sulphuric acid plants burning waste hydrogen sulphide. What was indeed new, however, was its use where a conventional plant would normally be chosen and where it was possible to exploit the high acid concentration - unattainable in an actual wet gas plant - to allow corrosion-free operation at high acid temperatures. Most of the current development work is aimed at detailed aspects of the process and, especially, at individual items of process hardware. The main motivation is not always straightforward economic gain or operational advantage. In various countries environmental regulations demand a degree of efficiency which is not justified on economic grounds - nor, it must be said, is it always entirely justified on rational environmental grounds, either! Aided by some spectacular damages awards in the USA, the safety of operating personnel is rightly being accorded progressively greater importance, and that translates into a need not only for greater vigilance to spot problems as they begin to appear but also greater durability and reliability in equipment and the

materials of which it is constructed. In the current climate of "downsizing" (now also known by a politically-correct euphemism, "rightsizing", presumably to disguise the implication of personnel redundancy), in which plants are obliged to run with lower spares inventories and minimum personnel, these attributes are clearly desirable, too. This policy of downsizing, by the way, has neatly shifted the responsibility for maintaining and financing a safe spares inventory from the operator to the equipment supplier, whose emergency response time must be concomitantly shorter. While not pretending to be comprehensive, this article reports on a representative selection of recent technological developments. Areas of development Currently the most active area of sulphuric acid plant investment is the metallurgical by-product acid area. The ores of most non-ferrous metals, including copper, lead, zinc and nickel, usually contain sulphides of the respective metal, and these are decomposed by pyrometallurgical processing (roasting and smelting) to give sulphur dioxide in quantities which, on account of the large scale of most smelting operations, are far too large to allow into the atmosphere. It is usual practice to convert the waste sulphur dioxide into sulphuric acid, even though the conditions are sometimes far from ideal. Acid produced in this way is referred to as "fatal" or non-discretionary, since it must be produced as long as the metal smelter is in operation, irrespective of the conditions in the sulphuric acid market. The growth in non-discretionary by-product sulphuric acid has resulted largely from recovery in the metals sector of the world economy and the widespread imposition of new sulphur dioxide abatement standards. It is something of a headache, both for its producers and for competing suppliers of elemental sulphur, the raw material used by the discretionary sulphuric acid producers. On account of its hazardous and corrosive nature, it is undesirable and unpractical to store sulphuric acid in large quantities for any length of time, which means that it has to be shipped to consumers as fast as it is produced. Often, however, the potential ultimate users of by-product acid are remote from its source - perhaps not even in the same country. The logistical feasibility of moving by-product sulphuric acid to consumers is a major consideration in any new non-ferrous project, and although that industry has recently won a respite in the form of an actual shortage of sulphuric acid on the world market, the likelihood of a global surplus in the longer term is one of its most serious concerns. Apart from the practical and economic disadvantages encountered in transporting and handling it, by-product sulphuric acid has certain commercial disadvantages as a substitute for sulphuric acid produced from sulphur in captive facilities. In the first place, it is cold and comes without any of the very substantial and valuable by-product energy

available in a sulphur-burning plant. That is an important consideration for phosphoric acid producers, for example, who need substantial amounts of heat for concentrating their product. It may, however, be less important in other instances, where there may be no correspondingly sizeable process use for the energy and it is used only in the cogeneration of power. On the other hand, non-fertilizer uses of sulphuric acid not infrequently require purer acid than phosphate processing. In the past, depending on the ores being processed, the specification could be difficult to satisfy in respect of impurities like arsenic and mercury. Today, however, these problems with impurities have largely been solved by optimization of the gas cleaning section and, where necessary, providing supplementary facilities for dealing with mercury, and metallurgical acid now rivals acid produced from elemental sulphur in purity. Efficient gas cleaning is also critically important to defend the sulphuric acid plant against damage and impaired operation. The last line of defence is the wet electrostatic precipitators, which are critically important in protecting the plant against damage by acid mist. Conventional ore roasting processes produce waste gases which, when adjusted to contain the correct [O.sub.2]:S[O.sub.2] ratio, give feed gases somewhat leaner in sulphur dioxide than the ideal produced by burning elemental sulphur (10.5-11.5%). Few problems are entailed in operating on feed gases in the range 58% S[O.sub.2], although fluctuations in the feed gas composition cause some problems in process control. With certain special measures, the sulphuric acid process can, in fact, be made to operate autothermally (i.e. produces sufficient reaction heat to sustain the catalyst beds at their operating temperatures) on gases down to about 1.5% S[O.sub.2], but the equipment (especially the gas-gas heat exchangers) becomes very large in relation to the throughput of acid. In past years sulphuric acid process designers have been somewhat preoccupied with the problem of efficiently processing these marginal sulphur dioxide feed gases. This aspect was covered recently in Sulphur.[1] Now, however, the challenge is shifting to the other end of the feed gas concentration range. The newer high-intensity metal ore roasting and smelting processes such as flash smelting generate waste gases with sulphur dioxide contents as high as 60% S[O.sub.2], from which it is possible to produce, though not yet to process, acid plant feed gases containing up to about 20% S[O.sub.2]. (That is a problem that Monsanto Enviro-Chem is working on at present). To make use of anything more concentrated than 11.5% S[O.sub.2] feed gas requires caution, on account not only of potential problems in the process itself (catalyst overheating, for example) but also of product quality considerations. At the higher temperatures in the metallurgical process appreciable concentrations of nitrogen oxides are formed and become incorporated in the product acid as nitrosylsulphuric acid, increasing its corrosivity and oxidation potential.

While conversion catalysts and critical equipment items - pumps, valves and acid coolers, for example - and the materials from which they are fabricated are the subject of continual research and development, the massive scale of recent projects (2,000 t/d and more) has necessitated new attention to the design of the heaviest and most permanent equipment items such as the converter, gas-gas heat exchangers and the drying and absorption towers and their internals. Gas cleaning: the wet precipitators Raw gases from a smelter have to undergo extensive cleaning and conditioning before admission to the sulphuric acid plant. This comprises cooling, dry dust removal, wet scrubbing to remove volatile impurities and remaining traces of dust, and, finally, removal of the acid mist which results from the reaction of the traces of sulphur trioxide in the feed gas with water vapour in the wet scrubber. On account of the high volumes of gas involved, electrostatic precipitators are used for both dry dust and acid mist removal because they impose lower pressure drop than any kind of filter or impingement device. Acid mist is one of the most destructive hazards encountered in sulphuric acid plant operation, and it is also one of the most difficult to remove because, on account of its exceedingly small ("sub-micron") particle size, it behaves as an aerosol. If allowed to come into contact with steel ducting or equipment shells, it causes corrosion, and the resulting iron sulphates build up in heat exchangers and on the catalyst, raising pressure drop and generally reducing efficiency. In a wet electrostatic precipitator the mist-containing gas passes through a corona discharge in the narrow space between two oppositely charged electrodes. A negative electrostatic charge is induced on the individual mist particles, which are then drawn to the collector electrode (the anode or positive electrode), where they coalesce to form a liquid film. The electrode surfaces are vertically disposed to ensure that the acid film drains away by gravity. The procedure depends for its success on low gas velocity through the device and adequate residence time in the electrostatic field. The electrodes must therefore be elongated and sufficient pairs must be provided to give the requisite low space velocity. Wet precipitators are therefore rather massive devices. The acid formed in a wet precipitator is fairly dilute, lying in a concentration range for handling which lead used to be the most favoured material of construction. Its corrosivity is increased by the presence of halides. For the large units needed to handle gas streams on today's grand scale lead is both far too expensive and far too heavy. Much lighter, more compact and cheaper devices can be made from other materials such as stainless steel or rigid PVC, and these materials can be worked and fashioned without the toxic risk to which the

fabrication and maintenance operatives of lead precipitators are exposed. On account of their vastly superior structural properties, these materials can be fashioned into tubular collector electrodes, the corona discharge emanating from a coaxial wire running the length of the collector tube. PVC is not, of course, electrically conductive; it is the acid film on its interior surface which acts as the electrode. Tubular precipitators are more stable, efficient and easier to control than the banks of flat lead plates which made up earlier wet precipitators. The concept is not new, but only recently has there been sufficient experience to prove it efficacious beyond doubt. The Chinese sulphuric acid industry, which still has numerous plants based on pyrite roasters as well as those feeding on smelter waste gases, has been using a tubular design making maximum use of PVC since the early 1970s.[2] In its largest embodiment to date, it comprises 330 vertical PVC tubes 4 m long with an internal diameter of 250 mm, making a collecting surface area of 16.2 [m.sup.2] per tube. The cathodes are lead-covered hexagonal wires with a maximum diameter of 10 mm which are maintained under tension by 7.9-kg lead weights. The upper and lower casings, which are 6.3 m in diameter, are also made of PVC, with appropriate strengthening ribs, internal bracing bars and external steel support members to give them the rigidity required to withstand the negative operating pressure. The M330 unit can handle a gas volume of 36,000 [m.sup.3]/h at a working pressure of -0.01 MPa. It operates at a voltage of 55-60 kV and a normal current of 150-180 mA (starting current is, however, 40-50 A), and it has an efficiency of 97-99%. In 18 years of operation of two M330 units in the Shanghai Wujing General Chemical Factory, only one tube has required replacement and no cracks or flaws have been found in any of the PVC structural components. The Editube wet electrostatic precipitator, marketed by Boliden Contech Chemical Technology, of Helsingborg, Sweden, is available in a variety of corrosion-resistant steels or metals selected to suit its application. For sulphuric acid-related service, Avesta 254 SMO, which has special resistance to halide-contaminated sulphuric acid, or, for less exacting conditions, SS 2377 have been specified. Eight units (one in 254 SMO, the others in SS 2377) with a total capacity of 150,000 N[m.sup.3]/h have been supplied since 1984 to Boliden Mineral's Skelleftehamn metallurgical sulphuric acid plant in Sweden. Recently Boliden Contech received an order for four 254 SMO units with a combined capacity of 60,000 N[m.sup.3]/h for Norzink's Odda zinc roaster/sulphuric acid works in Norway, and a single 14,000N[m.sup.3]/h SS 2377 unit is on order for Enichem's ammonium sulphate decomposition/sulphuric acid plant at Assemini, Sardinia. The Editube precipitator is assembled in the form of a tube bundle and, because the collector tube material is conductive, it can be enclosed in a stainless steel shell to form a vertical shell-and-tube cooler. The

additional moisture condensed out of the gas as a result dilutes and washes away the precipitated acid and its impurity content, reducing the risk of fouling. Cooling also minimizes the rate of corrosion, prolonging the life of the precipitator tubes. The operating principle is illustrated by Fig. 1. Gas enters the bottom chamber and rises up the collector tube, leaving through the upper chamber. Acid mist and other particulate impurities from the gas are drawn to the collector tube and drain under gravity into the lower chamber. The coaxial discharge electrode is made of high-alloy stainless steel and has radial needle-point projections at regular intervals along its length to assist the electrical discharge. As a result, the current obtained at a given voltage is increased by 50-80% [ILLUSTRATION FOR FIGURE 2 OMITTED]. Because of the intensity of the discharge from the needle tips, they tend to be self-cleaning and do not become fouled. The earliest Editube units are now ten years old, and experience so far has shown them to be almost entirely maintenance-free. While tubular precipitators are compact and have a more uniform electric field than plate types, cleaning and maintenance (when required) are less easy because of the confined working space. Nippon Dentetsu (ND), of Japan, has very considerable experience over more than 20 years as a supplier of over 200 plate-type wet electrostatic precipitators to Asian and African customers. Over 60 are in service in copper smelter sulphuric acid plants. Formerly their precipitators were of lead, but in 1973 the company introduced a conductive fibrereinforced polyester (C-FRP) plate-type precipitator. Since 1986 these C-FRP precipitators have been equipped with the more efficient crossneedle type of discharge electrode, though in lead-lined steel rather than stainless steel. They feature upward gas flow, a compact, prefabricated FRP casing, adjustable inlet vanes for optimum gas distribution, an intermittent flush system allowing intensive washdown, and optional continuous sprays to minimize the frequency of cleaning. At present ND is working on a novel precipitator designed for compactness and difficult applications. ND has recently appointed the US company Belco Technologies Corp., itself an experienced supplier of complete gas cleaning systems of some 30 years standing, as its North American licensee. Converters and heat exchangers The design of sulphuric acid converters has been addressed at some length in an earlier review.[3]

Today the main issues are size and the severity of the conditions that the converter must endure. In the conventional arrangement the catalyst beds are stacked one above the other in their own gas-tight compartments inside a single cylindrical vessel. The gas passes through them in a downward axial flow. Usually the gas leaves the converter after each catalyst bed to be cooled in an external heat exchanger before returning to the next catalyst bed. Occasionally one or more of the stages of cooling may comprise injecting cooler feed gas to the hot process gas stream, in which case an external heat exchanger is not necessary, but from the point of view of overall conversion that method is less efficient than the indirectly-cooled option. Good, even gas distribution over the catalyst mass is vitally important for achieving efficient conversion, and in the very large plants being designed today that is becoming harder to achieve. At the same time, as plant designers look at the tempting prospect of working with higher than normal gas strengths and concomitantly more exacting process conditions, something beyond the conventional construction of sulphuric acid converters (carbon steel shell, brick lining and catalyst bed support) looks desirable. About 11 years ago, the Canadian company Chemetics International installed a stainless steel converter in the Newark, NJ, works of Essex Chemical Co. Recently a major inspection was carried out during a turnaround to ascertain its condition, the results of which were reported at this year's AIChE Clearwater Convention.[4] The results should be of considerable interest to the operators of 21 other plants (metallurgical, sulphur-burning and spent acid regeneration) in Australia, Belgium, Canada, China, Kazakhstan, The Netherlands, Peru, UK and USA, who have invested in Chemetics stainless steel converters since 1981. Catalyst experience covers Topsoe and BASF rings and Chinese pellet catalyst. Some of these converters incorporated a Chemetics patented radialflow gas/gas heat exchanger in the central core; this takes the place of the external first-stage hot exchanger and thus eliminates the historically troublesome hot gas duct. In spite of some expressed reservations about maintenance access, none of the radial-flow heat exchangers has required any maintenance so far. In any case, the converter design allows full access to the top and bottom head shells, which is the same as for an external exchanger, while the entire unit can be lifted out if needed. The Chemetics converter has an all-welded construction which, depending on size, may be undertaken completely on site (largest units) or may be partly (medium units) or wholly (small units) prefabricated. The catalyst compartments are therefore much more gas-tight than a conventional cast iron grid-and-post design. There is no brick lining (a high-maintenance item in conventional converters)

and the shell does not need the metallizing treatment that is virtually vital to protect the interior of a carbon steel shell. The converter can be heated up rapidly on account of the thin construction, the low thermal capacity and general freedom from heat stress of the stainless steel construction. And by positioning the first bed at the bottom of the vessel instead of at the top, it has been possible to ease catalyst screening procedures considerably. Circular nozzles have been used in place of the more usual flattened "mouth-organ" designs, which give rise to maintenance problems. Finally, gas is introduced to each bed either radially from the converter core or through multiple entry pipes. The problem of scaling or flaking, so severe on unprotected interior surfaces of conventional converters, is completely absent in the stainless steel converters of sulphur-burning and spent acid regeneration plants, but a certain amount of scaling has been observed in the metallurgical plants. This appears to be worst with gas streams containing high sulphur contents and low oxygen contents. The corrosion-resistance of the 304H stainless steel of which the Chemetics converter is made depends on the build-up of a tenacious layer comprising mainly chromium oxide and chromium sulphide, which acts as a barrier to further reaction between the alloy and the gas. In highsulphur, low-oxygen gases, however, iron and nickel tend to react more readily, as a result of which more of them diffuses to the surface and forms a black oxide/sulphide scale. However, as shown in Fig. 3, the protective chromium oxide layer forms beneath this, and although thermal cycling resulting from the smelter operating mode may cause fragments of the superficial iron oxide scale to fall off, the scaling process does not proceed further unless something disturbs the underlying chromium oxide layer. The volume of the black iron oxide/sulphide scale is much greater than that of the metal lost, which makes the effect look much worse than, in fact, it is. Monsanto Enviro-Chem has entered into a licence agreement with Cecebe Technologies under which Monsanto now offers a "flexible membrane" stainless steel converter with structurally shaped beds and division plates, supported on a post-and-ring network [ILLUSTRATION FOR FIGURE 4 OMITTED].[5] This obviates the need for a top-to-bottom core tube, allowing full-diameter catalyst beds. Since the division plates and catalyst supports are shaped, they offer more start-up temperature differential freedom and require less material to provide the required support. The first commercial unit has recently gone into low-rate operation for Outokumpu in Finland. The Outokumpu plant has a capacity of 2,650 st/d and the converter, which incorporates an internal hot heat exchanger, is 15 m in diameter. Monsanto and Cecebe have also collaborated on a new radial-flow heat exchanger with improved thermal and mechanical performance. The gas flows from an open core to an outer annulus, providing low pressure drop, even thermal stress and optimum heat transfer. Because all the tubes are located within the baffles and none therefore

in the baffle windows, there is no longitudinal flow in the baffle windows, which detracts from the maximum attainable heat transfer coefficient. The tube fields within the annular bundle are laid out in either a hexagonal [ILLUSTRATION FOR FIGURE 5 OMITTED] or a pentagonal conformation. The patented latter arrangement allows closer spacing of the baffles, which is useful in the hotter exchangers. In comparison with a conventional double-segmental layout, the radialflow design gives a saving of about 20% in heat exchange surface. And because the shell is not close to the tube bundle, mechanical forces on the tube-tubesheet joints are minimized. This greatly extends the life of the heat exchanger. The first commercial examples of these heat exchangers have just completed their first full year in service. These include eight units installed in the 4 x 1,760 st/d sulphur-burning plants at Siape, Tunisia, which have been inspected at the annual shut-down when all was found to be well, and six bigger units at Magma Copper, Arizona. Mass transfer equipment Although venturi devices have been used to a limited extent for acid/gas contact devices in the sulphuric acid, notably by Lurgi, the majority of plants still use packed towers up which the process gas passes in countercurrent with irrigation acid distributed over top of the bed of packing medium.[6] Packings have improved considerably over the years, allowing the gas velocities to be progressively increased, but the best packing will not perform well unless the acid is distributed absolutely evenly across the entire cross-sectional area of the packing. Compared with other, more glamorous aspects of the sulphuric acid process, the acid distributors have until recently remained surprisingly simple and crude. For many years, they were made of cast iron, which corrodes in concentrated sulphuric acid but not too badly. Like the old serpentine acid coolers, which were also made of cast iron, these distributors were made with a generous corrosion allowance so they would last for perhaps five years before needing replacement. The corroded iron ended up in the product acid. Historically, distributors have usually been of two types: trough and pipe. Trough distributors are the most widely used. They comprise a series of parallel troughs or launders at about 0.75-1.5 m intervals, fed by a common pipe header. Acid overflows weirs disposed along the length of each trough into short tubes or "downcomers" which discharge it at low velocity below the top of the packing. This type of distributor has to be very carefully levelled, which is difficult in a large tower.
Table 1: Contaminant Levels in Product Acid (ppm) Sulphur-burning Metallurgical Contaminant plant plant

S[O.sub.2] Fe As N[O.sub.x] Ni Cr Hg

[less than]5 3 [less than]0.01 [less than]10 0.4 0.6 [less than]0.03

[less than]5 5 0.01 6 0.4 0.2 [less than]0.03

Pipe distributors, which distribute acid from perforations from branch pipes fed by a common header, cost less to make, but they have to be buried in the packing to prevent entrainment, which in itself restricts the area through which the gas can flow at the level of the distributor, which may lead to flooding and . . . entrainment! And it is almost impossible to control the flow in the individual distributor pipes in relation to one another. Special stainless alloys such as Lewmet or high-silicon alloys such as Saramet and SX effectively eliminate the corrosion and erosion problems as long as the acid concentration is kept within their best operating range, but they are expensive and they do nothing about the inherent physical shortcomings of the design. Cecebe Technologies has developed a hybrid distributor, which is a stainless alloy pipe distributor with Teflon downcomers.[7] To date six have been installed, all as replacements for earlier types in plants in the USA. Orders for three more, the largest of which will serve a 28 ft diameter tower, are currently being fulfilled for Mexicana de Cobre's 2,900 t/d plant in Nacozari, where they will replace cast iron spray distributors in all three towers. Cecebe has also looked carefully at the merits and demerits of the various existing types of tower packing and has developed an optimized ceramic saddle in which the hub of the saddle is perforated with sizeable apertures equivalent to about 30% of its area to facilitate through gas flow, while the wings (flanges) are notched with wide, shallow slots at their edges and perforated with small weep holes near the hub. This increases the flow of liquid over the surface and through the wings. The openings are large enough to prevent plugging by sulphate and are strategically located to preserve mechanical strength: a piece of the packing can withstand a force of 350 lb without breaking. Product quality As mentioned above, purity is an issue in acid originating from metal smelting operations. Some of the earlier purity problems of metallurgical acid have solved themselves as a result of improved technologies such as Monsanto's DynaWave scrubber[5,8] and the greater use of stainless steels in place of older, corrodible materials like cast iron. In almost every respect, including key impurities like mercury and arsenic, metallurgical acid from the most modern plants can now

be almost indistinguishable from acid from a sulphur-burning plant (Table 1).[5] Metallurgical gases from some of the newer, high-temperature smelter technologies, however, contain increased levels of nitrogen oxides. These are not effectively removed in the gas cleaning section and pass through the catalytic stages of the process unchanged. But a proportion of it is arrested in the mist eliminators in the drying and absorption towers and forms nitrosylsulphuric acid. This is a powerful oxidizing agent and increases the corrosivity of the acid, and it is therefore unacceptable in any more than the minutest traces. Even 100 ppm N[O.sub.x] in the feed gas can cause problems. Expedients such as selective catalytic reduction, which can be used to remove nitrogen oxides in combined N[O.sub.x]S[O.sub.2] abatement systems such as Topsoe's SNOX process or Lurgi's DESONOX process[9] are probably not applicable here, as the effect of introducing ammonia in the sort of amounts needed to decompose a small concentration of N[O.sub.x] into a gas stream containing very much higher concentrations of sulphur dioxide is uncertain and probably very difficult to control. There thus seem to be only two possibilities for curing the problem. One is to treat the acid with a reducing agent which will destroy its nitrogen oxide content without giving rise to any other undesirable residue in the acid. Hydrazine and sulphamic acid have both been proposed, hydrazine being the quickest and most effective, but expensive. The alternative is to collect the contaminated acid, strip the nitrogen oxides out of it and return it to the process. Lurgi Metallurgie has developed just such a stripping process [ILLUSTRATION FOR FIGURE 6 OMITTED][10] in which the acid from the candle filters is stripped by incoming feed gas and then returned to the main process. Even though the feed gas contains more nitrogen oxides, its sulphur dioxide content acts as a reducing agent for nitrosylsulphuric acid, itself being oxidized to sulphuric acid in the process. 2HNOS[O.sub.4] + 2[H.sub.2]O [right arrow] 2[H.sub.2]S[O.sub.4] + 2HN[O.sub.2] 3S[O.sub.2] + 3[H.sub.2]O [right arrow] 3[H.sub.2]S[O.sub.3] 2HN[O.sub.2] + 3[H.sub.2]S[O.sub.3] [right arrow] 3[H.sub.2]S[O.sub.4] + [N.sub.2] + [H.sub.2]O 2HNOS[O.sub.4] + 4[H.sub.2]O + 3S[O.sub.2] [right arrow] 5[H.sub.2]S[O.sub.4] + [N.sub.2] The process has been in use in an industrial plant operated by Sachtleben for the past 11 months.

N[O.sub.x] in sulphuric acid is a problem about which we shall doubtless hear more in the near future. References 1. "Processing options for low-S[O.sub.2] gases". Sulphur (237), 29-38 (Mar-Apr 1995). 2. Ma. J., Zhao, Z.: "Application and design of M330 hard PVC wet electrostatic precipitators". Sulphur 94 International Conference, Tampa, FL (Nov 1994). 3. "Converter design for S[O.sub.2] oxidation". Sulphur (219), 26-39 (Mar-Apr 1992). 4. Shaw, D., Harding, G.: "Stainless steel converter performance 11 years later." AIChE Clearwater Convention, Clearwater, FL (May 1995). 5. Cameron, G. M., Fries, R. M., Puricelli, S. M.: "Demonstrated new technologies for sulphuric acid plants of the nineties". Sulphur 94 International Conference, Tampa, FL (Nov 1994). 6. "More reliable and efficient towers". Sulphur (223), 31-44 (Nov-Dec 1992). 7. Cameron, G. M., Bhaga, D.: "Improving sulphuric acid tower performance using SMART[TM] acid distributor and high-performance (HP[TM]) tower packing". Sulphur 94 International Conference, Tampa, FL (Nov 1994). 8. McLean, J. E., Myers, J. R., Schleiffarth, D. A.: "Gas cleaning using Dynaware". Sulphur (216), 41-48 (Sep-Oct 1991). 9. "Wet catalysis sulphuric acid processes dispose of problem waste gases". Sulphur (215), 29-37 (Jul-Aug 1991). 10. Ludtke, P.: Private communication (Jul 1995). COPYRIGHT 1995 CRU Publishing Ltd. This material is published under license from the publisher through the Gale Group, Farmington Hills, Michigan. All inquiries regarding rights should be directed to the Gale Group.

Title: What's new for sulphuric acid service? Date: 3/1/1997; Publication: Sulphur; Author: Connock, Lisa

Over the past few years, the designers and constructors of plant, equipment, catalysts and materials for sulphuric acid service have been busy introducing new and improved products to the marketplace. Lisa Connock provides an update on some of the key developments. In recent years there has been a trend toward more stringent control of sulphur dioxide (S[O.sub.2]) emissions from sulphuric acid plants. Many plants are now faced with a requirement for 99.85% conversion, while others in certain areas require 99.9% conversion corresponding to a 100-150 ppm sulphur dioxide emission level. Existing technologies like tail gas scrubbing or triple absorption have the drawback of increased capital costs. New plants may be designed with five-bed converters in a 3:2 configuration, but this layout is less attractive for existing plants equipped with 4-bed converters. The Poseidon recycle process Poseidon Engineering have recently developed and are currently introducing a complete sulphuric acid plant concept using gas recycle. The process has been designed to provide a low capital cost design that can achieve the lowest S[O.sub.2] emissions compared to other processes. The main motivation for the process development was to achieve lower sulphur dioxide emissions from sulphuric acid plants. The Poseidon recycle process is shown in Figure 1. The plant uses a 3-pass converter in a 2:1 configuration (two passes upstream of the intermediate absorption and one downstream). The sulphur furnace operates with feed gas containing 12.5-14% S[O.sub.2] and at an exit furnace temperature of 1,2001,400 [degrees] C. The gas is cooled in a waste heat boiler, or a combo boiler and superheater, and is routed to the first pass, before entry to the second pass, by quenching with gases recycled from the plant stack. After the second pass, the gases are cooled in a process gas heat exchanger, where the third bed inlet gas heats up to its optimum conversion temperature. This is followed by an economizer to preheat the boiler feed water. After complete conversion, the gases are cooled in a second economizer and pass through the final absorber. While part of the offgas is led to the plant stack, a portion is routed to a mist eliminator and recycled to cool the first bed outlet gases. A gas booster is used to pressurize gases that are used for dilution after the third pass. The Poseidon recycle process is adaptable to both new plants and revamps. The process is currently being implemented in an existing single absorption plant in West Africa. The recycle process is also ready to be applied to double-absorption plants. Use of 13.75% S[O.sub.2] strength gas has been confirmed by catalyst suppliers. In a variation of the process, specially applicable for capacity enhancement of large capacity, tightly designed, 4-pass double-

absorption plants, a supplementary air drying tower, complete with its own blower, can be used for providing the dilution air. In such cases it is more beneficial to provide the quench air after the second converter pass. Comparison with alternative systems Alternative low-emission designs from other sulphuric acid plant designers are all based on double-absorption systems with five passes in the converter. They all use two heat exchangers for reheating the inter-pass absorber outlet gases. These processes operate with S[O.sub.2] concentrations of 11% at the inlet to the converter. Catalyst requirements are in the range 180-200 litres/tonne. In the Poseidon process by contrast, three passes only are adequate if low-ignition catalyst is used and the process requires only one gas-togas heat exchanger for reheating. The sulphur dioxide concentration at the inlet to the converter is 13.5%. Catalyst requirements are 140 litre/tonne and emissions are restricted to within 0.5 kg/tonne acid. The lowest emissions are expected to result from using low-ignition catalysts in the first and third passes of the converter. Computer simulations by Poseidon have shown that a total catalyst loading of 160 litres will achieve a sulphur dioxide emission of 0.3 kg/tonne of acid produced. Capital cost comparisons have been made between the total battery limits costs of sulphuric acid plants designed to the Poseidon recycle process and standard double-absorption plants designed for 100 ppm S[O.sub.2] emissions (5-pass converter) and for 1 kg S[O.sub.2]/tonne acid (4-pass converter). The Poseidon process plant shows savings of 5% over the 4-pass conventional plant and more than 10% over the 5pass plants. The capital cost for the Poseidon plant using caesium catalyst is still 2% lower than that of the 5-pass plant, yet it emits only half as much sulphur dioxide (0.3 kg S[O.sub.2]/tonne acid compared to 0.62 kg for the 5 pass unit). Reference plant with gas recycling Industries Chimique du Senegal has awarded Poseidon the design and engineering contract for uprating one of the world's largest sulphuric acid plants using its new gas recycling process. The assignment is to increase the plant capacity from the present level of 2,600 t/d to 3,000 t/d. The plant is located in Darou, Senegal, and is a single-absorption contact plant of Krebs design. In the modified design, the recycle quench is introduced after the third bed of catalyst. The freed dry air, which is presently being used for quench after the third pass, will be routed to the sulphur burners to generate the extra quantity of sulphur

dioxide for the capacity enhancement. Other modifications are being made to the acid circuit and waste heat recovery system. The plant will use normal catalyst and production will be increased while reducing the emissions from the plant.
Table 1: Case 1: Performance of final pass of a 3:1 double-absorption plant showing a 60% reduction in S[O.sub.2] emission after replacing VK38 with VK69 Catalysts type Inlet temperature, [degree] C Outlet temperature, [degree] C Overall conversion, % S[O.sub.2] in stack, ppm S[O.sub.2] emission, kg/t VK38 420 438 99.70 375 2.0 VK69 400 419 99.88 150 0.8

Basis: sulphur-burning plant with a feed gas S[O.sub.2] strength of 10.5%

The contract for this project was signed in November 1996. Process engineering and part of the detailed engineering work has been completed. The civil foundations of the plant are being taken up for modifications. Orders for the major equipment items have been completed and workshop fabrication of major equipment has started. Site erection and fabrication is scheduled to start in June 1997. The target date for project completion is March 1998 with commissioning taking place in April 1998. [TABULAR DATA FOR TABLE 2 OMITTED] New Topsoe catalyst cuts S[O.sub.2] emissions In response to the demands being placed on sulphuric acid producers to cut their S[O.sub.2] emissions, Topsoe has introduced a new caesium-promoted vanadium catalyst, designated VK69, which is designed for operation in the final pass of double-absorption plants. Existing caesium catalysts have been developed for operation in gases with high concentrations of sulphur oxides and when installed in catalyst passes following an interpass S[O.sub.3] absorber the activity advantage is much less pronounced, especially at normal operating temperatures above approximately 410 [degrees] C. VK69, on the other hand, provides more than double the activity of existing catalysts when installed in the final pass. The enhanced activity has been brought about by combining a revised composition of the active phase with an optimization of the physical properties of the silica support. In the form of 9 mm Daisy rings, VK69 has the same pressure drop characteristics as 10 mm smooth rings.

The doubling of activity offers a number of options: * Emissions from existing plants can roughly be cut in half without increasing the catalyst volume; * The acid production capacity can be increased by using higher strength sulphur dioxide without increasing sulphur dioxide emissions and plant pressure drop; * New acid plants may be designed with 50-100 ppm sulphur dioxide emission, eliminating the need for tail gas scrubbing. Case 1: Reduced emission Loading catalyst VK69 as a replacement for conventional catalyst in the final pass of an existing sulphuric acid plant enables a significant reduction in sulphur dioxide emissions (see Table 1). Such a plant will typically operate with approximately 95% conversion after the first three passes. This results in a gas containing around 0.62% S[O.sub.2] entering the fourth pass. By replacing VK38 with an equivalent amount of VK69 in the fourth pass the conversion is increased to 99.88%, giving a 60% emission reduction. Case 2: Increase of capacity For a 3:1 plant operating with 99.7% conversion of a 10.5% S[O.sub.2] feed gas, the typical conversion after the third pass would be 95%. Increasing the sulphur dioxide strength to 11.6% to obtain a 10% production increase would reduce the conversion prior to the intermediate absorber to 92.8% due to the increased load and less favourable [O.sub.2]/S[O.sub.2] ratio. The composition of the gas to the fourth pass would change from 0.62% S[O.sub.2] + 6.6% [O.sub.2] to approximately 1.0% S[O.sub.2] + 4.8% [O.sub.2], resulting in a drop in overall conversion efficiency and a 40% increase in sulphur dioxide emissions. Because of its high activity, by replacing VK38 in the fourth pass with VK68 it is possible to obtain a 10% capacity increase without increasing the total catalyst volume, i.e. without increasing the pressure drop through the plant (see Table 2). Case 3: Extremely low emissions In a number of cases local environmental legislation requires less than 100 ppm S[O.sub.2] emission corresponding to an overall conversion efficiency of around 99.92%. The normal way to achieve such high conversion efficiencies is to apply a 3:2 design and use air quench between the fourth and fifth passes. In addition to extra catalyst, this means an approximately 10% higher consumption in blower energy for provision of the quench air.

By using VK69 it is possible to apply a 3:1 layout. This requires operation of the fourth pass at an inlet temperature of around 385-390 [degrees] C. In addition to the savings in blower energy for quench air and the savings in capital costs achieved by avoidance of a fifth pass (extra ducting etc.) the catalyst volume becomes 15-20% lower. Another option is the possibility to design sulphuric acid plants with 50 ppm S[O.sub.2] emission, which is already the limit in some areas. Although this requires a fairly large catalyst volume, 220-250 litres per t/d of acid produced, depending on the composition of the feed gas and presumes close-to-ideal conditions in the converter, this may still be an attractive alternative to, for example, alkali or peroxide scrubbing. Centaur[R] S[O.sub.2] removal process In the early 1970s many S[O.sub.2] abatement processes were proposed as operators and designers searched for a cost effective means to meet sulphuric acid plant emission requirements. Lowtemperature oxidation of sulphur dioxide to sulphuric acid on activated carbon was one such process. Today there is renewed interest in this technology as a result of Calgon Carbon's patented Centaur[R] activated carbon. The Centaur S[O.sub.2] removal process for sulphuric acid plants was developed jointly by Calgon Carbon and Monsanto Enviro-Chem to provide a cost effective alternative to double absorption. In comparison with double absorption, the Centaur S[O.sub.2] removal process has less equipment, exports more energy, achieves lower sulphur dioxide emissions and can be brought on line faster without exceeding start-up emission limits. The carbon is regenerated on line with a periodic water wash to produce weak sulphuric acid. Since the weak acid is normally recycled as dilution water, there are no byproducts to dispose of or sell. The technology is applicable to both new plants and retrofits. Many features of the Centaur process are similar to or identical to those of previous carbon adsorption systems. The key difference is in the activated carbon. Compared to other activated carbons, Centaur has more than twice the catalytic activity, and this is expected to enhance the viability of carbon adsorption technology for sulphur dioxide removal. In addition to laboratory and bench-scale investigations, the Centaur process has also been studied in pilot plants representing up to a 320 fold scale up of the bench scale reactor. At present, one Centaur system has been sold on a grass-roots sulphur-burning plant. Applicability of the Centaur process is dependent on finding a use for the weak sulphuric acid generated in the wash step. In some

metallurgical plants, weak acid can be used for ore leaching. The Centaur process is most applicable to sulphur-burning plants, where the water balance usually permits the weak acid to be recycled as a source of dilution water. The Centaur process is shown schematically in Figure 2. Dry off-gas from the acid absorbing tower passes through a humidification section located in the duct between the absorbing tower and the Centaur reactor. The tower off-gas is contacted with a spray of medium strength acid circulated from a sump located in the Centaur reactor. The off-gas is partially humidified by the evaporation of water. Weak acid is continuously fed to the humidifying circuit to make up the evaporation loss and maintain the acid strength. The humidification step serves to cool the gas and dilute any strong acid mist leaving the absorption tower. It also concentrates the acid washed from the carbon bed during the wash step. The humidified gas stream enters a chamber in the Centaur reactor where the gas is separated from the acid spray. Acid drops out in a sump and the gas passes over a baffle wall and flows down through a bed of Centaur carbon, where sulphur dioxide is removed. After passing through the bed, the purified gas passes through a mesh pad demister that removes any entrained liquid before the purified gas is discharged to the stack. In the catalyst pores, sulphur dioxide, oxygen and water react to form sulphuric acid. Eventually, the active pores become filled with relatively strong sulphuric acid, resulting in a slower reaction rate. Given sufficient time the reaction/mass transfer zone thus moves through the bed until sulphur dioxide breaks through to the outlet. Thermocouples located within the carbon bed detect the approaching mass transfer front and trigger the wash step before that happens. The wash step regenerates the carbon to provide new capacity for adsorption and reaction. The washing is done on an intermittent basis while on line. The carbon can be washed with water or a combination of weak acid and water. The recovered sulphuric acid has a nominal concentration of 10-20%. The acid is further concentrated in the humidification step to a strength of 20-30%. Immediately after washing, the liquid film surrounding the carbon particle provides an additional resistance to mass transfer that can reduce S[O.sub.2] removal efficiency. To compensate for this phenomenon, multiple beds are washed sequentially. With a single bed, different sections of the bed are washed sequentially. In this way, peak S[O.sub.2] emissions are reduced. Any breakthrough that occurs during the wash cycle tends to be dampened and high S[O.sub.2] removal efficiency is maintained throughout the operating cycle. Bovar Western Research S[O.sub.2] analyzer

Bovar Western Research has developed a sulphur dioxide analyzer and sampling system for use in the process control of sulphuric acid plants. In the sulphuric acid process, the conversion efficiency of a catalytic bed is determined by the degree of catalytic activity and the temperature at which the catalyst bed is operated. Catalytic activity will vary with age reducing conversion efficiency and thereby increasing the plant S[O.sub.2] emissions. This effect could be partially offset by continuous optimization of the operating temperatures of the catalyst beds, thereby allowing the plant to run at full load while maintaining low emissions. Finding the optimum temperature is difficult, since the process reaction rates dictate that the temperature should be as high as possible, while maximum sulphur trioxide yield is favoured by low operating temperatures. To perform the optimization, a continuous measurement of either sulphur dioxide or sulphur trioxide is required. These measurements have historically proved difficult due to both the difficult sampling conditions and the wide range of sulphur dioxide which may be encountered. A process UV photometer has been developed by Bovar Western Research which is capable of performing the required analysis. The analyzer has seen extensive use in the sulphur recovery industry, as well as in stack gas emission monitoring. Analytical algorithms have been developed to provide accurate and reliable sulphur dioxide analysis for concentrations ranging over four orders of magnitude. The analyzer is capable of +/-2% of reading accuracy for concentrations varying from 100 parts per million to 50 mole per cent with automatic range switching. This exceptionally wide concentration range allows a single analyzer to be used to measure the concentration of sulphur dioxide at the inlet to the first bed, at the exit of the last bed, and at numerous intermediate points. Fuzzy logic is used to provide the most accurate results at all times. The analyzer performs a direct extractive analysis while maintaining the sample above dewpoint temperatures throughout the sample system. An operating temperature of 140 [degrees] C is typically used to minimize concerns about sulphur trioxide induced corrosion. In practice, the analyzer may be applied to continuous emissions monitoring or sulphuric acid plant feed analysis. With a multi-point sample system, the analyzer may be used to provide batch optimization of catalyst bed operation and a running measure of catalyst bed efficiencies. In this manner it can be used to minimize emissions and to facilitate plant turnaround planning. Process implementation

The preferred implementation uses two analyzers to provide simultaneous measurements of bed inlet and outlet concentration [ILLUSTRATION FOR FIGURE 3 OMITTED]. This ensures that load fluctuations do not significantly affect the results. In principle, the process could be run using only one analyzer. However, this would require that multiple measurements be taken across the bed at different times but the same operating temperature and an average conversion efficiency would need to be calculated to prevent the results from being biased by load changes. Belco expands its market for gas cleaning systems Belco Technologies Corporation is a supplier of specialized gas cleaning systems and technologies for a variety of industrial processes. Belco's ND[TM] Wet Electrostatic Precipitator designs were developed in Japan by Nippon Densetsu and have been used on a variety of non-ferrous metal processing and sulphuric acid production facilities. Typical applications include: smelters/roasters (copper, zinc, lead, nickel), spent acid regeneration, coke ovens, iron pyrite roasters and sulphur burners. In the past, Belco has concentrated on the Asian market and more than 100 wet electrostatic precipitator units have been put into service for sulphuric acid applications in this part of the world. Belco is now introducing the ND[TM] Wet Electrostatic Precipitator designs to the rest of the world. ND[TM] Wet Electrostatic Precipitators operate using basic principles of electrostatic precipitator devices: particle ionization with a high voltage emitting electrode system, migration of charged particles to an oppositely charged collecting surface, collection and cleaning of particles from the collecting surface. ND[TM] Wet Electrostatic Precipitators are radically different from most of the traditional designs from other suppliers. Many designs use collecting tubes, tube sheets, weighted wires or lead collecting surfaces. Problems associated with these designs include broken emitting wires, plugged collecting tubes and difficult internal access. Belco's design overcomes these problems with a design that features parallel up-flow gas passages, rigid mast emitting electrodes, and special conductive fibreglass reinforced plastic (C-FRP) collecting plates within a steel supported fibreglass reinforced plastic (FRP) housing. Figure 4 shows the ND[TM] Wet Electrostatic Precipitator design. Process gas enters at the bottom and flows vertically upward into the emitting and collecting section. Parallel collecting plates form large wide gas passages where uniform distribution is easily achieved. Uniform flow distribution is important in maximizing collection, avoiding build-up and ensuring proper operation. Adjustable inlet vanes allow for easy field adjustments. Low gas velocities and high residence times enhance performance without sacrificing costs.

The emitting electrode system uses large diameter rigid masts with corona spikes to ensure proper ionization without the breakage associated with weighted wires. This rugged system is top supported and extremely stable. Lower alignment/anti-sway insulators are not required, eliminating wet/dirty insulator problems common with many designs. A heated pressurized air flow maintains the cleanliness of top insulator compartments. Alloy or leaded steel emitting system components meet the severe chemical resistance demands. Specially developed C-FRP collecting plates withstand chemical attack and provide good conductivity over the entire collecting surface, wet or dry. Conductivity ensures proper charge dissipation, making collection uniform and effective. Electrical spark energy dissipates quickly, eliminating hot spots/burning that may be found with non-metallic designs that rely on a film of water for conductivity. Both sides of each collecting plate are used, maximizing collecting surface and minimizing components. Unlike lead, C-FRP is unaffected by material creep and softening from mercury absorption. Intermittent liquid sprays effectively clean collecting and emitting surfaces from above for typical inlet loadings. With heavy inlet loadings and tenacious dust, continuous sprays are used to clean collecting plates while maintaining full ionization and collection. These uniform sprays directly irrigate collecting plate surfaces for effective cleaning, unlike indirect cleaning systems that rely on misting or tube sheet flooding. Boliden effluent treatment process Boliden is one of the leading European industrial groups in the fields of mining and the production of non-ferrous metals. Due to the need to produce high quality, marketable sulphuric acid from the metallurgical gases and the stringent environmental regulations that were implemented in Scandinavia, earlier than most other countries, it has been necessary for Boliden to develop its own environmental technologies for metallurgical sulphuric acid plants including stainless steel wet electrostatic precipitators, and processes for mercury removal and effluent treatment. These technologies have been commercially proven and are available to companies outside of the Boliden Group through the engineering company Boliden Contech of Sweden. To date, there are more than 50 references outside the Boliden Group. The most recent technology development is the purification of waste water. This technology was implemented at a metallurgical plant in Chile (Enami, Las Ventanas) at the end of 1994 and has provided very good results. Purification of waste water

The thermal treatment of sulphide ore and concentrate does not only volatilize mercury but also elements such as arsenic and halogens. Furthermore, some dust, containing copper, lead, zinc, etc. still remains in the gas even after highly efficient dry gas cleaning. These impurities must be eliminated from the gas prior to the sulphuric acid plant in order to achieve a pure acid and to protect the acid plant. This final purification of the gas is carried out in a wet gas cleaning system of which there are several designs available. The impurities are then collected in the weak acid bleed where most of them are found in dissolved form due to the solubility of the dust in the acid. The acid bleed is normally treated as waste water. A typical composition of such waste water from a copper smelter is: As 500-10,000 mg/l; Cu 1001,000 mg/l; Zn 100-1,000 mg/l; Pb 10-30 mg/l; Hg 5-50 mg/l; [H.sub.2]S[O.sub.4] 2-15%. In Sweden, strict demands on the purification of industrial waste waters were established as early as the 1970s. This initiated development work within Boliden, resulting in purification processes which were installed in Ronnskar and Helsingborg. Over the years, the processes have been improved and they meet the most stringent demands known in the western world today. The Boliden effluent treatment process described below [ILLUSTRATION FOR FIGURE 5 OMITTED] is designed to yield an extremely pure liquid discharge, while at the same time precipitating the impurities in a form suitable for disposal in waste dumps. The liquid effluent is purified in three subsequent stages with precipitation and solids removal in each stage. In the first stage the liquid effluent is treated with lime and recycled slurries from stage 2 and 3. The solids formed are removed and dewatered. In the second stage, water from the first stage is treated with lime. In the third stage, water from the second stage is treated with iron reagent. Some oxidizing agent (e.g. NaCl[O.sub.3]) is added in the second and third stages to oxidize the remaining arsenic and iron to iron arsenate. Results from the copper smelter in Chile have demonstrated that the liquid can be purified to values well below the following figures: As 0.1 mg/l; Cu 0.5 mg/l; Zn 1 mg/l; Pb 0.5 mg/l; Hg 0.01 mg/1. The features of this patented process can be summarized as follows: * It yields a purified effluent with extremely low levels of contaminants; * Chemicals consumption is not higher than for a one-stage process thanks to countercurrent flow; * It is insensitive to disturbances, i.e. consistently high purification is achieved;

* It produces a manageable solid product. Because of its heavy metal content, the solid product should be disposed of in properly sealed dumps. Improved tower packings Acid towers play an important role in determining the overall performance and reliability of a sulphuric acid plant. Proper design of towers and the internals are critical for optimum performance. New ceramic packings and packing arrangements offer more economical towers and improved performance for both new and existing towers. The improved ceramic packings can increase tower capacity by 25-30% or cut packing pressure drop in half, while new distributors and packing arrangements offer the possibility of more effective mass transfer while essentially eliminating acid carry-over. Cecebe HP[TM] saddle packing Ceramic saddle packing has been extensively used for over 40 years in drying and absorption towers in sulphuric acid plants. Now a new high performance (HP[TM]) saddle ceramic tower packing [ILLUSTRATION FOR FIGURE 6 OMITTED] has been developed by Cecebe Technologies Inc. to enhance tower operation. As a leading producer of random saddle packing, Koch Engineering Company, Inc. is co-operating with Cecebe to bring this new product to the market. The saddle shape of HP[TM] packing has been modified to promote improved gas-liquid mixing and redistribution. The hub of the saddle is opened up by large apertures to break up the gas and liquid streams into much smaller streams to improve mass transfer and reduce pressure drop. The edge of the saddle wings have been slotted to provide many more interstitial transfer points which continuously renew the liquid surface and increase the mass transfer. Several deep weep holes on the wings allow liquid to flow from one side of the wing to the other, improving surface wetting. The new edge surface created by the openings compensates for the surface lost by cutting the openings. The openings are large enough to prevent plugging by sulphate. They are strategically located to preserve mechanical strength. Several ribs provide strength, additional surface and drip points as well as prevent surface overlap. The HP[TM] saddle packing is gaining acceptance in the industry, it has already been installed in two towers and it has been selected for seven more towers in the last four months. Tower duties include drying, interpass, final absorption and oleum production and the tower sizes range from 8-20 ft diameter. Another tower packing development is the Cecebe FC[IM] (Flow Correction) ring of smaller packing for use at the top of the tower to

minimize gas maldistribution due to the wall effect. This type of packing is currently operating successfully in a 25 ft diameter tower and is due to be installed in four more towers in the next three months. Koch Flexeramic[TM] structured packing Another major advance in the packing art is Koch's Flexeramic[TM] structured packing which is made of corrugated sheets of ceramic fused together with the corrugations at 45 [degrees] angles providing significant gas and liquid distribution capacity [ILLUSTRATION FOR FIGURE 7 OMITTED]. This structured packing has significantly more surface area per unit volume than the conventional saddle, and the pressure drop and capacity are similar to the HP[TM] saddle. Mass transfer rates are higher than the standard saddle. Its highly open structure and excellent distribution capability make it a good candidate for the primary packing immediately above the packing support. This packing is in use in sulphuric acid plants in a number of installations. Although this packing is more expensive than either standard or HPTM saddles it is very cost effective in overcoming production bottlenecks at the bottom of the tower. Mixtures of it and the HP[TM] saddle can be used to provide an optimum solution. Improved packing support Koch also designs, manufactures and installs the self-supporting Ceradome[TM] packing support [ILLUSTRATION FOR FIGURE 8 OMITTED]. The dome eliminates high local loading on the tower base and ensures packing support is loaded in compression - unlike traditional Aludur beam packing support that relies on the poor and unpredictable tensile strength of ceramic. Koch advocates ceramic dome packing support together with a dished bottom and careful attention to bricking details as the ultimate in brick lining for the tower that is critical for long maintenance-free operation. Internal access to tower for maintenance is also easier with the elimination of the brick columns or arches required for the traditional packing support. Bayer/Krupp VDM introduce new alloy Alloy 33, a new Cr-Fe-Ni alloy specifically designed for service in hot, concentrated sulphuric acid was first introduced to the sulphuric acid industry in 1995. The new material is the result of joint development work by Bayer AG and Krupp VDM. Although chromium at 33% is the predominant alloying element, the alloy has a fully austenitic structure, thanks to a nickel content of 31% and the additon of about 0.4% nitrogen. A low molybdenum content of about 1.6% ensures a very high degree of metallurgical stability. The result is a material with mechanical properties approaching those of the superduplex stainless

steels, which is readily weldable with a matching filler, and with high ductility so that it can easily be pressed into plate heat exchanger plates. The corrosion resistant behaviour of Alloy 33 is also unique. Laboratory tests and plant tests in sulphuric acid at concentrations in the range 96-99%, and at temperatures of 240 [degrees] C, have shown this material to have overall corrosion resistance superior to that of all other comparable wrought materials. Significantly, this excellent resistance to sulphuric acid is associated with a very high degree of resistance to corrosion by contaminated coolants. Tests show Alloy 33 to have resistance to localized corrosion in chloride solutions comparable to that of the super-austenitic stainless steels. Alloy 33 also demonstrates a very high degree of resistance to corrosion in such diverse media as caustic soda, nitric acid and mixed nitric-hydrofluoric acids. The corrosion resistance, mechanical properties and workability of Alloy 33 mean that it lends itself ideally to a wide range of equipment for the processing and handling of sulphuric acid. Plate heat exchangers in Alloy 33, handling both concentrated acid and more dilute contaminated acids, are already in service. The ability of the alloy to be welded in thick sections means that it can be used for large structures such as absorption towers. The availability of both seamless and welded tubing allows it to be designed into coolers and heat exchangers. In one application a plate heat exchanger is being used for cooling 98.9% [H.sub.2]S[O.sub.4] from 95 [degrees] C to 60 [degrees] C in a German chemical plant. Another unit is in service in a Finnish steel mill, handling waste sulphuric acid from the pickling line. Development work is being carried out to determine the possibility of using Alloy 33 in cast form for applications such as pumps and valves; early results are reported to be promising. Alloy 33 is thus rapidly establishing itself as a multipurpose material for sulphuric acid service. Riano rapid service sulphur gun Sulphur guns and nozzles in sulphuric acid plants operate with little routine maintenance or operator attention until the sulphur throughput drops off. Without a plant shutdown, little could safely be done hitherto to improve the gun's performance. Replacing the gun required a 1-2 hour shutdown and entailed handling a very hot 82 kg (180 lb) sulphur gun. A new type of sulphur gun design by Riano Equipment Co. has been patented recently in the USA which could dramatically improve operations. The new sulphur gun can drastically reduce shutdown time, improves safety and reduces the weight of the gun to about 8 kg (18 lb).

The "Riano Sulphur Gun Assembly with Rapid Service Capability" is composed of two separate parts, the casing and the insert. The casing is designed to be permanently installed in the sulphur furnace gun ports and should operate for many years without needing any maintenance. The insert consists of the sulphur feed pipe and the Riano nozzle, which only weights approximately 8 kg. Casing The casing projects into the furnace and supports the sulphur feed line. It is composed of two concentric pipes and connected together by a pipe cap at the casing tip inside the furnace and to the sulphur feed line flange. The space between the concentric pipes forms the cooling steam chamber, which protects the whole assembly, the internal sulphur line and the attached nozzle. Two rods are attached to the outside diameter of the inner pipe at the 3 o'clock and 9 o'clock positions. These rods run down the length of the pipe and wrap 360 [degrees] around. The diameter of the rod is such that when the outer pipe is placed over the inner pipe it forms a tight fit. This configuration forms two flow paths for the cooling steam; one path for the cooler steam to travel to the end of the gun and the other for the steam to travel back. Insert The Riano nozzle is attached to one end of a one-inch type 304 stainless steel pipe. At the other end is the sulphur inlet flange. A locking nut sealing the flange and a threaded area form the connection between the casing and the insert. The nozzle is supported in a bushing on the inside diameter of the inner concentric pipe of the casing. Commercial trial A prototype rapid service gun was put into service at Occidental's Swift Creek Chemical Complex (now PCS White Springs Corporation) in one of its Monsanto 2,000-t/d sulphuric acid plants on a trail basis. The gun was installed in November 1995 as a complete assembly. Occidental gave permission for the performance of the equipment to be visually checked and monitored. Checks were carried out two to three times per week for 20-30 minutes each time for a period of four months. The performance was found to be consistent throughout. Almost three months into the trial test the plant went down for a repair day and the insert was pulled out to inspect the nozzle and to test the "rapid service capability". The insert was replaced by two men in 26 minutes and the nozzle was found to be in excellent condition. As part of the close monitoring maintained on the equipment, production and maintenance were asked to pull out the whole

assembly for inspection at their earliest convenience, during one of the routine repair down days. This inspection took place in March 1996. At first glance a hairline crack was observed on the gun casing tip at the weld of the outer concentric pipe to the inner pipe. On detailed investigation this was found to be due to an extremely weak weld and insufficient weld penetration. The sudden temperature difference from 1,100 [degrees] C to the outside ambient temperature of approximately 7 [degrees] C on that day, plus the dousing of water caused thermal stresses which led to the failure. Riano decided to eradicate the stresses to make the gun less susceptible to common welding problems by adding an expansion joint. The conclusion of the study was that the device had stood the test for four consecutive months and would have performed for an indefinitely longer period of time in the absence of human error on the part of the welder at the fabricating shop. While the tests were successful, further development has continued. The original Riano nozzle, like most nozzles, would plug if a stone, aggregate or catalyst pellet enters the nozzle. However, Riano has now water-tested a new nozzle which has equal or better atomization that the original design but will not be appreciably affected in capacity or performance by a 6 mm stone. The design modification now places the most restrictive area in a place where debris does not restrict the flow and can be removed from the feed pipe. While the modification makes the nozzle more restrictive it actually increases the available flow area by over 300%. Advances in gas exchanger technology Gas heat exchangers are key components of the modern sulphuric acid plant, especially in metallurgical and waste acid operations, and represent a significant part of the total plant cost. They are a prime energy consumer and, if not designed properly, require frequent and costly maintenance. Sulphuric acid plants can heat S[O.sub.2] gases, air or tail gas while cooling S[O.sub.2] gas, S[O.sub.3] gas or combustion gas. Each of the following applications has different design and material constraints: * cold interpass heat exchangers; * hot interpass exchangers; * S[O.sub.3] gas coolers/tail gas reheater/air heater exchangers; * S[O.sub.2] gas/air preheaters; * dual service/three fluid exchangers; * bypass systems to control exchanger performance;

* internal heat exchangers. Nowadays, the larger plant sizes, changing process conditions and the need for higher process efficiencies, call for new improved exchanger designs. With the increasing equipment size, the availability of better materials at moderate cost, newer heat exchanger design techniques and different flow arrangements and tubing layout, today's operators are presented with a wide range of options in gas heat exchange equipment which can result in a significant increase in plant capacity and reliability, lower capital/operating cost, lower pressure drop and reduced maintenance. Many of the new designs also avoid or minimize problems such as acid condensation or cold or hot corrosion while keeping the plant simple. The ability to transfer heat between streams is significantly enhanced as well by use of exchangers in which two fluids can be heated instead of one. The temperature control is improved by placing the bypass valve within the heat exchanger. Simpler and more conservatively designed preheat systems can now heat not just one but two gas streams. This improves the operability of the acid plants when dilute gas is encountered while at the same time reduces sulphur oxide emissions. It also reduces the size and cost of the preheater furnace and the heat exchanger and improves system efficiency. Cecebe RF[TM] gas exchangers Cecebe Technology Inc. offers a range of heat exchange equipment either directly or under licence agreement with Monsanto Enviro-Chem. The Cecebe RF[TM] (Radial Flow) gas exchangers have gained wide acceptance over the past few years. Over the past four years a total of 47 exchangers have been installed or are on order. The sizes of the exchangers range from 10,000 [ft.sup.2] to 86,000 [ft.sup.2] with plant capacities as high as 3,850 t/d. Cecebe reports an excellent performance record and lower than expected pressure drop. Figure 9 shows a Cecebe radial flow exchanger with disc and donut baffles. The tubes are contained in an annular bundle with a dome space between the bundle and the shell and a core space inside the annular bundle. In this case, a three shell pass exchanger is shown in which the shell side gas is entering the exchanger at the top through a core connection. The radial design provides greater flexibility and shellside gas can enter or leave through either core or shell connections and the number of shell-side passes can be from one to any larger number. The designs are symmetrical which eases differential expansion concerns. Radial layouts are characterized by very modest shell-side flow resistance, allowing more pressure drop to be taken in the tubes where the heat transfer coefficient is higher. The result is a decrease in exchanger area along with significant savings in blower energy.

Figure 10 shows the tubing layout and baffles for a cold exchanger for a medium sized smelter acid plant. The unit was installed a couple of years ago and has been very effective. The exchanger contained 21,000 [ft.sup.2] heat transfer area and was fabricated in a shop and shipped to site. Cecebe S[O.sub.3] cooler Metallurgical acid plants in many cases are now receiving much stronger gases and the gas temperatures entering the absorbers have risen accordingly and in many instances cause visible emissions. The most effective technique to deal with this problem is to cool the gas further using air or tail gas in separate exchangers before absorption. Figure 11 shows a conventional design for a S[O.sub.3] cooler process flow arrangement. The exchangers have potential condensation problems when air is heated as the air temperatures are well below the S[O.sub.3] condensation temperatures. To avoid this condensation, the conventional practice has required recycling part of the air back to the exchanger inlet with larger fans and exchangers. Where tail gas is being heated, such recycling is not possible and extra care needs to be taken in the design to avoid condensation. A more recent improved design shown in Figure 11 has reduced significantly the size, cost and power consumption of S[O.sub.3] coolers. In the revised arrangements, the S[O.sub.3] gas flows in parallel through the S[O.sub.3] cooler and cold exchanger, thus raising temperatures to the exchanger and decreasing the flow to be cooled. Significant pressure drop savings are also obtained. A further innovation has occurred in the exchanger design as well. This revised approach on which patents are pending is shown in Figure 12. Here the S[O.sub.3] gas being cooled is introduced to the shell space at the two tubesheets and flows to a central takeoff. Cecebe SF[TM] preheater In the classic smelter or waste acid regeneration plant, furnace gas is used to preheat dry air or S[O.sub.2] gas in a countercurrent exchanger and the exhausted furnace gas is then vented to a stack. Where relatively high efficiencies are desired, a part of the furnace gas stream leaving the exchanger is normally recycled to the furnace and in some cases a separate air heater may also be included. In such plants the hot end of the preheat exchanger is the most critical point in the preheating system with the temperature between that of the preheated gas (850-950 [degrees] F or 455-510 [degrees] C) and the furnace gas temperature. Typically the furnace temperature will be in the range 1,3001,500 [degrees] F (705-816 [degrees] C). Furnace operation above these temperatures will rapidly damage the preheat exchanger due to excessive metal temperatures in the hot end of the unit.

In an improved design, the Cecebe SF[TM] (Split Flow) preheater, it has been found that metal temperatures can be moderated and a simpler design generated if the gas being heated is split and flows through the shell while the furnace gas flows through the tubes as shown in Figure 12. The shell gas then leaves at a point between the two tubesheets. The shell space thus uses cocurrent flow in the hottest zone which provides cool gas at the hot tubesheet and reduces the tubesheet temperature, allowing the furnace temperature to rise from classic values of 1,400-2,000 [degrees] F (761-1,094 [degrees] C). In the cold end of the exchanger the flow is countercurrent, allowing good energy recovery from the partly cooled furnace gases and the tubesheet is not at risk. Dual service/three fluid exchangers In many cases in modem acid plants there will be a need to split heat between two separate duties or streams. At the moment such splits are obtained by using separate exchangers for the two duties. A novel exchanger design concept has now been developed by Cecebe, and patents filed, which combines the two exchange steps in a single vessel and results in simpler layouts and lower costs. The split exchanger concept is shown in Figure 13 and is readily adaptable for use in S[O.sub.3] coolers, preheaters and hot exchangers. COPYRIGHT 1997 CRU Publishing Ltd. This material is published under license from the publisher through the Gale Group, Farmington Hills, Michigan. All inquiries regarding rights should be directed to the Gale Group.

Title: Fine tuning sulphuric acid plants.(Brief Article) Date: 7/1/2001; Publication: Sulphur; In this article we report on operator experiences to boost the capacity of a spent sulphuric acid recovery (SAR) plant, to reduce [NO.sub.x] and [SO.sub.x] stack emissions from a sulphuric acid plant, and to reduce mercury levels of concentrated sulphuric acid. Boosting SAR capacity Rohm GmbH in Germany is the largest producer of methyl methacrylate monomer (MMA) in Europe. At its main production site in Worms, MMA is produced by the acetone cyanohydrin (ACH) route. In this process, the production of one tonne of MMA is accompanied by

the formation of about three tonnes of spent acid, which is an aqueous solution of ammonium sulphate, sulphuric acid and organic residues. Rohm started operating its first spent acid regeneration plant in 1966. A second plant - a Lurgi plant with two vertical decomposition furnaces - was added in 1974. The first plant was replaced in 1994 by a second Lurgi plant which converts 750 t/d of spent acid into 500 t/d concentrated sulphuric acid and oleum. By the end of the nineties a further capacity increase was required. The principles of the existing SAR plant at Worms are shown in Fig. 1. Spent sulphuric acid is decomposed in two vertical furnaces at a temperature of 1000[degrees]C. Under these conditions the waste acid is decomposed to sulphur dioxide, oxygen and water vapour. The organic impurities are burnt to carbon dioxide and water. Ammonium sulphate is decomposed and ammonia burnt to nitrogen and water. Some ash resulting from inorganic salts settles in the furnace and heat exchangers. Leaving the furnace, the gases are cooled down to 350 to 400[degrees]C in a gas/air heat exchanger. One third of the hot air is used as combustion air, the rest to produce high-pressure steam of 75 bar. The steam is converted into electricity. Gases leaving the heat exchanger are quenched, demisted and dried before being led to the converter system to produce sulphuric acid and oleum. Each SAR plant consists of two vertical, refractory lined decomposition furnaces working in parallel. One of them is shown in Fig. 2. Spent acid is fed in at the top of the furnace and atomised with a specially designed nozzle using pressurised air as the atomising agent. The spent acid is injected into a hot flue gas stream, which is generated in externally arranged combustors. Heavy oil is burnt in two combustors with preheated air as oxidation agent to provide the energy required to decompose the spent acid. The furnace is also equipped with a sulphur nozzle to balance sulphur losses. The combustor technology limits the oxygen concentration in the combustion air to 21 vol-%. Higher concentrations increase the flame temperature to above 1850[degrees]C, resulting in damage to the refractory lining and an increase in the formation of thermal [NO.sub.x]. Since neither the enrichment of air with oxygen nor oxygen injection was possible, either the combustors had to be replaced or a new oxygen technology had to be developed. Rohm worked together with the Messer Group, which has specialist experience in the design and construction of oxy/fuel burner

technology to develop a new oxygen-based technology for its conventional SAR plants. Computer simulations and calculations of experimentally expected data were performed which led to the development of the new Cold Oxygen Acid Burner (COAB) process. The COAB technology utilises independently controlled streams of spent acid, fuel, air and oxygen to overcome the conventional limitations of increased oxygen use. It generates a flame with a low temperature. To avoid temperature peaks in the flame, fuel for decomposition is mixed with the spent acid feed and the fuel/acid droplet stream is enveloped in a special oxygen/air jet. The burner consists of the atomising nozzle, for which different constructions are possible depending on the flow rate of the acid/fuel feed, and of annular nozzles for atomising air and oxygen. Zirconium is used as the construction material for the tube and nozzle, which come into contact with the spent acid. All other parts of the burner are manufactured of stainless steel. Successful full-scale testing of the COAB technology at the Worms production site demonstrated that the spent acid decomposition capacity could be increased by up to 40% (a further increase up to 100% should be possible without any risk). Due to the oxygen feed, the specific fuel consumption is reduced by up to 15%.The [NO.sub.x] contents of the product sulphuric acid and oleum were unchanged. With this new concept it is possible to reduce the specific operating cost of the SAR plants by up to 10%. For economical operation of an oxygen-based SAR plant it is necessary to install an onsite oxygen plant, either with cryogenic or swing adsorption technology. Reducing stack emissions Budel Zink operates one of Europe's largest zinc smelters at Budel in the Netherlands. The plant produces more than 200,000 tonnes of zinc per year from concentrates that traditionally came from a variety of sources around the world. Since May 2000 Budel Zink has been using concentrate from parent company Pasminco's Century mine in Australia, Century concentrate has exceptionally low iron content, which eliminates the production of solid waste products (jarosite) that require permanent storage. Zinc production requires several internal cycles, including dross to the roasting section, which can generate [NO.sub.x]. Also the nitrogen containing organics of Century concentrate can contribute to a higher level of [NO.sub.x] in the gas stream leaving the roaster.

In 1988 Budel Zink contracted Kvaerner Chemetics in co-operation with Kvaerner Process (Zoetermeer) to undertake the acid plant modifications required to meet statutory requirements for [NO.sub.x] and [SO.sub.x] in the stack, as well as to meet the specification for [NO.sub.x] in the product acid. Budel Zink operates two zinc roasters in parallel, with the off gases feeding a common sulphuric acid plant. The original plant was a 2:2 design, four-bed converter, double absorption unit built in the early 70s. After the installation of a new converter with caesium catalyst on top of bed 3 (for start-up reasons) in 1996, the plant was capable of achieving 300-400 mg/[Nm.sup.3] of [SO.sub.2] at the stack. Based on tests carried out by Budel Zink, the [NO.sub.x] concentration in the gas entering the acid plant following the introduction of Century concentrate was expected to be in the range of 200-300 ppm. Budel Zink's design requirements for the plant following conversion to Century concentrate were: [SO.sub.2] in stack: 200 mg/[Nm.sup.3] (70 ppm) [NO.sub.x] in acid: 9 mg/[Nm.sup.3] (5 ppm) [NO.sub.x] in stack: 30 mg/[Nm.sup.3] (15 ppm) The [NO.sub.x] target of 30 mg/ [Nm.sup.3] was set to avoid a visible plume and is well below the statutory limit of 100 ppm. At the expected inlet [NO.sub.x] concentration, the plant would exceed the allowable limits for both the stack and the product acid. Therefore a 95% reduction of the incoming [NO.sub.x] was set as a design value. Several modification options were available to achieve an [SO.sub.2] level of 200 mg/[Nm.sup.3] in the stack including: * Installation of a tail gas scrubber * Switch to 3:1 configuration and add Cs catalyst * Switch to 3:2 configuration, with a new single bed converter installed before the existing bed 1. The tail gas scrubber option was discarded because of its higher operating costs. The 3:1 configuration with caesium catalyst was not feasible because the existing converter size did not permit the required catalyst volumes. The selected approach was the installation of an additional converter bed before the existing bed 1, to convert the plant to a 3:2 arrangement. This approach offered flexibility for future reductions in [SO.sub.2] limits as well as a low operating cost.

For this duty, Kvaerner Chemetics utilised its proprietary stainless steel converter with internal heat exchanger. This design eliminates the often troublesome hot ducting from the new bed to an external heat exchanger. Based on the relatively low [NO.sub.x] stack requirements, the only economically feasible option for Budel Zink to achieve its objective was SCR (selective catalytic reduction). Selective catalytic reduction of nitrogen oxides by ammonia over vanadia/titania type catalyst is by far the most important commercial process today for removal of [NO.sub.x]. However, prior to Budel Zink, the process had not been applied on a commercial scale in an acid plant. Based on their previous experience with [DeNO.sub.x] catalyst in strong [SO.sub.2] streams, Haldor Topsoe was selected as the [DeNO.sub.x] catalyst supplier and as licensor for the [DeNO.sub.x] process. Typically, [DeNO.sub.x] catalyst is housed in a separate, vertically mounted reactor. The ammonia injection occurs in the ducting well before the catalyst to allow adequate mixing of the ammonia prior to entry into the catalyst. Good mixing of the ammonia and a uniform gas velocity across the catalyst is critical for catalyst performance. Therefore, Haldor Topsoe designed the ammonia injection system and performed CFD calculations to verify a uniform gas flow pattern into the catalyst. One of the advantages of the Kvaerner Chemetics' converter design is the inherent uniform gas flow distribution. The gas enters through the core, then flows radially from the core to the catalyst bed. This arrangement ensures even distribution of gas to the entire catalyst bed. For this reason, it was decided that the best location for the [DeNO.sub.x] catalyst would be in the converter, immediately before the [DeSO.sub.x] catalyst (Fig. 3). Chemetics' standard design has the gas entering the vessel at the top, passing through the tube side of the hot exchanger, before being radially distributed at the bottom of the converter. Riser pipes through the first catalyst bed ensure that the gases always enter the catalyst bed from the top. This arrangement allows partial screening of a bed if required. As shown in Fig. 3, gas passes up the riser pipes, through a transition, then through the De[NO.sub.x] catalyst module. A total of eight catalyst modules are evenly spaced around the diameter of the converter. Once the gas exits the De[NO.sub.x] catalyst it turns, then passes through the new bed. Finally the gas passes through the shell side of the exchanger to be cooled prior to entering bed 1 of the existing converter. The design requirements of the plant called for the re-use of the existing blower to minimise the capital requirements of the project as

well as to maintain or reduce the operating costs associated with power consumption. Prior to the concentrate switch, the plant was already operating at its design point, and the additional new equipment required for the modifications resulted in several additional pressure drops. However, by replacing several of the existing cross flow exchangers with Chemetics' patented radial pitch exchangers it was possible to reduce the plant pressure drop. An added benefit of these changes was that the cold exchanger was redesigned to allow the plant to run autothermally at lower inlet [SO.sub.2] levels. Since commissioning, the average stack [SO.sub.2] concentration has been 40-50 ppm and has consistently operated well below the 70 ppm design limit. [NO.sub.x] inlet concentrations vary from 150 to 250 ppm, with outlet [NO.sub.x] levels of 4 to 6 ppm, which equates to approximately 97% [NO.sub.x] reduction. In addition, the product acid meets the quality specification of 9 mg/[NO.sub.x], without any supplementary treatment. Mercury removal from sulphuric acid IBC Advanced Technologies, Inc. (IBC) had developed a mercury selective ligand, which can be used by sulphuric acid producers as either a polisher or as the primary mercury removal technology to achieve extremely low mercury levels. The Molecular Recognition Technology (MRT) separations material, Super-Lig [R] 88, selectively binds [Hg.sup.2+], and to a lesser extent [Hg.sup.+], out of concentrated sulphuric acid. The MRT mercury removal system can be used alone for bulk removal on streams containing up to 150 ppm mercury, where no other mercury removal system exists, or in the polishing mode to supplement other technologies. The MRT mercury removal system was successfully piloted at Britannia Zinc Limited (BZL), Avonmouth, Bristol, in the UK. BZL has a need to produce high quality, very low mercury sulphuric acid, for sale to select markets. BZL operates a Boliden/Norzink process at its zinc/lead smelter in Avonmouth for bulk removal of mercury from smelter offgases. Sulphuric acid production capacity is app roximately 610 t/d. A commercial scale lump-sum turnkey plant for the removal of mercury from concentrated sulphuric acid has recently been designed, constructed and supplied by Bateman to BZL, which is owned by Mt Isa Mines (MIM), Australia. IBC of American Fork, USA provided the mercury-selective Super-Lig [R] separation media. Bateman was responsible for the design and construction of the plant. MRT Africa, a joint venture between Bateman and IBC, provided the technical expertise. The plant polishes 25,000 t/y of concentrated sulphuric acid from BZL's smelter in Bristol and produces acid containing less than 0.1 ppm mercury. The product is being used to determine the marketability of

purified sulphuric acid. The new polishing plant can be upgraded to treat 50,000 t/y acid (25% of BZL's capacity). In the BZL plant, five stages of extraction are used to reduce the mercury content of the sulphuric acid feed from 3 ppm to 0.1 ppm. The columns, in a lead-trail arrangement in which any column can be the lead column, are packed with IBC's SuperLig [R] 88 MRT resin. The mercury is eluted once per week from each column using thiourea in dilute sulphuric acid at a pH of about one. The plant was manufactured using PVDF (polyvinyl difluoride), CPVC (carbonated polyvinyl chloride), for high temperature and ultra-violet ray resistance) and the balance using mild and stainless steel to meet the stringent corrosion resistance requirements of the client. The plant was fully assembled and water-tested at the manufacturer's premises in Midrand, 25 km north of Johannesburg, South Africa. It took nine months to build and was then disassembled and shipped in seven containers to Bristol, UK. After two months in transit it was reassembled on site, in one month, under Bateman supervision. COPYRIGHT 2001 CRU Publishing Ltd. This material is published under license from the publisher through the Gale Group, Farmington Hills, Michigan. All inquiries regarding rights should be directed to the Gale Group.

Title: Advances in smelter acid technology. Date: 11/1/1997; Publication: Sulphur; Sulphur examines the continued modernisation of smelter acid plants, including some of the alternatives available to conventional sulphur dioxide and sulphuric acid production technologies. Today's smelter acid plants are highly sophisticated, operating under hotter and more demanding conditions than older plants. Environmental and economic incentives to increase efficiency and cut tail gas emissions have called for the modernisation of all sulphuric acid plants. As a result, plants have undergone a number of process improvements and equipment changes.

In the metallurgical area, the widespread adoption of flash smelting techniques has led to the supply of much stronger gases. These gas streams contain much more oxygen and sulphur than found in sulphur burning plants and can produce very high quality acid, rivalling the product of sulphur burning plants. Gas cleaning[1] On account of its varied impurities, smelter off-gas needs elaborate and costly purification before it can be admitted into a sulphur dioxide or sulphuric acid plant, while the variations in feed gas flow rate and sulphur dioxide content complicate the control of the sulphuric acid process and its own sulphur dioxide emissions. Cleaning of metallurgical sulphur dioxide gas streams involves the removal of a number of impurities which can be classified into four main categories, * Primary dusts * Fumes (zinc sulphate, lead sulphate) * Volatiles (arsenic, selenium, mercury, sulphuric acid mists, hydrocarbons) * Gaseous substances (HCl, HF, lower hydrocarbons) for most of which cleaning systems are well established (eg Lurgi [system.sup.2]). Dynawave[3] Dynawave[R] is a registered trademark used by Monsanto and E. I. Dupont with reference to their froth type gas cleaning and cooling equipment, which prepares the furnace and reactor gas for admission to the acid plant drying tower. Dynawave offers an improved scrubbing alternative to the traditional open tower-packed tower equipment used for cooling and cleaning smelter gas. Mercury removal Most sulphidic ores contain mercury, which is present to such an extent that the sulphuric acid produced in connection with thermal treatment of ores will contain too much mercury. The two most common methods for mercury removal in the industry, developed by Boliden Contech AB, are the Boliden Norzink [ILLUSTRATION FOR FIGURE 1 OMITTED] and Boliden thiosulphate mercury removal processes. The former is a process for the complete elimination of mercury vapour from a gas stream. The basis of the process is a very rapid and

complete reaction, which occurs when metallic vapour comes into contact with a scrubber solution containing dissolved mercuric ions, under appropriate conditions. A scrubber reactor has been designed wherein the mercury-containing roaster gas is scrubbed in a counter-current flow with a solution of mercuric chloride in a complex form. During the reaction between the gas and scrubber solution, insoluble mercurous chloride (calomel) is precipitated. Calomel may be sold or further refined into metal. The Boliden thiosulphate mercury removal process effectively eliminates the mercury in connection with the contact process. Physical absorption Developments in the 1980s by Linde AG in the physical absorption of S[O.sub.2] have concentrated on commercialising a newly modified version of the Selexol solvent (dimethyl ethers of a mixture of tri-, tetra-, and pentaethylene glycol), primarily used in the production of liquid sulphur dioxide. A new physical absorption process has been developed by Monsanto Enviro-Chem for an absorbent, which is particularly suited to sulphur dioxide (S[O.sub.2]). The process is applicable to the treatment of metallurgical off-gases and offers notable capital and operating cost advantages compared with other absorption methods. The operating principle of the absorber is that lower temperatures favour absorption since acid gas solubility is improved and the acid gas vapour pressure decreases. A higher stripper temperature promotes the opposite effect. The absorbent is cooled by a heat exchanger prior to the absorber. Either a reboiler or absorbent heater is used to raise the stripper operating temperature. An interchanger is placed between the absorber and stripper to lower steam and cooling water usage [ILLUSTRATION FOR FIGURE 2 OMITTED], and a stripping medium is used to assist in removing S[O.sub.2] from the absorbent (steam, nitrogen, or air). Absorbent cleaning may involve washing immiscible solvents with caustic, or ion exchange and electrodialysis for miscible solvents. This removes non-volatile impurities, such as sulphuric acid and ionic contaminants. Chemical absorbents form much stronger bonds with sulphur dioxide, since protons are donated and accepted, forming a variety of sulphur compounds. From a process vantage, the stronger chemical bond associated with chemical absorbents manifests itself in higher solvent losses and steam uses, when compared to physical absorbents. Figure 3 shows the S[O.sub.2] solubility curves in a physical absorbent,

dimethylaniline [[C.sub.6][H.sub.5]N[([CH.sub.3]).sub.2]], commercialised by ASARCO, and a chemical absorbent, xylidine [[([CH.sub.3]).sub.2][C.sub.6][H.sub.3]N[H.sub.2]]. The physical absorbent that Monsanto Enviro-Chem found bestsuited for sulphur dioxide is dibutyl, butyl phosphonate (DBBP). The selected absorbent has a high S[O.sub.2] loading capacity combined with low stripping requirements, low vapour pressure and low viscosity. Acidic washing reduces this vapour pressure even lower. The absorbent exhibits a slight toxicity, and is classified as a flame retardant. DBBP shows very low corrosion rates and Monsanto Enviro-Chem claim it to be very stable under a variety of conditions. Centaur[4] The Centaur S[O.sub.2] removal process for sulphuric acid plants was developed jointly by Calgon Carbon and Monsanto Enviro-Chem to provide a cost effective alternative to double absorption. Many features of the Centaur process are similar to with those of previous carbon adsorption systems (eg Lurgi's SULFACID process). The key difference lies in the activated carbon - Centaur has twice the catalytic activity of other activated carbons. As a result, the Centaur process, in comparison, requires less equipment, exports more energy, achieves lower sulphur dioxide emissions, and can be brought on-line faster without exceeding start-up emission times. Centaur is a virgin activated carbon that does not rely on metal impregnates to provide its catalytic activity, making it both adsorptive and catalytic (hence "Centaur", the half man, half horse from mythological times). The adsorption pore structure may appear similar to conventional activated carbon products, however, Centaur has 10 to 100 times more surface sites for electron transfer, providing enhanced catalytic functionality. In addition, Centaur promotes a wide range of chemical reactions where other carbons are ineffective, and its high catalytic activity promotes fast reactions, resulting in less carbon and smaller adsorption vessels. The "peroxide number" test was developed during the development of Centaur to provide a means of measuring catalytic activity. A known amount of hydrogen peroxide is added to a Dewar flask containing a known amount of carbon, and the reaction temperature measured as a function of time. The rate of temperature change is proportional to the rate of hydrogen peroxide decomposition. The peroxide number is simply the time required to achieve three quarters of the maximum temperature rise. Figure 4 contrasts tests for Centaur with those for a conventional activated carbon. Lower peroxide numbers correspond to more active carbons. Table 1 shows that Centaur carbons normally produce a peroxide number less

than 14 minutes, about one third that of conventional carbons. The peroxide number is an indicator of catalytic activity, and it correlates well with performance in specific applications.
Table 1: Comparison of catalytic activity of carbon products Carbon type Centaur BPL Peat Sub-bituminous Filtrasorb 300 Coconut shell Wood Peroxide number 14 40 45 50 90 120 [greater than]200

Reactions on Centaur are generally similar to those taking place on other catalysts. However, in this case, sulphur dioxide is adsorbed into the pores of the Centaur carbon. There it reacts with oxygen and water to form sulphuric acid. Once the catalytic sites are filled, they are restored by washing with water to release the reaction product as weak sulphuric acid. The process is illustrated in Fig. 5. Application Centaur can be used to achieve cost savings in new grass-roots acid plants, and in reducing emissions in older plants. Also, plants can be debottlenecked by simply increasing the gas strength. The increased sulphur dioxide in the off-gas can be processed while maintaining or even reducing stack emission. In some metallurgical plants, the weak acid, generated in the wash step, can be used for ore leaching. However, the Centaur process is most applicable to sulphur-burning plants, where the water balance usually permits the weak acid to be recycled as a source of dilution water. Centaur vs double absorption Table 2 highlights the characteristics of the Centaur process compared with the double absorption process using vanadium catalyst. The advantages of each process are summarised below: Centaur carbon * Lowest emissions * Least equipment * Lowest cost * Highest steam production

* Lowest pressure drop Double absorption (vanadium catalyst) * Strongest acid * No water plume * Widest applicability Double absorption requires the process gas to be heated to over 400 [degrees] C for the vanadium catalyst to function properly. Centaur carbon is effective at about 50 [degrees] C or lower and can operate at temperatures readily available after the first absorbing tower. Sulphur dioxide emissions from a double absorption acid plant with vanadium catalysts are about 300 ppm, compared to less than 100 ppm with the Centaur process. Additionally, the Centaur reactor can be brought online faster without exceeding start-up emission limits. The Centaur reactors operate under wet conditions, the effluent being a wet gas. This can result in a visible water plume under some climatic conditions. If stack gas reheat is necessary to meet specific local requirements, this will have a negative impact on the process economics. Elimination of double absorption in a new plant design results in significantly less equipment. The hot and cold interpass heat exchangers, the final absorbing tower and peripherals, an economiser, and potentially one or more catalyst passes are eliminated - this equates to lower capital cost for the Centaur process. Significant operating cost savings can also be achieved with the Centaur process. In the double absorption process, the gas leaving the last catalyst stage is cooled to recover heat before it enters the final absorbing tower. Some of this heat is rejected to the final tower and results in lost steam production. This heat loss does not occur in the Centaur process. This reduces the energy needed to operate the main blower. Increased steam production and lower energy consumption means more energy is available for export in acid plants employing the Centaur process. Low strength gases[5] Topsoe has developed a Wet gas Sulphuric acid process which effectively recovers S[O.sub.2] in off-gases from non-ferrous smelters and roasters, examples of which include the Molymet molybdenum roaster in Santiago, Chile, and the Metaleurop lead sintering facilities at Noyelles-Godault, France. Concentrated sulphuric acid is produced of

typically more than 96 wt% irrespective of S[O.sub.2] concentration in off-gas. The process does not generate waste products or waste water, and avoids the use of absorbents or other [TABULAR DATA FOR TABLE 2 OMITTED] chemicals. During the process, up to 99.3% of the S[O.sub.2] is converted catalytically into S[O.sub.3], which reacts with water present in the gas, forming gaseous sulphuric acid. The acid is condensed in a WSA condenser of proprietary design. No extra sulphur burning is required at any S[O.sub.2] concentration on account of excellent heat economy and a limited sensitivity to the water balance. If conversion of more than 99.3% to 99.5% is required, a simple caustic or ammonia scrubber is installed downstream of the WSA condenser, hereby reaching a S[O.sub.2] reduction of +99.7%. Topsoe's process is particularly well suited for treating off-gases where the S[O.sub.2] content is lower than approximately 5-6%, however, the process is equally effective at treating richer gas streams from flash smelters. The technology offers a viable alternative to several existing smelters entailing a considerably lower investment cost compared to rebuilding or replacing the smelter. The catalysts used in a WSA plant treating smelter off-gases belong to the well-known Topsoe VK series.[6] The VK-WSA catalyst has proven very durable amongst the humid gases of WSA plants, the only precaution is to avoid condensing water. Potassium and sodium promote the vanadium catalyst, which comes in 10 and 20 mm extruded rings. In cases where a high conversion is required, it is necessary to operate at an inlet temperature which is below 400 [degrees] C for the lower pass, which is considered the minimum normal operating temperature for the VK-WSA catalyst. For such applications, eg the WSA plant for lead smelter, the last bed is loaded with Topsoe's VK58 catalyst, a caesium promoted vanadium catalyst, which can operate at lower temperatures.[7] VK58 offers the following advantages: * Improved conversion in single absorption plants * Overcoming of heat exchanger limitations * Improved start-up and restart * Increase in capacity Figure 6 shows that by using the VK58 catalyst, it is possible to achieve a conversion of +99% in a WSA plant for a non-ferrous smelter using only two adiabatic beds. By introduction of a third catalytic bed, it is possible to achieve over 99.5% conversion in a single condensation WSA plant, producing sulphuric acid of 98 wt%.

In total more than 27 units have been built or are under construction for applications including flue gas from power plants to smelter offgases, to refinery off-gas such as hydrogen sulphide streams and FCC off-gases, as well as regeneration of spent sulphuric acid. Equipment[8] Converter For many years, the classical materials for the converter have been carbon steel with cast iron or brick internals. The cast iron sections, in the form of grids, were held on posts or beams. Gas entered the converter through oblong or rectangular nozzles on the side wall of the vessel, and the beds were arranged in order of temperature with the first bed on top and the last bed in the bottom of the converter. These converters were quite acceptable for conventional gasstreams, however, their operation, and that of the plant, has been disrupted by replacement and repair. Typical problems include scaling and creep deformation of carbon steel/cast iron equipment at elevated temperatures and corrosion. The loss of just one or two catalyst grids in the converter significantly reduces conversion, forcing the plant to reduce rates or shut down for repairs. In addition, continuous operation at elevated temperatures can shorten the grid life to five years. More predictable and improved performance has been achieved by implementing stainless steels and new design techniques. Monsanto Enviro-Chem Systems entered into a licensing agreement with Cecebe Technologies and now offers a new stainless converter with structurally shaped beds and division plates, supported on a post and ring network [ILLUSTRATION FOR FIGURE 7 OMITTED]. In this converter design the catalyst beds can be full-diameter; that contrasts with core-tube designs, in which the whole core from top to bottom is needed for catalyst and division plate support. Nozzles in the new design are oblong to keep the overall height down. Since the division plates and catalyst supports are shaped, they offer more startup temperature differential freedom and demand less material to provide the required support. Kvaerner Chemetics is currently involved in a smelter acid plant that will be processing high strength sulphur dioxide. The 2150 mt/d plant is being constructed for Thai Copper Industries, Ltd at Rayong Thailand. Figure 8 shows the converter under construction. The dry gas composition from the smelter lies between 12.9% and 14.8% S[O.sub.2]. The gas is somewhat diluted in the acid plant to adjust the oxygen level and improve the overall conversion. Therefore, gas strength to the converter will be between 12.3% and 13.2% S[O.sub.2]. The plant is designed to achieve 99.85% conversion of

S[O.sub.2] to S[O.sub.3]. The plant uses a top layer of caesium promoted catalyst in the first bed (approximately 25%); this allows gas to enter the first bed at 385 [degrees] C (725 [degrees] F) and exit at 625 [degrees] C (1155 [degrees] F), achieving a 64% conversion efficiency. The lower strike temperature of the caesium catalyst means that good conversion can be achieved in the first bed without exceeding the upper temperature limit of 630 [degrees] C (1165 [degrees] F) for the catalyst. Heat exchanger Monsanto Enviro-Chem also licenses radial-flow gas exchangers from Cecebe. These are especially suited to large acid plants, which have traditionally used single segmental, double segmental and cross-flow designs. Cross-sections of a variety of exchangers are shown in Fig. 9. Single segmental exchangers are not suitable in large plants and are susceptible to high shell velocities and pressure drops. Cross-flow designs are effective, but suffer from uneven thermal expansion in the tube field, causing cracked tube sheets, broken tube-tube sheet joints, and ducting distortion. Double segment designs have been used extensively by Monsanto, but are prone to longitudinal flow in the baffle windows, which detracts from the maximum attainable heat transfer coefficient. The radial-flow exchanger design incorporates the best of conventional technology and improves exchanger thermal and mechanical performance with a radial flow pattern. The gas flow is between an open core and an outer annulus. This provides low pressure drop, even thermal stress and optimum heat transfer. All tubes are located in the baffles, eliminating longitudinal flow with a no-tubes-in-the-window design. In addition, the concept allows a core connection to the shell space as well as connections to the outer annulus by way of a bustle. Inlet and outlet connections to the bustle can be made at any orientation and are not limited to 180 [degrees], as with single, crossflow and double segmental designs. This allows added flexibility and efficiency in duct layout and design. The radial symmetry and notube-in-window concept results in heat transfer coefficients which are substantially higher for the same pressure drop than conventional single and double segment designs. A saving of around 20% is found in heat exchanger surface compared to double segmental layouts. More importantly, the shell is not close to the bundle and it is possible to keep mechanical forces on the tube-to-tubesheet joints to very modest levels. This assures increased exchanger service life without mechanical failure and avoids the mechanical problems associated with many earlier designs. Another feature of the updated technology, which may be of significance in the long term, is the ability to start newer plants with low emissions.

Case study Boliden Mineral AB operates the Ronnskarr Works, situated on the Gulf of Bothnia, 40 miles east of the Boliden mine, in Sweden. The works treats mainly copper and lead concentrates from the mines of the Boliden Company. These activities give rise to a wide variety of byproducts, including sulphuric acid and liquid sulphur dioxide. Several different gas flows are generated at the copper and lead plants. Some flows are continuous but several are discontinuously generated. The maximum total gas volume is about 168,000 [m.sup.3] (n)/h when all the furnaces and converters are "under stack". The gas volume is reduced to about 70,000 [m.sup.3](n)/h when only gas from the continuously operating units is available. The different gas streams are described in Table 3. The process gases from the roaster, electric furnace and converters in the copper plant are cleaned in hot cottrells. Gases from the kaido furnace are cleaned in a venturi scrubber. These gases pass to the pretreatment plant before being distributed to the sulphuric acid and liquid sulphur dioxide plants (see Table 4). Pretreatment plant To comply with pollution regulations, and as a consequence of the expansion of copper and lead production, it was decided in the mid1970s to substitute the previous three washing steps with one single pretreatment plant, which has been in operation since December 1977. This improved system has a capacity of 300,000 [m.sup.3](n)/h, a total cooling capacity of 6x[10.sup.6] kcal/h and a process water consumption of 15 [m.sup.3]/h, allowing precise control of gas flow for maximum recovery of the sulphur content. The gases, of varying temperature (30-150 [degrees] C, 85-300 [degrees] F) and moisture content, enter first a mixing tower, which is followed by two parallel connected washing towers. All three towers are empty and equipped with separate circulation systems for scrubbing water, distributed from spraying nozzles at the top of the towers. The tower system effectuates mixing, cooling, and moisturising of the gases, and to some extent separation of dust from the gases. Additional cooling is effected in six parallel connected vertical tube and shell coolers, where the gases are indirectly cooled with brackish water to an exit temperature of less than 25 [degrees] C (77 [degrees] F). The scrubbing water supply is added as fresh water to the washing towers from which it flows through the system in counter current flow to the gases. A water stream is bled off from the mixing tower to remove slime and dissolved impurities. The effluent water is treated together with other waste waters with caustic soda, sodium sulphide and lime, in order to remove heavy metals and fluorine.

Some of the metallurgical processes do not operate continuously, causing considerable changes in the gas flow. The gas pressure in the mixing tower is kept constant by an automatic control system, which increases or decreases the capacity of the blowers in the sulphuric acid and S[O.sub.2] plant according to the changes in the gas flow from the metallurgical plants. A readjustable priority selection system is used to regulate the order in which the blowers in these four separate plants are influenced to change their capacity. Speed regulated fans after the coolers serve for gas transportation through the scrubbing system. Their speed is automatically regulated to keep constant draught in the output ducts. Production of liquid S[O.sub.2] The first S[O.sub.2] plant was established from the desire to reduce S[O.sub.2] emissions to the atmosphere and to get the maximum possible utilisation of the sulphur content. Furthermore, this plant made it possible to use gases with a concentration less than 3%, which were normally unsuitable for sulphuric acid plants. The S[O.sub.2] content in the process gas is absorbed in cold water in an absorption tower. The S[O.sub.2] is stripped off from the water with steam at atmospheric pressure. This process was chosen on account of the availability of cold sea water and surplus steam from the waste boilers. After drying with sulphuric acid, liquid sulphur dioxide is condensed. The first plant was completed in 1973 and was followed in the midseventies by a second liquid S[O.sub.2] plant, owing to stricter legislation on S[O.sub.2] emissions and an increase in metallurgical capacity. This plant, illustrated in Fig. 10, is still in operation today. The gases from the pretreatment plant are cleaned in wet electrostatic precipitators and are then compressed to 1.20 bar by a blower before being treated in two parallel selenium filters. These are towers containing a vertical cylindrical filter element consisting of seleniumcoated porous inert material. The gas [TABULAR DATA FOR TABLE 3 OMITTED] [TABULAR DATA FOR TABLE 4 OMITTED] containing mercury vapour is forced to pass through the filter element radially. Elemental mercury in the gas reacts with selenium to form HgSe. The removal efficiency of the filter is about 90%. Absorption The gases enter the bottom of the absorption tower in which the sulphur dioxide is absorbed in a counter current flow of cold water. The absorption efficiency is high, e.g. at a maximum gas flow of 100,000 [m.sup.3](n)/h containing 5.5% S[O.sub.2], with 1,200 [m.sup.3]/h water at 10 [degrees] C (50 [degrees] F), the S[O.sub.2] content of the gas leaving the top of the tower is less than 0.05%.

The amount of water required for absorption depends on the temperature. The water requirement at constant gas concentration and gas flow is about twice as great when water temperature is 20 [degrees] C (68 [degrees] F), as when it is at 0 [degrees] C. Stripping The water collected at the bottom of the absorption tower has a S[O.sub.2] content of 0.8-1.2%. The sulphur dioxide is stripped off at 60 [degrees] C (140 [degrees] F) in vacuum, at an absolute pressure of 0.2 bar in the stripping tower. Water supplied to this tower is heated in plate heat exchangers to about 52 [degrees] C (126 [degrees]F) by heat recovered from degassed water. The final heating to 60 [degrees] C is effected through use of waste heat from the sulphuric acid plant. For this reason the cooling water is circulated between the absorber acid cooler and a low pressure boiler, where the hot water is flushed to generate steam for the stripping process. A trim cooler operating on sea water is placed in the water loop to remove any excess heat when the acid cooler produces more heat than is required for steam production. The top of the stripping tower is designed as a cooling column to cool the exit gas and to condense its moisture content. For this purpose about 15% of the cold S[O.sub.2]-containing water from the absorber is sent directly to the top of this column without passing the heat exchangers. The hot degassed water from the stripping tower has a S[O.sub.2] content less than 100 mg/l. It also contains some small amounts of sulphuric acid. Neutralisation to pH [greater than]5 is achieved by automatically regulated addition of sodium hydroxide before the water is pumped through the plate heat exchangers and released to the recipient. Drying The gas from the cooling column in the top of the stripper is saturated at about +10 [degrees] C (50 [degrees] F) with moisture which is removed with sulphuric acid in a two-step drying tower. The acid flows counter-currently to the gas. In the first step most of the moisture is taken up by 75% acid which is cooled by sea water in a plate heat exchanger. The gas is totally dried in the following step, with 96-97% acid. The diluted sulphuric acid from the first drying step is sent to the acid plant for reconcentration. Liquefaction The dry gas is transported by a fan to a precooling tower where the gas is cooled and washed with liquid S[O.sub.2] from the condensers. The

precooled S[O.sub.2] gas is liquefied in tube-and-shell condensers in two steps using a freon R13 B1 refrigeration system. The first step involves liquefaction at about -45 [degrees] C (-49 [degrees] F), the second step at around -62 [degrees] C (-80 [degrees] F). The liquid S[O.sub.2] flows at about -50 [degrees] C (-58 [degrees] F) to a collection tank from which it is pumped to the precooling tower and from there to storage tanks. The liquid S[O.sub.2] produced contains less than 2 ppm acid and under 50 ppm water. Any remaining inert gases and uncondensed S[O.sub.2] gas are evacuated by a liquid piston type vacuum pump and is returned to the absorber. S[O.sub.2] water buffer tank As mentioned above, a great deal of the process gas flows are discontinuous which means that the S[O.sub.2] load to the sulphur plants can vary within a relatively wide range. Sometimes the amount of sulphur dioxide in the gases can exceed the capacity of the sulphur plants. During such periods one or more of the gas producing units have to stop until the total S[O.sub.2] load is lowered so that the process can start again. The limited S[O.sub.2] capacity therefore causes production restrictions in the copper and lead plants. However, the average capacity of the sulphur plants is sufficient for the utilisation of maximum S[O.sub.2] production from the metallurgical units, if the S[O.sub.2] could be equalised. Thus in order to increase the instantaneous S[O.sub.2] capacity in the sulphur plants and to equalise the S[O.sub.2] load, a 5000 [m.sup.3] storage tank for S[O.sub.2] water from the absorption towers in the S[O.sub.2] plants was constructed in the early 1980s. In this tank the excess S[O.sub.2] water, which cannot be directly treated in the stripping and liquefaction processes, is stored until available capacity is obtained during periods with low S[O.sub.2] load. Since then the original liquid S[O.sub.2] plant has shutdown. The equipment in the second plant has capacity enough for the equalised total S[O.sub.2] water flow from both absorption towers. The steam requirement per ton of S[O.sub.2] is much lower in the newer plant, and therefore much steam is saved due to the buffer tank. References 1. "Modern plants must be immaculate", Sulphur, 229, pp. 40-48 (NovDec 1993). 2. Ullmann's Encyclopedia of Industrial Chemistry, A25, Section 6.1, pp. 598-599, VCH Verlagsgesellschaft mbH, Weinheim (1994).

3. Longo, A., Boyd, W. K., Boillat, R.: "Inco Ltd - the world's largest single stream metallurgical gas [H.sub.2]S[O.sub.4] plant", British Sulphur Sulphur 1993 Conference, Hamburg, April 1993. 4. McAlister, D. R., Tully, J. J., Howes, M.D., Mazzoni, A. F., Lynch, R. T., Megonnell, N. E.: "Centaur(*) S[O.sub.2] removal process: a new approach to an old problem", British Sulphur Sulphur 1996 Conference, Vancouver, October 1996. 5. Bendixen, O. R.: "[H.sub.2]S[O.sub.4] from low strength gases", The South African Institute of Mining and Metallurgy Colloquium: Trends in Base Metals Smelting and Refining, Randburg, April 1997. 6. Jensen-Holm, H., Lyne, G.: "New options for smelter-based acid plants", Sulphur, 232, pp. 47-57 (May-Jun 1994). 7. King, T. D.: "Improving acid plant performance using Topsoe's VK58 caesium promoted catalyst", British Sulphur Sulphur 1991 Conference, New Orleans, November 1991. 8. Cameron, G. M., Fries, R. M., Puricelli, S. M.: "Demonstrated new technologies for sulphuric acid plants of the nineties", British Sulphur Sulphur 1994 Conference, Tampa, November 1994. Acknowledgements Sulphur wishes to thank Mr Bjorn Lindquist and Mr Klas-Goran Hultbom of Boliden Contech AB, Sweden, Mr Ken Williams and Ms Barbara Streicher of Enviro-Chem Systems, USA, Mr Ole Rud Bendixen and Ms Kitsten Leblanc of Haldor Topsoe A/S, Denmark, and Mr Barry Mcintosh of Kvaerner Chemetics Inc, Canada, for their kind co-operation in contributing to this article. COPYRIGHT 1997 CRU Publishing Ltd. This material is published under license from the publisher through the Gale Group, Farmington Hills, Michigan. All inquiries regarding rights should be directed to the Gale Group.

Title: Quantity vs quality. (Sulphuric Acid Trading) Date: 3/1/1994; Publication: Sulphur; Last year was a difficult year for a number of sulphuric acid traders. While the quantities moved were large, prices were low as traders had to compete both with one another and with the falling price of elemental sulphur to find buyers. This article looks at the trading

patterns in 1993 and some of the traders active in northern Europe and on the trans-Atlantic routes. Last year's weakness in the sulphuric acid market highlighted a major disequilibrium between production from the non-ferrous metals sector and consumption by the phosphate fertilizer industries. In recent years, the former has had to increase sulphur capture due to environmental pressures. At the same time, the latter was faced with low prices and falling demand for a number of reasons, including the environment, the recession and agricultural over-production in the European Community and elsewhere. In the first half of the year, the European surplus was such that one smelter was temporarily forced to close and declare force majeure on its metal sales. Another had only three days to go before it too would have had to be shut down. Detailed figures on acid imports and exports by country for 1993 are only available for a few countries. US imports rose for example by over a fifth to 2.4 million tonnes, while UK imports (in the first nine months) declined by 60 per cent to about 130,000 tonnes only. It would seem that product (particularly from smelters) was actually switched to Florida from Europe at the beginning of the year in order to protect the home market. Japanese exports meanwhile rose by 17 per cent. The price weakness has had a number of structural repercussions. First it pushed out some occasional suppliers, which reduced the volume of spot business; several traders recently told Sulphur that some 80-90 per cent of their businesses is now long term contract or equivalent. Second, the continuing low price of base metals and the fluctuations in the acid price encouraged smelters to find ways to reduce acid production, for example by opting to treat, wherever possible, lowsulphur concentrates. In addition, there have been one or two permanent metal smelter closures, in which the low acid price could have played a part. Third, the low prices resulted in local producers in several countries including the USA and Brazil, considering the possibility of filing antidumping suits. Though the situation improved during the course of the year, and, it would seem, legal investigations were put on hold, the threat of anti-dumping action remains. In the USA, the low prices were essentially a reflection of competition between acid traders seeking to dispose of larger than normal volumes of product. However, small price cuts were quite insufficient to cut into the sulphur burning/cogeneration market to the extent required. In the USA, for instance, the average cif import price for Tampa in the first quarter of last year was $15/t, compared with $26/t for the whole of 1992. In the second quarter, the mean fell to $12/t. Given the transAtlantic freight rates at the time were around $20/t, this would suggest

exports were leaving European smelters at negative numbers. In the third and fourth quarters, US imports from Europe declined somewhat, and prices improved. Fourth, in order to place the increased production elsewhere, some traders (together with one or two potential buyers) began looking at the feasibility of constructing a number of new import terminals in locations as far apart as Morocco, Senegal and the east coast USA. While the Moroccan terminal seems to be on hold at present, ICS in Senegal expects its terminal to be completed within a few years. Other locations under consideration last year included Brazil, west coast USA and India. Growing interest in low-Hg acid In spite of the large quantities of acid on offer, sellers of top quality product continued to secure a premium, highlighting the strength of demand in the sub-sector. At present, for instance in North West Europe, the going c+f rate for metallurgical acid is from the upper DM20s/t to the low DM30s/t; low mercury acid (for instance with 0.1 ppm Hg) apparently attracts a DM5/t premium over typical merchant grade product which has up to 0.5 ppm mercury. Indeed another reason for the increase in shipments across the Atlantic last year would seem to be the decrease in demand in Europe for high mercury acid. One trader even talked about an informal standard developing to limit the proportion of mercury, and other heavy metals in the acid. High quality product, which should be water clear is necessary for buyers in the food industry. Other users are keen to maintain stringent environmental standards either for their product and/or for their waste discharges; for example some large buyers in the Antwerp-Rotterdam Area as well as Scandinavia require acid with less than 0.3 ppm mercury in order to meet local water discharge limits. One other development on the quality front is the increasing demand from buyers for a ISO 9000 accreditation for their trader-based acid sourcing operations. One trader said that this was particularly apparent among customers in the industrial market and more generally in the UK. Keeping different tanks for different grades is a key part of the process of maintaining high quality supplies. The world-wide trading of sulphuric acid is dominated by three companies - Boliden Chemtrade, Interacid and MG Chemical; we look at these first. A number of other companies such as Borregard, Chemtrade, Contichim International and KGHM-Metraco operate generally at a regional level in Europe. Others such as Boliden Intertrade, Cali and SATCO operate at a regional level in North America. These will be the subject of a separate article.

Boliden Chemtrade Last year, the Boliden group traded approximately 2.6 million tonnes of acid: of this approximately 1.4 million tonnes was sea-going and 1.2 million tonnes was inland - and of this the vast bulk was within North America. From the La Caridad smelter in Mexico, Boliden has the exclusive contract for the offshore sales through Guaymas. Its main sales destinations for this acid are the United States and Chile. Indeed, Boliden's main geographical areas of interest include both North and Latin America as well as northern Europe, and the Mediterranean. Boliden Intertrade, based in Atlanta is responsible for the US and Canadian markets, and Boliden Chemtrade in Zug for the sea-going business. While both companies are 100 per cent subsidiaries of Trelleborg, it is the Zug office in Switzerland which is the responsible for all international trade. Boliden owns two terminals - in Tampa and in Rotterdam, each of which has 40,000 tonnes storage capacity. The terminal at Savannah, Georgia is on a long term lease and has 13,000 tonnes storage. Chemtrade takes its vessels either on long term charter or through Scan-Chem Chartering in which it has a 50 per cent stake. The latter joint venture gives it access to chemical tankerage, when required for an immediate shipment. Boliden's sea-going acid is almost entirely metallurgical, though it sometimes takes sulphur based or pyrites based product. In Europe, Boliden has installed mercury and arsenic removal units at its own metal smelting and refining operations in Sweden (Ronnskar) and Norway (Norzink and Falconbridge). The plants in Sweden use Boliden Contech's Editube wet electrostatic precipitators. Boliden Chemtrade is also in the process of applying for ISO 9000 recognition for its Rotterdam terminalling operations, in the belief that this will strengthen its intermediary role between companies which have achieved this quality standard. Interacid Interacid, in which IMIC has a majority stake and Sumitomo Corp a minority shareholding, traded around 2 million tonnes of acid in 1993. This excludes business on SATCO's own account. SATCO, which recently relocated within Tampa is the joint venture in which Freeport Sulphur has a 50% stake and Interacid the balance. Essentially all of Interacid's business last year was international and seagoing. Around half was sourced in Japan from the metal smelters and of this, about 50 per cent was shipped within the Far East (eg the Philippines) while the other half was exported further afield, for example to the USA and Mexico. The other two major sources of acid -

northern Germany and northern Spain - are also metallurgical. In addition, the company receives smaller quantities from other sites in the Mediterranean and Oceania. The company's main sales markets are North and Latin America (last year Brazilian buyers purchased 200,000 tonnes of product from Interacid), the Mediterranean and Northwest Europe, particularly the UK. The company's terminal, which is operated by SATCO, is at Tampa, where the storage capacity is 60,000 tonnes. Also the company is intending to open a terminal in northern Chile by the end of the year; its storage capacity will be 40,000 tonnes. Interacid charters all the vessels it uses for sea-going transportation. Metallgesellschaft Last year, MG traded approximately 1.5 million tonnes of acid. Of this 1.2 million tonnes, some four-fifths was international and of this, about 70 per cent was seagoing. This was mostly in North West Europe or across the Atlantic, and to a lesser extent in the Mediterranean. The other 30 per cent was traded, principally in the Benelux countries. The main sources of MG's acid are the smelters in Germany Norddeutsche Affinerie in Hamburg, Berzelius in Duisburg and Ruhr Zinc in Datteln. Steps have been taken, wherever possible, to clean this acid. In addition for its titanium dioxide plant at Sachtleben, MG produces acid both directly from pyrites, and indirectly from cracking the filter cake produced during acid regeneration. In Spain, MG recently took over the Rontealde plant at Bilbao (capacity 260,000 t/year) and at the same time switched from pyrites to sulphur-based production. This acid is suitable for special applications, the company says. Total storage capacity in Europe is 150,000-200,000 tonnes, with facilities at each of the company's production facilities. From these sites it is taken by barge or rail either to the buyer, or to a spotchartered sea-going tanker. MG Chemicals in Zug is responsible for sea-going business, while the Frankfurt office of Metallgesellschaft handles onshore contracts. Rontealde has its own distribution network in Spain. Borregard This Norwegian company is a key player in North West Europe, having traded in 1993, about 340,000 tonnes of product. As all its production is derived from Finnish pyrites processed at Sarpsborg in Norway, its acid does not contain heavy metals. Borregard believes the quality of its acid is of importance for those consumers that need a clean acid for environmental or public health reasons, such as the pigment, fertilizer, pulp and paper or food industries.

The company deals direct with consumers and distributors. Sea transport is typically arranged in co-operation with a Norwegian shipowner. The company, in this way, has access to the chemical tankers needed for shipment. Borregard is the processing division of the Orkla group, which is one of Norway's largest listed companies. Its activities include chemicals and chemicals-based wood processing. ChemTrans ChemTrans traded around 400,000 tonnes of acid last year - virtually all sea-going and international; most of its business is done in northern Europe, supplying from Germany and the Nordic region to the Benelux countries and the UK. While the bulk of ChemTrans' acid is metallurgical, a not insignificant portion is sulphur based. Both the latter and its metallurgical acid from Finland have low mercury levels. Another of the strengths of the company is its fleet; it either owns or has on long term charter three 8,000 tonne vessels and two 4,000 tonne vessels, all with a high ice class. ChemTrans is a privately owned company with its headquarters at Untergeri in Switzerland. Contichim International This Brussels-based company, which has been trading sulphuric acid since 1947, shipped just over 300,000 tonnes of acid last year. Contichim has an exclusive long term supply agreement with Metaleurope, the French-based non-ferrous metals producer as well as a number of other contracts with metal producers and chemical manufacturers in western Europe. Some four-fifths of its product is sold in North West Europe particularly France, Belgium, Holland and Germany, where it uses the river network to move product by barge. The balance is sold in the Middle East and other parts of the world, such as Latin America and the Far East. The company has two terminals - one in Antwerp and the other in Gent, with an overall storage capacity of 25,000 tonnes. These tanks enable Contichim to keep the 70 per cent of its acid which is metallurgical in origin separate from the sulphur based product (20 per cent) and the pyrites based (10 per cent) product. Hence the company is able to meet qualities, ranging from metallurgical acid with maximum 0.5 ppm Hg to water clear sulphur based material. Contichim International is part of the Conti-group (Contimine), in which Luxembourg-based Alsmin has had the majority stake from 1993. Companies such as Hoffmann La Roche, Enichem, Union Minire, RTZ

and Pechiney have, since the foundation of the company, together held a minority stake of just under 30 per cent. KGHM Metraco This Polish company is one of the smaller acid trading companies in Europe. In 1993, it traded around 100,000 tonnes internationally approximately a quarter of its output. From the Legnica and Glogow copper smelters in the west of the country, KGHM Metraco shipped most by rail, and the balance by barge. Contract business is done largely by rail. KGHM-Metraco was established in 1991 by state-owned KGHM, which is the Polish Copper Corporation; Metraco is a limited liability company selling a number of by- and downstream products from the parent firm's smelting and refining operations. In 1992, its turnover from chemical products (mainly sulphuric acid and silver-bearing anode slimes) was approximately $50 million. COPYRIGHT 1994 CRU Publishing Ltd. This material is published under license from the publisher through the Gale Group, Farmington Hills, Michigan. All inquiries regarding rights should be directed to the Gale Group.

Title: Pure sulphuric acid from contaminated ores. Date: 3/1/1990; Publication: Sulphur; Author: Solbu, E. Controlling arsenic, mercury and organics Pure sulphuric acid from contaminated ores In more than 60 years of operation, the Swedish mining, metals and chemicals group, Boliden (now part of the Trelleborg group) has accumulated considerable experience in roasting and smelting impure copper and zinc ores and pyrites and has devoted considerable attention to improving the purity and quality of the sulphuric acid generated from the sulphur dioxide-containing roaster gases. As a result the group has developed special roasting technology for arsenical copper ores and pyrites, processes for removing and recovering arsenic and mercury from roaster gases, and methods of purging mercury and organic matter from sulphuric acid. Boliden has also been a pioneer in the application of new materials of construction for sulphuric acid service.

Commercially significant non-ferrous metals, including copper, nickel, zinc and lead, frequently occur in nature in the form of sulphide ores, though by no means exclusively so. Because the metal sulphide content of these ores tends to be rather low, they are usually concentrated at the mine site by some kind of beneficiation treatment, such as flotation, in which much of the worthless component of the ore, or gangue material, is rejected. The concentrate is then processed to extract the metal values. Although the chemical route by which the metal is finally formed varies according to what particular metal it is, the initial procedure is mostly the same in principle for all: the concentrate is first roasted in air to burn off some or all of the sulphur values as sulphur dioxide. In the case of copper, the product of roasting is cuprous sulphide, which is converted to copper with more air or oxygen at a higher temperature. This produces further sulphur dioxide. [Cu.sub.2] S + [O.sub.2] [arrow right] 2Cu + [SO.sub.2] Zinc and lead ore roasting produce the corresponding oxides, but whereas the zinc is usually recovered by leaching and electrolysis, lead is produced by reducing the oxide with carbon. In the very early days of industrial non-ferrous metals production, the ores were roasted in the open air, with sometimes calamitous effects on the surrounding environment, as in the Sudbury area of northern Ontario. Later, the sulphur dioxide was dispersed into the atmosphere through tall chimneys, which merely distributed the ill effects more thinly over a much larger area. But large operations produce sulphur dioxide on such a scale that it represents a valuable sulphur resource, and it has been common practice for some years to convert it to sulphuric acid on the spot. Today, since there are few practical alternatives, this procedure has become virtually obligatory on account of the very tough regulations on sulphur dioxide emissions now in force in many countries. Iron pyrites, with a composition approximating to [FeS.sub.2], is also commercially processed by roasting. Since, however, other, more easily processed iron oxide ores are commonplace, the primary purpose for doing so is to exploit its sulphur content, which typically accounts for 40-46% of the mass of commercial pyrites ore concentrates, rather than its metal content. Nevertheless, it is possible to use the cinders from the process in steel production, provided they are of sufficient purity, or in cement production. The gas produced in roasting processes has to undergo a considerable amount of purification before it can be used as sulphuric acid plant feed gas. Entrained dust, which would clog the first catalyst bed of the sulphuric acid plant, has to be reduced to very low levels, usually by means of cyclones followed by dry electrostatic precipatators. The gas must be washed to remove any remaining traces of solids and to

absorb soluble gaseous impurities such as hydrogen chloride and hydrogen fluoride, which would cause great harm to the sulphuric acid plant equipment and catalyst. Finally, any sulphuric acid mist produced in the washing section by reaction between traces of sulphur trioxide and water must be eliminated, also to safeguard against corrosion downstream. Matters are further complicated when complex ores or pyrites are to be processed, particularly if contaminated with organic matter or volatile toxic elements such as arsenic and mercury. For not only will these find their way into the final product if not properly managed; great care is also necessary to ensure that the toxic materials are not discharged into the environment in effluents or wastes. Special attention must, therefore, be given to monitoring and controlling the composition of the ore mix entering the process, to designing the process to remove volatile impurities, and to arresting gaseous impurities such as mercury and organic compounds. Product purity also depends on the choice of suitably resistant materials of construction within the sulphuric acid plant itself. Outline of the Boliden experience in making pure sulphuric acid from contaminated ores In 1924 a body of contaminated chalcopyrite (copper pyrites; [CuFeS.sub.2], which contained considerable amounts of gold, silver and arsenic, was discovered at Boliden, a small community in northern Sweden, and mining started in 1926. Shortly afterwards, a new smelter to process this ore was built on the small island of Ronnskar in the Gulf of Bothnia, approximately 55 km from the Boliden mine. Since then, processing of contaminated ores has become a speciality within the Boliden group. Copper and lead ores are processed at the Ronnskar works, pyrites are roasted at the chemical plant in Helsingborg, and zinc ores at the partly-owned Norzink site in Odda, Norway. At all three sites, development work has been carried out to obtain high-quality products from the ores under environmentally acceptable conditions. Special efforts have been made concerning arsenic and mercury so that today's methods not only control emissions whilst producing high-quality sulphuric acid but can also recover mercury and arsenic as by-products, according to demand. The complex ores processed at Ronnskar cannot easily be processed by competitors who do not possess the special technology or equipment. After more than half a century of experience in producing sulphuric acid from contaminated ores, Boliden has developed equipment and technology addressing all the problems outlined above, and this knowledge is available to the world through Boliden Contech AB, the engineering company within the Trelleborg group. Materials planning system

Boliden has substantially improved the economics of the Ronnskar smelter by installing a computer-aided planning system. It controls the proportions of a variety of ores which come from Boliden's own mines and others, as well as a multitude of scrap and ashes entering the plant and recirculated wastes, such as arsenic solutions and sulphide sludge entering the roaster. The system integrates planning for materials purchasing with storage, transportation, and production planning, the last of which takes into consideration both copper and sulphuric acid product quality. Management of arsenic When processing an arsenical copper ore, it is essential to liberate the arsenic from the ore, otherwise it follows the copper through the smelting process and creates immense problems in the refining plant. In the production of sulphuric acid from arsenical pyrites, arsenic must similarly be removed from the cinder, in this case to get an iron oxide pure enough for use as a raw material for the steel or cement industry. In both cases, the solution is to roast the ore under reducing conditions. Chalcopyrite roasting at the Ronnskar Works The roasting of complex chalcopyrite ores is the most important feature of the copper process at the Ronnskar Works. The fluidized-bed roaster, which replaced four old multiple-hearth furnaces in 1980, not only has greatly improved the working conditions but also gives lower process gas volumes, which is, of course, beneficial for the operation of the sulphuric acid plant. In this furnace, arsenic is evaporated by partial roasting of the solid ore, and then oxidized with secondary air. The excess heat from roasting is utilized for the combustion of heavy metal sulphide sludge from the water treatment plant as well as process bleed water from the arsenic refinery, which gives total recovery of the metal values. The cinder, which is low in arsenic, is smelted in a subsequent electric furnace. The Boliden magnetite-yielding pyrites roasting process This process is based on the fact that when pyrites are roasted under slightly reducing conditions, magnetite ([Fe.sub.3] [O.sub.4]) is formed and arsenic is evaporated. If instead roasting is carried out with a surplus of air, haematite ([Fe.sub.2] [O.sub.3]) is formed. The arsenic reacts with the haematite to form iron arsenate ([FeAsO.sub.4]), which is a stable, undesired product.[1] A charge consisting of flotation pyrites is fed to a fluidized-bed roaster, in which the partial pressure of the oxygen is controlled by regulating the air/pyrite feed ratio to the furnace (Fig. 1). The pyrites burn at about 850 [degrees] C in the bed, which consists mainly of magnetite

cinder. The particle size and gas flow rates are such that the cinder is pneumatically transported out with the process gas leaving the furnace. Boiler tubes are submerged in the bed to control its temperature and recover energy, but some of the released energy is consumed in destroying sludge from the gas washing plant, which is also fed into the furnace. About 90% of the cinder is separated in cyclones and is transferred to a secondary fluidized-bed furnace, where more air is added, sulphur is removed, and the magnetite is transformed to arsenic-free haematite. This material is then cooled in a fluidized-bed cooler and exported for steel-making. The roaster gas leaving the cyclones still contains some elemental sulphur gas, which is oxidized in a post-combustion chamber just before the steam boiler. The temperature rise of this post-combustion is utilized for the control of the process. Since the roaster gases are under oxidizing conditions at a high temperature for only a restricted time, little sulphur trioxide is formed. After recovering the energy in the boiler, the gas is cleaned in a hot electrostatic precipitator. The Boliden dry arsenic separation process The sulphur dioxide-containing gas from the roaster passes through a two-stage gas filtration system (Fig. 2)[1,2]. In the first stage, dusts and fumes are removed in hot electrostatic precipitators working at 350 [degrees] C. Then the gases are cooled to 120 [degrees] C in evaporative coolers and passed through bag filters, where dry arsenic trioxide that has been condensed in the coolers is captured. The product may be used as raw material for an arsenic refinery. In addition, elemental mercury is partially removed in this process, probably because the gas is filtered through a very active layer of freshly formed arsenic trioxide, which acts as an adsorbent and as a base for the oxidation of the adsorbed metallic mercury to non-volatile mercury compounds. The Boliden wet arsenic separation process As an alternative to the dry process just described, the arsenic content of the roaster gases leaving the hot electrostatic precipatator may be removed in a wet arsenic separation process (Fig. 3), in which the gas is washed in a tower with about 50% sulphuric acid.[1] That is the concentration of sulphuric acid at which arsenic has the minimum solubility, and it is recovered as a crystallized product. A portion of the circulating acid passes through a thickener, where solids are removed, and the solids content of the acid returning to the washing tower is controlled. After washing, the crude arsenic trioxide is of high enough quality to be utilized as a raw material for the production of refined arsenic. Wet gas cleaning

Following the arsenic separation stage, the gas is washed and cooled in steps at controlled sulphuric acid concentrations to fix part of the mercury as mercury compounds and to condense out the halogens. Most of the dust particles are separated simultaneously. Open towers are preferred to packed systems, mainly because the latter are prone to clogging. The Editube stainless steel wet electric precipitator The Editube wet electrostatic precipitator (Fig. 4) was developed at the Ronnskar Works to replace some older lead precipitators, which had poor performance and extensive maintenance problems.[3] It is a modular-shaped unit, consisting of a stainless steel shell-and-tube bundle fitted with gas inlet and outlet chambers. Each chamber has a gas nozzle with built-in shut-off dampers. The lower (inlet) chamber is also equipped with a perforated plate for the purpose of distributing the gas uniformly among the tubes. This plate also acts as a platform during maintenance work. The gas flows through the grounded tubes, which act as collecting surfaces for the impurities to be separated. When cooling water is circulated on the shell side, the unit also acts as a shell-and-tube heat exchanger. Besides cooling the gas, this also protects the stainless steel by lowering the temperature and creating a condensate film, which dilutes and continuously washes away the impurities that collect on the surface. The newly designed Edirod emission electrodes are disposed axially inside each circular tube and create higher current densities than conventional discharge electrodes. They are made of the same material as the tube bundle. A rectifier transformer unit is placed in a local control cabinet at the top of the precipitator. This design has also proved to be efficient in the abatement of dioxin occurring in the gas. Mercury separation techniques Even though some mercury is separated from the gases in the various cleaning processes mentioned above, further treatment is required after the mist precipitators to ensure that the ultimate mercury content of the product acid does not exceed the low limits allowed for fertilizer production. In all, four mercury removal methods have been developed within Boliden: the Boliden/Norzink mercury removal process for gases with high mercury content (a standard method after zinc roasters), selenium filters for humid gases with moderate and low mercury content, activated carbon filters for dry gases with moderate and low mercury content, and the Boliden thiosulphate mercury removal process, which is a process integrated into the sulphuric plant itself. They are utilized in full-scale plants all over the world.[4] The Boliden/Norzink mercury removal process

The Boliden Norzink process (Fig. 5) is designed to eliminate high concentrations of mercury vapour from a gas stream. The basis of the process is a complete and very rapid reaction that takes place when metallic mercury vapour comes into contact with dissolved mercuric ions, in this case mercuric chloride. [Hg.sup.0] + [HgCl.sub.2] = [Hg.sub.2] [Cl.sub.2] (calomel) The cooled and precleaned gas enters a reaction tower, in which it is scrubbed in counter-current flow with a solution of mercuric chloride. During the reaction, insoluble mercurous chloride (calomel) is precipitated. This product is isolated from the system as a heavy sludge by decantation in settlers. A portion of the calomel is then separated from the process and may be sold or converted into mercury metal in an integrated process. The remaining calomel is reoxidized by chlorine to mercuric chloride in a chlorination tank. [Hg.sub.2] [Cl.sub.2] + [Cl.sub.2] = [2HgCl.sub.2] The resulting strong solution is pumped to a tank, from which it is fed back into the circulation system of the scrubber at a rate corresponding to the amount of mercury to be separated. Selenium filters A selenium filter (Fig. 6) consists of concentric stainless steel baskets placed in a vertical, cylindrical filter house. The spaces between the baskets are filled with pieces of porous silica. Often there are two layers, the inner one consisting of a mass acting solely as a dust filter, and then an active layer consisting of porous pieces of silica impregnated with selenium. The gas enters the centre of the filter and, as it passes the active layer, it comes into close contact with the selenium mass. Gaseous elemental mercury reacts with selenium to form mercury selenide (HgSe), a highly stable compound with a low vapour pressure. Using this method, gases containing from a few milligrams to a few micrograms of mercury per cubic metre have been cleaned in a single step. The method does not require continuous surveillance, it has better longterm results and is not influenced as much by water vapour in the gas as activated carbon. Units can be designed for any quantity of gas. Activated carbon filters Activated carbon filters are used in some cases as a final mercury removal step, when most of the mercury has already been separated, or when the original mercury content of the gas is low. The design resembles that of selenium filters. To operate successfully, the carbon filter must be carefully maintained at the temperature at which sulphuric acid condenses to form a film of the optimum concentration on the surface of the carbon. Filters of this design have been in

operation in the Ronnskar smelter since 1973, and three other filters of this type have been installed in Europe. The Boliden thiosulphate mercury removal process This method (Fig. 7) is used when the mercury content of the sulphuric acid has to be very low. As an added advantage, if several sulphuric acid plants are in operation at the same site, only one mercury removal plant is needed. The process relies on the fact that mercury is easily precipitated to very low concentrations if sodium thiosulphate solution is added to 80% sulphuric acid. The thiosulphate reacts with mercury to give insoluble mercury sulphide and elemental sulphur. The addition of Celite to the mixture facilitates the subsequent filtration. The treated acid, containing less than 0.5 gram of mercury per tonne, is used for dilution in the absorber loops, and the product acid has a correspondingly low mercury content. In order to be able to continuously bleed off 80% acid to the treatment process without disturbing the water balance, at least one of the plants must be equipped with a double drying system with a predryer utilizing 80% acid. A more efficient system is achieved if the post dryer is running on 99% acid, which absorbs mercury completely. The post dryer is integrated with a separate small absorber unit in order to control the high concentration of the acid and to oxidize the mercury. Removal of organic compounds Some complex ores contain organic compounds, which may be partially volatilized during roasting. These materials are not removed until the gas reaches the drying tower of the sulphuric acid plant where they react and form black acid. This is usually unacceptable to customers and therefore the organic impurities have to be removed. If the acid is contaminated with mercury and is being treated by the Boliden mercury removal process, the organics are removed as well as the mercury; otherwise, some other method must be used. One method commonly used comprises adding hydrogen peroxide to the product acid tank to bleach the acid, but this consumers an unsatisfactorily large amount of hydrogen peroxide to rather poor effect. Much better results have been obtained by introducing a controlled flow of hydrogen peroxide into the final absorption acid circuit. At the high temperature and acid concentration, and because of the long residence time in the system, brighter acid is obtained while the costs are dramatically reduced. Choosing materials for sulphuric acid service When all measures have been taken to clean the gases or the acid, the results should not be spoiled by using materials with high corrosion

rates that will contaminate the acid with corrosion products. Boliden has been a pioneer in the introduction of new materials in its sulphuric acid plants. The Ronnskar works was one of the first to use stainless steel in place of cast iron, and when it was equipped to recover energy from the absorption loop, it was the first installation in Europe of anodically protected coolers with piping in Hastelloy C. A couple of years later, the world's first district heating system based on energy from acid coolers was installed in Helsingborg. Finally, the very first installations of silicon alloy stainless steels for hot absorption acid service were installed at the Ronnskar Works.[5] All these measures have dramatically reduced not only corrosion but also acid contamination by corrosion products. [Fig 1 to 7 Omitted] References [1]Wiklund, E.: "Die Nutzung von Pyrit als Grundlage fur die Produktion von Schwefelsaure und Eisenoxyd". Aufbereitungs Technik 18 (1977). [2]Porle, K. and Lindquist, B.: "Electrostatic precipitators (ESPS) in two stages used for arsenic recovery at the Ronnskar Works". "Control of Emissions in the Non-Ferrous Metals Industry" Symposium, Monterey (1979). [3]Johansson, H. and Hedman, L.: "Wet electrostatic precipitator in stainless steel for sulphuric acid process - experiences and improvements". "Sulphur 88" International Conference, Vienna (1988) pp. 137-149. [4]Sundstrom, O.: "Mercury in sulphuric acid". Sulphur (Jan-Feb 1975). [5]Solbu, E., Lundell, U. and Berglund, G.: "Conversion of a Smelter Sulphuric Acid Plant to Double Absorption Introduction of a New Stainless Steel for Hot Absorption Acid Service". "Sulphur 85" International Conference, London (1985). E. Wiklund and E. Solbu are, respectively, with the Chemical Technology and Metals Technology sections of Boliden Contech AB. COPYRIGHT 1990 CRU Publishing Ltd. This material is published under license from the publisher through the Gale Group, Farmington Hills, Michigan. All inquiries regarding rights should be directed to the Gale Group.

Title: Acid balance tips to deficit. (Chilean sulphuric acid consumption to outstrip production)(Industry Overview) Date: 3/1/1995; Publication: Sulphur; Author: Harries-Rees, Karen By the end of the decade, Chilean sulphuric acid production is predicted to rise by 80-90%, while consumption could soar by as much

as 200%, leaving a likely deficit of 1 million tonnes. Karen Harries-Rees examines the industry. Over 90% of Chile's sulphuric acid output is generated as a by-product of copper smelting, with the balance coming from molybdenum and brimstone-based production. Current output in Chile is around 1.7 million t/y. However, stricter environmental regulations could cause this to rise to around 3.2 million t/y by 1999, although some sources quote a less optimistic figure of 2.8 million t/y (see Table 1). Current sulphuric acid consumption is around 1.5 million t/y. Over 80% of this is used in solvent extraction-electro winning (SX-EW) of copper, while the remainder is consumed by the paper industry (150,000 t/y), fertilizers (60-70,000 t/y) and the industrial sector (50,000 t/y). However, Chile is witnessing an explosion in the number of SX-EW operations: over half of the new copper mine capacity coming on stream during the next five years will be SX-EW. Consequently, acid consumption in the copper industry could soar to as much as 4.2 million tonnes by 1999, if all of the proposed projects come to fruition (see Table 2). Nevertheless, many observers are quoting a more conservative estimate of around 3.3 million t/y by 1999 for consumption. These figures indicate a deficit of between 0.1-2.2 million tonnes by the end of the decade. Smelter output rising The impetus behind the forecast rise in acid production is stricter environmental legislation. Under the Chilean government's new regulations, the impact of emissions on preselected zones is measured, using three independently run monitoring stations, and the limits are set accordingly. In the northern area (regions I-V), where the copper smelters are concentrated, emissions must not exceed an annual average of 80[[micro]gram] of S[O.sub.2] per [m.sup.3]. Foreign-owned operations are also tending to impose the stricter standards applicable in the USA or Europe. To comply with these new regulations, copper producers are having to make significant investments. In addition to installing and upgrading sulphuric acid plants, the older style reverberatory furnaces are being shut-down, since they produce a weak gas from which it is not economic to capture sulphur. They are being replaced with oxygenfuelled El Teniente converters and flash furnaces. Six main companies produce sulphuric acid in Chile, four as a byproduct of copper smelting, Codelco, Enami, Compania Minera Disputada de las Condes and Refimet; one as a by-product of molybdenum production, Molibdenos y Metales (Molymet); and one from a brim-stone-based plant, Minera Pudahuel.

Codelco Codelco produces sulphuric acid from two of its copper smelting operations, Chuquicamata in the [TABULAR DATA OMITTED] north and El Teniente in central Chile. The company is investing in improvements to reduce the S[O.sub.2] emissions at both facilities. Chuquicamata is an El Teniente converter and an Outokumpu flash furnace-based operation. There are currently four sulphuric acid plants in operation, with a total capacity of around 5,700 t/d. The latest was installed in August 1993. Codelco is upgrading acid plant no. 1, and expects the revamped plant to be operating at its new capacity in 1996, boosting acid production by around 100,000 t/y. The plant will continue to operate during the upgrade. The company is also planning to install a fifth acid plant in 1998, at which time acid plant no. 1 will be modified. Sulphur capture at Chuquicamata is currently around 45%, but this will rise to 68% with the installation of the fifth acid plant. The site has the capacity to store 45,000 tonnes of acid. At El Teniente, Codelco also operates a reverbatory furnace, which has been progressively modernized with oxygen smelting technology and El Teniente converters. The company has been planning an acid plant at this facility for some time, although it has been postponed on a number of occasions. However, the project now seems to be finally underway with the company opening an international bid in March, for the construction of a 1,500 t/d acid plant. It anticipates the plant will be operational in 1998, raising acid production from the current 27,000 t/y to 435,000 t/y. The new plant will increase sulphur capture from 5% to 50%. Codelco has no sulphur capture in operation at its third smelter, Potrerillos, which is in a remote location in the Atacama desert and at an altitude of 3,000 m, but it does have plans to upgrade the plant and install an acid plant by the beginning of the next century. The bulk of Codelco's sulphuric acid is used at its leaching plant at Chuquicamata. However, the company also supplies acid from Chuquicamata to Empresa Minera de Mantos Blancos; to leaching facilities within a 250 km radius, such as Lince and Ivan; and a small amount to the chemical industry, including boric acid producers. Codelco plans to use some of the acid to be produced at El Teniente in leaching projects at the site and to sell the remainder. Enami Enami operates two smelters, Las Ventanas and Paipote. The Las Ventanas operation is located 50 km north of Valparaiso in central Chile and comprises a reverbatory furnace, an El Teniente converter, three Pierce Smith converters, an oxygen plant, and a sulphuric acid plant, which was installed in 1990.

Modifications at the plant are necessary in order to comply with current and future environmental regulations. The company has had difficulty in meeting the present limits on S[O.sub.2] emissions and had to close the smelter during December last year, since the limit for the year had been reached. Enami's upgrading project, which will cost $35-38 million, involves the closure of the reverbatory furnace in 1996, leaving the El Teniente converter as the primary smelting unit, and the expansion of the sulphuric acid plant. Current sulphuric acid capacity is 300,000 t/y, representing a sulphur capture of around 35-40%. This will rise to 320,000 t/y in 1997,with a sulphur capture rate of 8090%. Enami also plans to reduce the amount of copper smelted from 460,000 t/y to 420,000 t/y, in order to cut the total amount of sulphur produced. The Paipote smelter is located about 10 km from Copiapo in the Atacama province of north-central Chile. It is a reverbatory furnacebased operation, which has been undergoing a modification programme, including installation of an El Teniente converter, and additional capacity in the acid plant. Enami plans to install an oxygen plant in 1998, at which time the reverbatory furnace will be phasedout. A second acid plant, which has been bought from Disputada, will be on-stream in early 1997. This plant will raise acid production from 75,000 t/y to 220,000 t/y and increase the sulphur capture rate from 40% to 65%. In 1994, Enami used approximately 20,000 tonnes of Las Ventanas acid at its four leaching plants - Ballenar, O. Martinez, Antonio Moreno and Panulcillo; sold 6,000 tonnes locally; 40,000 tonnes to the chemical industry; 90,000 tonnes to Brazil; and 30,000 tonnes to Disputada. Approximately 40,000 t/y of acid from Paipote was used internally, while the remainder was sold. In the past, Enami has shipped material from Las Ventanas to Codelco's Tocopilla terminal in the north to supply Carolina de Michilla copper leaching facility. However, Carolina's plant ceased operation at the beginning of 1994 and instead Enami exported the acid (90,000 tonnes) to Brazil. For 1995, Enami has agreed contracts to sell 40,000 tonnes to the chemical industry and 150,000 tonnes, under a one-year contract, to Interacid for the Zaldivar copper leaching project (see later and Table 2). However, since the start up of the project has been delayed, 40,000 tonnes will actually be sold in 1996. Zaldivar will start leaching in April, and Enami made its first shipment at the beginning of March. The shipment was to have been 16,000 tonnes. However, due to loss of

production because of a strike, over salaries, at Las Ventanas in February, only 10,000 tonnes was shipped. The next shipment, of 16,000 tonnes, will be made in April. Disputada Disputada completed an expansion project at its Chagres smelter in central Chile at the end of January. The project involved installing an Outokumpu flash furnace, additional converter capacity and a new sulphuric acid plant, and closing the old reverbatory furnace. The total cost was $240 million, of which the acid plant accounted for $40 million. The new acid plant will increase sulphur capture from 77% to 95%, which should reduce S[O.sub.2] emissions to a level which will comply with both Chile's environmental regulations and the standards of its parent company, Exxon. Chile's regulations currently allow Disputada to emit 6,000 t/y of S[O.sub.2]. The plant comprises a 150,000 [m.sup.3]/hour gas cleaning plant, supplied by Lurgi, a 1,590 t/d contact plant, supplied by Simon Carves, and a mercury removal system. When the smelter is in full production, which is not expected until mid-year, acid output is anticipated to be around 300,000 t/y, assuming an average sulphur content in the concentrate of 28%. The plant has a maximum capacity of 400,000 t/y. Previously, Disputada produced 70,000 t/y from a 20 year old plant, with a capacity of 250 t/d. This has now been dismantled and the company has sold the plant to Enami. To cope with the increased acid production, Disputada has built new loading and storage facilities. Two new 5,000 tonne storage tanks have been added to the three existing 1,000 tonne tanks, and foundations have been laid to build three more 5,000 tonne tanks if they are needed in the future. These would take three to four months to construct. The new loading facility has a loading rate of 2,000 t/d operating on two shifts. This replaces the old plant which had a rate of 400 t/d. Disputada has traditionally sold all of its acid to the paper industry in southern Chile. However, during 1994, it arranged new contracts. These include 100,000 tonnes for the paper industry and a five-year contract for 80-100,000 tonnes to Interacid for the Zaldivar operation. The remainder will also be sold to Interacid. In order to meet its contracts in 1994, Disputada had to buy 30,000 tonnes of acid from Enami in 1994 to supplement its output. Refimet

Refimet's La Negra smelter is located 50 km inland from Antofagasta. The reverbatory furnace-based smelter was commissioned in July 1993 and includes three Pierce Smith converters, and an acid plant which was brought on stream in September 1993. The company is expanding the existing acid plant by adding new gas washing stages, allowing more gas to circulate through the plant to recover a higher level of sulphur. This expansion will increase acid production from the current 50,000 t/y to 72,000 tonnes in 1995 and 100,000 tonnes in 1996. By the end of 1996, Refimet is planning to have installed an oxygen plant and increased the throughput of copper concentrate from 230,000 t/y to 390,000 t/y. To comply with environmental regulations at this higher throughput, a second acid plant will be installed, which will raise the sulphur capture rate from 63% to 93% and increase production to 280,000 t/y. Refimet makes use of the plant's location and sells acid to the neighbouring leaching operations. It will continue to supply this market after the expansion. Minera Pudahuel Minera Pudahuel operates the only brimstone-based sulphuric acid plant in Chile, at La Cascada. Production is around 100,000 t/y, which is currently used at the company's leaching operation at La Cascada. However, reserves at the leaching plant are expected to become exhausted towards the end of the decade. Nevertheless, Pudahuel is expected to continue operating the acid plant for external sales. Mantos Blancos used to operate a 80,000 t/y sulphur burning plant, but closed the facility in August 1992, when it signed a contract with Codelco. A 28,000 t/y facility, at Michilla, is also closed. The other producer is Molymet, which produces sulphuric acid at its molybdenum plant. It operates a 35,000 t/y wet acid plant, supplied by Haldor Topsoe in mid-1993. Acid use in SX-EW escalates The main use for the country's sulphuric acid is in SX-EW of copper. There are already several SX-EW operations in Chile, but projects proposed for the next five years could triple their number (see Table 2). The attractions of SX-EW are its lower cost, approximately $0.150.2/pound lower than the traditional smelting/refining method; and the abundance of suitable ores, principally in the north of the country. Of the vast number of SX-EW projects, some are more likely to come to fruition than others. Among the more certain are those that are

scheduled to start this year: Zaldivar, which will be commissioned in April and is expected to be in commercial production by October; and Mantos Blancos' Mantoverde operation, which is scheduled for start-up in October. Supply contracts for these projects have been largely established. Interacid has a contract to supply Zaldivar with 800 t/d of acid, and Mantos Blancos has called a private bid to secure supplies for Mantoverde. The company received bids from Interacid, Codelco, and Enami and expects to secure agreements with one or two suppliers. Looking towards the end of the decade, several large projects are in the planning stage (see Table 2). These include: El Abra, Radomiro Tomic, Ripios Mina Sur, and Leonor/Tesoro. The Leonor/Tesoro project is located in the Sierra Gorda mineral district, south-west of Calama. Two companies have been planning to exploit the orebody: the Chilean-based Luksic Group through its Tesoro project; and Equatorial Mining, an Australian company, through its Leonor project. The two companies have recently signed a letter of intent which is expected to lead to a joint operation. If a joint project is developed, acid consumption could be around 300,000 t/y, whereas if they proceed separately, Tesoro will consume around 100-150,000 t/y, while Leonor will use approximately 100,000 t/y. Start-up of the project in either joint or separate form is anticipated in 1997. Acid balance to tip Overall, supply and demand was roughly in balance during 1994. Around 140,000 tonnes was exported, mainly to Brazil for use in fertilizers. This arose because Carolina, one of Enami's customers, ceased operating leaving Enami with 90,000 tonnes. Also, the start-ups of the Quebrada Blanca and Cerro Colorado copper leaching projects (see Table 2) were delayed, leaving Codelco with 50,000 tonnes. The market can be expected to continue to be fairly balanced in 1995, with slightly more acid production than consumption and consequently some exports. By late-1996 or early 1997, the balance is anticipated to tip towards a deficit, although the timing will depend on start-up dates for both leaching projects and acid plants. If all the projects forecast to be on-stream by 1997 do come to fruition and are commissioned on time, the deficit could be around 750,000 tonnes in 1997, rising to as much as 1.6 million tonnes by 1999. However, industry sources take a slightly more conservative view that not all of the leaching projects will come on-stream, although the majority believe that, because of environmental legislation, most of the sulphuric acid plants will go-ahead. This leads to a prediction of a deficit approaching 1 million tonnes by the end of the decade.

This deficit will need to be met with imports, which will probably come from west coast Canada, California, Peru, Mexico, and Japan. Sources have also suggested that brimstone-based plants could be reopened or built, although it is unlikely that companies whose primary objective is copper production would be willing to invest in such projects. Looking beyond 2000, as environmental regulations begin to bite in the more remote regions, some of the deficit could be met by further acid capacity, at smelters such as Poterillos. Acid transport There is a surplus of acid in the central region and a deficit in the north. Consequently, acid is transported over considerable distances by road, rail and, increasingly, by ship. In 1995, approximately 40% of acid will be transported by road, a further 5-10% by rail and the remainder by ship. Before Interacid's terminal at Mejillones opened, the only shipments by vessel to the north were from Las Ventanas to Carolina de Michilla. The rail network, north from Santiago, no longer runs passenger trains and is now used exclusively for freight, primarily copper. It is also used for sulphuric acid shipments, although currently only used by Codelco to supply Mantos Blancos and Interacid to supply Zaldivar from Mejillones. However, in the near future, Escondida, Collahuasi, Leonor/Tesoro and Lomas Bayas could also receive acid by rail, bringing the quantity transported by rail to 1.5-2 million t/y. A typical freight rate for a cargo travelling by road is $0.04-0.05/t/km, amounting to as much as $50/t for a journey from Valparaiso to Antofagasta, although lower rates are negotiated for contracts. Shipping costs are around $10-14/t for the same journey, while rail freight costs around $0.36-0.4/t/km, around $6/tonne for the journey from Codelco's Chuquicamata to Mantos Blancos. Contract acid prices in Chile are quoted as being $35-50/t fob plant for the mining industry and around $60/tonne for the higher quality acid used by the paper industry. Traditionally, contracts have been arranged directly between consumer and producer. However, developments such as Interacid's terminal at Mejillones and Boliden/Sudamericana's plans for a terminal at Mejillones are changing trading practices. More companies are signing contracts with traders for sales within Chile. Consumers see such contracts as the best way to secure a good price. While both sellers and buyers feel it is safer, guaranteeing both acid to a consumer, and a market to producers. New terminals opening

There are a total of five sulphuric acid terminals in Chile, two in the central region, at Las Ventanas and Quinteros, and three in the north, at Mejillones, Tocopilla, and Michilla. As the country moves into deficit, these terminals, especially in the north, will become strategically important for imports. In order to take advantage of potential imports and to serve the leaching projects, two more terminals have been proposed, one in north-central Chile at Barquitos and the other at Mejillones. While, when the planned acid plant at El Teniente comes on stream in 1998, there is the possibility that a sulphuric acid terminal could also be built at San Antonio's port. However, with a slightly longer road journey, Codelco could alternatively move acid to either Quinteros or Las Ventanas. Enami owns and operates the terminal at Las Ventanas, which is located adjacent to its smelting operation, [TABULAR DATA FOR TABLE 2 OMITTED] and shares a jetty with the neighbouring power station. The terminal has four 7,500 tonne storage tanks, a vessel loading capacity of 800 t/h, although 480 t/h is normally used, and a truck loading rate of 600 t/h. Disputada operates the Quinteros terminal under a 10-year lease, which it signed with the owners Oxiquim in October last year. The terminal, which is located 2 km from Las Ventanas, has 20,000 tonnes of storage capacity, a truck loading capacity of 2,000 t/d and a vessel loading rate of 400 t/d. Interacid's sulphuric acid terminal at Mejillones was inaugurated on 1 December last year at a ceremony attended by over 300 people. The terminal, which has a storage capacity of 40,000 tonnes in two equal sized tanks, took 12 months to construct at a cost of $8.5 million. The facility has a vessel unloading rate of 450 t/h, and a rail truck loading rate of 400 t/h. The terminal also includes a link to the local railway and a track has been built to by-pass Antofagasta, 60 km to the south, to ensure there are no delays. Interacid has a 10-year contract to supply 800 t/d of acid to the Zaldivar copper leaching project, which is located 260 km from the terminal. As far as possible Interacid plans to source the acid from within Chile, and has contracts with Disputada and Enami, although if required it will also import from Peru, Mexico, Japan and Europe. Interacid has a contract with local shipowners Ultragas to use its 16,000 mt tanker "Vicuna", which will ship acid from Quinteros and Las Ventanas. Interacid is also close to an agreement to supply acid for the El Abra project, which is due to start in 1997. If an agreement is reached,

Interacid will build three additional 20,000 tonne storage tanks at Mejillones at a cost of $12 million. Codelco owns the Tocopilla terminal, which has a storage capacity of 24,000 tonnes and has recently been used for imports. The terminal at Michilla is operated by Minera Michilla. The facility at Barquitos is being developed by Mantos Blancos and is expected to be operational by the end of October. Codelco already operates a port at Barquitos for its copper shipments and owns the mining rights to the adjacent land. Codelco has signed an agreement with Mantos Blancos, for the latter to establish a terminal comprising 30,000 tonnes of storage capacity. Construction of the facility started early this year and is being carried out by B & R Engineers. The cost of the project has been included in the costs of Mantos Blancos' Mantoverde leaching project, which the terminal will serve. Mantos Blancos sees the terminal as a way of securing product at the best price, since it will be able to buy both domestic acid and imports. Codelco also plans to use the terminal to supply its leaching facility at Salvador, and will be charged a service fee by Mantos Blancos to cover the operating costs. A consortium comprising Boliden, Sudamericana, Ultramar and Belfi, a major port construction company, is planning to construct an acid terminal, with a storage capacity of 40-60,000 tonnes at Porto Mejillones, which is currently used for coal for the nearby power plant. The group has bought properties adjacent to the port and the project is currently being examined by the authorities prior to approval. Sudamericana estimates that it needs to secure 250-300,000 t/y in contracts, as an indication of support, in order to proceed with the project. If all goes well, it anticipates being operational in the first quarter of 1996. A number of sources in the industry are sceptical about the success of a second terminal at Mejillones, especially since Interacid's terminal would be well established by the time a second one could be opened. Instead, suggestions have been made that a terminal further north, near Iquique would be a better idea, to serve Collahuasi, Cerro Colorado, and Quebrada Blanca. COPYRIGHT 1995 CRU Publishing Ltd. This material is published under license from the publisher through the Gale Group, Farmington Hills, Michigan. All inquiries regarding rights should be directed to the Gale Group.

Title: A NEW MARKET DYNAMIC. Date: 5/1/2000; Publication: Fertilizer International; From its base near Hamburg, Germany, Norddeutsche Affinerie (NA) is one the world's leading copper producers and processors. Since 1998, NA has extended its portfolio to produce high-grade sulphuric acid from its copper smelting operations, and the new grade offers a purity equivalent to sulphur-based acid. In accordance with long-established NA practice, the plant operates to the highest environmental standards. Norddeutsche Affinerie (NA) is an integrated producer and processor of copper, and operates one of the world's most modern copper smelting facilities, with a capacity of around 370,000 t/a of copper cathodes. The copper is produced from primary (copper concentrates) and secondary (scrap) sources. Recycled materials account for about 30% of total NA copper production. The cathodes are processed in NA's own production plants, mainly as continuous cast rod and shapes. The main customers for these products are the cable, electric, telecommunication and paint industries and the suppliers to the construction and motor vehicle industries. NA is also active in the field of metal recovery from copper concentrates and recycling materials with the further processing of the copper produced. This long-established ability to produce and market co-products from copper smelting has enabled NA to avoid the costintensive disposal of residues. NA also gives high priority to environmental care, and in the past ten years, the c ompany has invested over DM 250 million ($112.5 million) in measures to protect the environment. This corresponds to about one third of total capital expenditure during this period. Located within the industrial heartland of north west Europe, NA is supremely well placed to be a world-ranking and competitive supplier of copper-related products, and NA's proximity to the port of Hamburg has given the company a strong logistical advantage. Innovative production has been combined with a drive throughout the company's history, for producing the highest quality materials which can be traced back to 1866, and NA has pioneered numerous innovations in its production process. The commissioning of the new smelter in 1972 led to the construction of the first double absorption sulphuric acid plant, consisting of two parallel lines, each with four layer converters. This plant supplemented one of 1936 vintage, which was replaced in 1991 , when a third double absorption unit (Line 3) was commissioned. Line 3 was designed with five catalyst beds in a 3+2 arrangement. The new plant was designed and constructed by Lurgi and conforms to the standards of the German Clean Air Act (TA Luft), as well as meeting the pollution control provisions set by the local authorities in Hamburg. The NA sulphuric acid plants have a combined capacity of 320,000 t/a.

NA emphasises that its copper production facilities offer one of the lowest [SO.sub.2] emission levels in the world, at around 6kg [SO.sub.2]/t Cu. The sulphuric acid plants have an [SO.sub.2] conversion rate of 99.7% Before being sent to the sulphuric acid plants, [SO.sub.2] gases from various smelters, such as the flash smelting furnace and converters are dedusted, scrubbed, cooled and largely freed from mercury in a Boliden-Norzink unit, which was installed in 1989. Recent investments in catalysts used in the final pass of the converters in Lines 1 and 2 have reduced [SO.sub.2], emissions still further. The major part of the weak acid effluent from the gas cleaning section is sent to a thermal acid decomposition plant, where the acid is decomposed to [SO.sub.2] and sent to the acid plant. A smaller stream of weak acid effluent is neutralised with sodium hydroxide. In the sulphuric acid plants, acid mist is captured by wire mesh or candle filters. These additional cleaning steps result in sulphuric acid of enhanced purity, which NA is marketing as a premium-quality product. Since August 1998, Line 3 has been producing sulphuric acid with a reduced mercury content, down from a typical value of 0.25 ppm to less than 0.05 ppm. Line 2 is due to be converted to premium quality in the second quarter of 2000. The improved quality has been achieved by installing a mercury removal tower based on Japanese technology after the gas cleaning section upstream of the acid plant. Mercury is removed via gas absorption. The new tower cost an estimated DM 6 million to install. A new market The high-purity sulphuric acid produced by NA is a major breakthrough. Sulphuric acid is the most widely used base chemical, with uses in almost all industrial sectors, but its main areas of application are in the production of fertilizers and pigments. Traditionally, in the assessment of sulphuric acid, a distinction is made between: * The qualitatively high-grade product produced from brimstone. * The less pure product which is recovered from copper smelters' [SO.sub.2] gases. In some areas of application -- particularly in the chemical industry-increased heavy metal contents (especially mercury) have traditionally prevented smelter acid from being considered as a suitable alternative to sulphur-based acid. The new NA sulphuric acid facility changes this perception, and in effect creates an entirely new market dynamic. NA plans to raise its sulphuric acid production from around 750,000 t/a currently to 1 million t/a by 2001 as a result of the increased

production from copper concentrates. Copper production will remain at present levels, but the sulphuric acid lines will be debottlenecked to accommodate the additional capacity. The additional acid will be marketed directly by NA. The company has in the past sold all of its acid via traders. However, NA has been recently establishing closer links and partnerships with its customers in order to provide a direct and more economical service. At present, some 40% of NA's output of sulphuric acid is destined for the fertilizer industry, with a further 40% supplied to the chemical industry. The tioxide/pigments sector accounts for a further 14%. With the new production, NA plans to market the product directly to the more accessible regions, mainly in Western Europe. The traders will have a continuing role in marketing acid in global markers not directly served by NA, such as Brazil, the United States, South Africa and parts of the Mediterranean. NA can reinforce its marketing policy with major logistical facilities. NA has storage capacity for up to 90,000 tonnes of sulphuric acid. This total comprises tanks with an aggregate capacity of 60,000 tonnes located at the Peute complex, together with two tanks, each with a capacity of 15,000 tonnes, at the deep-sea Dupeg tank terminal in the port of Hamburg. NA also owns two barges, each with a capacity of 1,000 tonnes of acid, which are employed to transport the acid from the plant site to the Dupeg terminal. NA plans to build an additional 15,000-tonnes storage tank, but has yet to decide whether to locate it at Peute or Dupeg. The decision will depend on whether its is possible to find or build a suitable sea-going barge that can navigate the low bridges along the River Elbe which connects Hamburg with the NA production complex. NA's transport inventory is completed by rail cars, which the company both owns and leases. Local hauliers provide road tankers, as required. The start of the new millennium has seen no relaxation in NA's drive for innovation and an emphasis on quality and environmental care. As part of its strategic plan, the company has repositioned itself over the past few years, identifying new business areas. The move into sulphuric acid marketing forms part of this plan. Emphasising these changes, NA has devised a new corporate image. The NA Internet website has also been upgraded and enhanced: it is well worth a visit at [less than]www. norddeursche-affi.de[greater than] NORDDEUTSCHE AFFINERIE: TWO CENTURIES OF INNOVATION 1770 Markus Salomon Beit constructs silver separation and smelting facility in Hamburg 1866 NA incorporated as a joint-stock company

1876 Inauguration of the world's first continuously operating copper tankhouse 1913 NA relocates to current site in the Peute industrial area 1936 World's first sulphuric acid contact plant at a metallurgical site Reverbatory furnace commissioned 1949 Continuous casting operations inaugurated 1972 First continuous cast copper rod plant commissioned 1979 Energy-saving Contimelt process introduced 1980 Second continuous cast copper rod plant commissioned 1985 Major modernisation and environmental protection programme launched 1989 New copper tankhouse in NA East Works commissioned 1990 North Smelter electric furnace completed 1992 East Smelter copper tankhouse capacity raised to 350,000 t/a (Now 370,000 t/a) 1997 Precious metals joint venture with Degussa 1998 Premium quality sulphuric acid plant inaugurated URANIA MEETS THE SPECIALISTS' NEEDS Urania Chemicals GmbH is a wholly-owned subsidiary of NA which produces and markets a range of high-value agrochemical products. These include copper-based plant protection products, speciality fertilizers, and plant growth regulator products for use in agriculture, fruit-growing, horticulture, and the forestry and leisure sectors. Urania markets its agrochemical products mainly within Germany, enabling the company to provide a comprehensive range of tailor-made products for growers and associated advisory services. These are supported throughout Germany by Urania's technical and sales advisers. R&D is a keystone in Urania Chemicals' operations. The company runs a research centre at Christinenthal, and in April, it gained approval as the first private testing centre in northern Germany for examining product efficiency. As a GEP-certified (Good Environmental Practice) centre, the test results undertaken by the Christinenthal laboratories are accepted as valid by the official plant protection agencies and can thus be used to support product registration procedures. This

endorsement follows Christinenthal's success in 1991, when the research centre obtained GLP (Good Laboratory Practice) certification. As part of NA's recent restructuring, Urania has taken over the parent company's copper chemical activities, with effect from 1 October 1999, and Urania's portfolio now includes non-agrochemical products, such as insecticides, cleaning agents and disinfectants, which require registration in compliance with biocide guidelines. Urania's international expertise in the registration of copper-based agrochemicals can be effectively used, while the company's research centre laboratory facilities can be harnessed for the development of new products in both agrochemical and copper chemical business sectors. The merger of the two activities has raised Urania's annual turnover to around DM 100 million ($49 million). NA HITS THE TARGET Norddeutsche Affinerie (NA) reported a pre-tax profit of DM 96 million ($47.1 million) in 1999 -- in line with the company's targets. Group turnover totalled DM 2.22 billion -- a 5% decline on the previous year's total of DM 2.34 billion. NA faced a tough start to the 1998/99 financial year, as continuing aftershocks from the Asian economic crisis affected the group's core copper business. Copper output fell during the year to 480,000 tonnes, compared with 526,000 tonnes in 1997/98. Low prices for copper in the first half-year also impacted on NA's results. However, a resurgent German economy, together with positive economic trends elsewhere in Western Europe, boosted demand for continuous cast rods and shapes, and NA's performance was further enhanced by new gains in productivity. Further gains are expected in 2000, as NA's investment in expanding the concentrate processing facilities bears fruit. NA's main plants for copper recovery operated at close to full capacity, and production of copper concentrates a nd copper cathodes was on a par with 1998/99 levels. The key financial figures are summarised below:
NORDDEUTSCHE AFFINERIE - FINANCIAL KEYNOTES (DM million) 1997/98 1998/99 Turnover 2,341 2,221 Earnings before taxes 152 9 Copper output (000 tonnes) 526 480 Copper price (average) ($/t) 1,747 1,526 Staff total (average) 2,303 2,190

COPYRIGHT 2000 CRU Publishing Ltd. This material is published under license from the publisher through the Gale Group, Farmington Hills, Michigan. All inquiries regarding rights should be directed to the Gale Group.

Title: Deep mine disposal for Swedish mercury wastes? Date: 1/1/1998; Publication: Haznews; Mercury wastes in Sweden could be disposed of in deep rock mines as it "would be the best solution from an environmental point of view", according to a recent investigation by the Swedish Environmental Protection Agency (NV). According to the NV, the recycling of such waste in Sweden or abroad is "not a good alternative . . . Mercury recycled abroad could be sold to markets where it could cause big problems and increase the global load." According to Bjoern Soedermark of the NV, "with known technology, storing the most toxic mercury waste in one or several deep rock shelters, at a depth of about 200-400 metres, is the best protection for the surrounding environment". He says that leaching would be COPYRIGHT 1998 Profitastral Ltd. This material is published under license from the publisher through the Gale Group, Farmington Hills, Michigan. All inquiries regarding rights should be directed to the Gale Group.

Title: Norddeutsche Affinerie makes the grade.(Hamburg, Germanybased copper producer continues to produce quality sulphuric acid) Date: 9/1/1999; Publication: Sulphur; Author: Connock, Lisa Since August 1998, Norddeutsche Affinerie (NA) in Hamburg, Germany has been producing a "premium quality" sulphuric acid from its copper smelting operation. The new grade has a purity equivalent to sulphurbased acid. New technology has been installed to reduce mercury levels to below 0.1 ppm. Lisa Connock reports on recent developments at NA and the company's strategy to increase the volume of acid marketed directly to customers. Norddeutsche Affinerie, one of Europe's largest copper producers, operates one of the world's most modern copper smelters with an annual production of about 370,000 tonnes of copper cathodes. The main copper products are electrolytic copper, continuous-cast rod, continuous-cast shapes and copper powders. NA is located on the southern outskirts of Hamburg, Germany, and has been in existence for more than 130 years. In addition to its core business, the production and refining of copper from primary (copper concentrates) and secondary (scrap) raw materials, NA also produces and sells major coproducts from copper production. In 1998 sales consisted of

740,000t sulphuric acid, 500,000t iron silicate stone or slag (used predominantly for river embankments), 7,500t lead, 300t silver and 8 t gold. Since 1910, the production plant has been located on 980,000 [m.sup.2] of land on the Peute, in the immediate vicinity of Hamburg's harbour, about 5 km from the city centre of Hamburg. Because of it's close proximity to the city, the implementation of state of the art pollution control measures has been important from an early stage. In 1936, NA was the first company in the world to install a sulphuric acid contact plant at a metallurgical production site (at that time a single absorption plant) for environmental protection reasons. [TABULAR DATA FOR TABLE 1 OMITTED] Commissioning of a new smelter in 1972, prompted the construction of the first double absorption sulphuric acid plant, consisting of two parallel lines each with four layer converters arranged in a 2+2 configuration. The 1936 vintage acid plant continued in operation for capacity reasons until 1991 when a third double absorption plant (Line 3) was commissioned. Line 3 was designed with five catalyst beds in a 3+2 arrangement. In addition to meeting the standards of the German Clean Air Act (TA Luft) the new plant also had to meet pollution control provisions issued by the Hamburg authorities. Lurgi was responsible for the design, construction and commissioning of all three acid plants which each have a capacity of 320,000t/y. Copper production with low S[O.sub.2] emissions According to NA, it has one of the lowest S[O.sub.2] emission levels for copper production in the world (6 kg S[O.sub.2]/t Cu) with only the Japanese achieving slightly lower levels (4-5 kg S[O.sub.2]/t Cu). The sulphuric acid plants have an S[O.sub.2] conversion rate of 99.7%. Before being sent to the sulphuric acid plants, S[O.sub.2] gases from various smelter units, such as the flash smelting furnace and converters are dedusted, scrubbed, cooled and largely freed from mercury in a Boliden-Norzink unit, which was installed at the site in April 1989. For the past two years, BASF Cs-promoted catalyst has been used in the final pass of the converters in Lines 1 and 2 to reduce S[O.sub.2] emissions. The major part of the weak acid effluent from the gas cleaning section is sent to a thermal acid decomposition plant where the acid is decomposed to S[O.sub.2] and sent to the acid plant.

A smaller stream of weak acid effluent is neutralised with sodium hydroxide. In the sulphuric acid plants, acid mist is captured by wire mesh or candle filters. Raw materials NA has long term supply agreements for copper concentrates originating from several countries around the world, including: Chile, Portugal, Argentina and Papua New Guinea. Ores with a metal content of 0.5% to 2.8% are processed by the mines to produce concentrates containing approximately 30% copper, 30% iron and 30% sulphur. NA currently has storage capacity for 140,000t of concentrate. Other raw material sources include copper scrap from eastern Europe and the FSU and blister and cathodes from other smelters. Increased sulphuric acid production NA will be increasing its acid production over the next few years from 750,000t/y to 1,000,000t/y (see Table 1) while keeping copper production at current levels. The three sulphuric acid lines will be debottlenecked to accommodate the increased capacity. The additional acid will come from increased production from copper concentrates. At present, concentrates represent the source of approximately two-thirds of NA's copper cathode production, the rest coming from the processing of blister copper and the recycling of scrap. Because of the great fluctuations in the scrap market, in future NA intends to produce virtually all of its copper from concentrate. All of the additional acid (250,000 t/y) will be marketed directly by NA. Initially, NA predicts that it will be necessary to export some tonnages of the additional acid overseas but, as the European market changes over the next five years, it is expected that it will be possible to place all of the acid within Europe. This is based on the assumption that there will be shutdowns of sulphur based capacities, for example companies with old single absorption sulphuric acid plants, when faced with the need, for environmental reasons, to replace their aging acid plants will opt instead to buy in high quality acid which will be in plentiful supply. Low mercury sulphuric acid Since August 21 1998, Line 3 has been producing premium quality sulphuric acid which reduces the mercury content of the acid from a typical value of 0.25 ppm down to typically less than 0.05 ppm (see

Table 2). In May/June 2000 Line 2 will also be converted to premium quality. The improved quality has been achieved by installing a mercury removal tower based on Japanese technology after the gas cleaning section upstream of the acid plant. Mercury is removed via gas absorption. Gas enters the top of the tower and exits the bottom after passing through a layer of pellets. The investment cost for the mercury removal tower was in the region of DM 6 million. Product acid samples are taken daily for laboratory analysis. Acid distribution and markets The vast majority of NA's acid sales (90%) are on a long contract basis with spot sales kept to a minimum. Of the 740,000t of sulphuric acid produced in 1998, 100,000t was distributed by truck and rail (approx. 50/50) to the local market, 65,000t was sold to German customers for delivery by barge or vessel, 500,000t was exported within Europe, and 75,000t was exported overseas e.g. to the Americas. NA currently depends on the fertilizer industry for 40% of its acid sales [ILLUSTRATION FOR FIGURE 1 OMITTED]. However, with the prospect of further phosphoric acid and fertilizer plant closures in Europe over the next 5-8 years, NA is looking to the chemical industry as it's most important market in the future. The synthetic fibres industry which requires one tonne of sulphuric acid for every tonne of caprolactam produced is seen as an important growth area. A second growth area is expected to be the pigment (titanium dioxide) industry. The investment in new technology to produce a premium quality sulphuric acid that is comparable to acid from sulphur burning plants places NA in a strong position to compete with sulphur-based sulphuric acid production. It is gratifying for NA that of the various projects in the pipeline, the first one has already led to a signed agreement. A long term cooperation agreement was recently concluded with a big German sulphuric acid consumer who, for the foreseeable future, intends to replace a large part of its current own production by Premium Quality acid procured from NA. During the joint deliberations, the quality aspect was given great attention. The agreement would not have been possible if NA's Premium Quality had not been accepted as an alternative to the sulphuric acid previously produced from sulphur. Other large chemical plants have also indicated a similar assessment. New marketing strategy In the past, NA has marketed all of its acid via traders. In recent years, however, the company has been actively establishing closer links and partnerships with its customers in order to provide a more direct and cost effective service. At present, all acid that is not covered by contractual volumes with traders is now marketed directly. This portion

is set to increase in the future, in particular when NA takes on all of the marketing of the additional 250,000t/y of acid following the expansion. NA's aim is to market its acid directly to markets that are easily accessible i.e. primarily in NW Europe (e.g. UK, the Benelux countries and France). The traders, however, will continue to play an important role in global markets in countries where NA is not represented e.g. in Brazil, USA, South Africa and parts of the Mediterranean. A further new development is the recently announced Co-operation Agreement between NA and Hays Chemicals in the UK for the marketing and distribution of sulphuric acid within the UK (see News p. 14). It has been agreed that acid from NA will predominantly be supplied to the east coast of the UK. The north and west of the UK will be served from Hay's own plant at St Helens with a capacity of 210,000t/y which was recently refurbished for [pounds]16 million. From this production battery acid, oleum and sulphur trioxide is also available. The Co-operation Agreement is designed to provide existing and potential customers with the strongest possible supply partnership in terms of quality, value, logistics and service. Logistics NA has storage capacity for up to 90,000t sulphuric acid (currently equivalent to 45 days of production or 33 days after the expansion). Tanks with a storage capacity of 60,000t are located at the plant site, comprising four tanks for barges and five smaller tanks for trucks and rail cars. Since September 1995 NA has also had two state of the art storage tanks, each with a storage capacity of 15,000t, at the deep sea Dupeg tank terminal in Hamburg's harbour. The tanks have a diameter of 22 m and a height of 22 m. They have a double bottom, double wall and are blanketed with dry air. The Dupeg site enables NA to load seagoing vessels of up to about 35,000t at a rate of 1000t/h quickly and safely. In 1998 480,000t of sulphuric acid was shipped from the Dupeg terminal. NA owns two barges, each with a capacity of 1000 t acid, which transport the acid from the plant site to the Dupeg tank terminal 2-3 times per day, Monday to Friday. There are two jetties at the Dupeg terminal which allow two ships of to be loaded simultaneously. Before the tanks were built at the Dupeg terminal, NA loaded the vessels at dolphins located behind the River Elbe bridges. Barges would shuttle the acid from the plant to the vessels. It took four times as long because the loading capacity was only 250 t/h. If necessary this option can still be used today and further increases the loading flexibility. An additional storage tank of 15,000t is planned but it has not yet been decided whether it will be located at the Dupeg terminal or at the plant

site. The decision will depend on whether it is possible to find or build a suitable seagoing barge that can not only negotiate the low bridges which are situated on the river Elbe between the port of Hamburg and the plant site but can also sail on rivers e.g. the Rhine. The draft of the river must also be taken into account. If the new tank is located at the Dupeg terminal, a new jetty will be built for the exclusive use of NA's barges, which will be making 4-5 trips per day after the expansion. In addition to its two barges, NA also owns and rents rail cars. Road tankers are provided by local transportation companies. All told NA looks well prepared for the challenges of the new millennium. I would like to thank Norddeutsche Affinerie for inviting me to visit them for discussions and to see their production and storage facilities. Special thanks to Claudia Limmer (Product Manager) for all her time and for making all the arrangements, Dr Werner Zickelbein (Sulphuric Acid Superintendent) for useful discussions and Uwe Ortmann (Superintendent, Dupeg Tank Terminal) for showing me the storage and handling facilities. COPYRIGHT 1999 CRU Publishing Ltd. This material is published under license from the publisher through the Gale Group, Farmington Hills, Michigan. All inquiries regarding rights should be directed to the Gale Group.

Title: Modern plants must be immaculate. (smelter acid plants) (Smelter Acid) Date: 11/1/1993; Publication: Sulphur; Today's smelter acid plants must often conform to environmental regulations every bit as strict as those applying to sulphur-burning plants, but under much less favourable operating conditions, while in the highly competitive market the product quality and purity has assumed greater importance than formerly. It is axiomatic that any pollution control installation costing millions of dollars should, if possible, reclaim the pollutant as some kind of saleable or at least reusable product. That will yield some kind of economic benefit to offset at least part of the cost of its operation, or even, in a few cases, to provide a return on the investment. In the case of sulphur dioxide pollution, the largest contributor to the global atmospheric burden is the electricity generation industry, but it is difficult and expensive to recover products from the exhaust gas

because of the enormous total gas volume and its very low sulphur dioxide concentration. Gas volumes in non-ferrous metal smelters, where sulphur dioxide is formed in the roasting and smelting of sulphide ores, are generally somewhat more manageable, and the sulphur dioxide content of some of them is ample to maintain autothermal operation of a sulphuric acid plant. Indeed, it has been common practice to process these suitable gas streams into sulphuric acid for some years. After all, since most of the sulphur that industry uses is still destined to be burned to sulphur dioxide and then converted into sulphuric acid, it is simple logic -- where it is possible to do so -- to convert smelter sulphur dioxide directly into sulphuric acid. Sulphur dioxide pollution from smelters has, however, remained a serious problem on account of the existence of other waste gas streams with insufficient sulphur dioxide contents to be processable in a contact plant. Recently, however, advances in both metallurgical processes themselves and in the selective beneficiation of the sulphide ores have helped to reduce, by a considerable margin, the net output of these lean waste gases. Regulatory authorities in the more environmentally aware countries have not been slow to take advantage of these new-found capabilities to demand a very substantial improvement in sulphur dioxide abatement standards for smelters. At a disadvantage There are, of course, problems. Smelters are seldom big users of sulphuric acid, so the majority of smelter acid has to be marketed. They are often located in remote areas, conveniently close to the ores they process but inconveniently far from major sulphuric acid consumers. The sulphuric acid on its own, without the bonus of the very considerable amount of high-grade heat co-produced in a sulphurburning sulphuric acid plant, is unattractive and commands very low prices in the market place, particularly as it is difficult to match the purity standards of the product of the latter. And on account of its variety of solid, volatile and gaseous impurities, smelter off-gas needs elaborate and costly purification before it can be admitted into a sulphur dioxide plant, while the variations in feed gas flow rate and sulphur dioxide content complicate the control of the sulphuric acid process and its own sulphur dioxide emissions. Yet the environmental authorities in many countries are not disposed towards leniency, in spite of the difficulties. Smelter acid plants therefore have to be designed to achieve the highest standards of efficiency and environmental cleanliness under less than ideal operating conditions, while the economics are adversely affected by the extra cost of the facilities required for impurity removal and process control, the lack of high-grade heat recovery, and the poor selling price for the product. The motivation for constructing smelter acid plants nowadays is not profit but necessity. More than ever, the challenge for the process design and engineering team is to provide a

plant which satisfies the efficiency and reliability criteria dictated by the environmental regulations at the minimum cost. Nonetheless, or perhaps because of that, the current generation of major projects associated with smelters are some of the most technologically interesting sulphuric acid plants to have been built so far. Two such projects were described in presentations at British Sulphur's Sulphur 93 international conference in Hamburg in April this year. Inco Copper Cliff project|1~ The world's largest single-stream metallurgical sulphuric acid plant so far was built for the Ontario Division of INCO Ltd as part of a $500million (Can) environmentally-motivated modernization project at its smelter in the remote Sudbury area of northern Ontario, in Canada. Supplied on a turn-key contract by Simon-Carves Fenco Inc., the Canadian licensee of Monsanto Enviro-Chem Systems Inc., the plant was commissioned in October 1991. It will ultimately produce about 2,900 t/d of sulphuric acid at three concentrations -- 93% and 98% | H.sub.2~S|O.sub.4~ and 25% oleum -- when new capacity in the smelter itself is completed in 1994. INCO has been involved m the smelting and production of copper and nickel at their Copper Cliff, Ontario, facility for over 75 years. During that time the company has continually developed and optimized pyrometallurgical techniques for recovering metals from the local sulphide ores. Part of this work has resulted in the development of the INCO "flash furnace" technology, which has been in use at the plant since the 1950s. Nickel/copper sulphide ores are smelted in the presence of high-purity oxygen to produce molten nickel/copper and slag. Off-gases from the furnace are very rich in sulphur dioxide, approaching 65 vol-% S|O.sub.2~. Such a high concentration of sulphur dioxide is ideally treated to produce sulphuric acid in a conventional acid plant. Indeed, in recent years, INCO has become the dominant producer of merchant sulphuric acid in eastern Canada and later in the north-east quadrant of the United States. Easy access to the Great Lakes water transportation system has enabled economical entry to the export market. In 1985, the Ontario government enacted legislation setting acceptable levels of emission of sulphur chemicals from industrial complexes with a compliance date of January 1994. INCO's engineers have met the challenge by developing new smelting technology to generate off-gas with higher sulphur dioxide content. Until the inception of this project, nickel and copper concentrates were separated in the mill and went to their respective processes to recover the metals. Some of the sulphur dioxide gas from these previous operations was too dilute to be processed economically into sulphuric acid. However, the new smelter processes today generate off-gas with

a sulphur dioxide content high enough to be converted economically into sulphuric acid. New milling technology was devised which rejects some of the sulphurbearing pyrrhotite to tailings and reduces the tonnage of sulphur to be recovered. The oxygen flash furnaces, handling bulk concentrates containing both the nickel and copper, are currently in the run-up phase. Nickel and copper are now separated by the Matte Separation Pro-cess. Major components of the project which generate sulphur dioxide include two oxygen flash furnaces and a copper processing vessel. Figure 1 shows the arrangement of the various stages of the INCO smelter. Construction began in 1988, and one flash furnace and the sulphuric acid plant were commissioned in October 1991. Gas cleaning An interesting feature of the gas cleaning system in this plant is the use of Dynawave froth scrubbers|2~ in place of the open tower packed tower combination traditionally used for cooling and cleaning smelter gas. This equipment was provided by Simon-Carves Fenco through a sub-licence agreement from Monsanto Enviro-Chem and E.I. Du Pont de Nemours and Co. There are three sets of this equipment, one at the gas outlets of each of the two furnaces and one on the copper processing reactor outlet, instead of one large central gas cleaning and cooling installation at the acid plant inlet. Contact plant The sulphur dioxide concentration of the oxygen flash furnace off-gas (65 vol-%) is far too high for direct use in the sulphuric acid plant. The gas is therefore diluted with air and other low-concentration off-gases to 12 vol-% S|O.sub.2~ before it is admitted to the drying tower. At full capacity the sulphuric acid plant -- designed to the Monsanto interpass absorption process -- can handle 230,000 N|m.sup.3~ of gas per hour. It was designed with an unusually high turn-down ratio of 5:1, not only to allow sequential start-up of the two flash furnaces and MK reactor but also to provide maximum flexibility for future operations. The tail gas contains less than 500 ppmv of sulphur dioxide. Two main blowers operating in parallel receive gas from the drying tower. Each is rated at 138,000 N|m.sup.3~/h or 60% of the plant design gas-handling capacity. These machines are of the centrifugal type and manufactured of cast steel designed to handle sulphur dioxide gas. They are driven by 4,000-kW electric motors. The converter is built of type 304 stainless steel to Monsanto's stayed design. Some 352,000 litres of Monsanto ring-type catalyst are installed in four passes. The first pass is located at the bottom of the vessel to give ready access for catalyst screening. The other passes are located at levels chosen to minimize the length and the number of

elbows in the gas ducts connecting them to the gas-to-gas heat exchangers. Three catalyst passes precede the interpass absorption tower and one pass follows. Gas-to-gas shell-and-tube heat exchangers heat the feed gas before it enters the primary converter stage and the process gas returning from the interpass tower to the final catalyst stage. The various heat exchangers are each in a single shell with the exception of the cold interpass exchanger, which consists of two shells in series. The hot heat exchanger which cools gas from the No. 1 catalyst pass is manufactured of Type 304 stainless steel. The high-temperature ducts are also stainless steel. Sulphur trioxide coolers of the shell-and-tube type precede the two absorbing towers. The cooling medium is tempered air from the atmosphere received from a dedicated blower. Some of the heated air is recirculated to maintain the tube wall temperature above the dewpoint. These coolers reduce the heat load on the acid coolers and reduce cooling water requirements. Tail gas from the final absorption tower is discharged to the atmosphere from a 110-m self-supporting stack. Acid circuits There are three interconnected main acid circuits in the plant. The drying tower and the interpass and final absorption towers are of brick-lined steel ranging in diameter from 6.5 to 8.0 m. The ceramic packing is irrigated with acid delivered from cast iron distributors. The drying tower is equipped with a mesh pad to protect the main compressors from acid carry-over. The interpass and final towers contain Monsanto HE (high-efficiency) mist eliminators to protect downstream equipment and to control acid mist in the stack gas emissions to the atmosphere. Part of the gas flow is diverted through a separate, smaller packed tower upstream of the interpass absorber to produce 25% oleum. Because an appreciable amount of sulphur dioxide is dissolved out of the feed gas in the drying tower, the drying tower acid is stripped with air from a dedicated blower in a packed product stripping tower before transfer to storage. The air from the stripping tower is added to the feed gas at the drying tower inlet. In that way, the sulphur dioxide is recovered and returned to the plant. The drying tower pump tank and the common tank for the interpass and final towers are horizontal, brick-lined steel vessels. They have been carefully designed to ensure complete mixing of dilution water and thus to avoid the formation of a layer of weak acid which might

corrode the circulating pumps. The pump tanks are located inside a heated building to prevent freezing in the cold winter climate. The acid pumps were supplied by Chas S. Lewis & Co. Two Lewis Size 14 pumps, each with a capacity of 22,500 litres per minute (5,945 US gallons per minute), operate in parallel to irrigate the interpass and final absorbing towers. An installed spare pump mounted in the pump tank can serve either absorbing tower. Performance of the Size 14 pumps had been successfully demonstrated in acid plants at Mexicana de Cobre (Sonora, Mexico), Farmland Industries (Florida, USA.), and Texasgulf (North Carolina, USA.). The materials of construction include LEWMET nickel-chrome alloy for internal parts such as the impellers, wear rings, journals and bearings and L-14 alloyed iron for heavy-wall cast parts such as the volutes, elbows and suction heads. These proprietary materials and Lewis' conservative mechanical design combine to provide pumps which can handle sulphuric acid at temperatures up to 132 |degrees~ C and provide the reliability at economical cost to keep the nickel and copper smelting process operating at high on-stream times. One Lewis Size 10 pump, with an installed spare, delivers 17,700 litres per minute (4,676 US gallons per minute) to the drying tower. One Lewis Size 6H pump, with an installed spare, delivers 3,785 litres per minute (1,000 US gallons per minute) to the oleum tower. Internal highvelocity and wear-resistant parts of these pumps are manufactured from LEWMET alloy. Acid coolers for the circulating systems are anodically-protected shelland-tube heat exchangers, designed and fabricated by Monsanto Enviro-Chem from stainless steel. The acid piping is also anodicallyprotected stainless steel. The concept of anodic protection for shelland-tube acid coolers was, in fact, pioneered at Copper Cliff in the mid 1960s by the then operator of the acid plant, Canadian Industries Ltd, and was subsequently marketed through its subsidiary Chemetics International (now a company in the John Brown group). The anodicallyprotected stainless steel acid cooler represented a dramatic improvement, giving extended leak-free, high-temperature, highefficiency operation and has largely replaced the previous "industry standard" cast iron cascade coolers. LEWMET alloy gate, globe and butterfly valves, ranging in diameter from 50 to 600 ram, are utilized in process flow control and block valve applications. LEWMET alloy orifice plates are also installed for flow measurement and control. Overall process control features a distributed digital instrument control system, which monitors plant operation from a central control station. Thanks to the all-alloy circulating system and anodically-protected storage tanks, product acid contains less than 6 ppm iron.

Storage/shipping facilities The new sulphuric acid plant has its own storage and shipping facilities. Two 10,000-tonne storage tanks store 98% acid, one 10,000-tonne tank stores 93% acid and one 5,000-tonne tank stores 25% oleum. These tanks are equipped with anodic protection which not only extends equipment life but minimizes iron content of the products. External heaters are used to maintain products in the liquid state during cold weather.
Table I NA's Main Products and their Capacities (t/a) Electrolytic copper Continuous-cast rod Continuous-cast shapes Lead Civil construction products Sulphuric acid 350,000 220,000 120,000 50,000 340,000 500,000

Twelve 100-tonne tank cars can be loaded simultaneously in one hour. A second parallel loading track is available to double loading capacity. A truck loading dock is also operated 24 hours per day to deliver acid consumed locally by the pulp and paper market. INCO's sulphuric acid loading and shipping terminal is probably the largest and most efficient in the world. Norddeutsche Affinerie, Hamburg|3~ Norddeutsche Affinerie AG (NA), one of Europe's largest copper smelters, is located on the southern outskirts of Hamburg about 5 km from the centre. The company, which has been in existence for more than 125 years, is today a stock corporation under German law whose main shareholders are Metallgesellschaft, Mount Isa Mining, and Degussa. It manufactures copper as its main product and various other non-ferrous metals and precious metals as subsidiary products. Its main products are shown in Table I. Because it was located so close to a major city, the plant was the first smelter in the world to be equipped with a sulphuric acid plant. The original contact plant was installed in 1936. Naturally it was of the single-absorption type, as the double-absorption process was not introduced until the 1960s. NA thus has over 50 years' tradition in the field of sulphuric acid production. Over the many years the company has always taken pride in adapting its sulphuric acid technology to the state of the art and incorporating its operational experience. TABULAR DATA OMITTED The metallurgical facilities comprise storage facilities for copper concentrates, a flash smelting furnace, copper converters, anode

furnaces, anode casting unit, electric furnace, what is perhaps the most modern fully automatic electrolytic plant in the world, continuous casting plant and a wire rolling mill. Table II details the main sources of sulphur dioxide-containing gases in the plant and Fig. 3 shows how they are arranged. When the smelter was commissioned in 1972, it was equipped with two new four-pass double-catalysis sulphuric acid plants in 2 + 2 configuration. Even today, these plants still meet the very stringent requirements of the German Clean Air Act (TA Luft). The original 1936 plant continued in operation, but eventually the authorities set a deadline of 31 December 1991 for its replacement. A third doubleabsorption plant with the same capacity as the other two (918 t/d) was therefore built. This plant had to meet not only the requirements of TA Luft but also additional ones imposed by the Hamburg authorities. Because of that, and because the feed gas composition is relatively weak and rather variable (4-8.4% S|O.sub.2~), it was designed with five catalyst passes in a 3 + 2 configuration. The contract was awarded to Lurgi Metallurgie, another company in the Metallgesellschaft group. In addition to the basic objective of meeting the statutory pollution control provisions like TA-Luft and the water ecology act, the plant was designed to achieve product quality in line with the purity requirements of the market, to use as far as possible equipment of the same makes and materials as the existing double-absorption plants, and to incorporate automatic control of temperatures, volumes and concentrations so that the new plant could be operated generally by the staff responsible for the other two lines without needing substantial additional manpower. The S|O.sub.2~ gases coming from the various smelter units like flash smelting furnace, converters, etc., are dedusted, scrubbed and cooled in the existing East Works gas cleaning plant and largely freed from mercury by a Boliden-Norzink process mercury removal plant. Gases from other sources are dedusted, scrubbed and cooled in the South Works scrubbing and cooling unit. From there they are routed via an approximately l-km long gas duct to the East Works and mixed with the cleaned gases originating there in a static mixing system which ensures that the three sulphuric acid contact plants are supplied with homogeneous gas. To prevent mists arising when the cooler gases in the long gas duct from the South Works are mixed with those from the East Works, they are first reheated in carbon shell-and-tube heat exchangers. The heating station and the mixing system were installed with the new sulphuric acid plant. After mixing, the gases are uniformly distributed over the three lines by a system devised by the instrumentation group of NA.

The new line 3 was designed for a nominal gas volume of 100,000 N| m.sup.3~/h at a maximum sulphur dioxide content of 8.4 vol-%. Depending on the operation of the metallurgical units, the three sulphuric acid plants are each fed with a gas volume between about 50,000 N|m.sup.3~/h and about 100,000 N|m.sup.3~/h and S|O.sub.2~ concentrations upstream of the converter ranging typically between 5 and 8.4 vol-% S|O.sub.2~. The basic load is provided by the flash smelting furnace, whereas the maximum load depends on the converter operation, which means that when one converter is put on stream it must be ensured that the additional gas and S|O.sub.2~ volumes can be absorbed by the sulphuric acid plant at short notice. Apart from its five-layer converter, the No. 3 acid unit includes certain other substantial improvements over the first two double-catalysis units. For example, the final absorber is equipped with a candle filter and the first four catalyst beds can be heated directly before start-up to optimize the starting conditions for S|O.sub.2~ conversion before any sulphur dioxide is admitted. Control of the gas side and operation of the plant is also largely automated. An essential prerequisite for the off-gases from the sulphuric acid plant was that their S|O.sub.2~ content should be restricted to 800 mg S| O.sub.2~/N|m.sup.3~ max. and their |H.sub.2~S|O.sub.4~ + S| O.sub.3~ content to 50 mg S|O.sub.3~/N|m.sup.3~ max. TA-Luft prescribes that the sulphur dioxide conversion rate in a doubleabsorption sulphuric acid plant fed with gases containing on average less than 8 vol-% S|O.sub.2~ should be not less than 99%. But if the sulphur dioxide content of the feed gas is consistently 8 vol-% or more, the conversion efficiency must be at least 99.5% under fluctuating gas conditions or not less than 99.6% under constant gas conditions. If necessary, the sulphur dioxide and sulphur trioxide emissions must be further reduced by using the Peracidox process, a fifth catalyst bed, or some equivalent measure. In Germany, some authorities are extending the provisions of TA-Luft to start up equipment. In the case of NA, therefore, the N|O.sub.x~ content in the flue gas from the natural-gas-fired preheater of the converter group must not exceed 200 mg N|O.sub.x~/N|m.sup.3~. To conform with the requirements of the Water Ecology Act, a closedloop intermediate circuit was provided in the blower oil cooling system to safeguard against oil leaking into the Elbe River via the cooling tower blow-down system in the event of oil cooler damage, while the complete drying and absorbing systems are located in a concrete trough with acid-proof lining.

The new sulphuric acid plant line 3 was started up successfully on schedule, on 24 October 1991. After performing the standard operating and performance tests in the new plant, the old single-catalysis plant was finally closed in early November 1991. Plant description A part stream of the cleaned dust-free cooled and demisted | H.sub.2~O-saturated S|O.sub.2~ gases coming from the mixing system at 30-40 |degrees~ C is routed to the drying tower of the new sulphuric acid plant 3. There the water contained in the gas is absorbed in 96% sulphuric acid. The drying tower is a homogeneously lead-coated bricklined packed tower 6.4 m in diameter. The packing is arranged on a column grate. The feed gas flows upwards through the packing in countercurrent with the sulphuric acid. Above the stainless steel trough irrigation system there is a Begg Cousland PTFE wire mesh filter. The separate pump tank also has a brick-lined leaded steel shell. Bungartz horizontal pumps, of a similar type to those installed in the other plants, where they have rendered satisfactory service, drive the acid circulation and the cross flow to the intermediate absorber. For the sake of operational safety and to ensure high plant availability, a total of three pumps have been installed ready for operation, two of them working in normal operation and the third one provided as a standby. The same kind of arrangement is also used in the absorber circuits. The acid is cooled in Alfa-Laval plate-type coolers made of Hastelloy C 276 whose number and distribution are adjusted to the pump concept. The intermediate absorber is an unlined stainless steel venturi absorber with a diameter of 4,800 mm. The process gas enters downwards through the centrally-arranged venturi tube and is irrigated cocurrently with part of the circulating acid. The sulphur trioxide formed in beds 1-3 of the converter is absorbed in sulphuric acid of about 99% strength. The water needed for sulphuric acid formation is supplied from the dryer mainly in the form of 96% sulphuric acid. As it rises up the annular space around the venturi tube, the gas passes through a sieve tray filled with 99% sulphuric acid -- the socalled "turbulent layer". Above the turbulent layer there is another Begg Cousland PTFE wire mesh pad. The separate pump tank is in this case a brick-lined stainless steel vessel. Pumps and coolers are the same as in the drying acid circuit. Like the drying tower, the absorber is a brick-lined stainless steel packed tower. Any residual S|O.sub.3~ forming in layers 4 and 5 is absorbed in a countercurrent flow of sulphuric acid of about 99% concentration. The water required for the formation of sulphuric acid is supplied directly as process water. A Begg Cousland candle filter removes most of the acid droplets and acid mist in the exit gas, which

is discharged to atmosphere through the existing 150-m brick-lined concrete stack. The acid pump tank, pumps and coolers are the same as in the intermediate acid circuit. The product pump tank includes a static mixer followed by a mixing tank to ensure that no fluctuations occur in the acid concentration in spite of the varying production rates in the course of operation. That means that it is possible to control the system exactly between minimum and maximum capacity. In the mixing section the acid is diluted by adding process water, from about 99% |H.sub.2~S|O.sub.4~ to 96% |H.sub.2~S|O.sub.4~. The product pump tank is a homogeneously lead-coated steel vessel with brick lining. Here again, horizontal Bungartz pumps are installed to deliver the produced acid to the storage tank. The acid is cooled to about 35 |degrees~ C in an AlfaLaval plate-type heat exchanger made of Hastelloy C 276. With a few exceptions, the acid piping is made of stainless steel, mainly material 1.4571 (316L) and material 1.4539 (Uranus B6) for specific areas; these materials have proved to be adequate specifically for turbulent-flow areas and elevated temperatures (up to 90 | degrees~ C). Rheinhutte valves made of high-grade stainless steel casting were installed in accordance with NA standards for the acid valves. The main blower is situated at the exit of the drying tower. It is a speed-controlled overmounted radial-flow unit, made by KKK. It is driven by an asynchronous Siemens motor electrically cascade speedcontrolled. The blower is additionally furnished with a vane control, which is operated at minimum speed. Only when the vane control is fully open will the motor speed be raised so that the delivery rate can be adjusted between 30% and 100%. The blower with its motor is located in a building. Cost analyses and the experience gathered with this type of drive in the other two plants have shown that for the case where gas volumes are changing frequently a speed-controlled motor is more costeffective compared with a fan operated at constant speed and equipped only with a vane control, and that the additional expense for the speed control system pays off in three years maximum as a result of energy savings. The maximum speed is 3,900 r/min and the maximum pressure increase 650 mbar. Installed motor power is 2,750 kW. The blower delivers the feed gas to the shell-and-tube gas-gas heat exchangers. Figure 4 shows the arrangement of the converter and associated heat exchangers. They heat it to the first-pass inlet temperature of about 430 |degrees~ C in counter-current with reaction

gases from catalyst beds 1, 2, 4 and 5 of the converter. The converter is a brick-lined five-layer unit with partitions made of brickwork. All five layers are filled with BASF ring-type catalyst. The choice of the bricklined converter instead of the now usually employed reactors made of steel and stainless steel was made principally because of the heat capacity of the brick lining. This ensures that in the event that the S| O.sub.2~ content of the entering gases temporarily falls below 4 vol-%, the system still contains sufficient heat to provide the gas temperatures needed for S|O.sub.2~ conversion until additional heat is available from the preheater, for instance, or the S|O.sub.2~ content has gone back to normal. After the third bed the S|O.sub.2~/S|O.sub.3~ gas (S|O.sub.2~ conversion up to 93%) is delivered to the intermediate absorber. Before entering the absorber it is cooled in a shell-and-tube heat exchanger group in countercurrent with the gases returning from the intermediate absorber. The S|O.sub.3~-free gases from the intermediate absorber are heated in the mentioned heat exchanger to the requisite reaction temperature of about 400 |degrees~ C for further S|O.sub.2~ conversion in bed 4. Between beds 4 and 5 of the converter, the reaction gases are again subjected to intermediate cooling. After leaving the fifth bed the gases are routed to the final absorber for absorbing the residual S|O.sub.3~. A special feature of this plant is the S|O.sub.3~ cooler arranged upstream of the final absorber. It controls and limits the gas temperature at the inlet of the final absorber to minimize the burden on the acid circuit cooling system. Should the S| O.sub.2~ concentration in future be steadied so that the plant operates at S|O.sub.2~ contents in the nominal design range, heat from this cooler could be optimally utilized for steam generation, for instance.
Table III Sulphuric Acid Product Quality (mean values) |H.sub.2~S|O.sub.4~ Fe S|O.sub.2~ Mg Cl (chloride) NxOy (expressed as N) As Hg Cu Ni Cd Pb Zn Mn Cr Colour Table IV 95-97% |is less than~30 ppm (summer: 40-45 ppm) |is less than~30 ppm |is less than~5 ppm |is less than~5 ppm |is less than~5 ppm |is less than~1 ppm |is less than~1 ppm |is less than~1 ppm |is less than~1 ppm |is less than~1 ppm |is less than~1 ppm |is less than~1 ppm |is less than~1 ppm |is less than~1 ppm |is less than~30-40 Hazen

S|O.sub.2~ Content of Tail Gas from Lines 1/2 and Line 3 (mean values attained) Lines 1 and 2 (4-bed converters) Line 3 (5-bed converter) 400-1,200 mg S|O.sub.2~/N|m.sup.3~ 100-800 mg S|O.sub.2~/N|m.sup.3~

The converter preheater consists of four double-shell tubes, each of which is equipped with a combustion chamber with an integrated natural gas burner. It in fact serves for both heating up and cooling down the converter system in the case of shut-downs and also for heating a part stream of the S|O.sub.2~ gases routed to the first converter layer whenever the heat of reaction alone is not sufficient to heat the cold gases to the requisite operating temperature, and to cover thermal losses due to radiation, etc. To attain optimum S| O.sub.2~ conversion efficiency when starting the sulphuric acid plant with S|O.sub.2~ gases, it is possible to heat the catalyst beds individually to the desired optimum reaction temperature. The Saacke type burner/combustion chamber system ensures that in all load ranges of the preheater the N|O.sub.x~ content is kept below the maximum limit according to the TA-Luft standard of 200 mg N| O.sub.x~/N|m.sup.3~. Whereas the gas cleaning station and the drying and absorption circuits of lines 1 and 2 use water from the Elbe canal for cooling, a cooling tower was installed for the No. 3 sulphuric acid plant. The main reasons for this are the limitation on the permissible rate of extraction from the canal and on the return temperature. The latter implies high water costs and would require heat exchanger sizes which are no longer economical in view of the fact that, in full summer, the canal water inlet temperature may be above 25 |degrees~ C. Supplied by GEA-Kirchner, the tower is a wooden structure placed on a cold water basin. It contains four separately irrigated cells. The packing consists irrigation grids, ensuring safe, uniform operation even in the event of sludge, slime and algae fouling due to the water quality. Each cell is provided with a two-speed fan. The sulphuric acid analyses are summarized in Table III. The iron content has been kept down by using stainless steel in the acid circuits. In order to minimize the chromium and nickel contents as well, the temperatures and acid concentration are adjusted accordingly. The sulphur dioxide content in the tail gas is substantially below the stipulated limit of 800 mg S|O.sub.2~/N|m.sup.3~. At nominal load with 8.4 vol-% S|O.sub.2~, the stipulated 800 mg S|O.sub.2~/N| m.sup.3~ corresponds to a sulphur dioxide conversion efficiency of 99.72%. On average, however, values of about 300 mg S|O.sub.2~/N| m.sup.3~ were attained corresponding to a sulphur dioxide conversion rate of 99.89%. Table IV compares the sulphur dioxide content ranges

of the tail gas in the four-pass double-catalysis plants 1 and 2 and the five-pass line 3. The additional capital outlay -- in the range of DM 2.0 million -- and the current energy costs for the fifth layer are exclusively justified by the attained improvement of the waste gas conditions: the additional sulphuric acid output is negligible. References 1. Longo, A., Boyd, W. K., and Boillat, R.: "Inco Ltd -- The world's largest single-stream metallurgical gas |H.sub.2~ S|O.sub.4~ plant". Sulphur 93 Preprints, pp. 101-111. 2. "Gas cleaning using Dynaware". Sulphur (216), 41-48 (Sep-Oct 1991). 3. Windhager, H. J., Ludtke, P., and Winkler, E.: "A modern metallurgical sulphuric acid plant for an urban environment". Sulphur 93 Preprints, pp. 115-234. COPYRIGHT 1993 CRU Publishing Ltd. This material is published under license from the publisher through the Gale Group, Farmington Hills, Michigan. All inquiries regarding rights should be directed to the Gale Group.

Title: Assuring acid quality: high quality sulphuric acid commands better prices on the market. Klaus Hasselwander of Outokumpu Technology discusses current technologies for assuring the quality of sulphuric acid from both sulphur burning and metallurgical sulphuric acid plants and Dr Hanno Hintze of Norddeutsche Affinerie reports on the improvements to acid quality at NA's smelting facilities in Hamburg.(SULPHURIC ACID QUALITY) Date: 7/1/2005; Publication: Sulphur; Author: Hintze, Hanno The quality of sulphuric acid has become of greater importance to many acid manufacturers who are influenced by the need to maintain acceptable acid prices. This applies to acid produced from burning sulphur (premium acid), and especially to sulphuric acid produced from S[O.sub.2] gas in non-ferrous smelters, as these gases often contain many contaminants, dust and fumes that need to be removed to avoid contamination of the product acid. Typical requirements for sulphuric acid are listed below:

Appearance: Colour: Mercury (Hg):

water clear 40 Hazen

Acid from sulphur In sulphur burning sulphuric acid plants, solid sulphur is first melted and then burned to sulphur dioxide. The sulphur dioxide is converted to sulphur trioxide in a contact plant. The sulphur trioxide is then absorbed in sulphuric acid. In this type of plant the only cleaning stage is in the sulphur melting and filtration section. The molten sulphur is filtered before being burned. For the production of premium sulphuric acid from sulphur it is important to apply reliable filtration technology. Leaf type filters, which require precoating, are typically used (Fig. 1). The quality of the sulphur is also important to ensure that the individual parts of the melting and filtration stage can be operated safely over a long period. In some plants, hot gas filters are installed in the contact section to collect dust and particles upstream of the first catalyst layer. However, they are no replacement for a good filtration unit. Outokumpu considers hot gas filters unnecessary. In some cases air filtration may be recommended. Acid from S[O.sub.2] gas The S[O.sub.2] gases originating from nonferrous smelters are usually very contaminated with all sorts of fumes vapours and dust. To make sure that a sulphuric acid plant can be operated safely it is of utmost importance to have a reliable hot and wet gas cleaning system (Fig. 2). For hot gas cleaning, electrostatic precipitators (ESPs) with several electrostatic fields are typically used. Wet gas cleaning systems consist of several unit operations arranged in series: the quench and scrubbing section followed usually by a vapour condensing section. In these two sections of the plant the major portion of the dust is eliminated from the S[O.sub.2] gas. Downstream of the gas cooling section the remaining dust and the sulphuric acid mist is removed from the S[O.sub.2] gas by wet ESPs. The individual parts of the wet gas cleaning system must be carefully designed with respect to material selection and process conditions to ensure the safe and reliable operation that is needed to ensure the required acid quality and sulphuric acid plant performance. In the case of high halide content in the gas, special precautions have to be taken to minimise the resulting load of HCl and HF in the gas. Different measures can be used for fluoride removal--fluoride towers,

elimination by reaction with sodium silicate, or operation of the wet gas cleaning system within a careful range with respect to the concentrations of halides in the scrubbing liquid. The most important aspect concerning quality of sulphuric acid manufactured from S[O.sub.2] gas is the mercury content. The standard type of mercury removal plant is the so-called BNZ process (Boliden Norzink Process) or Calomel process (Fig. 3). In this process, the gaseous metallic mercury reacts with a dissolved mercuric chloride (Hg[Cl.sub.2]) to form solid mercuric chloride ([Hg.sub.2] [Cl.sub.2], calomel). Mercury removal reaction: Hg[Cl.sub.2] (dissolved) + Hg (gaseous) [right arrow] [Hg.sub.2] [Cl.sub.2] (dispersed solids) Chlorination reaction: [Hg.sub.2][Cl.sub.2] (dispersed solids) + [Cl.sub.2] [right arrow] 2Hg[Cl.sub.2] In the solid form the calomel can be easily removed from the reaction circuit by a settler. The BNZ technology for mercury removal permits mercury removal to less than 0.5 ppm in the acid. For enhanced mercury removal (< 0.1 ppm), e.g. when premium acid is required, a second mercury removal system is installed downstream of the BNZ unit. Outokumpu's Swedish organisation (formerly Boliden Contech) has developed a system consisting of a scrubber and an absorber installed in series. In the scrubber, the remaining traces of gaseous mercury chlorides are eliminated, while the remaining traces of metallic mercury vapour are absorbed on a layer made up of metallic selenium on a carrier mass. Outokumpu is presently investing huge efforts in the development of new types of scrubbers and wet electrostatic precipitators. Another solution to achieve very low levels of mercury is the Dowa process, which is being used successfully by Norddeutsche Affinerie (see box). Acid cleaning In some applications it is not possible to prevent all contaminants from reaching the acid and hence the product acid. Before the acid can be marketed, some cleaning is required.

Acid cleaning is typically necessary when there is an unacceptable colour, N[O.sub.2] and mercury content of the acid. These problems often apply to acid plants installed at sinter plants. The black colour of sulphuric acid usually is due to the evaporation of organic compounds (hydrocarbons, flotation agents) in the sinter machine. These hydrocarbons pass the gas cleaning system and are collected in the acid, where they are decomposed and the resulting carbon particles give the acid a black colour. Acid bleaching is typically carried out by adding hydrogen peroxide to the acid. The mixture is agitated for a retention time long enough to allow the hydrogen peroxide to react with carbon to form carbon dioxide. Mercury removal In most cases it is more economic to eliminate the mercury from the S[O.sub.2] gas by the means of the BNZ process. However, in same cases it may be necessary to eliminate the mercury from the acid itself. The Thiosulphate process is a potential solution for eliminating the mercury from diluted acid resulting from a predryer. Mercury contents of less than 0.1 ppm can be easily achieved. N[O.sub.2] removal from acid Due to process constraints in some upstream processes, the formation of nitrogen oxides cannot always be fully avoided. The N[O.sub.2] portion of the nitrogen oxides reacts with the sulphuric acid to form nitrosyl sulphuric acid. When this acid is diluted it releases N[O.sub.2] in the form of a brown plume. In most sulphuric acid plants the release of a brown plume is unacceptable. Nitrosyl sulphuric acid can be decomposed by addition of a reaction agent. However, these agents are expensive and may significantly increase acid production costs. An economic alternative is the installation of a specially designed plant in which, for example, the candle filter trip, which usually has the highest amount of dissolved N[O.sub.2], reacts with water and S[O.sub.2] to form sulphuric acid and nitrogen. The plant is usually supplied as a skid-mounted system consisting of a packed tower, which serves as S[O.sub.2] saturator, and an acid circulation system with pumps, acid coolers and reactor. Using this system N[O.sub.2] values in the product acid can be easily reduced to less than 10 ppm. The payback period for the installation may be less than one year compared to using reaction agents. General design and operation

Using highly alloyed stainless steels in the absorption area (dryer, absorbers) improves acid quality by reducing the concentrations of iron and other elements that result from acid attack on the metallic parts of coated materials. Operating the absorption area with low temperatures also reduces the corrosion rate and contamination of the product acid with iron and other elements resulting from acid attack on the metallic parts of the plant. Finally, good quality dilution water should be used when producing premium quality acid. RELATED ARTICLE: Acid quality improvements at Norddeutsche Affinerie Norddeutsche Affinerie (NA) has been steadily working on its gas cleaning techniques to improve the quality of its sulphuric acid while increasing the smelter production. Several key improvements have been made including the addition of the Norzink process, a new cyclone cooler, an extra scrubbing unit treating secondary smelter off gas, and the addition of the Dowa process to one of the three sulphur acid production lines. These measures have enabled NA to reach quality levels not previously possible. Big smelter expansions in 2000 and 2003 added approximately 40% additional capacity. In order to at least maintain the acid quality, adjustments needed to be made to the gas cleaning process: * New cyclone coolers and plate heat exchangers were fitted to provide for the increased heat input and accelerated reduction of heat transfer, due to the increased biological activity of the cooling water from the River Elbe. The biological activity of the river increased following the closure of industrial sites in Eastern Europe. The mercury and halogen removal efficiency was maintained at at least the previous level. * The second wet ESP stage was modified by replacing the four ESP chambers dating from 1971. Upon increasing the production, the level of mist carried into the ESP stages also increased. Therefore, the secondary ESPs were exchanged to minimise acid mist entrainment. * A second Dowa tower was built to treat the gases of the second sulphuric acid plant. The new tower doubled the production of premium quality acid. Having two independent plants also helped to ensure the continuous production of premium quality sulphuric acid. COPYRIGHT 2005 CRU Publishing Ltd.

This material is published under license from the publisher through the Gale Group, Farmington Hills, Michigan. All inquiries regarding rights should be directed to the Gale Group.

Title: Improvements in gas cleaning systems for cold-gas sulphuric acid plants. (Sulphuric Acid Technology) Date: 7/1/1989; Publication: Sulphur; Progress in the quest for efficiency, energy economy, effluent control Improvements in gas cleaning systems for cold-gas sulphuric acid plants Elemental sulphur used in sulphur-burning sulphuric acid plants is usually of such high purity that the combustion gases can be passed directly as feed gas to the conversion stages with no preliminary cleaning treatment. In stark contrast, [SO.sub.2]-containing off-gases resulting from the thermal treatment of sulphide ores, waste sulphates or waste sulphuric acid are heavily contaminated with dust and with chemical impurities, which may not only impair the operation of the sulphuric acid plant but also appear as unacceptable constituents in the product acid. To remove them to high standards of purity necessitates treatment in a massive, elaborate and costly gas purification system. The ideal combination of simplicity and cheapness with high efficiency, low energy consumption and zero pollution is about as elusive as the philosopher's stone; nevertheless, there have been a number of quiet improvements in the various parts of gas cleaning systems over the years, and some of the latest designs are beginning to shake off the old clumsy image and to offer the prospect of definite improvements in the economics of sulphuric acid production from off-gases. In the operation of a sulphuric acid plant a very pure feed gas is an important prerequisite. This is necessary not only to ensure that the product will be of an acceptable purity but also in the interests of efficient and safe operation of the plant. Feed gases produced as offgases from other processes rather than from the combustion of elemental sulphur almost always contain a heavy loading of impurities of various kinds, and that is, indeed, one of the adverse economic factors common to all of them. Clearly the range of impurities and their concentration depends on how and from what input material the off-gas has been produced. Metallurgical operations (pyrites and non-ferrous ore roasting) usually produce the greatest diversity and the greatest loadings, and it is that type of plant which is contemplated in the rest of this article. Outline of a metallurgical gas cleaning system

Impurities from such sources fall into four broad categories: dusts, fumes, volatiles and gaseous impurities. Dusts are discharged as such from the roaster. The loading and particle size range depend on the type of furnace and the nature of the ore being processed. A fluidizedbed roaster processing flotation pyrites (very fine pyrites separated from certain copper sulphide ores by flotation), for example, is likely to emit a higher proportion of fine dust than an old-fashioned multiplehearth roaster processing coarse-grained pyrites. Fumes are aerosols of ultra-fine solid particles of materials, especially lead and zinc compounds, which are vaporized at the very high temperature in the roaster but resolidify in the exhaust gas at relatively high temperatures (300-400 [degrees] C) as it cools. They range in size between about 0.01 and 2 m. Volatiles remain in the vapour phase to lower temperatures; they include compounds of arsenic, selenium and mercury, and sulphuric acid. Gaseous impurities include hydrogen chloride, hydrogen fluoride, carbon dioxide and small quantities of carbon monoxide. The latter two are not harmful in the concentrations at which they normally occur. In the first process step of the sulphuric acid plant, sulphur dioxide is oxidized to sulphur trioxide as it passes through a solid catalyst. Any dust or ash present in the feed gas will be filtered out in the first catalyst bed, occluding the voids through which the gas passes and in which the all-important contact between the gas and the catalytic surface takes place. As the dust accumulates, the resistance to gas flow increases, to compensate for which more power must be used in the main blower, while the efficiency of the catalyst falls off somewhat. Eventually the pressure drop becomes unacceptable and the plant must be shut down to permit screening of the first-bed catalyst. This has to be undertaken as a necessary maintenance operation from time to time during the service life of any sulphuric acid plant, but (for obvious reasons) as infrequently as possible. So it is necessary to exclude entrained solids from the feed gas to a very high standard. Arsenic, selenium and mercury compounds will pass in the vapour phase through all the catalytic stages of the plant and will be absorbed into the product acid. They are all toxic, and only very low concentrations are permissible in product acid, especially that destined for use in the food or pharmaceutical industries. Arsenic additionally damages the catalyst, while mercury compounds can build up in heat exchangers, reducing efficiency and even causing failures. For those reasons, and on account of technological problems in post-treating high-concentration sulphuric acid, it is usual practice to remove them from the feed gas before it enters the sulphuric acid plant. Hydrogen chloride and hydrogen fluoride damage the silica-supported vanadium pentoxide catalyst by chemical attack. They also become absorbed in the product acid and cause corrosion in the acid circuits. Since they are vapours, they must be removed from the feed gas by wet scrubbing.

Under the conditions in the scrubbing process, the small concentration of sulphur trioxide always present in the feed gas will react with water to form sulphuric acid, which condenses as an aerosol of exceedingly fine liquid particles known as acid mist. This effect is much exacerbated if fume has not previously been removed from the gas, since it acts as a nucleating agent for the mist particles. Mist will create havoc in contact with any metal surfaces later in the plant, and it must be rigorously excluded, but on account of the exceedingly fine size of the particles this is very difficult and requires especially effective measures. The gas cleaning system must therefore perform a number of discrete operations under differing conditions. In order, these are dust and fume removal, wet scrubbing, mist elimination and mercury removal (if required). As will be explained below, it is also necessary to cool the gas between the scrubbing section and the final mist eliminators. For technical reasons, all parts of the system must function at high efficiency but, for economic reasons, all must cause the bare minimum of pressure drop. It is the balance between these opposing criteria -- for the price of efficiency is nearly always pressure drop -- that determines the type and design of the individual stages of the gas cleaning system. Nevertheless, there is still scope for variation in design philosophy, at least in some parts of the system. Recently, also, new environmental regulations have necessitated changes in the way liquid effluents from the wet stages are handled in some systems. Dust and fume removal Conventional gas cleaning systems remove as much as possible of the solids and fume from the gas stream in a dry state. Pressure drop considerations rule out the use of mechanical impingement devices such as fabric filters for collecting dust from the sizeable volumes of gas involved. With few exceptions, the coarser dust particles are collected in dry cyclones, which may typically reduce the dust content of the gas from 50-150 g/[Nm.sup.3] to 10-15 g/[Nm.sup.3] for a pressure drop of 5-10 mbar. The raw gas is first cooled, if necessary, to 250-400 [degrees] C. This is low enough for fume components to resolidify from the vapour phase but far enough above the dewpoint of corrosive constituents to obviate the need for special materials of construction. To remove the remaining fines, the only device efficient enough at an acceptably low pressure drop is an electrostatic precipitator. The gas passes through a corona (silent) discharge between banks of electrodes, which are alternately grounded and maintained at a negative potential of 10-80 kV. Electrons streaming from the charged electrodes collide with neutral gas molecules, converting them to negative ions, and these in turn attach themselves to dust particles, which are consequently drawn towards the grounded (collector)

electrodes, where they are discharged. To attain the charge intensity needed to produce a corona discharge at the lowest possible potential, the charged electrode needs to have a very small surface area, whereas the collector electrodes should have a large surface area to ensure the most efficient possible capture of the charged dust particles. For that reason dry precipitators normally comprise a series of parallel collector plates, vertically mounted so that the discharged dust can fall from them by gravity into discharge hoppers beneath, with rows of discharge wires, which may be fluted or barbed to enhance the corona effect, suspended in frames in the spaces between them. Mechanically operated hammers are provided to dislodge accumulated dust from the collector electrodes. The gas flows horizontally through the precipitator.[1,2] Electrostatic precipitators are extremely efficient (99%+) at minimal pressure drop (about 1 mbar), but they are of necessity very large on account of the need to keep gas velocities below the level at which the already precipitated dust will be re-entrained to any significant extent. Their initial cost is therefore high. Electricity consumption is about 1.52.5 kWh per 1,000 [Nm.sup.3]. Quenching, scrubbing and cooling It is necessary next to remove any dust which may have passed through the precipitator as well as sub-micron fume, volatiles and gaseous impurities. For that purpose the gas has to be cooled and then scrubbed. Scrubbing will saturate the gas with moisture, and since it will be most efficient if the gas is already in that condition, it has long been the practice to cool the gas by quenching with aqueous scrubbing liquor in a void spray tower. Under the essentially adiabatic conditions, the gas is cooled by evaporation of water from the scrubbing liquor until the temperature reaches saturation point, normally somewhere between 50 [degrees] and 80 [degrees] C. The gas then passes into the scrubber. In early plants this was always a tower scrubber, either packed or with tray internals of some kind. Many plants have been built with the saturator and a tray scrubber integrated in a single tower; this type of device is known as a Peabody or Swemco tower. In recent years towers have been replaced increasingly by other kinds of gas-liquid contact device. In the quench/scrubber section, most of the volatile impurities such as arsenic and selenium compounds condense and dissolve in the scrubbing liquor. Gaseous impurities such as hydrogen chloride and hydrogen fluoride are also largely absorbed. The small proportion of sulphur trioxide in the gas reacts with the water vapour, and sulphuric acid condenses, mostly as a fog of sub-micron particles known as acid mist, though some dissolves in the scrubbing liquor.

The wash liquor in the scrubbing system is cooled, for two reasons. First, it enhances the scrubbing efficiency for the most volatile impurities, hydrogen chloride and hydrogen fluoride. Secondly, the moisture content of the saturated feed gas at the temperature at which it leaves the quench tower is too high to maintain a high product concentration in the subsequent sulphuric acid plant, especially if the feed gas is lean off-gas from a smelting operation: not enough sulphur trioxide would be produced in the sulphuric acid plant to use up the water absorbed in the drying tower. Therefore further cooling is required to condense out the surplus moisture. The lower value represents the lowest product concentration that can be handled in a normal contact sulphuric acid plant without recourse to special materials of construction. Because the scrubbing liquor is recirculated, its sulphuric acid concentration and impurities content will build up unless a bleed stream is withdrawn and replaced with water or more dilute liquor from elsewhere. How large a portion of the circulation has to be bled, and consequently the sulphuric acid concentration of the scrubbing liquor, are determined by the maximum permissible vapour pressure over the solution of the gaseous impurities such as hydrogen chloride and hydrogen fluoride, which depends on their concentration in the solution and on the temperature. Where the feed gas contains unusually high concentrations of hydrogen fluoride, a siliceous material may be dispersed into the wash acid, or the gas may even be passed through a supplementary scrubbing tower filled with siliceous material, to react with the hydrogen fluoride to form fluosilicic acid, which has a much lower vapour pressure. In general, the wash acid contains between 5% and 60% [H.sub.2SO.sub.4]. The advantage of maintaining the higher concentration is that acid of this strength can be purified and utilized or, if circumstances permit, upgraded by addition to the absorption circuit of the acid plant. Since sulphur dioxide is soluble to an appreciable extent in dilute sulphuric acid, the wash acid is circulated through a stripping column swept by the incoming air which is needed to adjust the oxygen content of the feed gas to the desired [O.sub.2]/[SO.sub.2] ratio. The wash acid circulating in the wet stages of the gas cleaning plant is very corrosive, and lead was for long the traditional acid-resistant material of construction. It is still used to some extent but, on account of its cost and the scarcity of skilled lead solderers, its place has largely been taken today by plastics. Today most saturation/scrubbing equipment is constructed with a carbon steel shell protected from acid attack by a plastic liner, which is itself protected from hot gases and erosion by acid-resistant bricks. An additional layer of carbon brick may be needed to protect the acid bricks from fluorine attack. Over the past 20 years, a cheaper, more compact alternative to conventional scrubber systems -- the Venturi contactor -- has been

proved in an increasing number of installations and has, indeed, become virtually the industry standard. The gas passes downwards through a constriction into which the scrubbing liquor is injected in the same direction from spray nozzles arranged around its periphery. Because of the intensity of the gas-liquid contact in this type of scrubber, it is possible to dispense with the quencher-saturator, although conservatively designed installations may still include it. For a given pressure drop, a Venturi scrubber can achieve greater efficiency at a lower liquid circulation rate than a spray tower operating at the same pressure drop. And because the gas and liquid are admitted in cocurrent, the gas-side pressure drop can be reduced or eliminated altogether by using a higher liquid circulation rate.[4] Operating at a pressure drop of 12.5 mbar, a Venturi scrubber is about 75% efficient at removing sub-micron lead or zinc oxide fume.[5] Lurgi GmbH has a two-stage scrubber design incorporating a downdraught Venturi saturator as its first stage. It has been used in a number of non-ferrous metal smelters, steel works and waste incineration plants. After passing through the Venturi contactor the gas is collected into a short funnel-shaped duct, emerging radially through the gap between its lower end and the annular rim of a horizontal circular deflector. Scrubbing liquor is introduced into this zone through a single, central, large-aperture nozzle. The clearance between the bottom of the duct and the deflector is adjustable according to the gas volume, ensuring that the velocity of impingement between the gas and the scrubbing liquor is maintained at its optimum under the varying conditions that are so characteristic of non-ferrous smelting operations. As the gas emerges through the gap, guide vanes impart a cyclonic motion to it. This throws liquid droplets and wet dust against the inside surface of the scrubber casing, where they coalesce and run into the sump. A separate cooler is needed after a Venturi scrubber to reduce the moisture content of the gas and to increase the solubility of hydrogen halides. This may be a conventional tower cooler, as used in current Swemco designs, or -- provided the sulphur dioxide concentration in the gas is about 6% or more -- it is possible to use graphite ("Karbate") shell-and-tube coolers in place of tower coolers. (At lower sulphur dioxide concentrations the surface area requirement is too high.) These coolers are mounted vertically so that the moisture condensing from the gas drains down the tube walls. A small amount of condensate is recirculated as irrigation liquor to prevent fouling if abnormal amounts of dust are carried over. Since the concentration of dissolved material in the liquid film is continuously declining along the length of the tube as moisture condenses into it, hydrogen fluoride and hydrogen chloride still present in the gas are efficiently absorbed in the liquid film. Lurgi has an indirect counter-current shell-and-tube cooler design known, from the cross-sectional shape of the tube walls, as a "star cooler".[5] The tubes, which are made of extruded lead, have fins on

the interior (gas-side) surface to improve heat transfer. The total surface area on the gas side, and therefore its efficiency as an absorber for gaseous impurities, is in fact as high as that of a packed tower/acid cooler system of equivalent cost. Pressure drop in a cooler of this type designed to lower the gas temperature from 60 [degrees] to 40 [degrees] C is about 15 mbar. In a new 2,200-t/d sulphuric acid plant which Chemetics International Co., of Canada, is building for Noranda at a smelter in Quebec, quench cooling is used for initial cooling of the very hot gas from the smelter. This means that the heat and moisture loading are much higher downstream, and the saturation temperature in the gas washing system is about 80 [degrees] C. This is too high for lead, and the sudden moisture collapse which would result from cooling the unusually moist gas would rule out the use of graphite. Therefore Chemetics is installing a two-stage shell-and-tube cooler system in high-alloy stainless steel, the hotter of the two coolers being made of UNS N10276 (Hastelloy 276) and the colder of UNS 531254 (Avesta 254-SMO). These coolers have been designed with large-diameter tubes to eliminate the possibility of plugging and are symmetrical so that they can be reversed after a number of years in operation to extend their service life.[7] Mist elimination On account of its low particle size, acid mist is notoriously difficult to remove from a gas stream. It passes readily through all kinds of scrubber and would pass through the sulphuric acid plant drying tower, to cause havoc in the heat exchangers which raise the temperature of the feed gas up to the [SO.sub.2]/[SO.sub.3] conversion temperature. It must therefore be very thoroughly removed from the gas as the last stage of the gas cleaning process: in general, the efficiency has to be greater than 99% and the gas must be optically clear. The difficulty arises from the extremely small size of the mist particles. About 40% of the acid mist particles in washed sulphur dioxide feed gas are 1 [micro]m or less in diameter.[8] The simplest form of separation device, an impingement filter such as a fibre pad filter, only works effectively if there is a big difference in momentum between the entrained particles and the gas molecules, so that they collide with the fibres of the filter medium while the gas molecules pass easily round them. At a particle size below about 1 [micro]m, the difference in momentum is becoming rather small, and such a fine-mesh filter is needed to produce a good separation that it presents a considerable resistance to the flow of gas.[8] Once again, therefore, electrostatic precipitators are used on account of their high efficiency at low pressure drop. On account of electrostatic effects, wet precipitators operate more efficiently at low mist loadings than they do at high ones; therefore it is

common practice to have two precipitators, or two sets of parallel precipitators, in series. Sometimes the first set is placed upstream of the gas cooler. Wet electrostatic precipitators are nowadays of a markedly different design from dry precipitators. Collector electrodes are not plates, as in dry precipitators and in earlier designs of wet precipitator, but vertical ducts, typically about 0.25 m across. Their length is determined by the relation between the gas velocity and the migration rate of the charged mist particles and is typically 5-6 metres. The discharge electrodes run along their central axes. Both must be resistant to corrosion by the precipitated acid. Formerly lead was almost always used, as a structural material or as a lining for steel components, but it has been replaced progressively by plastics (for collector electrodes) and highalloy stainless steels. These are more durable and permit a far greater degree of prefabrication. Plastics are, of course, electrical insulators and have hydrophobic surfaces, and in order to ensure that the inside surface of the ducts will be coated with a continuous film of conductive liquid, the plastics are specially treated. As in dry precipitators, the object is to produce a corona discharge to charge the mist particles so that they will be repelled towards the grounded collector electrodes. Corona discharges form most easily round points or along sharp edges, and to obtain a satisfactory corona discharge at a potential unlikely to cause sparking, discharge electrodes are usually made as thin circular wires, or barbed or longitudinally ribbed wires or rods. It is also clearly important to ensure that the structure is sufficiently robust to maintain the designed minimum clearance between the discharge and collector electrodes at all times, otherwise there is a danger of sparking. This is a factor of importance, for example, in the design of precipitators with plastic collector electrodes, which may distort in service if inadequately supported. From the point of view of theoretical efficiency, the ideal collector electrode is a tube of circular cross-section, since that is the only shape in which it is possible to establish a perfectly uniform electric field. Like the tubes in a heat exchanger, these are usually anchored in tubesheets at their ends (rigidly at at least one). Unlike a heat exchanger, however, there is no need for space between the tubes, but this cannot be avoided with cylindrical tubes; a precipitator with circular tubes therefore occupies a larger site area than one of the same capacity with square-section tubes, which fit together snugly. Square tubes can also be bonded or welded together to make a completely rigid structure, eliminating all risk of distortion under normal service conditions. Square-section collector electrodes also have a larger surface area than the largest cylindrical electrodes that will fit into the same plan area; however, the electric field is decidedly non-uniform, and the operating potential must be limited to a value which will not produce sparking between the discharge electrode and

the middle of each face of the collector, which is well below the ideal potential across the longer distance between the discharge electrode and the corners of the collector electrode. As a compromise, some current precipitator designs have polygonal tubes. In the Hugo Petersen precipitator,[9] which is constructed of leadlined steel, the tubes are octagonal. With a special design of discharge electrode, the electric field distribution closely approaches that in a circular tube. This precipitator is entirely prefabricated, obviating the need for lead solderers in the field. In 1980 Lurgi introduced a design based on a honeycomb structure of extruded hexagonal PVC tubes, bonded together with glass fibre-reinforced polyester (FRP). This design is in successful operation in at least 25 units and is replacing the company's earlier design based on circular tubes. During the middle of the present decade, Boliden Mineral AB developed a tubular design, now manufactured and marketed by Edifo AB, to replace an earlier square-tubed precipitator series at one of its smelters in Sweden.[10] On account of the severe winter temperatures and the outdoor siting of the precipitators, stainless steel was chosen as the electrode material in preference to both lead and plastics. After a certain amount of experimentation with different discharge electrodes, a square rigid rod carrying a series of sharp needles welded to each face was found to give the best results. Another feature of this precipitator is that the insulators for the support frame of the discharge electrodes are not kept dry by continuous ventilation by heated air, as in many other designs, but are housed in a sealed box and heated electrically. In a further development of the concept, the functions of precipitator and cooler have been integrated in a single unit, in which cooling water circulates between the collector electrodes. In some circumstances, it has been stated, single precipitator-cooler units can replace the need for a second set of conventional precipitators. Although a small-gauge electrode is needed to produce a good corona discharge, a wide-gauge, non-discharging electrode is more efficient at repelling the charged particles towards the collector electrode. The American company Beltran Inc. markets a two-stage precipitator design in which the first stage is optimized for particle charging and the second for particle collection.[11] For applications with sulphuric acid not exceeding 50% concentration it is normally fabricated in plastics (FRP). The residence time in the charging zone is considerably less than in the single-stage type of precipitator, and as no corona current is flowing in the collection zone, the overall power consumption is stated to be less than one third that of a single-stage precipitator of the same efficiency. Mercury removal

Mercury occurs as an impurity in a number of commercial non-ferrous ores, most notably in zinc sulphides, the roasting of which is one source of [SO.sub.2]-containing off-gases used in sulphuric acid manufacture. During roasting, it is liberated in elemental form as its vapour, which is only partially removed in the normal gas cleaning train; the remainder finds its way into the product acid. With increased awareness of the toxic hazard of mercury, the industry now has specifications for maximum mercury levels in sulphuric acid for most purposes, and in some metallurgical acid plants these would be infringed without special treatment. Though it is possible to remove mercury from sulphuric acid by chemical treatment, it is generally preferred to remove it from the roaster gas. Most of the development work has been undertaken in Scandinavia, and of the various procedures investigated one, the Boliden-Norzink process, which is licensed to Lurgi, is most usually practised. This process is incorporated as the last stage in the gas cleaning system, downstream of the wet precipitators. The roaster gas is washed in a packed tower by a liquor comprising a solution of mercuric chloride, [Hg.sub.2Cl.sub.2]. This is separated from a sidestream in a thickener. To compensate for the depletion of the mercuric chloride in the scrubber circuit, a portion of the thickened slurry is subjected to oxidation with chlorine, which regenerates mercuric chloride, and is returned to the circuit. A mist eliminator in the top of the scrubbing tower prevents entrained droplets of scrubbing liquor from being carried over to the sulphuric acid plant. The process, which is in operation in a number of units, is highly efficient: the product acid mercury level in acid produced from a zinc concentrate containing 350 ppm Hg is 0.3 ppm or less, which indicates an overall mercury removal efficiency greater than 99.9%.[12] Unconventional gas cleaning systems The conventional gas cleaning train as described above is clearly a quite complex and expensive installation. It also produces acidic liquid effluents containing some harmful and unpleasant substances. Apart from the developments in the individual stages, some of which have been mentioned above, improvements have been directed mainly at simplifying and cheapening the whole gas cleaning system and at eliminating effluent discharges. Conditions in some of the contemporary metallurgical installations have also presented some challenges in the design and materials specification of gas cleaning systems. Chemetics has a licence for the EDV (ElectroDynamic Venturi) gas cleaning system developed in France by LAB SA. The gas passes sequentially through two cross-flow scrubbing towers, downwards through the first and upwards through the second. Wash acid is

introduced through a series of specially designed spray nozzles disposed down the central axis of the scrubber. Each produces a flat double conical spray pattern extending across the entire cross-section of the spray tower. The intense contact between the gas and the liquid cools and saturates the gas, thoroughly wets all particulate material, and arrests the coarser particles. Atop the second scrubber is a Venturi, and the adiabatic expansion which it causes cools the gas and promotes condensation to form on the fine particles. Above the scrubber is a high-intensity spray which entraps most of the remaining particulates. Finally, the gas passes through a an "electro-filtering Venturi module", designed to take the place of conventional wet precipitators. Further condensation takes place in the throat of another Venturi, and then the gas passes through a corona discharge issuing from the point of a negative electrode immediately above a spray nozzle. Particles and mist in the gas become charged negatively, while a positive charge is induced in the droplets from the spray nozzle. The attraction between the oppositely charged particles and spray enhances the scrubbing effect. Though successful at removing dust, heavy metals and halides, Chemetics' first EDV system, installed at a 770-t/d sulphuric acid plant for Vieille Montagne in Belgium in 1985, was unable to meet acid mist guarantees on a consistent basis. A single stage of wet precipitators had to be installed downstream, which solved the problem. Further development is in progress to eliminate the need for that in future. The three-stage gas cleaning system based on froth scrubbing technology, developed by E. I. Du Pont de Nemours & Co., that Monsanto EnviroChem Systems Inc. has installed as a replacement for a traditional gas cleaning system at American Cyanamid's spent sulphuric acid regeneration plant at Hannibal, MO. It is now Monsanto's preferred gas cleaning technology for spent acid regeneration and metallurgical sulphuric acid installations. Hot gas at about 315 [degrees] C enters a reverse-jet scrubber, which quenches and saturates it and removes solid particulate. After passing through a separator, the gas passes through a "froth column" and a final reverse-jet scrubber, which cools the gas, condenses and collects acid mist, and removes any remaining solid particulate. All parts of the system are made of FRP, with the exception of the hot gas duct, which is brick lined. The portion of the first reverse jet scrubber above the spray zone is protected from thermal damage by irrigation with wash acid. An emergency water system is provided to maintain a water flow as long as required in the event of a failure in the wash acid circulation system. The turbulence induced in the scrubber by the contrary motion of the gas and the liquid jet produces a volume of froth containing large, rapidly resonating, non-atomized liquid volumes which present a large effective surface area to the gas. The froth zone and scrubbing

efficiency can be maintained at high turn-down rates. The liquid is not atomized to any significant extent. Pressure drop is about 10 mbar. The froth column is a flooded baffle tray column in which the gas and liquid flows are arranged to create frothing conditions. It is stated to be 50% more efficient at cooling and scrubbing than conventional designs operating at the same pressure drop, and can be designed for flow rates and temperatures that minimize the formation of acid mist. Because the primary reverse jet scrubber is so efficient at removing particulate material, the scrubbing liquor in the froth column/final reverse jet circuit contains very little solids and can be cooled in a plate cooler. The installation is compact enough to be shop fabricated. The reverse jet scrubbers have only one or two large, wide spray nozzles, which are unlikely to become choked. Overall pressure drop is about half that of a spray tower/Venturi/gas cooler system. And mist levels in the cleaned gas are apparently so low that no wet precipitators are deemed necessary; certainly, none has been provided at the Hannibal plant. Effluent management In common with many other industries, sulphuric acid manufacturers have come under increased pressure in recent years to minimize the environmental impact of their operations, not just from gaseous emissions but also from liquid effluents. The Ralph M. Parsons Co., for example, recently undertook a contract to modify a gas cleaning system, which formerly used sea water as the scrubbing liquor and discharged it after stripping to recover sulphur dioxide, to a recirculating system with indirect cooling by sea water. The new installation included bleed water treatment comprising neutralization followed by precipitation of heavy metals and separation of solids.[13] In its Total Recovery Concept, Hugo Petersen has avoided the waste of sulphuric acid values involved in neutralizing and discharging bleed liquor.[9] The following outline description is representative only: in practice, each plant would be custom-designed to suit the conditions of the individual site. Whatever the sulphur dioxide/moisture content of the gas, the sulphuric acid concentration of the wash liquor in the scrubbing circuit is maintained at 50-60%. To ensure good absorption of hydrogen halides, the acid concentration in the subsequent cooling stage must be kept down to 2-3%, so a separation device is installed in the gas line after the scrubber to knock out entrained scrubber acid. The cooled acid passes through a two-stage wet precipitator installation using the octagonal-tubed design described earlier. Drainage from the precipitators is introduced as make-up into the scrubbing liquor circuit. The moderately concentrated acid in the scrubbing tower circuit, containing almost all the solids (largely metal sulphates in both

dissolved and insoluble form) is filtered and the solids are recycled to the roaster. Special treatment is needed to deal with impurities such as arsenic and selenium, which report only in the roaster gas and do not occur in the slag or cinder. The acid filtrate is further treated to precipitate the dissolved metals as sulphides, which are also recycled to the roaster, along with mercury values removed in the mercury recovery system (if included). The acid is then introduced to the acid plant absorber system in place of process water. The standard of purification is therefore governed by the product acid specification. The weak acid from the cooler circuit has to be neutralized and disposed of, but it amounts to only 10% of the effluent from a normal plant. It is neutralized in two stages, in the first of which most of the dissolved metals are precipitated as hydroxides, which are separated and returned to the roaster. In the second stage the sulphate values are precipitated, usually as calcium sulphate. This can sometimes be disposed of into a metallurgical process, the calcium values ending up in the slag, but when this option is not available it can be discharged safely on account of its low heavy metals content. The liquid remaining after neutralization is pure enough to be discharged without ill effect. References [1]"EGR Dust Collection". Lurgi Express Information S 1272/2.78. [2]"Horizontal Precipitators". Lurgi GmbH publication No. T 170 e (Sep 1982). [3]Sander, U. H. F., Rothe, U., and Kola, R.: "Sulphuric Acid". In "Sulphur, Sulphur Dioxide and Sulphuric Acid" (ed. More). British Sulphur (1984), p. 288. [4]Friedman, L. J.: "The sulfuric acid plant: Recent advances review and analysis". In "Sulphur 88": Preprints for British Sulphur's 13th International Conference, Vienna (Nov 1988), pp. 429-452. [5]"Scrubbing and Cooling System in Sulphuric Acid Plants". Lurgi Express Information No. T 1270/7.83. [6]Black, B. (Swemco Ltd): Private communication (Jun 1989). [7]Bhaga, D.: Private communication (Jun 1989). [8]Daum, K.-H., and Schmitt, H.-D.: "Recent developments in gas cleaning systems for coldgas sulphuric acid plants". Presented at "Sulphur 85": British Sulphur's 9th International Conference, London (Nov 1985). [9]Daum, K.-H.: Private communication (Jun 1989). [10]Johansson, H., and Hedman, L.: "Wet electrostatic precipitator in stainless steel for sulphuric acid process -- experiences and improvements". In "Sulphur 88", pp. 137149. [11]Beltran, M.R., and Surati, H.: "Use of two-stage electrostatic precipitators in metallurgical roasting and sulphuric acid applications". In "Making the Most of Sulphuric Acid": Proceedings of British Sulphur's 5th International Conference, London (Nov 1981). [12]Steintveit, G.: "The Boliden-Norzink mercury removal process for purification of roaster gases". Norzink A/S, Odda, Norway. [13]Haydon, B. C.: Private communication (Jun 1989). COPYRIGHT 1989 CRU Publishing Ltd.

This material is published under license from the publisher through the Gale Group, Farmington Hills, Michigan. All inquiries regarding rights should be directed to the Gale Group.

Title: The wet gas sulphuric acid plant: part 1.(Acid Plant Design) Date: 5/1/2004; Publication: Sulphur; Author: Friedman, Samantha J. The recovery of sulphur dioxide from metallurgical and spent acid regeneration gases for the production of sulphuric acid has been an effective means of reducing S[O.sub.2] emissions from non-ferrous smelters, and for producing fresh sulphuric acid from waste or spent acids. Leonard J. Friedman and Samantha J. Friedman of Acid Engineering & Consulting review each of the unit operations in the gas cleaning section of the wet gas sulphuric acid plant, discussing various equipment designs, materials and the handling of gas stream variables and impurities. ********** Metallurgical gas feed to a sulphuric acid plant is partially treated in the smelter before entering the acid plant. The gas is collected in hoods or off-gas take-offs, and is partially cooled to about 250350[degrees]C in a waste heat boiler, radiant air cooler or by partial saturation with water sprays. Bulk solids are removed in a dry, platetype, 99% efficient electrostatic precipitator, or bag house (with solids recycled to the smelter). Spent acid plants decompose the spent or waste acid feed to sulphur dioxide gas in a decomposition furnace and partially cool the gas in a waste heat boiler before it enters the gas cooling and cleaning system. The wet gas (metallurgical or spent acid regeneration) sulphuric acid plant is composed of two main sections: * the gas cooling-cleaning-purification area, where impurities and water are removed; * the contact section, where the sulphur dioxide is catalytically converted to sulphur trioxide and reacted with water to form sulphuric acid. For the purposes of this paper, it is assumed the metallurgical gas has been pretreated as above at the entrance to the acid plant gas cleaning section, and the regeneration plant gas has been partially cooled in a waste heat boiler. Gas cleaning

The gas cleaning area must treat the gas to remove impurities, S[O.sub.3] and sufficient water for the production of sulphuric acid in the contact section. Treatment is required to allow production of concentrated sulphuric acid while preventing catalyst plugging or degradation and corrosion of the equipment in the contact section of the plant. The effects of some of the impurities are summarised below: * S[O.sub.3] -- forms sulphuric acid mist causing corrosion of contact section equipment, and may cause high acid mist emissions to atmosphere. * Excess water -- dilutes the concentrated acid and causes corrosion of strong acid piping and equipment. * Halogens (F, Cl) -- cause catalyst degradation and corrosion of stainless steel components in the strong acid system. * N[O.sub.x] -- contaminates product acid and causes corrosion of the strong acid carbon steel components, e.g. piping, product storage tanks, shipping cars. * Solids -- cause plugging of mist eliminators and catalyst, contaminate product acid and may make it un-saleable. * Arsenic -- causes catalyst degradation and contaminates product acid. * Mercury -- builds up in contact section equipment (heat exchangers) causing failures and contaminates product acid. To remove these impurities and condition the gas for the contact section, the gas cleaning area is composed of three basic unit operations: * Gas saturation. Gas is saturated with water, cooling the gas to its adiabatic saturation temperature, normally 50-80[degrees]C. This unit also provides the first stage of impurity scrubbing and converts S[O.sub.3] in the gas to sulphuric acid mist for later removal. * Gas cooling. The second impurity scrubbing stage cools the gas to condense sufficient water for the production of concentrated sulphuric acid. * Mist removal. A tube type electrostatic precipitator removes greater than 99% of sulphuric acid mist and residual solids. For plants with high levels of mercury, an additional mercury removal system is added.

The three basic unit operations are common to all wet gas sulphuric acid plants (Fig. 1). With proper equipment selection and design, the gas cleaning system will provide a properly cleaned gas for the contact section of the plant. Our experience has shown the majority of corrosion, equipment failure and down time problems in a wet gas acid plant occur in the contact section of the plant and are traceable to problems in the gas cleaning system. For example, in one plant we were called in to investigate severe strong acid system corrosion problems causing pump, tower distributor and piping failures. The problem was determined to be poor gas cooling allowing too much water to enter the contact section of the plant, diluting the strong acid just enough to be highly corrosive. Modification of the gas cooling system corrected the problems. In another plant, severe corrosion was experienced in the contact section main air blower and gas-gas heat exchangers. We determined the problem to be acid mist resulting from poor electrostatic precipitator performance due to high inlet loadings. Rearranging the precipitators for parallel sets of two units in series and addition of monitoring and control instrumentation to insure precipitator performance solved the problem. From an operator's viewpoint, proper gas cleaning system design and operation are critical to the operation and maintenance of a wet gas sulphuric acid plant. The gas cleaning system is the place to put in extra thought, use a conservative design, and put extra money to avoid expensive downtime, maintenance, equipment failures, and early equipment replacement in the contact section of the plant. Gas saturation--scrubbing The hot (250-450[degrees]C) gas from the smelter or acid decomposition furnace and waste heat boiler is cooled to its adiabatic saturation temperature by evapouration of water from a circulating stream of weak (5-10% to as high as 30%) sulphuric acid. The saturation temperature, in the range of 50-85[degrees]C, is a function of the inlet gas temperature and water content, and the concentration of weak acid. By definition, adiabatic saturation is saturation of the gas with no change in the total heat content of the gas. In addition to gas cooling, the gas saturation system removes some of the larger solid particles and is the first stage of impurity scrubbing. To meet gas saturation and scrubbing requirements, the equipment chosen must be an effective gas-liquid contacting device. Two basic types of contacting devices have been used: open spray towers and venturi type contactors. Open spray towers have been used for over fifty years either as separate towers or as the lower section of a combined gas saturation and cooling tower. Combined towers, sometimes referred to as Peabody Scrubbers or Swemco Scrubbers (named after the vendors who supplied them), included a lower liquid circulating spray tower and

an independent upper liquid circulating and cooling tray tower in one vessel. The spray tower is an acceptable contacting device for gas saturation and scrubbing. With proper spray arrangement and design for liquid particle size and spray angle, it will perform its required function at a relatively low pressure drop--in the order of 75-100 mm [H.sub.2]O. Its major disadvantages are brick problems in the wet-dry interface area, its relatively high capital cost and its poor efficiency compared to other available gas-liquid heat and mass transfer contacting devices. A much better contacting device, in service for over 40 years, is the venturi contactor. In fact, the majority of the gas saturators installed in wet gas acid plants around the world in the last 25 years have been the venturi type. The venturi is an efficient liquid gas contactor and effective solids and gas scrubbing device. It is normally designed for a gas pressure drop of 75 mm [H.sub.2]O, but can be designed for zero pressure drop or even as an eductor providing a pressure rise using higher pressure liquor sprays. Liquid circulation is significantly less in a venturi compared to a spray tower, reducing piping and pumping costs. Overall, the venturi contactor is an efficient, low-cost scrubbing device. In the last few years, a countercurrent spray tower design has been offered by Monsanto using downward flow of gas with up-flow of the liquid spray in a high gas velocity (120 ft/sec) Fibre Reinforced Plastic (FRP) flow tube, called a Dyna-Wave contactor. The FRP tube wall is protected from the high gas temperature by a weak acid liquid film flowing down the tube wall. Numerous interlocks are included to prevent FRP device failure from high temperature. Recently, Inco installed a Dyna-Wave quench system treating gas from the Inco flash furnace, but used Incalloy 825 in place of FRP. Materials of construction for gas saturation equipment are similar for all equipment types (except the FRP Dyna-Wave). The device is normally constructed of a steel shell and an impervious liner resistant to weak sulphuric acid, usually rubber or FRP, covered by an acid brick lining for temperature and erosion protection. For gases that contain fluorides, an additional carbon brick lining is used to prevent fluoride attack on the silica in the acid brick. Many years ago, lead was the common impervious liner material, but is not used today. The inlet gas duct is carbon steel and care must be taken in the design to insure the wet-dry interface is in the lined portion of the vessel to avoid corrosion of the steel inlet duct. The outlet duct is FRP. Weak acid circulating pumps are vertical plastic or plastic-lined pumps, with graphite and Wilfley type plastic-lined horizontal pumps also acceptable. Metal pumps of high nickel alloys (Hastelloy C-276, C-22) have also been used, but are more expensive. Weak acid circulating piping is either FRP or polypropylene lined steel, with spray nozzles of silicon carbide (Refrax) or Hastelloy C276 for temperature and erosion corrosion protection.

Gas cooling The saturated gas flows to a gas cooling system where the gas is cooled to condense sufficient water for production of concentrated sulphuric acid in the contact section of the plant. Efficient liquid-gas contacting in the gas cooler also provides a second stage of impurity scrubbing. Figure 2 shows the temperature the gas must be cooled to for production of 93 or 98% sulphuric acid as a function of S[O.sub.2] gas strength, at sea level with a gas cooler exit pressure of -350 mm [H.sub.2]O, and an allowance for 10% water to be added in the contact section. A high S[O.sub.2] gas strength minimises the cost of the gas cooling system. Conversely, low S[O.sub.2] strength increases the difficulty of water removal and system cost, and at some point alternative and expensive cooling systems must be used to obtain proper water removal. Equipment devices used for gas cooling include: a graphite shell and tube heat exchanger, used in systems with S[O.sub.2] gas strength over 6-7%; tray towers using sieve or impingement type trays, with indirectly cooled circulating liquor (Swemco or Peabody scrubbers); and packed towers, also with indirectly cooled circulating liquor. Tray towers were used for many years as the upper stage of a combined gas saturation-cooling tower system. They are rarely used today because of high tray pressure drop for efficient heat and mass transfer, corrosion problems with the metal tray material in some plants, and their relatively high cost compared to alternate devices. A packed cooling tower is the most widely used system in wet gas cleaning systems. The system consists of an FRP tower packed with 3 inch polypropylene saddle packing. Gas flows countercurrent to the liquor and is cooled by direct contact with a circulating, indirectly cooled weak acid stream. The circulating weak acid is cooled in watercooled Hastelloy C-276 or C-22 plate type heat exchangers. Packed towers provide efficient heat and mass transfer at low gas pressure drop (about 100 mm [H.sub.2]O). Tower diameter is a function of gas flow and liquor circulation, and liquor cooler heat exchanger size is based on the S[O.sub.2] gas strength and cooling water temperature. It is common practice to provide a spare plate liquor cooler to maintain gas cooling during exchanger cleaning. Shell and tube graphite gas coolers are used in plants with gas strength above 6-7% that contain a minimum amount of impurities, until recently primarily in plants with gas from fluid bed roasters (pyrite and zinc) and spent acid regeneration plants. The unit consists of parallel vertical shell and tube exchangers with graphite tubes and tubesheets in a carbon steel shell. Gas flows downward through the tubes and is cooled by cooling water on the shell side of the unit. Impurities in the gas are scrubbed by the condensed water augmented by a small recirculating stream of gas cooler condensate. The unit is economical

for high S[O.sub.2] gas strength systems and is the preferred choice in systems with minimal impurities for its low cost, ease of operation, and low maintenance. As S[O.sub.2] gas strength decreases, heat exchanger surface area required for the final increments of gas cooling increases dramatically, increasing shell and tube gas cooler cost above the alternative packed tower system, with the break-even point about 6-7% S[O.sub.2]. Gasses with high levels of impurities require efficient scrubbing and a packed tower is the choice. Mist removal The final treatment stage of a wet gas acid plant gas cleaning system is the removal of residual solids and sulphuric acid mist (formed by reaction of S[O.sub.3] in the gas with water). Mist and solids removal efficiencies of greater than 99% for particles less than one micron (producing an optically clear gas) are required to protect contact section equipment from acid corrosion, solids contamination of product acid, and catalyst plugging. The device used for mist and solids removal for over 50 years is the tube-type electrostatic precipitator, usually arranged in parallel sets of two units in series. The units are constructed of up to 240 tubes (250 mm in diameter and 5-6 m long), supported between tube sheets. The tubes are grounded and have a discharge electrode running down the center. The gas flows upward through the tubes where mist and solid particles are charged by a corona (which ionises molecules by electron collision in a region of high electric field strength) at the tube entrance, generated by the high voltage potential between the electrode and the grounded tube wall (normally 50-90 kV). As the gas and particles move up through the tube, charged particles are repelled by the similar charge of the electrode and are attracted to the grounded tube wall. The tube must be sufficiently long to allow time for the charged particles to migrate to the wall and be collected. The efficiency of an electrostatic precipitator can be represented, in simplified form, by the Deutsch-Anderson equation: Eff = 1 - exp(W*A/Vg) where: A = area of collecting surface Vg = gas flow rate W = precipitator rate parameter The precipitation rate parameter, W, is a function of particle size and resistivity, distribution of gas, back corona and re-entrainment, electrical field strength, particle charge, gas viscosity, and particle

density. Increasing the collecting area relative to gas velocity increases collection efficiency. Precipitators are operated at the maximum voltage potential, up to the point of arcing (sparking) for maximum efficiency. Allowable voltage potential (spark point) decreases with increasing inlet loading; therefore, for maximum mist removal, precipitators are arranged in parallel sets of two 90% units in series so the second unit will operate at maximum voltage potential and efficiency at all times. Acid mist precipitators are constructed of lead or plastic tubes supported between lead-lined or plastic tube-sheets and heads. Electrode wires are usually lead star wires. The system includes a power rectiformer to convert AC power to constant voltage DC at 6090kV, and control instrumentation to drive the voltage potential to a maximum level--up to the point of sparking. Two problems with lead precipitators led to the introduction of FRPplastic precipitators about 30 years ago: the lack of available lead burners and fatigue failure of the tubes over time, especially in systems with variable gas flow. The first plastic tube precipitator installation in North America started up at the Anaconda smelter in 1973. Plastic precipitators are FRP or polyethylene tubes supported in FRP tubesheets and heads. They use a liquid layer on the tube wall to provide the conductive ground, and are an acceptable alternative to lead, with the choice dependent on economics. Recent cost analysis indicates plastic precipitators to be lower in cost than lead units. Impurity scrubbing--purge treatment Impurities in the gas are removed by the gas saturator, gas cooler, and mist precipitator. For efficient scrubbing, liquor is routed from the least contaminated, mist precipitator, to the gas cooler, and finally to the gas saturator. For efficient fluoride removal, silica is usually added to the gas cooler solution producing a low vapour pressure silicon fluoride. Mercury, for the most part, will travel through the traditional gas cleaning system untouched and requires a separate treatment step. Mercury can be converted to a sulphide in the gas phase by addition of hydrogen sulphide and absorbed on activated carbon beds. It can also be converted to a chloride by scrubbing with a circulating hydrochloric acid stream in a packed tower, with the insoluble mercurous chloride recovered by filtration. Another technique converts the mercury to a sulphate in a pre-drying tower using 70-85% sulphuric acid. The sulphate is then converted to insoluble sulphide by the addition of thiosulphate and removed by filtration. Each of the systems will effectively remove mercury, with the chloride route preferred by most. Saturator liquor is usually maintained at a maximum of 3-5% undissolved solids, corresponding to a sulphuric acid content of 5-15% depending on the S[O.sub.3] level in the gas. To maintain the solids level in the saturator liquor, some plants with high inlet solids loadings

require the addition of make-up water to augment the water condensed from the gas. Excess saturator liquor (from water condensed from the gas and make-up water) is purged from the saturator and treated prior to reuse or disposal. The purge liquor is first air stripped of dissolved S[O.sub.2] in a packed stripping tower. Next lime is used to neutralise the acid and precipitate the impurities as calcium salts or hydroxides, and last it is filtered. In most cases the treated purge water is reused in the smelter or plant, but it can be discharged. Effects of inlet gas variables Each of the gas stream variables will have an effect on the gas cleaning system. A thorough understanding of the effects of gas stream variables is required to properly select, design, and operate gas cleaning system equipment. Gas flow and S[O.sub.2] strength The sizing and cost of the gas cleaning system is largely a direct function of the gas volume. For a particular smelting or acid production rate, a specific quantity of sulphur as S[O.sub.2] is routed to the sulphuric acid plant. As S[O.sub.2] gas strength increases, the gas volume and cost of the gas cleaning system decreases (see Fig. 3). Variation in gas flow (typical in a plant receiving gas from Pierce Smith converters) is handled effectively in the plant, but will cause accelerated fatigue failure of the lead tubes in the mist precipitator. Solid and halogen impurities Metals and metal salts will generally be converted to sulphates by reaction with the weak acid circulating liquor and be removed in the saturator, gas cooler, and mist precipitator. Vapour components, such as arsenic oxides, will condense and also be efficiently removed. As mentioned above, fluorides require silica addition to produce the low vapour pressure silicon fluoride for removal. The quantity and size distribution of the solids in the gas will affect the quantity of weak acid purge and the sizing of the purge treatment system. At high levels and small size, mist precipitator sizing will also increase. Sulphur trioxide Sulphur trioxide in the gas will be converted to sulphuric acid on contact with water in the gas saturator. The majority will form submicron mist particles by a phenomenon called "fog formation", and pass through the saturator and gas cooling systems to be removed in the mist precipitator. Care must be taken to design the mist

precipitators conservatively for the highest levels of acid mist and solids anticipated. Higher than design mist and solids loadings will back-off precipitator voltage, reducing efficiency. Nitrogen oxides Nitrogen oxides (formed in increasing levels by oxygen smelting) will pass through the gas cleaning system and must be removed in the contact section of the plant. Most will go through the plant to the stack. The rest, fortunately, will collect as nitrosyl-sulphuric acid in the high efficiency mist eliminators of the contact section absorption towers, where they can be easily removed and treated. Strong sulphuric acid contaminated with N[O.sub.x] has an enormous effect on the corrosion properties of the acid. Stainless steels are passivated, with corrosion rates dropping to near zero, while corrosion rates of carbon steel (used for product piping, storage tanks, and shipping cars) are increased by the order of 1/2 inch per year or greater. A number of acid plants over the past 25 years have experienced a dramatic increase in carbon steel corrosion. About 15 years ago, Kennecott materials group published the results of laboratory test work on N[O.sub.x] contaminated acid that confirmed and quantified plant operating experience. This article will be concluded in the July-August 2004 issue of Sulphur with a review of the unit operations in the contact section of the wet gas sulphuric acid plant. COPYRIGHT 2004 CRU Publishing Ltd. This material is published under license from the publisher through the Gale Group, Farmington Hills, Michigan. All inquiries regarding rights should be directed to the Gale Group.

Title: Lurgi environment business profits up 39% Date: 4/1/1997; Publication: Haznews; Lurgi Energie und Umwelt GmbH (LEU), the energy and environmental services subsidiary of the German engineering group, Lurgi, reported a pre-tax profit of DM36.2 million ($24.1 million) for the year ended 30th September, 1996. This was up by 38.7% compared with DM26.1 million ($18.2 million) in 1995 (see HAZNEWS, March 1996, p. 4), and was attributable to the high rate of turnover for the period, according to Lurgi's 1995/96 annual report. LEU contributed 28.6% of Lurgi's consolidated pre-tax profits of DM126.5 million. LEU's turnover in 1995/96 was up by 40.3% to DM901.0 million compared with DM642.0 million in 1994/95. The firm made the largest single contribution

(32.7%) by a subsidiary to Lurgi's consolidated turnover of DM2,751.8 million. The value of LEU's orders for 1995/96 rose by 22.0% to DM559.4 million, but "fell short of the budget" due to delayed contract award decisions for some large projects, said Lurgi. The firm's order backlog fell from DM1.8 million in 1994/95, to DM1.4 million in 1995/96, again due to high turnover, said Lurgi.

1993/94 Turnover Pre-tax profit Order inflow Order backlog 420.7 -66.4 905.0 2.7

1994/95 642.0 26.1 458.5 1.8

1995/96 901.0 36.2 559.4 1.4

LEU financial results (DM millions), 1993-96

Shortly after year-end, LEU was restructured to form Lurgi Umwelt GmbH and assumed the environmental activities of its sister firm, Lentjes AG. In turn, LEU's engineering activities were transferred to Lentjes. Both firms are subsidiaries of Metallgesellschaft, the German metals, energy, engineering and environmental services group, which aimed to eliminate the duplication of environmental business within its group (see HAZNEWS, November 1996, p. 5). According to the annual report, in 1995/96, the majority (80.0%) of the orders received by LEU were from Europe. However, Southeast Asia "is contributing an increasingly large proportion of the order inflow outside Europe; this is a trend which will continue in the medium term". Lurgi says it intends to expand its activities in this region. The European contracts were predominantly for waste water treatment sludge incineration plants and municipal waste incinerator flue gas cleaning plant. However, during the year, LEU was awarded a contract with Lurgi UK Ltd. to construct a thermal oxidation unit for the combustion of gaseous pollutants for the UK petrochemical company, BP Chemicals Ltd., at its Hull works, north-east England. The unit will have an hourly capacity of 175,000 m3, and is the second unit from Lurgi at the site (see HAZNEWS, August 1996, p. 8). LEU was also awarded two contracts to build incineration plants for liquid and gaseous wastes: one for Alusuisse-Lonza Holding AG, the Swiss aluminium and chemicals group, at its Visp site in southern Switzerland; and one for European Vinyl Corporation in Runcorn, northwest England. LEU also continued construction work during the year on a 30,000 tonnes-per-year hazardous waste incineration plant, in Izmit, west Turkey (see HAZNEWS, March 1995, p. 4). The plant is due to go

on stream in 1997. In 1995/96, LEU received 10 orders for wet-type electrostatic precipitators, most of which were supplied to nonEuropean countries. The orders included a scrubbing and cooling system for mercury removal at a copper smelter in Thailand, and a DM10 million contract from Union Miniere, the Belgian mining and smelting group, for pollution control equipment at its copper-lead smelter in Hoboken, north Belgium (see HAZNEWS, November 1996, p. 9). COPYRIGHT 1997 Profitastral Ltd. This material is published under license from the publisher through the Gale Group, Farmington Hills, Michigan. All inquiries regarding rights should be directed to the Gale Group.

Title: Smelter acid takes on sulphur burning.(Huntsman Tioxide to overhaul plant)(Company Business and Marketing)(Company Operations)(Company Profile) Date: 7/1/2000; Publication: Sulphur; Author: Cunningham, Chris A leading sulphur burning site in the north of England has made the switch to merchant acid supplies as part of a major investment in cost saving and environmental compliance. Chris Cunningham reports on a key development in the emerging market for 'premium' grade sulphuric acid. Huntsman Tioxide plans to spend [pound]30 million ($45 million) on an overhaul of its Grimsby pigment plant and on the supply of raw materials to the plant. The driving forces behind this major project at Tioxide Grimsby are operating cost and environmental compliance. Many options were available to Huntsman in its selection of the best route to meet a range of targets. The special interest in this case lies in a full scale switch from sulphuric acid production at one of the UK's major sulphur-burning sites to total reliance on imports of merchant acid. Whilst on the face of it this is poor news for the European sulphur trade, Huntsman's scheme does mean the preservation of at least one leading site for the sulphate route to titanium dioxide production, at a time when the alternative, chloride route has been picking up most of the crumbs of new demand for white pigment (see Sulphur 268 p15). Perhaps more significant is that -- under a long-term sulphuric acid supply agreement with ICI Sulphur Chemicals -- Huntsman Tioxide will be importing acid generated in copper smelters. Until comparatively recently the level of contaminants in commercial 'fatal' acid supplies, in

particular the mercury content of acid captured from a copper smelter, would have been unacceptable under European legislation. Now the emergence of 'premium' smelter acid supplies indicates direct competition between acid and brimstone -- at least in greenfield developments or in major refits at acid-consuming sites in the tightlypacked collection of nations around the North Sea. With annual production of around 250,000 tonnes of acid, closure of its three sulphur burners means that Huntsman Tioxide will remove about 80,000 tonnes of brimstone from the market North West Europe. Sources of acid for Huntsman will be copper smelters run by Outokumpu at Harjavaalta in Finland, and Boliden in Sweden, which is commissioning new premium acid capacity at its Ronnskjara plant. BGT Chemtrade will handle supplies of acid from Boliden under an existing acid-removal contract, whilst Chemtrade's Swiss neighbour Chemtrans will control movement of acid from Outokumpu to the dockside serving Huntsman's Grimsby site. Whatever selection had been made for the Tioxide site, changes were certainly needed. Adaptations to the site over time had left three sulphur burners, one double absorption unit and two configured for single absorption. The three units supplied process steam from three boilers, supplemented by further boilers firing on heavy fuel oil. In the early 1990s, [SO.sub.2] emissions from the site stood at 9000 t/y, Process improvements have cut emission levels back to 3000 t/y, says site operations manager Colin Deas. The eventual target is a further cut to less than 700 t/y. With a new European limit on sulphur in heavy fuel oil -- no more than one per cent -- due to come into force at the end of 2002, and single absorption acid production going the same way, the best option for the Grimsby plant to meet tightening environmental standards is to discard its major sources of atmospheric [SO.sub.2] This would mean losing the steam-raising bonus of sulphur burning. However, according to Mr Deas, a raft of changes at the Grimsby site will mean cheaper operations. Huntsman has signed a 10-year agreement with the combined heat and power (CHP) wing of National Power under which National Power Cogen will build and operate a CHP plant to cover all of the site's energy needs. The gas-fired CHP system is scheduled for completion in late 2001. The ability of smelting companies to overcome inherent problems of impurities in their acid products -- mercury content in particular -- has been a key enabling factor in the decision to switch from sulphur burning to acid imports at Grimsby. "We didn't have to do this," says Mr Deas. "We could have invested in a big new sulphur burner." But acid quality and local opportunities for the management of acid supplies swung the final decision. "Shutting down a sulphur burner is a once-ina-lifetime decision," says Colin Deas, site operations manager at

Grimsby for Huntsman Tioxide. "The quality of the material [sulphuric acid] has to be right." ICI contracted the logistics for supplying acid to the Tioxide plant to Simon Storage. Simon is an independent bulk storage operator with plenty of experience handling acid through Immingham and Teesside on England's east coast. However, the landing point for Scandinavian acid destined for Huntsman's Grimsby plant is currently committed to elemental sulphur. According to a 10-year deal with ICI, Simon Storage will convert one of two sulphur storage tanks at the Pan American Sulphur Co (Pasco) terminal in Immingham to hold 96 per cent sulphuric acid. "The other tank will be put to alternative use," Simon Storage's marketing director, Peter Rendell, told Sulphur. The other component of acid delivery will be construction of a stainless steel pipeline which will follow an existing wayleave alongside a rail track to the Huntsman site. Immingham Storage, the Simon subsidiary which operates the Pasco terminal, will fully fund the 10-year project and, says Mr Rendell, will earn operating income by "charging a fee to reflect our capital investment" in the scheme. Details of the fee scheme are confidential, but conversion of the existing sulphur storage tank and installation of the acidcarrying pipeline are expected to begin as soon as the project receives local planning permission, with completion scheduled for October 2001. So why convert a sulphur storage tank to take acid? "There's no realistic opportunity to build a new acid tank [closer to the Huntsman site]," says Mr Rendell. In particular, there is no satisfactory opportunity for deepwater unloading between Immingham and Grimsby. "With a well-established infrastructure, two good jetties and a tank farm, it makes sense to convert a tank that's right for the task. The volume of acid required is substantial and we're confident that we can turn the ships around." "It's a simple scheme to add," says ICI Sulphur Chemicals' business manager, Keith Metcalfe. "And it runs all the way into the Tioxide plant," he adds, pointing out that an element of the scheme's environmental advances will be removal of sulphur-laden trucks from the roads between Immingham and Grimsby. The principal advantage in supplying acid with lower levels of mercury is a matter of environmental regulation rather than potential level of product contamination. For instance, delivery to Kemira's Pernis fertilizer plant has had to comply with a local requirement which assumes that all of the hazardous constituents of a consignment of acid would be discharged to the local river following waste water treatment. At 0.1 ppm Hg, compliance with best environmental practice is an easier matter than with smelter acid of standard quality. Outokumpu has been producing premium grade acid at its Harjavalta smelter in Finland for several years. With the more recent startup of

premium grade acid production at Norddeutsche Affmerie (NA) in Hamburg, and the current commissioning of premium production at Boliden's Ronnskjar smelter, the elements of a competitive market in lowmercury acid are already in place. Whilst the future shape of the market may be difficult to predict, according to Jan van Saaze, vice president of trading operations at BCT Chemtrade, what is clear, he says, is that premium grade sulphuric acid does not necessarily attract a premium price. For the future, "If you want to supply [acid], you need quality," he told Sulphur. Smelter companies who want to continue producing a lower grade of acid may find a market "only if they ship it far away," he says. COPYRIGHT 2000 CRU Publishing Ltd. This material is published under license from the publisher through the Gale Group, Farmington Hills, Michigan. All inquiries regarding rights should be directed to the Gale Group.

Title: Sulphur.(world sulfur supply and trade)(Statistical Data Included) Date: 1/1/2001; Publication: Sulphur; The range of destinations for Canadian tonnes retrenched into key markets as the year wore to an end. The booming Chinese market suffered a slow-down in demand for Vancouver shipments. Opportunities in North Africa should be on the rise for Canadian shippers during 2001, although the current regional squeeze on prices may present problems for price negotiations. Arabian Gulf supplies -- more than ever the prime international marker for trade -- faced severe pricing pressure, with the Jordanian decision to switch to low-priced Iraqi product adding to the tension. Major markets, including India's, were holding off in anticipation of first quarter contract negotiations. China's customs authorities released details of the running total of brimstone imports. Some 2.31 million tonnes reached Chinese ports in the first nine months of 2000. Of that total, Canadian suppliers accounted for 1.48 million tonnes, 350,000 tonnes were from Japan, 140,000 tonnes from South Korea, and 270,000 tonnes from Iran. Slower than usual Stocks at the main receiving ports stood at an estimated 400-500,000 tonnes, which accounted for slower than usual movement during November when Canadian shipments were little more than 100,000

tonnes (see Table 3). The total into China during December was expected to be in the region of 150,000 tonnes. Canadian offers for first quarter shipments were reported at $48-49/t cfr, but bids in the mid-$40s/t with credit were emerging. Reluctant An unconfirmed report suggested that more than half of China's pyrites producers have become loss-making enterprises. During the last two years, the Chinese government has been reluctant to step in on behalf of companies in the red, and it remains to be seen whether the spectre of protectionist measures in support of the pyrites producers will hit trade in elemental sulphur. The other factor affecting future demand in China is the rising level in domestic recovered sulphur. One major producer of sulphuric acid has recently switched to supplies from local petrochemicals companies (see Industry News, p11) as part of an expansion programme, although the switch was from pyrites burning. First-quarter price negotiations with Florida phosphate producers were expected to start in mid-December, with the likelihood that there would be no settlement before the start of the new year. Some Canadian tonnes loaded in Vancouver arrived in the US Gulf Coast during November, taking advantage of the tighter availability left by the closure of the Main Pass Frasch mine. Whether this will be a factor affecting the tight position in Tampa remains to be seen. The Big Bend Transfer joint venture between phosphate producers and suppliers to build a sulphur remelting terminal made progress through local permitting procedures, but is certain not to make an impact on supplies into Florida during 2001. As if mounting pressure from suppliers' price negotiations was not enough, US phosphate producers face further pressure from the transport sector. Rail dispatches from Canada were set for an increase early in 2001, the amount of the hike depending on whether rail cars are owned or leased by either the shipper or buyer, or are the property of the rail companies. Price drama There was more talk than action in the Abu Dhabi sulphur business, as the moratorium on loading during port reconstruction and upgrading continued into December. But product discussions from a key pricesetting supplier were nonetheless dramatic. The word from Adnoc and Adgas indicated a level of $28-29/t fob Ruwais. This indicates new contract price levels slipping into the mid$20s/t fob and is an 18-month low for the Arabian Gulf. The companies had set their prices some $5/t fob higher during November (although they were unable actually to supply any product). Adnoc's discussions with at least one of its major outlets, Jordan, will

draw much interest in the light of Jordan Phosphate Mines' earlier decision to strike a deal with Iraqi sulphur miners for all of its supplies for 2001. Hydro Agri's decision during December to pull the plug on its projected Hydro Agri Jordan joint venture will not leave much room for Arabian Gulf loaders. Playing catch-up Saudi Aramco, another major supplier to Jordan, found itself in a similar situation and new business will see Jubail exports playing catch-up to allow for significant cuts in established contract supplies. One such contract is expected to be with a South African buyer. Aramco's discussions with traders on first quarter pricing will for the first time include Interacid; as reported previously, the Swiss-based trader is expected to handle shipments around the Atlantic rim, with Brazil a likely candidate for much of its Saudi tonnage. The start of December saw plenty of activity around the Mediterranean. The outcome of all of this was downward pressure on brimstone prices. In Italy, Prai was awarded a contract to move all of the formed product produced in Sicily's refineries, expanding its position from an earlier contract solely with Erg refineries. The deal covers internal and external markets and was quickly into its stride with supplies to Enichem and Nuova Solmine on the mainland at around $50/t on a 90 days credit basis, with further domestic shipments to follow. If Prai's operations follow established markets, their destinations outside Italy will chiefly include Greece, Croatia and Spain. Early opportunity An order for up to 15,000 tonnes from Fertiberiak in mid-December was thought to be an early export opportunity for Prai in its new, bigger role, although the Spanish fertilizer outfit was also likely to be negotiating over the load with its appointed contract suppliers. Global warming was also playing a part in heating up the Mediterranean market. Barge routes used for brimstone from Russia and Ukraine remained open beyond expectations, hence further supplies from the former Soviet Union were expected to bump up supply levels. In Russia, the future supply situation from Astrakhangazprom (AGP) awaited clarification. The company is believed to be close to a decision on its next major forming installation, which will add further premium product to the markets AGP has so successfully developed during 2000. Similarly, details of the new supply contract between AGP and ICEC are still to emerge. ICEC is expected to handle 500,000 Russian tonnes in the latter three quarters of this year, but it is understood that there may be geographical limitations on these shipments with unconfirmed reports that they will be destined for the North African phosphates industry.

In Israel, the Rotem Amfert phosphates operation announced an expansion of its sulphur receiving terminal at Ashdod. The company, which has extensive holdings in Europe, will provide a deeper draught for incoming vessels together with more warehousing capacity. Whether this will be good news for Canadian exporters remains to be seen. Vancouver distribution lost much of its dominance of Israeli supplies to Russian exports during 2000. Tender hints Activity in the Indian market was relatively low in response to expected further falls in Arabian Gulf prices. Price indications in early December came from a tender by CFL for 8,000 tonnes, delivery due in the second week of January. Agents were looking at the mid-high $40s/t cfr, whilst CFL's thoughts were believed to lie in the low $40s/t. An early December shipment of 17,000 tonnes from Iran to Hindustan Lever Chemicals was priced at $42-43/t cfr, whilst a 40,000 tonne consignment from the Arabian Gulf arriving at Oswal Chemicals and Fertilizers in Paradip landed at $4141.50/t cfr. An 8,000 tonne consignment with Tradeline ex-Bahrain was destined for several buyers at $43/t cif with 90 days' credit. Small crushed lump operations in India were setting a mark around $33.50/t cfr. Sulphuric acid German copper giant Norddeutsche Affinerie has begun shipments of acid following a turnaround which has raised capacity to 1.3 million t/y. The first loads out of Hamburg were reported destined for the UK and Belgium. Extra capacity at Hamburg and from expansion at leading Scandinavian suppliers is likely to create a severe over-supply situation in Europe early in 2001. Producers of non-premium grade acid are likely to have to look for farflung outlets to move their product in future. A note of relief for the acid market came with news from Bulgaria that Agropolychim is close to completing 24,000 tonnes of new acid storage at Devnya, although the company has put off construction of new phosacid storage. Also in Bulgaria, the joint venture between local copper smelter Union Miniere and Oiltanking of Germany to build a sulphuric acid export terminal at Vama expects the operation to start up in the middle of this year. Storage capacity there will be 22,000 tonnes.
International price indications ($/t) [*]

Dry bulk sulphur fob Vancouver 38-40 33-37 33-36 33-36 fob Middle East 32-33 32-33 32-33 27-35 c&f India 48-53 46-50 43-45 41-43 c&f North Africa 52-53 52-53 43-47 45 c&f Med Europe 52-53 52-53 49-52 49-51 Liquid sulphur ex-vessel NW Europe 60-65 60-65 60-65 58-63 Sulphuric acid cfr Mediterranean 5-15 5-15 5-15 15-20 ex-term Tampa, Fl ($/st) 15-17 15-17 15-17 17-22 Notes: (*.)end of month prices Sources: Fertilizer Week, Sulphur US sulphur spot proce indications Oct Nov 2000 2000 fob Tampa, FI NM NM del Houston, Tx (recovered) NM NM Note: (*.)end of month prices Source: Fertilizer Markets Candian sulphur Shipments ex-Vancouver '000 tonnes Jan-Nov 2000 Nov 2000 Argentina 39.9 0 Australia 326.9 21.7 Brazil 959.3 140.9 Chile 36.1 0 China 1649.6 106.4 Cuba 157.2 27.5 Guatemala 7.9 0 Indonesia 71.8 0 Israel 216.8 0 Mexico 288.5 0 Morocco 185.2 0 New Caledonia 5.4 5.4 New Zealand 230.0 29.1 Philippines 88.4 0 Senegal 97.8 0 South Africa 421.8 70.0 Uruguay 33.0 0 USA 41.1 41.1 Vietnam 68.6 23.3 Total 4924.4 465.3 Jubail sulphur shipments Q3 2000 '000 tonnes Jul Aug Sep Total Morocco 66.6 67.7 60.0 194.3 Jordan 59.0 25.0 31.0 115.0 India 40.6 87.4 0 128.0 S Africa 0 26.3 64.5 90.8 Malaysia 0 12.0 0 12.0 Thailand 22.0 0 0 22.0 Total 188.2 218.4 155.5 562.1

Jul 2000

Aug 2000

Sep 2000

Oct 2000

Nov 2000 33-36 30-31 41-46 45 48-50 58-63 15-20 17-22 ($/lt) [*]

COPYRIGHT 2001 CRU Publishing Ltd.

This material is published under license from the publisher through the Gale Group, Farmington Hills, Michigan. All inquiries regarding rights should be directed to the Gale Group.

Title: Mist eliminators: guardians of the sulphuric acid plant's fabric, performance and economics. Date: 1/1/1990; Publication: Sulphur; Mist eliminators: guardians of the sulphuric acid plant's fabric, performance and economics In the contact process for sulphuric acid, the gas entering the plant (air in the case of a sulphur-burning plant, air plus sulphur dioxide ([SO.sub.2]) in a spent-acid or metallurgical plant) is dried by contact with 92-98% [H.sub.2][SO.sub.4]. Sulphur dioxide, present in the feed gas in metallurgical and spent-acid plants or obtained by burning sulphur in sulphur-based plants, is oxidized by atmospheric oxygen to sulphur trioxide ([SO.sub.3]) in contact with a heterogeneous catalyst in a reactor vessel known as a converter. Because the reaction produces a substantial amount of heat, the catalyst mass is divided into four or, occassionally, five sections known as beds or passes, and the gas emerging from each is cooled. The sulphur trioxide is then absorbed from the gas stream into recirculating 98.5% sulphuric acid in one or more absorption vessels. In most plants, these are packed towers irrigated from the top with sulphuric acid; the gas is introduced at the bottom and flows upwards in countercurrent with the descending acid stream. According to the degree of conversion required, there are two types of contact plant. In the "conventional" or single-absorption process there is one absorption tower after the final catalyst pass; in the more efficient double-absorption process there is an intermediate absorption tower after the second or third catalyst pass as well. The sulphur trioxide reacts with the sulphuric acid to form disulphuric acid, which is converted back to sulphuric acid by reaction with water, as shown in the equations below. [H.sub.2SO.sub.4 + SO.sub.3] = [H.sub.2S.sub.2.O.7] [H.sub.2S.sub.2O.sub.7 + H.sub.2O = [2H.sub.2SO.sub.4] How mist forms The main reason for adopting a recirculatory system using highly concentrated sulphuric acid as the absorption medium, rather than a "once-through" system using water, is to minimize the formation of a

troublesome aerosol of extremely fine liquid sulphuric acid particles known as acid mist. Mist is distinct from acid spray, which is formed in the absorption tower or towers by the purely physical process of aspiration into the gas stream of liquid droplets; mist results, in fact, not from the contact of the sulphur trioxide with liquid water but from the condensation of sulphuric acid from the vapour phase after it has been formed by reaction of sulphur trioxide with water vapour. Mist formation is therefore governed by the partial pressure of water vapour over the liquid absorption medium, and that is inversely proportional to the concentration of the sulphuric acid in the liquid. Were water to be used as the absorbing medium, its vapour pressure would be high enough to cause a very substantial amount of acid mist in the absorption tower. This effect would also be exacerbated because the reaction between sulphur dioxide and water is very violent indeed, producing a massive amount of heat, which would drive off even more moisture into the gas space within the absorption towers. Using concentrated sulphuric acid as the absorbing medium and then adding water to the acid circuit outside the absorption towers greatly moderates the heat output in the absorbers, although the heat output is still very substantial. By definition, mist particles are less than 10 [mu]m in diameter, and (depending on how and under what circumstances they are formed) a sizeable proportion may be smaller than 1 [mu]m in diameter. Acid spray, on the other hand, has particles greater than 10 [mu]m[sup.2]. The distinction is important, because the larger spray particles coalesce quite readily and can therefore be arrested quite easily; mist, on the other hand, is extremely difficult to separate from the gas stream and tends to be carried through the remaining parts of the plant, where it can cause accelerated corrosion, and out into the atmosphere, where it is not only a very harmful and objectionable pollutant but also represents a loss of product. The great fineness of the particles of acid mist is due to the rapidity with which they are formed. Sulphuric acid is a very non-volatile liquid (it boils at about 330[degrees]C), so it has a very low vapour pressure under the conditions prevailing in the absorption section of a sulphuric acid plant. It therefore condenses almost instantaneously, faster than it can be removed by mass transfer in the conventional packed-tower absorber. As the previous equations show, sulphur trioxide will react with 100% sulphuric acid, over which the partial pressure of water vapour is effectively zero; but this would not actually eliminate mist entirely. That is because the drying process, in which the combustion air for a sulphur-based plant or the acid gas feed in a metallurgical or spentacid plant is contacted with sulphuric acid, is not 100% efficient. Furthermore, in a sulphur-burning plant, if the sulphur is not entirely free of organic impurities, a certain amount of moisture will be formed

during combustion. Thus sulphuric acid will form in the process gas as it passes from the hot catalyst stages to the cooler parts of the plant and will therefore be present in the process gas when it enters the absorption section, irrespective of the concentration of the absorber acid. And the equilibrium vapour pressure of sulphur trioxide over sulphuric acid increases steeply at concentrations above about 99%, so that the absorption efficiency declines in proportion. From the environmental point of view, there is little to choose between sulphur trioxide and acid mist when they are emitted from the exhaust stack, since the former turns very rapidly into the latter. The concentration of 98.5-98.75% used in most plants represents the best and most efficient compromise between water vapour pressure and residual sulphur trioxide vapour pressure (Fig. 1)[1]. Since the catalytic oxidation of sulphur dioxide requires a temperature of 390[degrees]C or more, the process gas leaving the converter system has to be cooled, usually to a temperature of about 180220[degrees]C, before it is admitted to the absorber. It is essential to ensure that the wall temperature in the gas coolers never drops below the acid dewpoint - about 110-160[degrees]C, depending on the gas composition. As mentioned, a substantial amount of heat is generated from the absorption of sulphur trioxide and the formation of sulphuric acid, and the acid temperature rises in consequence by a margin which depends on the acid circulation rate. The temperature has to be controlled by indirect cooling of the circulating acid; the upper limit is determined more by the corrosion characteristics of the process considerations. Until a few years ago the maximum allowable temperature was limited to about 90[degrees]C, but with the introduction of anodic passivation and, more recently, of corrosion-resistant alloys such as SX and Saramet, higher absorption temperatures (up to 220[degrees]C) are now being used to increase the grade of the heat withdrawn through the coolers so that it can be used in raising steam or in process heating applications. As in any mass transfer system, uniform acid and gas distribution in the absorber are critical factors for efficient sulphur trioxide absorption, but so is maintaining concentration of the absorber acid at the optimum value. Water is, of course, absorbed into the acid in the dryer, and in a metallurgical plant, where the process gas is saturated in moisture, the entire process water requirement may be supplied in this way. Otherwise the acid concentration is controlled by introducing water into the acid circuit at a rate controlled by a concentration measuring device. The attainable [SO.sub.3] absorption efficiency is generally above 99.9%. However efficiently the feed gas is dried and however carefully optimum conditions for sulphur trioxide absorption are maintained, it is impossible to safeguard entirely against mist formation, especially

during start-up or shut-down. Plants where there is an oleum tower upstream of the intermediate absorber are even more susceptible because the process gas may be overcooled. In such cases, mist may already have formed before the gas enters the intermediate absorber. Ordinary wire mesh spray separators have no effect on these mists, so special mist eliminators are necessary to remove them from the gas stream and thus to avoid corrosion in the downstream heat exchangers and to diminish mist emission from the final absorber[3]. Collection mechanisms The initial object of any device for separating entrained sulphuric acid droplets and mists from the process gas stream is to make the individual particles coalesce into a continuous liquid film on a solid surface, from which it can drain away. There are several mechanisms by which, alone or in combination according to the nature of the mist involved, this can take place. They include inertial impaction, direct interception, Brownian movement, and electrostatic attraction. Particles larger than 3 [mu]m are relatively massive, and advantage can be taken of their momentum to collect them by inertial impaction. When the gas stream encounters an obstruction such as a fibre, its path or "streamline" is deflected round the obstruction, but the momentum of the +3 [mu]m particles carries them onwards so that they collide with the fibre and are arrested. Particles between 1 [mu]m and 3 [mu]m are collected by direct interception. They are light enough to follow the deflected gas streamline but, when they pass close enough to a fibre, they are also light enough to be attracted to it by weak interactive forces and are once again collected. A particle of diameter 1.0 micron, for example, is collected if it passes less than 0.5 micron from a fibre. Extremely fine particles (less than 1.0 [mu]m) are small enough to exhibit random Brownian movement, caused by collisions with gas molecules. This may be in the direction of, opposite to or across the direction of the gas flow; in the last case when movement is across the direction of the gas flow, a particle following the gas streamline may be displaced laterally by sufficient extent tent to collide or be captured by the fibre. Brownian movement increases as the particle size decreases: thus a 0.1 [mu]m particle will have about five times the Brownian movement of a 1 [mu]m particle, greatly increasing the probability of collision with a fibre. These collection mechanisms are illustrated in Figure 2[4]. In each case, collection results from impingement due to the motion of the particles, and separators designed around them are known collectively as impingement separators.

The final mechanism, electrostatic attraction, comes into play when the gas stream is passed through an electric field between charged electrodes. Electrostatic charges are induced on the particles, which are attracted in consequence to the oppositely charged electrode. Whereas inertial impaction relies on the motion of the gas stream for its effect, the other mechanisms function better at low gas velocities. This has an important influence on the scale and design of practical entrainment separation devices making use of them. Types of separator Three main types of entrainment separator are used in sulphuric acid plants today. Mesh pad separators are porous blankets of metal wire or plastic filaments in which both inertial impaction and interception occur to coalesce droplets. Usually the mesh pad is installed horizontally in a support ring inside a vessel sandwiched between a bottom support and a top retaining grid. In general, wire mesh pads consist of a bed, 10-15 cm (4-6 inches) deep, of fine-diameter wires (0.125-0.25 mm; 0.0050.01 in) interlocked by a knitting operation to form a wire mesh pad with a high free volume (94-95%) to allow gas to pass through at relatively high velocity and low pressure drop. As liquid collects on the wires, droplets grow in size, run to the bottom of the pad and drain by gravity. The gas velocity through the mesh must be kept below the value at which significant re-entrainment occurs. Several factors govern the maximum allowable gas velocity: densities of the gas and liquid, the surface tension of the liquid, the viscosity of the liquid, the specific wire surface area of the wire mesh, the liquid-entrainment loading, and the suspended solids content. Mesh pads are generally designed to remove liquid particles above 5 [mu]m in diameter. In some plants, knitted wire or fibre mesh coalescers are installed in front of the mesh pad to coalesce finer particles i.e. below 5 [mu]m. Fibre bed mist eliminators (also known as fibre filter mist eliminators) come in a variety of fibre densities, operating at various velocities and efficiencies. They are similar to mesh filters except that the filaments are extremely fine fibres, randomly but very closely spaced. Commonly this type of mist eliminator is constructed in a cylindrical form (candle filter) between two concentric open mesh bed formers, and hangs from or stands on a horizontal tube sheet, but it can also be constructed from flat panels, which are mounted vertically in a polygonal configuration. The fibre bed is either packed or wound, fabricated from glass, ceramic, plastic or metal fibre in bulk-staple (loose fibres) or roving (rope) form [5]. Because of the vertical disposition, liquid accumulating on the fibres is moved horizontally through the fibre bed by the drag of the gases and drains by gravity down the downstream side to the bottom of the fibre

bed, whence it is collected and returned to the process. The collection mechanism (inertial impaction and direct interception) is similar to that of the mesh pad for larger particles i.e. down to about 1 [mu]m in diameter, but the real advantage of fibre bed mist eliminators is that they also collect fine mist particles by the Brownian movement collection mechanism. Since Brownian movement is appreciable for all particles below 3 [mu]m, reducing the gas velocity increases the efficiency with which they are collected, and high pressure drops are not required for high collection efficiencies. The capital cost for fibre bed units decreases as higher pressure drops are utilized since fewer elements are required at higher gas velocities, but additional pressure drop increases power costs. Electrostatic precipitators are very efficient but are also very costly in comparison with impingement devices on account of their large size. Their operating principle has been described recently in Sulphur [6]. Selection of mist eliminators The type of mist eliminator that is most suitable depends on the nature of the mist, especially its particle size. For example, inertial impaction separators are best for trapping particles above 1-3 [mu]m, while submicron particles are more efficiently trapped by diffusion (Brownian movement) separators. Solid particles present in the gas stream will, of course, also be removed by mist eliminators, to an extent that depends on the nature of the solids and the type of mist eliminator. This may cause little or no problem if the solid is soluble in the collected liquid, since it merely drains away, but if it is not the solid may accumulate on the collecting surfaces and create a serious plugging problem. Problems encountered with mist eliminators In sulphuric acid plants, plugging is normally caused by a build up of iron sulphate, produced as a result of corrosion upstream. Excessive sulphate is usually the result of water in the system. A second cause of plugging occasionally encountered is sublimed sulphur, which normally results from improper operation of the sulphur burner, typically during shutdown. These plugging problems are usually rectified by removing the mist eliminator from the tower and washing with water to dissolve the sulphate deposits. Sublimed sulphur is normally removed by washing the elements with a 0.5% sodium sulphide ([Na.sub.2S]) solution. Before the sodium sulphide solution is used, the elements must be thoroughly neutralized with soda ash or equivalent since

sodium sulphide in an acidic environment will generate toxic hydrogen sulphide gas. Furthermore, frequent washings with an alkaline solution can damage glass fibre. A second problem area associated with mist eliminators in acid plants is the entrainment of large particles as a result of excessive inlet loadings or gas velocities, drain plugging, or gas bypassing. When a reentrainment problem is indicated, the first step should be to review the plant operations. Particular attention should be given to gas flow rates and other conditions that could potentially generate excessive mist loadings. The next step should be a physical inspection of the unit. Bypassing the mist eliminator can often be detected by disturbances of the sulphate deposits, which are normally seen on the tube sheet. Liquid seals should be inspected to ensure that they are in good operating condition. A third problem is a persistent visible plume from final towers. This is often caused by unabsorbed [SO.sub.3] or small acid mist particles. If the plume is a result of [SO.sub.3] slippage, changes in the operation of the absorption tower and/or tower maintenance are required. In an acid plant that is operating correctly, [SO.sub.3] vapour loadings are generally 10 [mg/m.sup.3] (actual). When plume problems are caused by acid mist, two basic causes should be investigated. One of these is the presence of excessively high inlet loadings which can be determined by either sampling or monitoring of the drainage rate from the mist eliminator. With high velocity mist eliminators, a change in particle size distribution can also affect performance. If inlet mist and [SO.sub.3] vapour loadings are normal, the problem probably lies within the mist eliminator itself. Occasionally, persistent plume problems are the result of excessive nitre (nitrosyl pyrosulphate/bisulphate), which causes small mist particles. The nitre level in acid collected from the mist eliminator is typically less than 500 parts/million. Higher nitre levels can result from operating a sulphur burner at excessive temperatures causing nitrogen fixation. This problem can usually be controlled by isolating the mist eliminator drainage where the nitre tends to concentrate. There is obviously no single design of mist eliminator that will offer the optimum in collection efficiency, pressure drop and resistance to plugging for all applications. Selection of the optimum mist eliminator design is a compromise of capital and operating costs along with specific performance characteristics. It has already been mentioned that mist control is normally required in an acid plant when the gas stream is cooler than the acid dewpoint. Typical locations include the drying and absorption towers. Exit gases from any drying or absorption tower can contain large [H.sub.2 SO.sub.4] mist droplets (mechanical entrainment), small mist droplets (condensation and/or reaction of [SO.sub.3] vapour with water) as well

as [H.sub.2 SO.sub.4/SO.sub.3] vapour (equilibrium content or incomplete absorption). Mist eliminators for drying towers The severity of the mist formation problem in drying towers depends mainly on the concentration of the drying acid. The drying towers of modern sulphur-burning plants are generally run on 98% acid, whereas in older sulphur-burning plants and cold-gas plants operating on spent acid or metallurgical gases 92% drying acid is more common. In plants running on 98% entrained spray ([is greater than 10 [mu]m]) perhaps 175-350 [mg/m.sup.3] - is more significant the submicron mist, though some is formed. In plants running on 92% acid, mist formation is more severe. Sulphur dioxide, weak sulphuric acid mist, and some insoluble solids are present in the water-saturated gas stream. The severity of the duty is primarily determined by the design and operation of the gas purification system upstream of the drying tower. Sulphuric acid loading and particle size distribution to the drying tower can range from 175-3,500 [mg/m.sup.3] (actual) and particle size from 0.6-10 [mu]m. In spent acid and especially in metallurgical plants, there is potential for solids to be present in the gas stream. Either mesh pads or impaction type fibre-bed mist eliminators are normally used in drying towers. Fibre bed mist eliminators are not used in many metallurgical plant drying towers because of the potential for plugging. Mist eliminators for primary absorption towers The primary absorption tower means the first absorption tower after the converter. In a double-absorption plant, it is therefore the intermediate absorption tower, whereas in a single-absorption process it is the one and only absorption tower. The mist eliminator collects large acid mist droplets formed by mechanical carryover from the packed tower and small aerosol droplets formed by reaction/condensation in the bottom of the tower. Typical mist loadings are 500-1,750 [mg/m.sup.3] with 175-350 [mg/m.sup.3] as spray and the rest as mist. In plants which do not produce oleum, the typical particle size is 1-2 [mu]m. In oleum-producing plants, the total acid loading is similar but the particle size is smaller, typically 0.6 [mu]m. Mist eliminators are used in primary (interpass) absorption towers to protect the downstream cold heat exchanger from corrosion. The problem lies in achieving high efficiency without high pressure loss, which leads to a drop in overall plant production rate, yet without resorting to a large number of filters, leading to an "oversize" and

expensive absorption tower. Thus a balance is struck between protection, production, capital and running cost. In an intermediate absorption tower the main purpose of mist control is to minimize acid carryover into the downstream equipment, especially the heat exchangers, where it would cause corrosion. In singleabsorption plants the mist eliminators are mainly for emission control. The most effective mist eliminator equipment for this service is Brownian fibre bed mist eliminators. Some conventional plants have add-on interpass systems built onto their plant for sulphur dioxide emission control. In these cases, existing mist eliminators should be evaluated to make sure the add-on equipment is properly protected from acid mist corrosion. Mist eliminators for final absorption towers The final absorption tower is the second absorption tower in a double absorption plant. As in the primary absorption tower, large acid mist droplets formed by mechanical carryover from the packed tower and a limited quantity of small aerosol droplets formed by reaction/condensation in the bottom of the tower are collected by the mist eliminator. The acid mist loading is 175-350 [mg/m.sup.3] (actual) with a typical particle size of 2-3 [mu]m. Mist eliminators are required for final absorption towers in order to comply with stipulations for air control e.g. acid mist emissions and opacity. Individual country requirements can determine the selected mist eliminator type. Mesh pads and fibre bed mist eliminators are used for this service. Mist eliminators for ammonia scrub systems In some older plants, ammonia scrubbers are installed after single absorption plants to remove sulphur dioxide. The mist eliminator, which is usually a Brownian fibre bed mist eliminator, collects ammonium salts [Mathematical Expression Omitted] [NH.sub.4 HSO.sub.3], etc. formed in the tail gas scrubber, as well as sulphuric acid mist carried over from the absorbing tower or formed from unabsorbed sulphur trioxide vapour. Reaction of ammonia and sulphur dioxide forms very small particles which are very difficult to collect and, if uncontrolled, cause especially severe stack opacity. Installation Availability of space can cause serious constraints on mist eliminator selection. Provided that the existing equipment has sufficient room to house the mist eliminator, the total installation cost involved will only be a fraction of the total cost for a new, separate vessel with a mist

eliminator. As the majority of mist eliminators are relatively low pressure drop devices, it is essential to provide either sufficient space in the vessel or internal baffles to ensure uniform gas flow to the inlet and outlet of the mist eliminator. If no suitable vessel exists to house the mist eliminator, a vessel must be designed and purchased either from a mist eliminator vendor or from a vessel manufacturer. The vessel can be designed by the mist eliminator vendor or the customer. In the case of electrostatic separators, the housing is part of the installation and will be equipped by the mist eliminator manufacturer. Fibre bed mist eliminators can sometimes be installed in existing equipment but, in many cases, the special size and shape considerations for the equipment requires a vessel which will be supplied as part of the purchase package. Monsanto Enviro-Chem The complete line of Monsanto Enviro-Chem mist eliminators (known by many people in the industry by their tradename, Brink(R) mist eliminators or simply Brinks) operate in a similar manner. Gases containing mist particles are directed horizontally through a fibre bed (see Figure 3). Particles collect on individual fibres of the bed, coalesce to form liquid films which are then moved through the bed by the gas flow, and finally drain off the downstream face of the bed. The ES Energy Saver fibre bed mist eliminator is Monsanto EnviroChem's most recent development in the field of mist removal, it is state of the art technology for high efficiency Brownian diffusion fibre bed mist eliminators and a further demonstration of Enviro-Chem's leadership in fibre beds. The Energy Saver has a patented, bicomponent fibre bed which uses a special liquid drainage layer to virtually eliminate reentrainment of collected mist even at greatly increased gas flows and mist loading conditions. The proprietary process used in manufacturing this product ensures a more uniform, computer-designed bed, consisting of a special glass fibre layer surrounded by a tough fibre mat on the downstream face. The bicomponent fibre bed was named the energy saving fibre bed because of the reduction in pressure drop due to its unique high efficiency mist collection layer and consequently lower blower energy cost. The ES element has been designed to handle an increase in gas handling capacity by up to 20%, whilst still maintaining the desired collection efficiency. As a result, savings can be enjoyed in a number of different ways. New installations can be installed with up to 20% fewer elements than is possible with conventional fibre beds, yet still handle the same volume of gas. This reduces capital costs for both the elements themselves as well as for smaller containment vessels and other auxiliaries required. Existing installations installed with the same

number of elements will enjoy up to a 20% reduction in the pressure drop and energy needs to propel mists through the system. As an alternative to saving energy, replacement of conventional elements by ES elements can permit plant debottlenecking by allowing an increase in the gas exhaust stream by up to 20% with the same collection efficiency and without the need to replace the expensive vessel or tube sheet. The ES fibre bed provides added protection during atypical operating conditions. If the exit gas volume or inlet mist loadings exceed the process conditions for which the mist removal system was designed, the ES can handle up to a 20% increase, without a visible plume or unacceptable emission level. This feature permits the expansion of plant operations without subsequent reentrainment problems. Figure 4 illustrates the control of reentrainment using a bicomponent layer compared to a conventional fibre bed. In the event that repacking of fibre bed elements is required, the unique construction of the ES bed makes it easier to unpack than the conventional design. The ES reduces the time consuming process of removing the fibre from between screens as with bulk packed elements. The ES outer screen can be easily removed, and the fibre quickly cut off. With this unpacking procedure there is a significantly lower possibility of damaging the element shell and the substantially lighter empty shell will also result in a considerable reduction in shipping costs [7]. The ES is designed to remove 99.95% of particles 3[mu]m and smaller, and virtually 100% of all larger particles. The pressure drop is in the range of 4-20 inches [H.sub.2.O]. ES elements are available in two basic configurations: reverse-flow-upside-down in which the mist eliminator is placed vertically on a tube sheet and permits the use of longer elements and vessels of reduced size; standard-flange-forwardflow in which the element hangs from a tube sheet making installation and maintenance easier. The ES is manufactured in lengths from 6-20 feet with a standard diameter of 24 inches. The element cage is constructed of any weldable metal or fibre reinforced plastic. The ES mist eliminator elements are recommended for use in interpass absorption towers, final absorption towers, single absorption towers and ammonia scrub systems. Monsanto Enviro-Chem has also carried out work on its impaction type fibre bed mist eliminators. CS (Cost Saver) mist eliminators have been redesigned to further improve performance. The elements now include an alloy metal mesh acting as an integral reentrainment control layer downstream of a new, special glass fibre collecting mat. In situations where the inlet loading is exceptionally high, an optional baffle screen preseparator may be specified.

The CS-I eliminator was developed primarily as an alternative to mesh pads for drying towers in sulphuric acid plants. It is a cylindrical element 30 inches in diameter and 65 inches long with a stainless steel wire cage. The pressure drop across the CS-I is 3-5 inches w.c. The element, which stands in a vertical position on a tube sheet, is less susceptible to sulphate plugging than mesh pads. The glass fibre does not corrode in sulphuric acid and the stainless steel cage will withstand many years of continuous exposure to sulphuric acid environments without losing its structural integrity. CS-I is repackable and offers a collection efficiency superior to that of the mesh pad. Other benefits include: a greater throughput per element than traditional fibre bed mist eliminators (13,280 actual cubic feet per minute); increased collection efficiency (as much as 80% below 1 micron); special chemical resistant glass fibre which is highly resistant to corrosion. The new CS-II mist eliminator was developed to offer high efficiency collection on particles greater than 0.5[mu]m. A typical application being sulphuric acid final absorption towers. Like the CS-I, it is a cylindrical element but is 26 inches in diameter by 40 inches long. The CS-II element incorporates the benefits of having a smaller size and lower pressure drop than that of similar equipment. Some of the other benefits are: a greater throughput per element (9,500 ACFM); moderate pressure drop (5-9 inches w.c.); increased collection efficiency (as much as 95% [is less than] 1 micron]); its repackable; easy to install in new or existing plants; improved protection of downstream equipment - heat exchangers, ductwork and fans. Figure 5 shows the collection efficiency versus particle size for different types of mist eliminator. Monsanto Enviro-Chem has extended its mist eliminator range even further by joining forces with ACS Industries to supply mesh pads constructed of Sandvik SX Sulphuric Acid Steel[TM]. In the past, sulphuric acid plants using mesh pads in absorption towers or drying towers have long been plagued by the relative short life of 316 stainless steel, Alloy 20 and even Teflon[R] mesh pads. Many plants replace such pads every two or three years, and in some cases every year. Alloy 20 and 316 stainless steel corrode with the resultant sulphate build up reducing collection drop. Plant upsets can overheat Teflon[R] mesh pads, causing Teflon[R] to melt. Sandvik SX is a new, high-nickel nickel austenitic stainless alloy specifically for concentrated acid service, it will withstand temporary deviations in operating temperature and has much greater resistance to corrosion than both 316 stainless steel and Alloy 20. With corrosion rates in the order of four to thirty times slower than Alloy 20, SX has proved to be one of the best alloys ever produced for the protection against corrosion by concentrated sulphuric acid. Principal applications are in 98% and 93% absorption and drying towers.

Exclusive marketing rights for the SX alloy, which is manufactured by A.B. Sandvik Steel in Sweden, were acquired by Monsanto and in 1984 Monsanto Enviro-Chem began supplying the new alloy in the form of pipes and vessels. Early in 1988, Sandvik SX Sulphuric Acid Steel became available in fine wire suitable for mesh pad mist eliminators. Typical pads contain many layers knitted from 0.011 inch diameter wire. Monsanto Enviro-Chem then teamed up with a major supplier in the business - the Mistermesh[R] division of ACS Industries. Now the superior SX alloy is available in ACS mesh pad mist eliminators of any style. Figures 6 and 7 show the superior performance of Sandvik SX compared to other alloys in both 98% and 93% sulphuric acid service. ACS fabricates pads to suit the design requirements of individual units. Alloy 20 is adequate for the grid frame that supports the SX mesh pad. In some installations where Alloy 20 pads were replaced every six months, SX pad from ACS Industries are being guaranteed to last for years. Where throughput is a problem, ACS recommends mesh pads that incorporate a patented feature called Mist-Master[R]. This entails an array of tightly rolled mesh cylinders mounted at intervals against the underside of the pad. Trapped liquid drains readily through these cylinders instead of building up in the lower part of the pad. MistMaster[R] pads permit greatly increased flow rates without loss of mist elimination efficiency. In concentrated sulphuric acid applications, a reduction in the quantity of bubbling liquid in the pad means slower corrosion. Koch Engineering Company In 1965, Koch Engineering Company Inc., a wholly-owned subsidiary of Koch Industries Inc., introduced its first mist eliminator equipment in the form of mesh pads, now known as Fleximesh[R] mist eliminators. Within the next decade Flexichevron[R] was made available and later its Flexifiber[R] mist eliminators. With more than 30,000 installations worldwide to date, Koch is now recognized as one of the international leaders in entrainment separation technology. Koch's mesh pads are used for sulphuric acid service in the drying tower and in the final absorption tower. Porous blankets of knitted metal wire or plastic mesh provide nearly 100% removal of entrained droplets down to 10 [um]m. Knitted wire mesh mist eliminators have been widely acknowledged to be an economical and efficient way to remove liquid entrainment from gas and vapour streams. Fleximesh is a knitted mesh structure consisting of asymmetrical interlocking loops of metal wire, fiberglass or plastic filaments or combinations of these materials. Multiple layers of mesh are used to produce a porous blanket which can be fabricated into any required size and shape to fit new or existing process vessels.

When vapour and entrained liquid droplets pass through a Koch mist eliminator, the vapour passes through the mesh pad easily but the liquid droplets, because of their greater inertia, are unable to make the sharp turns required and are thrown into contact with wire surfaces. As more and more droplets accumulate on the wires, the droplets coalesce, increase in size and run down the wires to the bottom surface of the mist eliminator. When a sufficient liquid head has developed to overcome the force of the vapour flow, the liquid drains from the lower face of the mesh and the vapour has been stripped free from entrained liquid droplets. The unique characteristics of Koch's mesh pads are the result of the knitting process which forms a sleeve of interlinked wire loops. The variables (wire diameter, knitting machine size, number of needles around the cylinder, courses per inch of mesh length, depth and type of crimp) can be combined into numerous styles of mesh for use in almost any separation application. Koch mesh pads are available in any metal which can be drawn into wire, and most plastics. The usual diameter of the wire is 0.011 inches. Because of the small size of the wire used, corrosion resistance of the wire is of extreme importance. As an alternative to metal, plastics such as polypropylene and "Teflon" can be used provided that their temperature limits will permit it. Knitted wire mesh pads have a wide tolerance for changes in operating conditions such as velocity, temperature, molecular weight, pressure etc. and can continue to give good separation efficiency when other types of entrainment separation equipment would perform poorly. Since the kinetic energy of a droplet is determined by its velocity and mass, it is obvious that droplet size is an important factor in separation efficiency. For example, on a weight basis, it takes 1000 one micron droplets to equal one ten micron droplet. At proper velocities, a Koch mesh pad can remove 3-5 micron droplets at over 90% efficiency. As droplet size increases, efficiencies also increase. Where significant amounts of droplets sized less than 10 [um]m are involved, higher operating velocities will result in better separation efficiency because of the greater kinetic energy of the droplets. The pressure drop across wire mesh pads is usually low, normally less than one inch of water. It is affected by vapour and liquid flow rates and increases with increased liquid entrainment rates since, a greater portion of the void volume is filled with liquid and less volume is available for vapour flow. There are four major factors which determine the separation efficiency of a wire mesh separator: droplet size of the entrainment, diameter of the wire in the mist eliminator, number of targets in the path of the liquid droplet and vapour velocity.

Small droplets are more difficult to remove than large ones because of the greater mass of the large drops and thus large drops tend to travel in straight lines until they impinge a wire. In studies it has been determined that wires with a smaller diameter are more efficient in the removal of small liquid droplets. The thicker the mesh pad and the more layers of mesh used, the more targets there are in the path of the liquid droplet and the higher the percentage of liquid drops which will be removed by the gas stream. Because a mesh pad consists of stationary targets it is the velocity of the vapour stream that must provide the inertial force required to ensure a collision between the liquid droplet and the wire and at very low vapour velocities, small droplets tend to pass through the mesh avoiding the targets [8]. For submicron efficiency Koch supply Flexifiber [R] mist eliminators which are mainly used for the intermediate absorption tower. Fibre beds capture liquid and soluble solid mist particles down to 0.1 micron and below and can reduce or eliminate visible stack gas plumes to satisfy air pollution codes. The different types of Koch fibre bed mist eliminators are given in Table I. Since Flexifiber [R] types IC, IP and IS operate primarily by impaction, the collection efficiencies given in the table drop off at gas flows below about 75% of design rates and depend on the specific gravity of the collected liquid. Type BD is normally cylindrical in shape and available in a wide variety of materials and sizes. In addition to bulk packed elements, wound beds are also available for lower initial cost, ease of repacking and with equivalent collection efficiency at equal or lower pressure drop. Type IC is also cylindrical and available in a variety of materials and sizes. Types IP and IS are more commonly rectangular and are available in various metals. [Tabular Data Omitted] Koch's most recent product Flexeramic [TM] is a structured packing suitable for conditions of high temperatures and a corrosive atmosphere. It was designed primarily for use in applications such as sulphuric acid plants, but is also seriously being considered by some sulphuric acid plant operators in the U.S.A. as a replacement for mesh pad mist eliminators in air drying towers. Koch expects to install this new product in a sulphuric acid plant early in 1990 for tests. Joy Technologies Inc. The Western Precipitation Division of Joy Technologies Inc. designs and installs acid mist precipitators for acid plant service. In fact, this application was Joy Technologies' first successful demonstration of the electrical precipitation process in 1907. Since then, Joy Technologies has installed over 300 precipitators in acid plants around the world. The precipitators are configured with vertical pipes that result in 100% of the gas being treated with no possibility of gas bypassing the treatment zone. This has become more important as acid plants are making high purity acid with fewer contaminants. The precipitator

designs can accomodate various shell materials including lead, and lead bonded to steel or plastic whilst keeping to the traditional features of low energy requirements and low pressure drop. Begg, Cousland & Co. Established for over 130 years, Begg, Cousland & Co. manufacture a range of mist eliminator equipment for use in sulphuric acid plants. "Becoil" Demisting Units are separators of the impingement type consisting of multiple layers of fabric knitted from metal or plastic monofilaments, crimped and then assembled so that the crimps cross in successive layers. Pads fabricated in this way have a very uniform voidage with an extremely high ratio of filament surface area per unit volume of pad. The high voidage achieved ensures pressure drops are correspondingly low, while removal efficiencies of droplets larger than 5 [um]m are essentially 100% provided that the demisting unit is correctly designed for the operating conditions. Units - usually with support grids - can be supplied either in one piece or, in the case of larger units, in sections to pass through the installation manways. The grids are of the ladder type manufactured from 25 X 3 mm flat bar and 6 mm diameter rod in a suitable material. When fluctuating conditions of operation or high pressure drop is encountered, both top hold down and bottom support grids are advised. "Becoil" Demisting Units are recommended for drying tower service. The primary design consideration is the velocity of the gas through the demisting unit, and the Saunders-Brown expression is a convenient means for expressing the equation for calculation of allowable vapour velocity based on liquid and gas densities. The basic equation is: Mathematical Expression Omitted Where Vmax = maximum allowable velocity PL = liquid density PG = gas density K = constant dependent upon liquid and gas densities, viscosity and surface tensions of the entrained liquid. For most applications the value K can be taken as 0.105 to express V in metre/second. It is usual to design working velocities on 75% of the calculated Vmax. To further the collection efficiency of the demisting unit to below 5 [mu]m, Begg, Cousland & Co. has developed the "Becone" Coalescer. This unit is a pad fabrication from a composite fabric consisting partly of monofilaments and partly of a staple fibre yarn exhibiting along its length the ends of the staple fibres composing it. These fibres are much smaller in diameter than either the yarn into which they are spun or the monofilaments - consequently forming a more efficient filter. The

multitude of fibrous ends presented to the gas flow reduces the streamline effect, trapping the fine droplets within the coalescer, and the coarse droplets so formed are reentrained in the gas stream leaving the coalescer. These larger droplets are then easily removed by a conventional "Becoil" Demisting Unit. The combined "Becone" and "Becoil" installation increases collection efficiency to 98% in the 2-5 micron range. the pressure drop is increased but not dramatically since the "Becone" coalescer still has a considerable free volume even allowing for the introduction of the fibrous yarn. "Becofil" Non-Wettable Fibre Filters - commonly referred to as candle filters - originally developed in the research laboratories of ICI plc are intended primarily for the complete removal of very fine mist particles of less than 2 [mu] m. They are recommended for use in absorption towers and also drying towers. Each filter is composed of millions of fibres and although the efficiency of each individual fibre is low, the cumulative effect is very high. Experimental work has been carried out using glass fibres with differing surface properties and diameters and with varying densities. A fibre was eventually discovered and a packing density established which exhibited a high efficiency. It drained easily and produced an acceptable pressure drop. Research established that if the fibres were water repellent, bunching did not occur when mist passed through the bed. As the particles were collected on the fibres dropwise rather than as a film, the fibres remained substantially dry. The "candle" filter is repackable and comprises preformed elements packed into a 5 cm annular space between two concentric cylinders fabricated from corrosion resistant mesh. The candles are installed vertically and gases pass horizontally through the filter wall, the trapped particles coalescing and draining down through the filter bed. Gas flow through candles can be either inside/outside or outside/inside depending on the siting of the installation and the method of securing the candles in place. Otto H. York Company, Inc. For sulphuric acid mist elimination, York manufacturers wire mesh mist eliminators (DEMISTER[R]) for use in the drying tower, for the absorption tower York manufacture Fiberbed Candles and the Type "S" scrubber, which is unique and available only from Otto York. The DEMISTER[R] is an assembly of Yorkmesh[TM] knitted mesh supported on and held down by high open area grids. It is made to any size and shape and may be installed in all new and existing process

vessels. Wire used in DEMISTER[R] fabrication is drawn in York's own wire mills for highest quality control. It is smooth, clean and bright for rapid liquid drainage. Stainless steels and exotic alloys are fully annealed to provide maximum corrosion resistance. York-Fiberbed mist eliminators consist of a packed bed of fine glass or polypropylene fibres sandwiched between flat or concentric cylindrical screens made of a variety of metals or plastics. Standard size elements including cylinders and rectangular panels are available but customdesigned units are also supplied. Assembled elements are engineered for mounting with gaskets to a support tube sheet. Fibre bed devices provide the highest particle removal efficiencies of any type of mist eliminator, capturing particles as small as 0.1 micron. Pressure drop varies with design but generally is 2-20" w.c. Every sulphuric acid plant discharges a plume of very fine acid particles from the absorber stack, some of which are submicron particles. Because the elimination of this problem required the use of expensive equipment, Otto York designed The York Acid Mist Scrubber Type "S" low cost equipment to eliminate the fine mist plume, recover additional sulphuric acid and to assure compliance with new air pollution control regulations. The Type "S" scrubber is proven technology with approximately 100 installations worldwide (see Table II for performance data). The scrubber features a moderate pressure drop; high efficiency; all teflon construction; sectionalized, light weight internals; high gas velocity, compact size; structurally very strong, self sealing and no threaded fasteners. Benefits include long life, low maintenance cost, simplified installation one-quarter to one-half the cost of alternative systems. For sulphuric acid mist, the performance of the York Scrubber is equal to that of electrostatic precipitators which are three to five times more expensive. Residual sulphuric acid in the discharge gas from a York Acid Mist Scrubber is well below 2 milligrams per actual cubic foot. Since the York Scrubber removes the acid from the gas stream without dilution, collected acid is drained directly to the acid mix tanks or it can be returned directly to the absorber through liquid seal traps. A glass section may be installed in the line to provide visual assurance that the scrubber is draining properly. [Tabular Data Omitted] The Type "S" scrubber, containing contacting and collecting stages, is furnished as a vertical vessel for mounting directly on top of the absorber with a top outlet sized for hook-up to the discharge stack. Figure 9 shows the scrubber with its two stage assembly. One of the contactor stages is designed for removal of the coarse fraction of acid mist, while the other stage accomplishes removal of the very fine mist particles contained in the gas stream. The use of corrosion-resistant internal contactors of Teflon[R] and a shell of stainless steel, results in very low maintenance costs. The absence of moving parts assures long life.

The York Scrubber requires no additional absorber height when building new plants, and consequently requires no alteration of usual absorber design, thereby effecting important savings in absorber steel and brick lining. It is recommended that stacks be offset and supported separately; however, the York Scrubber is of adequate strength to support a stack of stainless steel of reasonable height. Sight glasses, manways, support lugs, and connections for external acid drain lines and pressure drop taps are provided. The scrubber is manufactured in any size for any capacity. In most cases, York Scrubbers are manufactured to standard size for installation on sulphuric acid absorbers. The largest produced to date is a single York Scrubber for a plant producing 2,200 tons per day of sulphuric acid. References [1.] Duros, D. R., and Kennedy, E. D.: "Acid mist control". Chemical Engineering Progress (Sep 1978). [2.] Perry, R. H., Chilton, C. H., "Chemical Engineers' Handbook" p. 18-82. McGraw-Hill Kogakusha, 5th Edition (1973). [3.] Sander, U.H. F., Rothe, U., and Kola, R.: "Sulphuric Acid". In "Sulphur, Sulphur Dioxide and Sulphuric Acid" (ed. More). British Sulphur (1984), p. 298. [4.] "Mist Eliminators", Monsanto Enviro-Chem Systems Inc. (1989). [5.] McKetta J. J., Cunningham, W. A.: "Mist removal equipment, design and selection". Reprint from "Encyclopedia of Chemical Processing and Design" (1989). [6.] "Improvements in gas cleaning systems for cold-gas sulphuric acid

plants". Sulphur (203), 24-36 (Jul-Aug 1989). [7.] Moran, T. M., "New bicomponent fiber bed offers performance breakthrough in aerosol control". 73rd Annual Meeting of the Air Pollution Control Association (Jun 1980). [8.] "Fleximesh Design Manual". Koch Engineering Co. Inc. (1974). [9.] Warner B. J., and Scavzillo, F.: "The design of fibrous filters for mist elimination". Gas Conditioning Conference, University of Oklahoma (1963). PHOTO : One of Begg Cousland's 13 foot high "Becofil" non wettable fibre filters being packed for dispatch. COPYRIGHT 1990 CRU Publishing Ltd. This material is published under license from the publisher through the Gale Group, Farmington Hills, Michigan. All inquiries regarding rights should be directed to the Gale Group.

Title: Preventing the sulphuric acid plant from devouring itself - and its surroundings. Date: 3/1/1991; Publication: Fertilizer International; Sulphuric acid is a strong mineral acid and is extremely corrosive to most metals, but though it has been immensely important since the dawn of the chemical industry, its complex corrosive properties were not properly understood until relatively recently. Very highly concentrated sulphuric acid (95-100% H[sub.2]SO[sub.4] is not, in fact, particularly corrosive, but at lower concentrations it is savage, and especially between about 80% and 95%. Up to 80% concentration, it behaves simply as a strong acid, so its corrosive effects are primarily a function of the hydrogen ion concentration in solution. At higher concentrations, above 80%, its oxidizing effects become most

prominent. In combination with the elevated temperatures encountered within the equipment of a working sulphuric acid plant, its effect is potentially devastating. Designing and, in particular, developing materials of construction for those parts of a sulphuric acid plant that handle liquid sulphuric acid is therefore a very exacting challenge. Unfortunately, too, the problem does not stop there. Sulphuric acid is a very heavy, non-volatile liquid. It boils at 330[degrees]C, and when it does it partially decomposes into sulphur trioxide and water vapour. Conversely, whenever these two materials are present together in a vapour mixture at below the dew-point of sulphuric acid, sulphuric acid condenses, and because this happens even at very low concentrations, the sulphuric acid is exceedingly finely dispersed, in the form of a fog. This so-called "acid mist" is very difficult indeed to arrest, so if it is allowed to form in a sulphuric acid plant it may be entrained in the gas flow and transported throughout the plant, exposing every surface upon which it impinges to the threat of corrosive attack. And if it is allowed to escape into the atmosphere, it can wreak havoc wherever it eventually settles. Much can be done to minimize the formation of acid mist in a sulphuric acid plant by careful selection of the process conditions. Much can also be done to minimize its ill effects by careful selection of materials of construction in places where its presence can be predicted. In addition, mechanical mist elimination devices are installed at strategic points in the process, not only to safeguard the materials from which the plant is fabricated, but also to prevent emission to the environment. This article briefly surveys the measures that are available for combatting this dual threat. Process outline Simply expressed, sulphuric acid is made by contacting a mixture of sulphur dioxide - made by burning sulphur or some other sulphur mineral - and air with a catalyst at a moderately elevated temperature and then cooling the gas and absorbing the sulphur trioxide into a circulating aqueous sulphuric acid solution.
2SO[sub.2] + O[sub.2] [in equilibrium] 2SO[sub.3] SO[sub.3] + H[sub.2]O [right arrow]H[sub.2]SO[sub.4]

Both these reactions produce heat. The process principles and many of the major economic considerations have previously been described in some detail in Fertilizer International.(1) Figure 1 is a typical flowsheet. In actual fact, after the formation of sulphur dioxide by whatever means, there are essentially four process stages.

To minimize the risk of acid mist, in most plants moisture is rigorously excluded from the system. (So-called "wet-catalysis" plants have successfully been built to operate on moist feed gas, but they have to be specially designed.) In a sulphur-burning plant, the act of melting the sulphur ensures that it is dry, as it melts well above the boiling point of water, so it is only necessary to dry the combustion air. hi socalled "cold-gas" plants associated with pyrites or non-feffous sulphide ore roasting, the sulphur dioxide feed gas is moist on account of the elaborate cleaning needed to remove solid and gaseous impurities, so the entire feed gas is dried. This is done by contacting the gas with sulphuric acid in a packed tower or venturi contactor. This acid is taken from, and subsequently returned to, the product acid circuit. In a sulphur-burning plant the dried air then passes to the sulphur burner, which generates a great deal of heat. The hot combustion gas i m a waste heat boiler to reduce its temperature to around 420[degrees]C and is then introduced into the catalytic converter. In a cold-gas plant, the dried feed gas is heated to this temperature in a sequence of heat exchangers taking heat from the converted process gas. In the converter, the catalyst mass is divided up into three, four or five static beds, according to the preference of the process designer, and the gas is cooled at the exit of each. The process gas finally passes through the absorber, which is often a packed tower but in some designs is a venturi contactor. Here it is contacted not with water but with circulating 98-98.5% sulphuric acid. The combined vapour pressure of water and sulphur trioxide over sulphuric acid is lower at that concentration than at any other, so mist formation is minimized. In most new plants built within the past 20 years, absorption takes place in two stages, with the gas stream passing back to the converter so that the maximum amount of sulphur dioxide can be converted into trioxide. Finally, the warm absorber acid is cooled, and some of it is cycled through the drying tower, while the remainder goes to storage. Water is added to the acid at a rate corresponding to the rate at which it reacts with sulphur trioxide minus the rate at which it is absorbed in the drying tower to maintain its concentration. The gases from the converter are usually cooled to about 200[degrees]C before they pass to the absorber, but the temperature must not go below the dewpoint, which is between 110-160[degrees]C, depending on the gas composition.

The basic chemistry of sulphuric acid production is extremely simple; most of the complexity of a sulphuric acid plant is attributable to heat management and utilization. Major equipment items Obviously, the major equipment items in a sulphuric acid plant are built very much with corrosion in mind. Moist gases containing sulphur trioxide can be handled in carbon steel equipment, provided the gas temperature is kept above the sulphuric acid dewpoint. Below the dewpoint, alloys and more corrosion-resistant materials must be used. Plastics have not proved of interest; they may be inert enough to resist corrosion but are not sufficiently strong and have poor thermal conductivity. Carbon steel is also suitable for containing concentrated sulphuric acid, within certain concentration ranges and at relatively low temperature. In sulphuric acid production, construction materials have traditionally been the cheapest which are effective. The drying tower usually consists of a cylindrical carbon steel vessel lined with acid-proof bricks. These are fixed with silica-based acidresistant mortar. Pipe nozzles are often made in cast iron, and acidproof ceramic packings fill the tower. Often ceramic tiles are also used. The catalytic converter is built to withstand corrosion at high temperature. Traditionally, these cylindrical vessels are also made from carbon steel lined with acid-proof brick, although sometimes cast iron is used. More recently, stainless steel converters have come into use. Since the oxidation of sulphur dioxide to trioxide is highly exodermic and proceeds in stages as the gas stream passes through the beds of catalyst, heat exchangers are needed between the catalyst passes to keep the gas temperature down. These are usually gas/gas exchangers, which are less prone to corrosion than liquid/gas devices. As long as there is no risk of mist formation, carbon steel is an acceptable material, though not an ideal one, for such exchangers as well as for associated gas ducts, but the latter may also be lined with brick, especially in the hottest part of the plant between the first two catalyst passes). Like the drying tower, the absorber is usually a tower, in which the gas stream is contacted in countercurrent with concentrated sulphuric acid. Again, a brick-lined carbon steel vessel is the usual form. Other precautions, such as ceramic tiles and barrier coatings between the bricks and the outer steel shell, may also be employed. The acid coolers traditionally used to consist of open-air banks of serpentine cast iron tubes, cooled by a cascade of water. Although cast iron is reasonably resistant to corrosion by sulphuric acid, especially at

relatively low pipe velocities, the bends are very maintenanceintensive. This type of cooler also occupied a lot of space. More compact designs made of stainless steel have now largely taken their place. Modern incentives and economic pressures Sulphuric acid is a relatively low-value basic chemical- and, for that reason, corrosion protection and mist control are only a practical proposition if they can be realized at a realistic cost. The production economics do not justify elaborate and sophisticated measures. However, in recent years the drive to improve energy efficiency in the process industries in general has extended to the sulphuric acid plant. By virtue of the very large amount of high-level heat that could be recovered from the process gases into high-pressure steam, the sulphur-burning sulphuric acid plant was already one of the most lucrative sources of by-product energy in the whole chemical industry. With vast amounts of low-level heat available in the acid circuits, it was potentially even more so, but for the lack of sufficiently corrosionresistant materials. Recent advances in materials of construction have made possible notable improvements in low-level energy recovery. In the mist control area, effective and relatively inexpensive means have been available for many years in the form of various designs of fibre-bed mist eliminator. The principal challenge there is to find ways of reducing the pressure drop of these devices without jeopardizing their performance and without markedly increasing either their size or their initial cost. Recent developments Gas/gas heat exchangers In the gas/gas heat exchangers at the converter, the construction materials are exposed to a mixture of sulphur dioxide and sulphur trioxide at temperatures up to about 620[degrees]C. Under these conditions carbon steel is readily oxidized and a sulphate scale forms on the exposed surface. This reduces heat transfer efficiency and increases the pressure drop. It can also flake off and be carried over into the catalyst beds. Typical carbon steel heat exchangers must be re-tubed at intervals of 4-6 years. Stainless steels with high chromium content (around 18%) have been used for such heat exchangers, with positive results. The extra cost of material is offset by the thinner tube walls possible and the better heat transfer which results. Chemetics International, of Canada, for example, patented in the mid-1980s gas/gas heat exchanger design made entirely out of stainless steel, for use in heat exchange duty

following the first two catalyst beds - i.e. before interpass absorption where the gas temperatures are well above 480[degrees]C. The extra cost of high-performance stainless steel does not, however, go unnoticed in sulphuric acid manufacture, and other alternatives have also been explored. The life of carbon steel tubes and ductwork can be substantially increased by the very effective proprietary "Alonizing" treatment developed in the United States by Alon Processing, Inc. The component is placed in a retort and heated up to 925[degrees]C with a mixture of powdered aluminium and alumina. The aluminium diffuses into the surface of the steel, producing a surface alloy. Provided it is kept free of condensation, this is more resistant to corrosion than type 304 austenitic stainless steel (18/8 chrome/nickel) (Fig. 2). Alonized components in properly designed and operated sulphuric acid plants appear to last in a scale-free condition for 20 years or more. Acid coolers Many of the developments in stainless steel since the mid 1980s have been specifically connected with acid coolers and handling hot, concentrated sulphuric acid. Until recently, despite the very high heat output in the absorption section of the plant, heat recovery was not considered worth while because the temperature of the circulating acid could not be allowed to exceed about 80-100[degrees]C. Cast iron has relatively good resistance to sulphuric acid corrosion up to about 100[degrees]C as long as the velocity of flow is relatively low. Its fabricated thickness also means that the material is durable, but on account of the maintenance requirement of the multitude of pipe bends (where corrosive and erosive damage are worse), coupled with the absence of heat recovery potential, this system has been superseded. Simple chromium-modified stainless steels, however, do not have sufficient resistance to sulphuric acid attack at temperatures above 50[degrees]C to be serviceable, especially bearing in mind the thinner wall thicknesses employed compared with cast iron. Adding other components such as nickel and molybdenum raises the temperature limit somewhat but, as with cast iron, corrosion increases with the temperature and the pipe velocity. Although they have been in use since the early 1970s, unprotected stainless steel heat exchangers - whether shell-and-tube, spiral, plate or tank-coil types - have had a practical temperature limit in hot sulphuric acid service of about 90[degrees]C. To recover useful heat from the acid it is necessary to operate the acid circuit at much higher temperatures than that. Acid coolers are today being called on to operate at 200[degrees]C. Anodic protection

One of the first developments to be introduced, around 1980, was the concept of passivation, or anodic protection. Metallic corrosion is an electrochemical effect, in which the metal is transformed into ions in solution because of an electrical potential between the ions and the metal. By artificially polarizing the metal/ electrolyte system using an applied voltage, it is possible to inhibit or modify the corrosion process. In anodic passivation, the metal to be protected is charged positively - it becomes an anode - so that the initial corrosion effect produces a coating of metal oxide on the surface, thus protecting the metal from further attack. Various designers, including Lurgi, GEA, Alfa-Laval, APV, Chemetics, Monsanto and others, used the technique on a number of commercially available stainless steels. Early research showed that by using passivation, 316L stainless could tolerate acid inlet temperatures up to 110[degrees]C and other materials such as passivated Hastelloy C could tolerate even higher temperatures, up to about 125[degrees]C the possibility of temperatures on the water side well above 100[degrees]C. Subsequent improvements in the technique have allowed operating temperatures to go even higher: corrosion resistance up to 140-160[degrees]C has since been claimed for 316 stainless in acid cooler service. New steels Of course, an obvious drawback of the electrical passivation concept is the likelihood of some breakdown in the electrical system, leading to severe corrosion in a short period of vulnerability. Sentiments of this nature have been behind the development of specialist stainless steels specifically for hot sulphuric acid duty. Sandvik SX, marketed by Edmeston AB, a Sandvik group company, is one example of a specialist steel of this kind. Edmeston designs sulphuric acid cooling and heat recovery systems under licence from Monsanto, including complete absorption/drying circuits. SX is an austenitic stainless steel with a high chrome/nickel content, together with lesser amounts of manganese, molybdenum and copper. The full composition is given in Table 1. Without anodic protection, it is suitable for use with sulphuric acid above 95% concentration at temperatures up to 160[degrees]C. SX was first put into commercial service in 1985, since when it has been installed in a number of systems. Latterly another Sandvik steel, Sanicro 28, has been used for water-side applications because it is more resistant to chloride corrosion than SX. SX coolers of shell-and-tube shown heat transfer coefficients as high as 1,700 W/m[sup.2]/K.

Similarly, Chemetics International Co. has developed Saramet, a highsilicon austenitic steel. This was initially developed for nitric acid service, but corrosion tests with sulphuric acid began as long ago as 1980. Compared with 316L stainless, which has a corrosion rate of I mm per year in 98.4% sulphuric acid at 125[degrees]C, Saramet has a corrosion rate of just 0.025mm under similar conditions. Figure 3 compares the corrosion behaviour of some stainless steels and alloys in 98% sulphuric acid. Other equipment Although it is undoubtedly coolers and heat exchangers handling concentrated sulphuric acid that were the initial targets for much of the development work in these new stainless steels, once they have been demonstrated, their use in other parts of the plant also becomes possible. Thus, such materials have found use in the construction of absorption towers and pipework, where resistance to severe corrosion warrants it. The requirement to operate the acid circulation circuit at higher temperatures has also resulted in the need for pumps and valves able to withstand these more aggressive conditions. In general, cast materials are more corrosion-resistant for pump internals than other fabrications. Pump manufacturers such as Chas. S. Lewis & Co, of St Louis, MO, and Rheinhutte, of Wiesbaden, Germany, have developed new designs with fewer moving parts, made either from silicon cast iron or various high-performance high-alloy steels to meet the new demands. One material in particular, a high-chrome semi-austenitic cast material known as 1.4136 HRS, is claimed by Rheinhutte to be sufficiently resistant to handle 95-100% sulphuric acid up to 190[degrees]C and 97-99% acid up to 200[degrees]C. Mist eliminators Mist particles are generally defined as being smaller than 10 m in diameter, and some may be smaller than 1 m. Fineness depends to some extent on the precise conditions under which the particles are formed, and on their rate of formation. The severity of mist formation in the drying tower depends chiefly on the concentration of the drying acid. In older acid plant designs and the "cold gas" plants based on metallurgical gas feedstock, drying acid of 92% concentration is more usual. Modem sulphur-burning plants generally use 98% acid in the drying tower. At the latter concentration, mist formation is less severe, but acid spray (particles greater than 10 m) is more significant. Loadings can be anything up to 3,500 mg of particles between 0.6 and 10um per cubic metre of gas. In double-absorption plants, mist loadings in the intermediate absorber may typically be 500-1,750 Mg/m[sup.3] in the 1-2pm range, and it is

essential to prevent this mist from being carried into downstream equipment, such as the gas/gas heat exchangers and the converter itself. In the Anal absorption tower, as in the intermediate absorber, mist droplets are formed primarily by mechanical carryover from the packing and, t( a lesser extent, by aerosol formation by reaction/condensation. The loading is typically 150-350 mg/m[sup.3] in the 2-3 pm range. Acid mists can also be formed in emission control equipment, for example in ammonia scrubbers for sulphur dioxide removal. Such fine particles can effectively be removed from gas streams using electrostatic precipitators, but these are extremely expensive in capital terms and operating costs. Because of this, mesh or fibre pads working mainly by impaction and interception of the droplets so that they coalesce to a continuous liquid film - are most commonly used as mist eliminators. Many proprietary systems are available. Mesh pad separators consist of a woven metal wire or plastic mesh, with successive layers knitted together to form a pad 10- 15 cm deep. The pad has a high free volume, in the region of 95%, so that a relatively high gas velocity can be maintained at low pressure drop. However, the gas velocity must be kept below the level where further entrainment would occur. Droplets coalesce and collect on the strands of the mesh and the liquid formed then drains by gravity from the bottom of the pad. Fibre bed eliminators consist of fine fibres randomly packed, rather than a woven mesh. The fibre density varies considerably from one type to another, and gas velocity and pressure drop vary accordingly. The fibres may be glass, ceramic, plastic, metal or mineral, as bulk staple (loose fibres) or in rope form. Generally speaking, individual proprietary systems utilize either the mesh pad or the fibre bed principle, and sometimes a combination of both. The well known Brink m st eliminator, used extensively over many years in Monsanto acid plant designs, is of the fibre bed type. More recently, Monsanto has introduced two further improved devices, the CS Mist Eliminator and the ES Energy Saver, with the accent on cost saving. The CS design is an impaction-type fibre bed incorporating an alloy mesh, while the ES device is a bicomponent fibre bed using the principle of Brownian diffusion for highly efficient removal of small aerosols. ACS Industries, of the USA, has developed the "Mistermesh" and "Mistmaster" designs of mesh pad system, and since 1988 has been

supplying mesh pads made from Sandvik SX wire. Koch Engineering Co., Inc., also of the USA, supplies both mesh ("Fleximesh") and fibre ("Flexifiber") types, as does Begg, Cousland & Co in the UK. Begg Cousland's "Becoil" units are knitted mesh - either metal or plastic while the "Becofil" is essentially a fibre filter. The company's "Becone" coalescer is a composite of fabric and staple fibre. Otto H. York Co. Inc., which began by making wire mesh "Demisters", has also now developed its "Fiberbed" mist eliminator using glass and polypropylene fibres. Scrubber systems, incorporating mesh and fibre de-entrainment and using the resulting acid droplets for scrubbing duty, are also known. Modern plant design Running the acid circuits at higher temperatures makes it possible not only to recover heat for external uses, such as district heating, pulp mill liquor preheating and phosphoric acid concentration, but also to rearrange the way heat is utilized within the sulphuric acid plant itself At present the ultimate example of this chain of innovation is Monsanto Enviro-Chem's new plant concept developed out of the company's HRS (Heat Recovery System). This is the first significant change to the general appearance of sulphuric acid flowsheets since the doubleabsorption concept was introduced in the 1960s. HRS is claimed to recover 90-95% of the total reaction heat developed in the sulphuric acid process, paradoxically by using a different approach to the presence of water within the process. It is based on the observation that sulphuric acid of 99%+ concentration is considerably less corrosive towards a number of modern alloys even than the 98% acid used in conventional absorber circuits, let alone the 93-95% acid used in many drying circuits, even at temperatures up to 220[degrees]C. At such a high temperature, it is possible to recover heat very efficiently as medium-pressure (10-bar) steam. In tests of over 400 stainless steels, more than a dozen high-chrome alloys were found suitable for such a duty. (Table 11). However, the key to the new process, first piloted in 1983, is the operation of the converter under "wet-catalysis" conditions. Although normally air to the converter is dried to exclude moisture from the catalytic section of the process, sulphuric acid plants using hydrogen sulphide as feedstock have always used wet catalysis, since the combustion of this gas to sulphur dioxide leads directly to the formation of large amounts of water vapour which cannot reasonably be removed.

The technology is well proven, still uses normal vanadium catalysts, but does not have the need for any drying tower; the conditions within the converter are controlled to prevent water vapour causing acid mist. Because there is no drying function, dilution within the acid circuit does not take place and the required 99- 100% concentration can be maintained. Thus partially cooled gas from the second catalyst pass of the converter, which would normally be further cooled in heat exchangers before entering an intermediate absorber, passes instead to an absorber which also acts as a heat recovery tower (Fig. 4). Hot concentrated sulphuric acid from the two-stage heat recovery tower is used to raise steam in a boiler, while the gas goes back to the converter for further catalytic oxidation and then to final absorption in the conventional way. Water control in the process is critical, and in fact the sulphur trioxide from the converter is absorbed in the 1% water in the 99% acid plus the condensate from the moisture fed into the converter with the process air. With this arrangement the high acid temperature (around 200[degrees]C maintained to ensure no unexpected condensation or mist formation takes place. It is crucially important to maintain the high concentration of the circulating acid, since if it is allowed to fall, even for short periods, devastating corrosion must be expected. The process, first commercialized in 1987, has now been proved in several large-scale plants. Compared with plants built 20 years or so ago, the sulphuric acid plant of today is a decidedly high-tech beast. Because of the low market value of the product, all the major developments have been self financing i.e. have paid for themselves in terms of process or energy efficiency improvements. Nevertheless, the most basic challenge is much the same as it was 100 years ago, to stop the plant being eaten away from within, or corroding away from the outside. References 1. Fertilizer International (271), 28-37 (March 1989). COPYRIGHT 1991 CRU Publishing Ltd. This material is published under license from the publisher through the Gale Group, Farmington Hills, Michigan. All inquiries regarding rights should be directed to the Gale Group.

Title: Sulphuric acid plant transformation. (Lurgi GmbH) (Process Technology)

Date: 9/1/1992; Publication: Sulphur; The German engineering contractor Lurgi GmbH is currently involved in a project to transform a sulphuric acid plant based on pyrites roasting to an elemental sulphur burning plant. The existing sulphuric acid plant, owned by Prayon-Rupel and located at Engis, Belgium, treats the sulphur oxide gases from a fluid bed roaster for pyrites. The plant was constructed in 1973 and has a capacity of 280 tonnes/day |H.sub.2~S| O.sub.4~, 100%. In addition to transforming the existing plant to a sulphur burning plant the project also includes increasing the production capacity from 280 t/d to 455 t/d |H.sub.2~S|O.sub.4~, 100%. In the newly-designed plant, the sulphur combustion unit will be incorporated into the existing acid plant ahead of the converter group; the sulphur furnace will be of Lurgi design and features the Lurospinning-cup-burner. A preconverter will be installed ahead of the converter to meet the increased capacity requirements. The installation of a waste heat boiler unit, comprising a boiler, superheater and economizer, will enable the reaction heat from sulphur combustion and the oxidation reaction of sulphur dioxide to sulphur trioxide to be utilized for the generation of 50 bar superheated steam. This steam will be fed into a back-pressure turbine to drive the main air blower; at the outlet of the turbine the low-pressure steam will be available for individual consumers. The existing converter will be operated as beds two to five; the resulting converter system is a five-layer system with intermediate absorption after layer three. The off gas from a sulphur dioxide liquefaction plant will be treated with the sulphur-burning gases and fed into the plant ahead of the main air blower. Figure 1 shows the Lurgi energy recovery system which will be incorporated into the intermediate absorption circuit to generate steam at 7 bar. All acid-containing equipment, apart from the acid pump, will be constructed of Cronifer 2803 (1.4575). The design of the system is such that the plant can also operate without the energy recovery system. COPYRIGHT 1992 CRU Publishing Ltd. This material is published under license from the publisher through the Gale Group, Farmington Hills, Michigan. All inquiries regarding rights should be directed to the Gale Group.

Title: Anaconda acid plant to be the world's largest sulphur-burning unit. (Anaconda Nickel's new sulphuric acid plant) Date: 5/1/1997; Publication: Sulphur; Anaconda Nickel has chosen Monsanto Enviro-Chem Systems, Inc to build a 4,400 t/d sulphuric acid plant for its Murrin Murrin nickel project in Western Australia. The plant will be the largest single train sulphuric acid plant in the world using elemental sulphur as a raw material. The Murrin Murrin nickel/cobalt project is a US$675 million joint venture between Anaconda Nickel and the metals trading group Glen-core International that is due to be in production by mid-1998. Initial production will be 45,000 t/y of nickel, with operating costs said to be the lowest in the world. The sulphuric acid production programme has arisen following the decision to manufacture acid on-site rather than commit to massive purchases on the open market and rail the product the considerable distance to Murrin Murrin, about 200 km north of Kalgoorlie; and the massive scale of the requirements stems from the option to use a high pressure leaching process with sulphuric acid rather than a smelting route to recover the nickel and cobalt (see Sulphur No 248, pages 3334). The annual sulphur input to the acid plant will equate to some 480500,000 tonnes at capacity operation, and the bulk of this is reported to have been sourced under contracts with suppliers in Canada. COPYRIGHT 1997 CRU Publishing Ltd. This material is published under license from the publisher through the Gale Group, Farmington Hills, Michigan. All inquiries regarding rights should be directed to the Gale Group.

Title: Sulphuric acid plant output increased by installing ring catalyst. Date: 5/1/1989; Publication: Sulphur; Author: Van San, R. Less pressure drop to start with, less build-up as time goes on Sulphuric acid plant output increased by installing ring catalyst The shape of the individual particles of a catalyst has a marked effect on its performance. For many years the normal form of sulphuric acid catalysts was cylindrical pellets, but as more durable catalyst formulations have been developed, it has become possible to produce catalyst particles with more open structures, which have a larger

surface area and present less resistance to gas flow and so increase both the energy and conversion efficiency of the process. Recently, BASF has introduced ring and star-ring catalysts which not only have better initial pressure drop characteristics but also are subject to less increase in pressure drop across the catalyst with time. This article describes their installation and their advantages in comparison with traditional pellet catalysts. Sulphuric acid is manufactured by oxidizing sulphur dioxide to sulphur trioxide and then allowing the sulphur trioxide to react with the free water content of concentrated sulphuric acid. Leaving aside the method used to produce the sulphur dioxide, for which there are various options, this process is inherently quite efficient from the point of view of product efficiency, but the oxidation reaction, being a chemical equilibrium, is not quite 100% efficient, and it is the most significant factor limiting the overall efficiency of the process. Since the conversion of sulphur dioxide to sulphur trioxide is exothermic, releasing 99 kJ of energy for every mole of sulphur dioxide oxidized, the equilibrium is more favourably positioned the lower the temperature is kept. But the reaction is kinetically inhibited and must therefore be conducted at elevated temperature to secure a useful rate of reaction. A catalyst is used to enhance the rate of reaction, allowing the working temperature to be reduced. Effectively all sulphuric acid plants use a solid (heterogenous) catalyst in random-dumped fixed beds. Nowadays the principal active component of the catalyst is invariably vanadium pentoxide, to which minor proportions of various alkali metal compounds are added as promoters. These active principles are supported on an inert silica carrier. Under normal operating conditions, the vanadium pentoxide and the promoters are in the molten phase and are completely absorbed by the inert support. Physical strength is an important attribute of any catalyst, as the small fragments produced by physical degradation of the catalyst block up the interstitial spaces in the catalyst bed and increase its resistance to gas flow. Traditionally, sulphuric acid catalysts were produced as cylindrical pellets, which were reckoned to be the most rugged form possible, but these have a fairly low specific surface area while presenting a high effective cross-sectional area to the gas flow, which manifests itself in practical terms as a high pressure drop across the reactor. Since heterogeneous catalysis is a surface effect, conversion efficiency would be improved by increasing the specific surface area, and this is most effectively achieved by making the catalyst particle hollow, which also has the beneficial effect of reducing its effective cross-sectional area. In recent years, catalyst formulation techniques have been improved to produce compositions with better inherent crush- and attrition-resistance, while computerization has enabled durable hollow particle forms with higher specific surface area and lower effective cross-section to be designed. In combination, these

improvements have allowed manufacturers to introduce a variety of different shapes of catalyst, such as rings, star-rings, ribbed extrudates and spoked wheels. BASF AG, a major producer of catalysts for sulphuric acid, ammonia, methanol and other industrial chemicals production, is currently offering ring and star-ring shaped catalysts which have a lower pressure drop in comparison with the traditional cylindrical shape. This has a very practical effect on the pressure drop across the reactor at conventional gas velocities of 0.35-0.4 m/s, which can be 50-17% of the pressure drop caused by traditional cylindrical catalyst, depending on the pellet size of the conventional catalyst. The advantage of lowering the pressure across the converter can be exploited in various ways, according to choice. For example, it is possible to increase the throughput of process gas, and thus to increase the production rate, although the reduction in the pressure drop will then be partially offset by slightly higher pressure drops in the ancillary equipment. One important factor that must be taken into consideration is that increased stream volumes may have a significant effect on the heat balance of the plant, and hence process temperatures. Alternatively, the plant can operated with the same gas throughput and production rate, in which case the lower pressure drop translates directly into a reduction in blower power requirements and consequent savings in energy costs. The energy savings can be calculated from the pressure drop characteristics of the catalyst and the performance of the blower. Catalyst manufacturers and engineering companies have simple methods of calculating energy savings. The value of the energy savings, and consequently the incentive to switch to a low pressure drop catalyst shape, will depend on the local conditions at the plant, which include the cost of electricity and the availability of steam, to name but two. In some cases where additional process steps have been added to a plant to increase the purity of the product -- for example, to remove mercury from the process gas in metallurgical plants -- reducing the pressure drop in the converter by changing to ring or star-ring catalyst is a convenient means of compensating for the additional resistance which the extra process units cause in the system. Debottlenecking: a case history Nevertheless, to exploit the undoubted advantages of low pressure drop catalysts to the full may necessitate other modifications elsewhere in the plant. Accurate and efficient management of energy is of fundamental importance in the highly exothermic sulphuric acid process, and care must be taken to ensure that energy saved through

lowering the pressure drop in the converters is conserved and put to good use elsewhere, otherwise the exercise will be largely pointless. It is of the double-absorption type, with intermediate absorption after the third catalyst bed. The installed catalyst volume is 100 [m.sup.3], giving a specific catalyst volume of 200 litres per t/d [H.sub.2] [SO.sub.4] (100%). Originally, the first catalyst bed was charged with 6mm extrudates, amounting to 15% of the total catalyst inventory. Beds 2-4 were charged with 4-mm extrudates, containing respectively 17%, 30% and 38% of the total charge. Under typical operating conditions, the plant processed 50,500 [m.sup.3]/h of feed gas containing 9.3% [SO.sub.2] and 11.6% at the inlet ([O.sub.2]/[SO.sub.2] = 1.25). The gas velocity at the inlet face of the first catalyst bed was 0.36 m/s. But under these conditions it was not possible to reach the design (calculated) output of 500 t/d; the best that it was possible to achieve was 93% of design, or 465 t/d. And because the sulphur feedstock was not filtered before combustion, it was necessary to screen the first-pass catalyst every year to remove accumulated dust. Installing ring catalysts in all four beds had a dramatic effect on the production capacity. Output in December 1985 was 58% greater, at 730 t/d, than the July 1976 output of 463 t/d. This was achieved partly by raising the feed gas flow from 46,500 N[m.sup.3]/h to 59,000 N[m.sup.3]/h and partly, thanks to the greater activity of newgeneration catalysts, by increasing its sulphur dioxide concentration from 9.3 vol-% to 11.5 vol-%. Despite the substantial increase in the gas flow, the pressure drop in the system was actually slightly reduced, allowing the blower to be run at a slightly lower outlet pressure (3,182 mm WC before the change, 3,142 mm WC after) while the pressure in the unit was slightly raised (3,034 mm WC before, 3,079 mm WC after). Inevitably, increasing the gas flow raised the pressure drop across other equipment items in the gas line. These increases were partially compensated for by the significantly lower pressure drops across the catalyst beds. The very marked improvement in the pressure drop characteristics of the drying tower was partly achieved in 1982 by replacing the cast iron acid distributor with one made of 316L stainless steel. The old distributor had become so badly corroded that the deposits of iron sulphate were obstructing the gas flow. Dust distribution The feed gas flow rate, the blower outlet pressure and the pressure drop across the reactor over the period November 1982 to April 1986. During this period, the conventional extrudates were replaced by rings in two stages. In the first stage, in October 1983, the extrudates in the

first bed were replaced by rings. At this point the catalyst volume of the first bed and, consequently, the bed height was increased by 25% so as to accommodate the projected increase in production rate. With 8% more gas flowing through the plant, the total pressure drop across the converter at this stage was 1120 mm WC, only 126 mm WC above the initial start-up value with extruded catalyst in the first bed. But the main advantage of replacing extrudate with rings is the slower rate of increase in pressure drop. This is seen by examining the pressure drop profile of first bed between November 1982 and October 1984. In the production cycle November 1982 to October 1983, when the catalyst bed was still charged with 8 mm extrudate, the pressure drop increased from 994 mm WC at the start of the run to 1435 mm WC, at a gas volume of 50 500 [m.sup.3]/h, an increase of 440 mm WC. In contrast, from October 1983 to October 1984, after the bed had been recharged with ring catalyst, the corresponding pressure drop was from 1,120 mm WC at the start of run to 1,275 mm WC, at a gas volume of 54 500 [m.sup.3]/h, an increase of only 155 mm WC. The reason is that ring catalyst, with its much more open structure, can accumulate a larger amount of dust without undue increase in resistance to gas flow. So pressure drop builds up more slowly, and the intervals between screenings can be increased significantly. In December 1985, ring catalysts were installed in all beds. To match the new gas capacity, the total installed catalyst volume and corresponding bed heights were increased by 27% over the original design. Even with the higher catalyst loadings and at a gas rate (59,000 N[m.sup.3]/h) of 117% of the original design, the initial converter pressure drop was 904 mm WC -- 10% lower than in November 1982, when the whole catalyst charge was extrudate. As mentioned, the increased gas flow rate resulted in higher pressure drop in the ancillary equipment, more than offsetting the reduction achieved in the converter, so the blower discharge pressure had to be increased by 15%. The present production capacity is about 735 t/d sulphuric acid, at a gas volume of 59,000 [m.sup.3]/h with a [SO.sub.2] concentration of 11.6 vol-% ([O.sub.2]/[SO.sub.2] = 0.80). To accommodate the increase in output all the available converter volume has been utilized and a total of 127 [m.sup.3] of catalyst is installed (specific volume = 173 litres per t/d [H.sub.2][SO.sub.4]). These figures reflect the improved conversion abilities of the present generation of improvedactivity catalysts. The catalyst selected for the first bed was BASF Type 04-110, which allows greater flexibility with respect to the inlet temperature, as it possesses the unusual combination of good low- temperature activity and the ability to operate at temperatures up to 620 [degrees] C. BASF Type 04-111 catalyst was installed in the lower passes. This is one of

the most active sulphur dioxide oxidation catalysts commercially available today. Both catalysts have an inside diameter of 5 mm and an outside diameter of 10 mm, large pore size and high void volume, while being capable of at least matching, if not surpassing, the mechanical stability of conventional extruded catalyst. Heat balance As the oxidation of sulphur dioxide and the absorption of sulphur trioxide in water is exothermic, increasing the acid production to 735 t/d causes an increase in the gas-side heat load of 42.5 GJ/h. Of this extra heat, 30.1 GJ/h is evolved in the sulphur furnace while the rest is evolved in the four catalyst beds. Therefore the waste heat boiler after the sulphur burner must remove about 70% of the extra heat. This necessitated fitting an additional tube bundle to the fin-tube boiler, which had been originally designed with enough space to do that to allow for a possible future increase in production. At the same time, the capacities of the heat exchangers related to the converter operation were increased from a total surface area of 1,672 [m.sup.2] to 2,876.6 [m.sup.2]. In some cases the original superheaters were replaced with gas-gas heat exchangers. These measures improved the heat balance of the unit. Steam production increased from an original 1.06 tonne per tonne sulphuric acid to 1.3 t/t. At a sulphuric acid production rate of 735 t/d, this translates to an export of 40 tons steam per hour, at a pressure of 20 bar and 225 [degrees] C. The changes in the acid circuit cooling system, from which it can be seen that the additional production capacity has been channelled primarily into the production of oleum. This necessitated increasing the capacity of the oleum pump by 220 [m.sup.3]/h. The other main change that was needed to enable the plant to handle the increased gas flow without undue increases in pressure drop was to enlarge the acid mist elimination systems. The wire mesh filter area in the dryer was almost trebled, from 4.53 [m.sup.2] to 12.57 [m.sup.2]. This reduced the gas velocity through the filter from 3.1 m/s to only 1.3 m/s, substantially lowering the presure drop in the dryer. The number of candle elements was increased from 23 to 30 in the intermediate absorber and from 24 to 30 in the final absorber. The total investment in plant equipment and catalyst required for the conversion to ring catalyst and the associated debottlenecking operation was in the order of 2 million DM (approximately $1 million). The pay-back time for the investment was 18 months. Today, after three years of operation with the ring catalysts, the revamped plant is still achieving a final conversion of above 99.7%.

PHOTO : Two views showing the parlous state of the cast iron acid distributors in the drying tower PHOTO : before they were replaced with v316L stainless steel distributors in 1982. COPYRIGHT 1989 CRU Publishing Ltd. This material is published under license from the publisher through the Gale Group, Farmington Hills, Michigan. All inquiries regarding rights should be directed to the Gale Group.

Title: CODELCO sulphuric acid plant Date: 2/1/1995; Publication: Haznews; CODELCO, The Chilean National Copper Corporation, is to construct a sulphuric acid recovery plant at the El Teniente division of its Caletones copper smelter (see HAZNEWS, May 1993, p. 16). Four pre-qualified consortia are submitting bids, project manager, Gustavo Sanchez, told HAZNEWS. The consortia are lead by US engineering firm Davy International; the German engineering group Lurgi; the Canadian joint venture Simon Carves/Fenco Engineers; and Mitsubishi Chile/Mitsubishi Heavy Industries. CODELCO said it expects to start examining the bids in February. The plant will have a daily capacity of 1,500 tonnes, and will produce up to 433,000 tonnes of sulphuric acid per year. Bids can be submitted for construction only, or for construction and limited provision of staff and services. The contract also includes a facility for the treatment of acidic effluent containing arsenic. The El Teniente division will also be constructing other related facilities, including a sulphuric acid storage and transfer terminal and a solid and liquid waste disposal system. This is part of the Caletones smelter general clean-up plan, which is expected to cost some $100 million. Copyright 1995 Profitastral Ltd. COPYRIGHT 1995 Profitastral Ltd. This material is published under license from the publisher through the Gale Group, Farmington Hills, Michigan. All inquiries regarding rights should be directed to the Gale Group.

Title: Converter design for S/O.sub.2~ oxidation. (converting sulphur dioxide to sulphur trioxide)

Date: 3/1/1992; Publication: Sulphur; Faced with increasing environmental pressures, sulphuric acid plant designers have developed improved converter designs. A greater understanding of the fundamentals of the S|O.sub.2~ oxidation process may be the key to future optimizations. In general, improved plant operation may be achieved by a greater understanding of the fundamentals of a process. With this concept in mind, Ney R. Luchi, a consultant process engineer in Brazil, has analysed the catalytic oxidation process for converting sulphur dioxide (S|O.sub.2~) to sulphur trioxide (S|O.sub.3~) in sulphuric acid production. The purpose of Luchi's work was twofold: firstly, to find out more about what happens during the oxidation reaction on a microscopic scale, and secondly, to acquire a better knowledge of the effect of lower-thannominal capacity on catalyst performance. In the first section of this article we report on his findings. In the second section of the article we report on the trends in converter design for sulphuric acid production. I - Process fundamentals In the contact process for sulphuric acid, sulphur dioxide is catalytically converted to sulphur trioxide under adiabatic conditions. In the converter, sulphur dioxide gas is passed through a series of fixed catalyst beds (or trays), usually four, with intermediate cooling between each of them. The catalyst is generally vanadium pentoxide, promoted with potassium and sodium sulphate, and dispersed on a silica carrier. The catalyst beds are made up of extrudates or ring-shaped catalyst. Under the operating conditions, the catalyst forms a surface liquid melt in the pores of the solid catalyst. It is in this liquid phase that the oxidation of sulphur dioxide is thought to take place. In modern sulphuric acid units S|O.sub.2~ conversions in excess of 99.3% can be attained. This value is very close to the thermodynamic equilibrium conversion. The uncertainty in predicting the performance of a sulphuric acid converter can be attributed to a number of factors: - non-uniform gas flow across catalyst beds - deviations from mass and heat transfer expressions - uncertainty about the kinetics

Because of these uncertainties, catalyst manufacturers use safety factors to specify the catalyst inventory for converter beds. On a microscopic scale, several other factors relating to the chemical reaction and heat and mass transfer in the catalyst bed must be taken into account for a greater understanding of the oxidation reaction taking place in the converter. Luchi studied the following steps: - diffusion of reagents through the gas film around the catalyst particle - diffusion of reagents in the catalyst pores - chemical reaction - diffusion of S|O.sub.3~ from the catalyst pores to the external surface - S|O.sub.3~ diffusion through the gas film into the bulk gas. For each of these steps a resistance value can be assigned; the sum of the individual values is termed global resistance. Each resistance value can be appraised using a specially-designed computer simulation of the converter. The gas flow rate through the reactor has an effect on the gas-film resistance. Consequently, a reduction in the gas flow rate of an existing reactor will influence the global resistance of the process(1). Effectiveness factor The effectiveness factor |Mathematical Expression Omitted~, which is used in the analysis of the sulphuric acid converter, is useful in characterizing catalyst-pore-diffusion effects(2). It is the ratio of actual reaction rate per unit mass of catalyst to the rate that would result if the complete internal surface of the catalyst were available for reaction. The significance of the role played by internal pore surfaces in catalytic activity can be appreciated since the internal surface areas of most porous catalysts are several orders of magnitude greater than the external surface areas. An alternative expression for the effectiveness factor |Mathematical Expression Omitted~ is: |Mathematical Expression Omitted~ An analysis of the sulphuric acid converter is given on the following page. Analysis of the Sulphuric Acid Converter The analysis presented considers the gaseous mixture in the presence of a solid catalyst. S|O.sub.2~ + 1/2|O.sub.2~ |right arrow~ S|O.sub.3~ |delta~ H = 23.4 kcal/gmol S|O.sub.2~ (1)

S|O.sub.2~ flux through gas film around catalyst particle per mass unit of catalyst km.a.(|p.sub.S|O.sub.2~~ - |p.sub.S|O.sub.2~,s~) (2) where: |k.sub.m~ = mass transfer constant a = external surface per mass unit of catalyst |p.sub.S|O.sub.2~~ = S|O.sub.2~ partial pressure in the bulk gas mixture |p.sub.S|O.sub.2~,s~ = S|O.sub.2~ partial pressure on external catalyst surface Reaction rate for a pseudo-first order reaction |Mathematical Expression Omitted~ (3) where: (-r) = reaction rate per mass unit of catalyst |Mathematical Expression Omitted~ k* = reaction rate constant of the pseudo-first order reaction Under steady-state conditions (2) = (3); hence |Mathematical Expression Omitted~ Substituting this expression in (3) gives |Mathematical Expression Omitted~ (4) where: l/|k.sub.m~.a = resistance to mass transfer (interparticle resistance) (5) |Mathematical Expression Omitted~ (6) The term |Mathematical Expression Omitted~ represents the combination of pore diffusion and chemical reaction resistances. It can be expressed as the sum of these two resistances as shown below: |Mathematical Expression Omitted~ (7) From equation (7) |Mathematical Expression Omitted~ (8) Substituting (5), (6), (7) and (8) in (4) results in |Mathematical Expression Omitted~ (9)

Assuming the rate of S|O.sub.3~ formation as a driving force (S| O.sub.2~ partial pressure) divided by a global resistance, the denominator of (9) can be seen as this global resistance. Hence: |Mathematical Expression Omitted~ (10) where: |R.sub.G~ = global resistance for S|O.sub.2~ oxidation to S|O.sub.3~ | Mathematical Expression Omitted~ l/k* = chemical kinetic resistance In S|O.sub.2~ oxidation to S|O.sub.3~ thermal effects are significant. As the reaction occurs a temperature gradient between catalyst particle and the bulk of gas mixture is established. Figure 1 schematically represents the combination of the aforementioned resistances. The kinetic expression for equation (1) on traditional vandium pentoxide promoted with sodium and potassium is not of the first order. Various kinetic equations have been proposed to represent this chemical transformation, for example: |Mathematical Expression Omitted~ (11) where |k.sub.pm~ = reaction rate constant |K.sub.M~ = constant that depends on temperature only |p.sub.i,S~ = partial pressure of component i on catalyst surface |K.sub.p~ = thermodynamic equilibrium constant of equation (1) |k.sup.*~ = pseudo-first order reaction rate constant However, it is commonly recognized that any single rate expression for a certain catalyst is adequate only for a narrow range of temperatures and gas compositions. In equation (11) we have: |Mathematical Expression Omitted~ (12) In non-first order reactions, the kinetic resistance is expressed as a function of partial pressures and adsorption parameters of the substances involved under catalyst conditions. For the converter simulation, heat and mass transport parameters were estimated by using empirical correlations established from analysis of experimental data for a variety of gas-solid systems.

Evaluation of results The computer program was used to simulate a sulphuric acid converter with four adiabatic catalyst beds, each with a diameter 7.5 metres, and double absorption with a 3+1 configuration. The capacity of the simulated unit corresponded to 600-t/d |H.sub.2~S|O.sub.4~ with a gaseous feed to the first bed containing 11 vol-% S|O.sub.2~. The catalyst used in the four beds was type VK38 10-mm ring-shaped catalyst from Haldor Topsoe. The industrial converter was simulated for different capacities. Results obtained were evaluated in terms of temperature difference between the bulk gas and the catalyst, global resistance in the first bed, and contributions to global resistance. Temperature difference between gas and catalyst Owing to the highly exothermic oxidation reaction occurring in the converter, a temperature gradient is created between the catalyst particle and the gas flowing through the bed. This temperature difference is more pronounced in the first bed, where the rate of reaction is greater. Calculated temperature values for the bulk gas and catalyst particles in the first bed are shown in Fig. 2. The linear dependence of the bulk gas temperature with S|O.sub.2~ conversion comes from the approximate constancy of gas heat capacity throughout the reactor. In the first bed, a reduction in gas flow rate results in an immediate increase in the temperature difference between the catalyst particle and the bulk gas. Figure 2 indicates that the temperature difference between the bulk gas and the catalyst surface when operating at nominal capacity may be up to 15|degrees~C. However, calculations carried out by Haldor Topsoe show a much smaller difference of 7-8|degrees~C. Global resistance in bed 1 Figure 3 shows the global resistance for the oxidation reaction in the first bed of an industrial converter over a range of capacities. A slight variation in global resistance can be detected at different operational capacities. This arises from the mutual compensation of the different resistances. As the flow rate decreases, there is an increase in film resistance and a reduction in the chemical resistance. In the first bed, two different regions are noted. In one region, global resistance decreases with a reduction in flow rate. In the other region, the opposite occurs, that is, global resistance increases with a reduction in flow rate.

The border between these two regions occurs at a point before the halfway mark for the total S|O.sub.2~ conversion reached in bed 1. The global resistances at the beginning and end of the first bed differ significantly at different flow rates. The initial layers of the first bed of a given reactor have a lower global resistance when operating at a lower than normal gas flow rate. Caesium-promoted catalyst The low-temperature, caesium-promoted, vanadium catalyst that became available in the late 1980s, Haldor Topsoe's VK58 catalyst, has enabled the design of acid plant for far higher S|O.sub.2~ strengths than previously possible. As a result, the catalyst may give rise to reductions in equipment size and improvements in the economics of plant operation because of the smaller gas volume to be processed. With conventional catalysts the maximum S|O.sub.2~ concentration that can be treated in an acid plant is typically 10-12%. If higher S| O.sub.2~ concentrations are treated the exit temperature of the first pass exceeds the temperature limits set by the catalyst and the materials of construction. By combining the use of stainless steel converters and caesiumpromoted catalysts, the processing of strong, oxygen-rich S|O.sub.2~ gases is now possible. This option has become particularly interesting with the increasing tendency to use oxygen enrichment in, for example, copper smelters and sulphuric acid recovery plants. One such case is a Canadian acid plant processing off gases from a copper smelter. The gas contains 11-14% S|O.sub.2~ and 10-15% oxygen. The operation of the smelter was previously restricted by the limit on the first-pass outlet temperature, which was imposed to protect the Meehanite grids and carbon-steel converter. This restriction was overcome by installing a separate Chemetics stainless-steel first pass, which was loaded with 50% Topsoe VK58 Cspromoted catalyst and 50% conventional Topsoe VK38. The installation of VK58 in the upper part of the bed (it is pointless to use VK58 for the whole of the pass, since a conventional catalyst will work just as well at the higher temperatures further down the bed) enabled the plant to operate at a first-pass inlet temperature of 380| degrees~C yielding an exit temperature not exceeding approximately 635|degrees~C. An inlet temperature of 410-420|degrees~C required for a loading of conventional catalyst would have taken the exit temperature close to 660|degrees~C.

Since completion of the revamp, the plant has realized a substantial increase in copper production. Although it is hard to quantify VK58's contribution exactly, the plant personnel feel that the use of VK58 in the first pass has removed a significant constraint on production. Other benefits of installing caesium-promoted catalyst in the upper part of first passes are that it can reduce the start-up time and extend the period during which the plant can be restarted without using a start-up heater. There are also several cases where caesium-promoted catalysts have been installed in the last passes. The main purpose of this arrangement is to increase the conversion efficiency in single absorption plants by enabling operation at low inlet temperatures. Although diffusional restrictions are severe in the last pass, there is a benefit to be had from the increased activity of the caesium catalyst. In fact, the same improvement in overall conversion efficiency would not have been obtained by installing the caesium catalyst in the first pass although mass-transport resistances are not as pronounced there. The selection of ring-shaped catalyst or extrudates is dependent on the desired pressure drop. However, diffusional restriction considerations play a role for the catalyst suppliers' recommendation of particle size and explain why extrudates have to be smaller than rings. For example, larger particles may be installed in the upper pass(es) to obtain lower pressure drop and higher dust tolerance without sacrificing activity. Diffusional restrictions are also taken into consideration when developing shape-optimized catalysts. Conclusions Luchi concludes that the performance of chemical processes can generally be improved if more attention is devoted to understanding the fundamentals. In the first bed of the sulphuric acid converter there is a high temperature gradient between the bulk gas and the catalyst particles. This gradient increases when the gas flow rate to the converter is reduced. The global resistance for catalytic oxidation of sulphur dioxide in the first bed is higher at the bed extremes. For the bulk of the bed, the variation in global resistance is moderate. This small change can be attributed to the variation in interparticle and chemical kinetic resistances. Pore diffusion in the catalyst controls the S|O.sub.2~ conversion for most parts of all catalyst beds in a sulphuric acid converter. The kinetics (intrinsic catalyst activity) also plays an important role in S| O.sub.2~ conversion, for example, even if kinetics contribute to only

10% of the global resistance, a 30% increase in intrinsic catalyst activity will yield a 20-25% increase in apparent catalyst activity. II - Converter design In the design and construction of any converter intended to attain a guaranteed maximum S|O.sub.2~ conversion, proper attention to the removal of reaction heat is of vital importance. As the reaction is generally carried out under adiabatic conditions, the temperature of the solid catalyst bed rises, thus limiting the attainable S|O.sub.2~ conversion in accordance with the thermodynamic equilibrium. To achieve a high final S|O.sub.2~ conversion it is therefore necessary to divide up the total catalyst mass into several beds and the hot gas leaving each bed is cooled before entering the next. Figure 4 shows a typical converter scheme for double absorption with a (3+1) configuration. Normally the converter is designed as a vertical cylindrical vessel, with the catalyst beds mounted one above the other in separate, virtually gas-tight compartments. The gases enter and leave through lateral nozzles and pass upwards or downwards through the beds. The catalyst mass is supported by a metallic bed grate. A base layer of ceramic packing prevents direct contact of the catalyst with the grate which could give rise to corrosion. The catalyst bed is covered with another layer of packing. This serves the dual purpose of helping to ensure uniform gas and temperature distribution over the surface of the catalyst and of preventing the catalyst itself from blowing around and leaving cavities in the bed, which could also adversely affect the gas and temperature distribution in the main body of the catalyst bed(4). The design of a converter requires careful optimization because of the great number of interacting parameters. This has been made considerably easier by the development of computer programs. The most important variables are the sulphur dioxide concentration and the gas flow rate, the number of beds, the specific catalyst quantity and its distribution between the individual beds, the gas pressure drop and the gas inlet temperatures for the individual beds. Other criteria include whether the process is single absorption or double absorption, the size of the plant, where it is located and the influence of the investment cost on the overall project. Pressure vessel codes Converter design is an area in which change has taken place both to upgrade the long-term reliability of the plant, and to address a number of short-term needs. As safety and environmental regulations change, there will likely be a requirement to review converter design in relation to pressure codes. This will necessitate a move to improved materials of construction for this important part of the acid plant. Carbon steel

converters are unable to meet the material requirements of pressure vessel codes. It is becoming increasingly apparent in Western Europe that some legislative bodies and operating companies already perceive the converter to be a pressure vessel, requiring stringent quality assurance procedures as well as extensive non-destructive testing, and in some cases, an air pressure test. Traditionally, converters were fabricated from a combination of carbon steel and cast iron grids and posts, with the carbon steel around bed 1 protected from high-temperature oxidation either by metallizing (also referred to as aluminizing) or refractory lining. Aluminizing is a process in which aluminum is diffused into the steel to form a thin layer of an iron-aluminum alloy which has superior heat resistance. It is commonly used with carbon steel/cast iron converters to prevent scaling caused by the hot gases. Unfortunately, carbon steel has very low creep strength and oxidation resistance above 400|degrees~C. This means that the converter designer has been restricted in bed lay-out by having to place bed 1 at the top of the converter. If situated at the base of the converter, the carbon steel shell is unable to sustain the combination of gas pressure forces and weight of the other beds. Even being placed at the top of the converter has often resulted in bulging of the shell where the carbon steel is unable to resist the stresses induced by the gas pressure. This bulging of the shell causes gas bypassing around the cast iron grids and, in many cases, has resulted in the actual collapse of beds. Carbon steel has to be protected from high-temperature oxidation to prevent large quantities of oxide from flaking off the shell and contaminating the catalyst bed. Protection by aluminizing is partially successful but is a high-cost maintenance item because of the short life of the coating in the environment of bed 1. Protection by refractory lining is also only partially successful because of the impossible situation of the shell having to be insulated on the outside while having a refractory lining on the inside. The metal temperature cannot be reduced much below the bed temperature because of the outside insulation. This means that the shell expands away from the refractory lining causing it to collapse. The problems with these carbon-steel converters have become worse over the years, as plants have begun operating at higher S|O.sub.2~ strengths and consequently higher temperatures. In 1980, after a number of years of in-house experience with stainless steel in a radial-flow converter at an acid plant in Sudbury, Ontario, Chemetics introduced a totally new converter design concept to the industry, the use of 304 austenitic stainless steel as the material of

construction. This new converter design concept overcame all the operating and design limitations of the traditional post and grid converters. Converter types Being the paramount vessel in the contact sulphuric acid plant, the converter has always drawn the attention of sulphuric acid plant designers. This attention has intensified, particularly over the past two decades when environmental requirements have demanded improved designs. However, the old and proven designs are still justified in certain cases. There are four main types of converter: the fully brick-lined converter, converters with integrated heat exchangers, plate-type converters and stainless steel converters. Brick-lined converters The interior of the shell in this older type of converter is completely lined throughout with acid-proof bricks. The compartment separators are self-supporting domed structures made of shaped bricks. They carry brick columns which support the catalyst bed grates. The advantages of this converter design lie in the heat capacity of the large volume of bricks. For plants which have to treat a gas of fluctuating strength and volume this heat capacity is able to straighten out the thermal effect of these fluctuations on conversion, as well as on the material stress and strain. This design also has the advantage of staying hot for a long time after shutdown (for more than 24 hours), a feature which is highly praised by operators of plants treating metallurgical gas sources. Its drawbacks are its size limitations (a reasonable technical limit for the converter diameter is about 12 m) and, for a lot of countries, the very high investment cost resulting from labour-intensive bricklaying. Converters with integrated heat exchangers The merit of this design is also its heat conservation, which also makes this design best suited to metallurgical gas plants (lead/zinc sinter machines, copper smelters, etc). Heat conservation in this case is achieved by the compact arrangement of the heat exchangers, thus reducing the amount of ducting. The main disadvantage of this design lies in its size limitations. Plate-type converters Plate-type converters, which replace bricked domes and bricked shells by straightforward mild steel plate designs are applied in the majority

of sulphuric acid plants. The design may include a central column, which in recent years has been used as a duct. This provides many improvements such as a reduction in the amount of ducting, and central gas inlet/outlet of a critical layer of catalyst, which results in better gas distribution and reduces the strain on the construction materials, especially the metal domes and catalyst supports. The design also enables the catalyst beds to be arranged differently, for example, the first layer can be arranged in the lower part of the converter to facilitate catalyst screening. Its main advantage is the comparatively low investment cost, even if low-alloy plate is used. The drawbacks are the low heat capacity of the vessel, a fact which would not have any bearing in the case of a sulphur-burning plant, and the need for aluminizing the shell and domes in large hot areas of the vessel. Stainless-steel converters Stainless-steel converters have become a convincing design. The merits of introducing stainless steel are not so much a means of dealing with the mechanical strength required at elevated temperatures, rather they lie in the excellent anti-scaling properties which means that no aluminizing is required. Any design which is not brick-lined may be constructed of stainless steel, thus making it an ideal solution for replacement jobs. These tasks, where shutdown time of an existing plant must be kept to an absolute minimum, require a design which can be fully fabricated (preferably with lagging and cladding) in parallel to plant operation, and then lifted and installed into place. Chemetics The Chemetics converter, which is covered by patents worldwide, is an all-welded fabrication consisting of two vertical concentric cylinders connected by dished annular plates, referred to as "blooper plates". The top and bottom heads of the vessel and the internal series of blooper plates are preformed into dished shapes to enable them to resist the pressure forces of the converter gas. Constraining gas pressure with thin curved plates instead of the more traditional methods of thick flat plates combined with beams or pipes results in an extremely strong structure. These thin curved plates are far superior in withstanding the high thermal stresses induced in the converter because the high bending stresses inherent in conventional beams and pipe designs are reduced to a minimum by subjecting the material to mainly membrane stresses. The curved plate or blooper construction also provides the flexibility for the vessel to sustain the high thermal expansions experienced with the use of stainless steel. The high creep strength of stainless steel at high temperatures also provides the designer with the freedom to place bed

1 at the base of the vessel to facilitate catalyst screening. The oxidation resistance of stainless steel at elevated temperatures eliminates the requirement for metallizing or refractory lining, and the all-welded construction totally eliminates the problem of gas bypassing between beds, giving the highest possible conversion efficiencies from the catalyst. Other companies besides Chemetics offer stainless steel converters. Chemetics points out, however, that some of them merely perpetuate the principles adopted in the early carbon steel/cast iron designs, except that the material has been changed to stainless steel. Consequently, these converters not only cost significantly more than the carbon steel designs, they also exhibit many of the early problems of gas bypassing and duct nozzle leaks. Chemetics maintains that this is because not all companies have recognized the importance of applying a converter material which has a very high thermal expansion and poor thermal conductivity compared with carbon steel. Chemetics regards its converter design as extremely cost competitive when compared with the carbon steel/cast iron grid designs. Replacing carbon steel and cast iron grids with 304 stainless steel now enables converters to have the potential to be designed, if necessary, in accordance with the various national pressure vessel codes. Two of Chemetics' converter installations in the UK have been subjected to air pressure tests, in order to comply with specific client safety standards. Chemetics' converters can also be designed to meet ASME allowable material stress levels. The blooper plates which provide the catalyst support are perforated and covered with stainless mesh to support the quartz pebbles and the catalyst. This blooper plate/concentric cylinder design does not limit the converter size. Existing units of up to 14 m in diameter have proven successful and diameters of up to 20 m can be accommodated. A notable feature of the Chemetics design is the open access above and below each catalyst bed, which is completely free from posts, beams and other access-restricting devices. Gas distribution over the catalyst beds is one of the main problems of conventional converter designs. This problem has been addressed in the Chemetics converter design by always utilizing the central core cylinder for distributing the gas to each bed radially through slots. This ensures uniformity of gas distribution and hence maximum utilization of the catalyst. This feature is especially important with the new developments in low pressure drop catalyst. Working on the principle that rectangular nozzles, gussets, brackets and heavy sections all introduce high stress concentrations and tendencies for materials to crack at high temperatures, Chemetics has developed a circular nozzle transition design for all converter nozzles.

This eliminates one of the major maintenance items on conventionallydesigned acid plants. The concentric-cylinder design of the Chemetics converter also facilitates one of the converters' major patented features, the placement of the hot exchanger inside the core cylinder. This feature removes the necessity for an external duct between the outlet of bed 1 and the hot exchanger. The hot duct and its connections have been the single biggest cause of gas leaks on conventional acid plant designs. The low thermal capacity of the Chemetics stainless steel converter and the flexible design allows rapid start-up times without heat retention problems during short plant shutdowns. For example, a 14-m diameter Chemetics converter was able to restart after a 22-hour shutdown during extreme Canadian winter conditions without the aid of a preheater. Fifteen Chemetics converters have now been successfully installed and operated in seven countries around the world. A significant advantage of the Chemetics converter, evident in the construction phase, is the facility for modular construction. Sections of the converter can be fully shop fabricated and simply welded together on site. Complete converters can also be constructed on site and moved into position with a single crane lift. This principle was used at the Peridot plant in New Jersey. These features of the Chemetics converter considerably simplify and shorten retrofit times and reduce field costs on new plants. TABULAR DATA OMITTED Lurgi As mentioned earlier, the design of a sulphuric acid converter depends on a number criteria and is carried out on a case by case basis. This is illustrated by two of Lurgi's recent projects. Case 1 In February 1989 Lurgi was awarded the contract for the construction of a new sulphuric acid contact plant at the MHO-Hoboken works in Belgium. The main products from the MHO-Hoboken works are lead, blister copper and precious metals which are recovered from lead and copper ores and their residues, which are likewise processed. Sulphuric acid is produced from the sulphur dioxide-containing gas arising from ore processing(5). The new sulphuric acid plant was to replace a tower plant, built in 1930, which produced sulphuric acid with a strength of 78% from smelter gas. Owing to its long production record, the tower plant increasingly required repair and maintenance. Other factors influencing the decision to shut down the tower plant included the current difficulty

in selling sulphuric acid of 78% strength at a favourable price and the problem of nitrogen oxides in the stack gas. The main objective of the new sulphuric acid plant was to process the S|O.sub.2~-containing gases arising from the various metallurgical operations to yield an easily marketable product, whilst improving the environmental impact. Depending on the kind and capacity of the smelters and the raw materials processed, the gas volumes to be treated at the works can vary during operating periods and have extremely diverse sulphur dioxide and oxygen contents. The main gas streams originating from the sinter plant, roaster and converter contain 2-10 vol-% S|O.sub.2~, 5.5-14 vol-% |O.sub.2~, and 1.5-6 vol-% C| O.sub.2~. The gas volumes vary from 7-19 N|m.sup.3~/s. An important prerequisite for the new plant was that the sum of the S| O.sub.2~ + S|O.sub.3~ + N|O.sub.x~ contents in the stack gas should not be higher than for a comparable gas supply to the former tower plant. Table I shows the maximum sulphur dioxide contents of the stack gas at the nominal gas volume and the maximum gas volume as a function of the sulphur dioxide concentration of the gases entering the converter. For a single-absorption plant, these stack gas characteristics mean a lower limit. It was therefore necessary to select the catalysts most suited to these conditions, i.e. active at extremely low temperatures, and to use great care when defining the catalyst fill and designing the converter. A four-tray stainless-steel converter of compact design was selected. Trays 1 to 3 were filled with standard-quality ring-shaped catalyst; tray 4 was filled with a caesium-promoted catalyst, which allows operation at temperatures 20-30|degrees~C lower than with standard-quality catalyst, thus permitting an increase in S|O.sub.2~ conversion by shifting the reaction equilibrium. The converter group is shown in Fig. 5. The dried sulphur dioxide gas is extracted from the dryer by a gas blower and delivered to the converter system. The gas is indirectly heated in tube-bundle heat exchangers to the temperature required at the inlet of tray 1 (410| degrees~C), in countercurrent with the reaction gases from the converter. The gas passes through the four catalyst-filled trays of the converter in series. Intermediate cooling takes place after each of the first three trays. This cooling is necessary to utilize the heat of reaction for preheating the cold sulphur dioxide-containing gases and to cool the reaction gases in order to shift the reaction equilibrium in favour of a higher S|O.sub.2~ conversion.

The heat exchanger after the second tray was designed as an annular heat exchanger arranged around the converter shell, whereas the heat exchanger between trays 3 and 4, which has an extremely small exchange surface, was installed in the central tube of the converter. This design allowed optimum arrangement of the converter group on the existing premises. The plant, which was designed as a single-absorption unit in view of the frequently extremely low S|O.sub.2~ gas contents, included provisions to be extended to double-absorption. The plant went on stream on October 1, 1990 in accordance with the agreed completion date. Case 2 In November 1989, Lurgi was awarded a contract to revamp a sulphuric acid converter in a chemical complex near Frankfurt(6). The converter formed part of a sulphuric acid plant which was put into operation by Lurgi in 1967 and then modified in 1975. The original plant treated roaster gas to produce sulphuric acid, oleum and liquid sulphur trioxide. For economic reasons the sulphuric acid plant was revamped in 1975 to accommodate the burning of liquid sulphur. In 1989 there were indications that the original brick-lined converter, which was in accordance with the state of the art when it started up in 1967, may have been damaged. The converter comprised four layers of catalyst arranged from top to bottom. The catalyst rested on perforated plates supported by brick domes. The cylindrical converter consisted of a brick-lined plate shell with thermal insulation comprising mineral wool and sheets of aluminum. The converter had been operating trouble-free for over 20 years and the operators were very satisfied with its service. On planning a repair or replacement, two essential aspects were taken into account. Important production facilities at the works are dependent on the product 100% S|O.sub.3~. Procurement from outside is not possible. Storage of the sulphur trioxide in liquid form without stabilization is only possible for a few weeks; storage capacity for a maximum of 3 weeks was available. That meant that replacement or repair of the converter would have to be carried out within an overall shutdown period of 18 days, including cooling down and heating up. Thus, repair to the existing converter was out of the question because the brickwork for the domes, etc. would definitely take longer, as would a new bricklined converter.

In view of the need for access to the overall converter system, the possible duct routing to the tray inlets and outlets (a total of 8 nozzles), and the construction site conditions, the new converter had to be located on the existing converter foundation. These two criteria led to the decision to build a stainless steel converter with no brick lining and, thus, replace the brick-lined converter with bricked domes (Fig. 6). Lurgi utilized its past experience in the construction of carbon steel and stainless steel converters. The largest Lurgi-built converter has a diameter of 12.2 m, installed in a sulphuric acid plant producing a maximum 1,500 t/d sulphuric acid from 7% gases. In order to fulfil the two criteria - short shutdown periods and location on the existing foundation - it was necessary to design the diameter and base of the new stainless steel converter in such a way that the existing foundations could be used without alteration (for schedule reasons). The existing gas lines were retained to the greatest degree (cost and time savings), whilst taking into account the greater thermal expansion of the stainless steel, the charging of sufficient quantities of catalyst, and above all, retaining the plant performance to date, including optimum S|O.sub.2~ conversion. Furthermore, the new converter was supplied prefabricated to the greatest degree and then completely assembled and insulated on an available open space. The revamp comprised a number of steps. The supplier shop-fabricated the converter in the largest possible sections. The transport routes to and within the facility, the size of the individual parts, as well as the completion date and the sequence of the sections, had to be precisely planned. The sections were transported to the customer by ship, in accordance with a detailed transport and assembly schedule. The new converter was assembled on an available space next to the existing contact system. The pipe racks in the plant could not be modified, nor could the operation of the plant be disrupted for transporting the components in the works to the erection site. The assembly sequence for the converter with insulation and catalyst charge were precisely planned with the customer, as were the shutdown of the sulphuric acid plant with blow out, disconnection of the old converter and its removal. After disconnecting the old converter from the heat exchangers and cutting out the sections of the gas duct, the converter was raised

hydraulically, placed onto heavy rollers and taken away on a supporting structure. This was completed in one day. During the remaining work on the new converter and the new sections of ducting and duct connections, the foundation was repaired as necessary. Finally the new converter was lifted onto the foundation with a 1,000tonne crane and the prepared pipe sections were positioned and connected in accordance with the detailed installation time schedule. The sulphuric acid plant was ready for operation one day ahead of schedule. The mode of operation with the new converter is practically the same as for the previous one. During operation the new stainless steel converter proved to have a number advantages over the old brick-lined converter. The heating up time was shorter. The time taken to reach normal operating conditions after start-up was shorter. The S|O.sub.2~ conversion was higher, due at least in part to the welded partition between trays 3 and 4 being absolutely tight. Intermediate absorption takes place between these trays and the bricked domes in the old converter were no longer absolutely gas-tight after 20 years of operation. Monsanto Enviro-Chem Monsanto Enviro-Chem has designed over 700 converters for sulphuric acid plants ranging in capacity from 20 to 3,000 t/d. The same design principles apply to all plants. The main aim is to obtain the maximum conversion per pass in the most economical way. A second consideration is to have the lowest maintenance possible within reasonable economic parameters. As makers of both catalyst and converters, Monsanto looks at the overall balance of cost, quality, and efficiency when determining the final design. Two well-proven designs of converter can be offered, carbon steel/cast iron converters or stainless steel converters. Both converter types are available in sizes up to 50 ft (15 m) diameter. There have been no converter size limitations for any of the plants that have been built or under construction. The conventional axial converters with carbon steel shells and cast iron catalyst supports are still the most popular design in many countries. This is because in regions where stainless steel is not locally available the cost for importing stainless steel makes the stainless steel converter more expensive.

The stainless steel converter design has a number of technical advantages over the carbon steel/cast iron type. The stainless steel design permits the base and roof of the converter to be tied to give greater structural stability, which is particularly important for larger units. The horizontal beams which support the catalyst support grid or mesh are of such a length that they either span as a chord across the reactor or at least one end of the beam abuts a vertical support column with sufficient clearance to allow for thermal expansion(7). Stainless steel converters can be used with high gas strengths, over 12% S| O.sub.2~, without the risk of damage due to high gas temperatures. No aluminizing is necessary. Because of its higher strength, 304 stainless steel also allows optimization of pass arrangement. For example, pass 1 (catalyst bed 1) can be placed at ground level, allowing faster gas cleaning. With the first stage at the bottom of the reactor, there are no structural problems to prevent making the first stage of larger diameter, if desired, than subsequent catalytic stages. This allows the use of shallower catalyst beds in the first stage, with less pressure drop through the bed and lower bed velocities so that residence time of the gas or other fluid in the catalyst bed need not, unless desired, be reduced. This feature also enables the designer to minimize ductwork, which reduces the pressure drop, maintenance and cost. Browder Over the past 42 years Tim J. Browder Company has designed 82 sulphuric acid plants in 24 countries with converter diameters ranging in size from 1.8 m to 14 m. Of these plants, 32 have been double absorption and 13 plants have had conversion efficiencies in excess of 99.93%. These high-efficiency plants have had stack emissions as low as 70 vppm S|O.sub.2~, and in all cases, the guaranteed exit gas after 2 years has been less than 100 vppm S|O.sub.2~. The world's first double-absorption metallurgical sulphuric acid plant to have a guaranteed S|O.sub.2~ conversion of 99.2% and a stack emission of less than 100 vppm S|O.sub.2~ was designed and built by Browder for Tomakomai Chemical Company Ltd in 1972. The plant, located on the island of Hokkaido, north of Japan, was designed with a converter comprising five catalyst beds in a (3 + 2) configuration and a converter diameter of 10.5 m. Gas distribution has not been a problem with Browder converter designs. In many cases the gas inlet nozzles on the converter shell have been as wide as one-third the diameter of the converter shell. These nozzles are oval shaped and include deflector swirls which uniformly distribute the gas in a rotary motion. Browder claims to be able to design converters with diameters in excess of 20 m and conversion efficiencies in excess of 99.93%.

Using the Browder Dry Air Atomizing Sulphur Gun in a sulphur-burning plant it is possible to convert 25% of the 10-11% sulphur oxide gases to sulphur trioxide before they enter the converter. This, together with the furnace design and some special S|O.sub.2~ recycling techniques in the absorption system, enable guarantees of stack emissions less than 20 vppm S|O.sup.2~, with total sulphur recovery efficiencies in excess of 99.98%. Browder is currently designing a 200-t/d sulphuric acid plant in Thailand with this 99.8% recovery efficiency. Browder's current converter design for sulphur-burning plants uses gas inlet flows of 1,450-1,550 N|m.sup.3~/h per square metre of flow area in the catalyst bed using 10-11% sulphur oxide gases. The gas entering the top bed of the converter may already have an S|O.sub.3~ content of 2.5%. A converter with five catalyst beds, using a total of about 210 litres of catalyst per tonne of plant capacity, can achieve overall conversion efficiencies in excess of 99.94%. The currently preferred catalyst is ring shaped with a 12-mm diameter. The catalyst beds are supported on high-strength Meehanite columns, grids and division plates from the base of the converter. The columns, grids and division plates for the upper catalyst beds are constructed of Meehanite HR/1, which has a working tensile strength of more than 250 kg/|cm.sup.2~ and provides excellent service for many years at temperatures as high as 630|degrees~C. The Browder design represented in Fig. 7 shows the self-locking feature of the Browder design. The grid and division plates are locked into recessed hubs which ensure complete stability during construction and operation. This design of interlocking all the internal plates and columns has been used for the past 27 years and can withstand earthquakes registering 6.2 on the Richter scale. Browder currently uses fire-box quality carbon steel plate with a 304 stainless steel cladding for all exposed internal surfaces of the converter shell. This type of cladding, first used by Browder in 1956, has given excellent service over the years. In certain areas where the catalyst bed temperature is high, insulating brick lining is used to control the temperature and expansion of the converter shell. Institute of Catalysis The principles of the reverse-process of S|O.sub.2~ oxidation for sulphuric acid production, developed by the Institute of Catalysis, Novosibirsk, have been covered in earlier issues of Sulphur(8,9). The basic idea of this process is the periodic reversal of the direction of a gas flow, which has a low initial temperature, within a fixed catalyst bed or beds. At present there are nine industrial plants using this process in Russia, Kazakhstan and Bulgaria. The feed gas for all of these plants comes

from the non-ferrous metal industry and varies substantially in S| O.sub.2~ concentration and gas flow rate. The reverse-flow converter is extremely stable under these fluctuating conditions. Detailed design of the contact unit is developed by different engineering groups familiar with the design of equipment for sulphuric acid plants, based on the know-how provided by the Institute of Catalysis. This know-how has been acquired through thorough mathematical simulation of the converter and over 10 years of experience with pilot and industrial plants. It is now possible to define typical converter types for applications(10). The primary objective of the first five installations using reverseprocess technology was to reduce the amount of sulphur dioxide gas being vented to the atmosphere by utilizing it in the production of sulphuric acid. These objectives were met and S|O.sub.2~ conversions have been satisfactory. For example, an S|O.sub.2~ conversion efficiency of up to 98% can be obtained when treating gases containing less than 3-4% S|O.sub.2~ The converter design for the reverse-flow process is quite similar to that of traditional plants as regards construction materials and the design of the bed supports etc. At the Pechenga nickel plant, situated on the Kola Peninsula, a 12-m diameter converter constructed of traditional materials has been operating for more than 4 years. A converter design with a large-diameter central column in which heat exchangers can be installed looks promising for future designs, especially for large plants. The Institute of Catalysis and the Fertilizer Institute (Moscow) jointly proposed the converter design shown in Fig. 8 which has two heat exchangers in the central column of the converter. This design was successfully realized in 1990 at a Bulgarian plant processing the gases from the Plodiv non-ferrous metals smelter. This design enables a higher conversion efficiency due to the optimized temperature profile and the location of the heat exchangers enables high thermal stability to be maintained. Standard industrial catalyst is used in the reverse-flow converter. It has been shown that temperature fluctuations do not have a deleterious effect on the mechanical stability and activity of the catalyst in comparison with traditional plants operating under similar conditions. As with traditional plants, large ring-shaped catalyst can be used to increase the linear velocity. Other benefits of using larger catalysts in the reverse-flow converter are the decreased temperature of the catalyst bed and a higher conversion when treating gases with a high S|O.sub.2~ content. Part of the catalyst loaded into cold boundaries of the bed can be replaced with inert packing.

The avoidance of hot spots and cold spots in the catalyst bed is more important for reverse-flow converters than traditional ones. The Institute of Catalysis has, therefore, developed rational methods to ensure against hot spots and cold spots. One additional problem to be solved when the reverse-flow technology is applied is the minimization of "dead volume" in the converter. Dead volume refers to the volume of unconverted gas which is expelled each time the direction of flow is changed. This volume can be minimized such that the conversion losses are no more than 0.2-0.3%. A sulphuric acid plant with a reverse-flow converter also has largediameter switching valves. The switching time must be very short (no more than 2-4 seconds) and gas leakages through closed valves must be negligible. Industrial experience has shown that these requirements can be met. At the Pechenga nickel plant the three-way switching valves, which have a diameter of 1.8 m, have been operating successfully for over 4 years. Owing to the simplified flow sheet and lower pressure drop, the Institute of Catalysis believes the reverse-flow technology is applicable to converters of larger capacity, especially for treatment of gas with a low S|O.sub.2~ content. References 1. Luchi, N. R.: "Sulphuric acid units: implications of fundamentals in the practice of S|O.sub.2~ reactor". (Jan 1992). 2. Perry, R. H. and Green D.: "Perry's Chemical Engineers' Handbook". Sixth Edition. McGraw-Hill Book Company (1984) pp. 4-38 to 4-41. 3. Jensen-Holm H. and Rud-Bendixen, O.: "Industrial experience with the Topsoe VK58 sulphuric acid and the WSA-2 process. Preprints from British Sulphur's Sulphur 1990 International conference, Cancun, Mexico, (Apr. 1990) pp. 291-310. 4. Sander, U. H. F., Fischer, H., Rothe, U. and Kola, R.: "Sulphur, Sulphur Dioxide, Sulphuric Acid" (ed. More). British Sulphur (1984) pp. 289-295. 5. Ludtke, P., Winkler, E., Steenhoudt, L., Seeldrayer, P. and Boillat R.: "MHO-Hoboken replaces sulphuric acid plant". Preprints from British Sulphur's 19th International conference "Sulphur 91", New Orleans, USA, (Nov. 1991) pp. 139-158. 6. Ludtke, P. and Winkler, E.: "Converter replaced in 18 days". AIChE Convention 1991. 7. Betteken, J. C. and McDaniel, J. D.: "Unitized catalytic reactor construction". US Patent No. 4,195,064 (Mar. 25 1980).

8. "Unsteady-state oxidation of sulphur dioxide for sulphuric acid production". Sulphur No. 183 (March/April 1986) pp. 23-30. 9. "Sulphuric acid process technology round-up". Sulphur No. 210 (September/October 1990) pp. 24-35. 10. Matros, Yu. Sh. and Bunimovich, G. A.: "Reverse-process of S| O.sub.2~-oxidation in sulfuric acid production". Preprints from British Sulphur's Sulphur 1990 International conference, Cancun, Mexico, (Apr. 1990) pp. 249-265. COPYRIGHT 1992 CRU Publishing Ltd. This material is published under license from the publisher through the Gale Group, Farmington Hills, Michigan. All inquiries regarding rights should be directed to the Gale Group.

Title: Acid leader on-stream and on probation. (Industry News: Ukraine).(JSC Rivneazot's sulphuric acid plant)(Brief Article) Date: 1/1/2003; Publication: Sulphur; One of Ukraine's biggest sources of sulphuric acid is back on stream-on a trial basis--following an 18 months shutdown. JSC Rivneazot's acid plant has a capacity of 2,000 t/d. The trial run is to evaluate its condition and look at the possibility of re-starting it commercially. If the plant can be refurbished to an acceptable level of operation, Rivneazot still has to counter the problem that customers for its acid have found other suppliers. Additionally, production of phosphate fertilizers is declining in Ukraine. Initially the company plans to produce sulphuric acid in small batches, which will be sold for the treatment of water at thermal and nuclear power plants, as well as in chemical fibre production. In addition Rivneazot plans to reinstate production lines for non-phosphate fertilizers to absorb some of its acid production. It is one of Ukraine's largest chemical producers, with a product range including ammonium nitrate, ammonium phosphate and diammonium phosphate. COPYRIGHT 2003 CRU Publishing Ltd. This material is published under license from the publisher through the Gale Group, Farmington Hills, Michigan. All inquiries regarding rights should be directed to the Gale Group.

Title: HRS reduces sulphuric acid production costs. (Heat Recovery System) Date: 3/1/1990; Publication: Sulphur; Performance proved in commercial units HRS reduces sulphuric acid production costs A sulphuric acid plant, particularly one which burns elemental sulphur, produces a prodigious amount of high-level waste heat. Not only is the sulphur burnt at high temperatures but also the subsequent conversion of sulphur dioxide to sulphur trioxide is conducted at quite high temperatures. It has long been the practice to combine the very necessary expedient of moderating process gas temperatures in the plant with the very desirable one of energy recovery by means of passing the hot gases through waste heat boilers and associated steam superheaters and boiler feed water preheaters. Modern sulphuric acid plants produce up to 1.4 tonnes of high- and medium-pressure steam per tonne of monohydrate (100% [H.sub.2][SO.sub.4]); this can usually be put to very effective use in other process units on site (a phosphoric acid/granular fertilizer operation, for example) or in generating electric power. There is another very substantial source of heat within a sulphuric acid plant, but for many years it was overlooked on account of its very low grade. That is the heat produced by the reaction of sulphur trioxide in the absorption system and by the dilution of sulphuric acid in the air (or feed gas) drying tower. In quantitative terms, it can amount to as much as one third of the thermal output of a sulphur-burning plant, but in the case of a "cold-gas" sulphuric acid feeding on metallurgical off-gases or on the gaseous products of a spent acid regeneration plant, it represents virtually all the recoverable process heat. Nevertheless, until recently it was rejected through the acid coolers because, to protect the fabric of the plant, the acid circuit operating temperatures were limited. Some years ago, in the wake of the "energy crises" of 1973/4 and 1979, operators of large sulphuric acid plants began to look wistfully at the very large amounts of heat that they were rejecting from their acid circuits and to wish that they could recover it and re-use it in some economically effective way. In the 1970s the adoption of anodically passivated stainless steel in acid coolers began a trend towards higher acid circuit operating temperatures. It became practicable to recover acid waste heat not only for on-site boiler feed water heating but also for external applications such as district heating schemes or pulp mill process water heating. With experience and good design, it became possible to operate acid circuits in the range 120-150 [degrees] C, heat recovered from which was of sufficient grade to be used in concentrating phosphoric acid or in raising low-pressure steam.

Monsanto Enviro-Chem's Heat Recovery System (HRS) represents the furthest development in this progression that has entered commercial use so far. It can recover low- or medium-pressure steam, which can be utilized in different ways according to site conditions. It is not so much of a revolution in sulphuric acid technology as a careful optimization of the acid circuit to maximize heat recovery, based on the observation that certain commercial materials of construction corrode very much less quickly in sulphuric acid of 99-99.5% concentration than in 98.5% acid and can therefore withstand higher temperatures - 200 [degrees] C or more - at this concentration. (The acid concentration is habitually maintained at 98.5% in conventional sulphuric acid plants because the combined vapour pressure of [H.sub.2]O and [SO.sub.3] is lower at that concentration than at any other; therefore mist formation is minimized.) On account of its potential influence on sulphuric acid plant operating economics, HRS is arguably the most important single development in sulphuric acid technology since the introduction of the double(interpass) absorption process scheme some 25 years ago. In fact, as originally introduced, the double-absorption process, although very necessary to reduce sulphur dioxide emissions, was actually less efficient, by about 7%, at high-grade energy recovery. The shortfall was later redressed by adopting energy-saving features such as running at higher feed gas sulphur dioxide concentrations and introducting lowtemperature economizers. The main features of HRS have already been covered in previous editions of Sulphur.(1,2) The first commercial unit went into operation in Korea in November 1987 in a 1,350-t/d sulphuric acid plant belonging to Namhae Chemical Corporation.(3) Following the success of this initial unit, HRS has been incorporated in several other commercial-scale sulphuric acid projects, including a 1,000-t/d sulphurburning double-absorption plant which is currently nearing completion at Tessenderlo Chemie's Ham works in Belgium. Speaking at the European Conference on Energy-Efficient Production of Fertilizers, jointly sponsored by the Energy Technology Support Unit and the Fertiliser Society, in Bristol in January, Tony Phillips of Simon-Carves Ltd, the Monsanto licensee responsible for the Tessenderlo Chemie plant, demonstrated the adaptability of HRS to alternative ways of utilizing the steam(4). The breakdown of energy input for a 2,000-t/d sulphur-burning plant is given in Table I. Most of the energy from the first four inputs listed (88.6 MW out of a total of 101.7 MW) can be recovered as highpressure superheated steam; losses are essentially the sensible heat in the gas entering the two absorption towers. In the past, these losses, along with the heat of formation of the sulphuric acid, were dissipated in a cooling system or, in certain circumstances, partly or completely recovered in the form of hot water (80-90 [degrees] C). The Heat Recovery System recovers most of this low-grade energy (34.1 MW)

directly as medium- or low-pressure steam by replacing the standard interpass or primary absorption tower and cooling system with the HRS equipment. The proportion of the total energy recovered in the form of steam is thus raised from around 65% to over 90%. It has to be said that especial care is needed in controlling the operating conditions so as to avoid unacceptable corrosion. The HRS acid concentration, in particular, must be maintained within the desired range by ensuring all instrumentation is in service and by carrying out regular laboratory checks. Methods of utilizing HRS steam Depending on the conditions within the plant, the steam recovered in the HRS system is only of low or, at best, medium grade. Its great value is that it can be used in place of steam previously raised from highergrade heat, allowing better use to be made of this energy in generating extra high-grade steam. The following three examples show different ways in which HRS can be used to good effect in a 2,000-t/d sulphuric acid plant. In the scheme shown in Fig. 1, both high-grade steam at 62 bar g, 480 [degrees] C and HRS steam at 9 bar g are converted to electricity in a fully condensing turbogenerator. A small quantity of steam, equivalent to about 9 t/h, is taken from the HRS steam for heating sulphur and feed water. The power produced in the turbogenerator is such that, after deducting the sulphuric acid plant's own consumption, there is a surplus of 30 MW for export. In Fig. 2 all the steam is exported at 4 bar g; the high-pressure steam is expanded in a back-pressure turbo-generator. In this case, there is a surplus power of nearly 10 MW plus 144 t/h steam. The arrangement shown in Fig. 3 is typical of a phosphatic fertilizer works, where the phosphoric acid concentration plant requires about 2 tonnes of steam at 4 bar g per tonne of [P.sub.2] [O.sub.5]. A significant part of this steam can be provided by the HRS unit, thus allowing the majority of the high-grade steam to be used for power generation in a turbogenerator. A surplus of power equivalent to 22 MW is available for export to the grid or the rest of the works. In general, HRS gives a bonus equivalent to about 0.5 tonne of steam per tonne of [H.sub.2] [SO.sub.4]. It can generate up to 75 kWh of additional electric power per tonne of acid by replacing LP or MP export steam or by direct turbo-generation from HRS steam. Based on calculations valuing power at $65 per MWh, this represents a reduction in production costs of nearly $5 per tonne of [H.sub.2] [SO.sub.4] or $15 per tonne of [P.sub.2] [O.sub.5]. On that basis, the additional capital cost of installing HRS on a world-scale plant would be paid off in about two years.

The Tessenderlo Chemie plant at Ham mentioned above, which is due for start-up in the second quarter of 1990, includes HRS and a 15-MW turbogenerator. The HRS will produce 20 t/h of 10 bar g steam, part of which will be used to satisfy internal consumption, while the rest will be passed into the turbogenerator at the appropriate stage to supplement the high-pressure steam. The HRS circuit also preheats feed water, thus reducing the steam demand on the deaerator. A further feature of the plant is its ability to produce hot air as well as steam in the waste heat recovery system. This hot air, produced at 300 [degrees] C, can then be used for an existing drying application, thus making a saving in fuel consumption. Combining these features will make the plant the most energy-efficient plant of its kind in Europe. Where to now? It was mentioned above that the double absorption process in its original form had a lower energy recovery efficiency, and the two objectives of maximizing energy recovery and minimizing pollution are, to some extent, mutually opposed. To obtain a proper perspective on the benefits of either energy recovery or sulphur dioxide emissions reduction, they must be considered together, and not necessarily only within the context of the sulphuric acid plant. Any significant reductions in emission rates will have an impact on process design parameters. This may take the form of operating with a more favourable [O.sub.2]: [SO.sub.2] ratio in the converter, thus increasing gas volumes, or it could be the adoption of triple absorption, a route that has yet to be tried. Both of these, but in particular the triple-absorption route, will diminish the amount of high-grade energy recovery. A triple-absorption sulphuric acid plant would produce about 6% less high-pressure superheated steam than a state-of-the-art doubleabsorption plant. Taking into account the loss of energy produced in the turbo-generator and the increased electrical power required by the process, the amount of electric power available for export from a 2,000-t/d plant would fall by about 2.5 MW. For example, suppose the 2.5 MW reduction was the penalty incurred in effecting a reduction in sulphur dioxide emissions of 100 kg/h. If this deficit in power has to be made up from the grid, then the portion of the sulphur dioxide content in the flue gas emitted from the power station that is attributable to the extra 2.5 MW should also be taken into account. A coal-fired station might typically discharge 25 kg/h [SO.sub.2] in producing 2.5 MW, which would offset 25% of the sulphur dioxide reduction effected at the acid plant. In terms of the degree of energy recovery, 90% recovery as steam is already achievable with HRS. Overall recovery of energy can be extended to 95-96% with current technology where there is a demand for some hot water as well as steam in adjacent plants. Low-grade

energy recovery as steam is here to stay, since it offers the most efficient means of recovering, transporting and utilizing energy. In the future, HRS is likely to be a standard part of many new plant specifications, although refinements are likely to be made and alternative materials of construction may be tried out. There should be many opportunities to retrofit HRS into an existing plant, particularly when it can also be used to convert a plant to double absorption. Owing to the competitive market, most acid and fertilizer producers have to operate within tight margins. By significantly lowering production costs, HRS could transform a borderline operation into a viable enterprise. In many countries without indigenous energy sources, HRS can also benefit the balance of payments by reducing fuel imports. [Figure 1 to 3 Omitted] [Tabular Data Omitted] COPYRIGHT 1990 CRU Publishing Ltd. This material is published under license from the publisher through the Gale Group, Farmington Hills, Michigan. All inquiries regarding rights should be directed to the Gale Group.

Title: Giant new acid plant up and running. Date: 5/1/2000; Publication: Sulphur; Author: Campbell, Steven WMC Fertilizers Limited (WMOF) has recently brought into operation the world's largest metallurgical sulphuric acid plant at Mount Isa, NW Queensland, Australia. The plant will provide feedstock in excess of one million tonnes/year for downstream use in the manufacture of ammonium phosphates, 150 km SE of Mt Isa at Phosphate Hill. Steven Campbell, project manager at WMC Fertilizers, describes the project. WMC acquired the world class phosphate deposit from Broken Hill South some two decades ago and since that rime, many feasibility studies have been carried out to determine a product mix to provide the best return on capital. In December 1996, the WMC board sanctioned capital in excess of $700M AUD to produce in excess of one million t/y of ammonium phosphates. The Phosphate Hill Complex consists of the following: * 300 Ph beneficiation plant designed by SKM and constructed by Theiss. * 1500 Pd phosphoric acid plant constructed by a Mistui/ABB/ Clough consortium using Hydro Agri technology (single-stage hemhydrate process).

* 600 t/d ammonia plant constructed by Linde. * 135 t/h granulation plant constructed by Fluor Daniel using Jacobs technology. The final product is transported by rail to the Townsville port, a distance of some 1000km. The complex was commissioned during the last quarter of 1999 and has currently produced in excess of 20,000 tonnes of product. Mt Isa Projected acid requirements for the fertiliser complex dictated that the sulphuric acid plant design would include the provision for burning sulphur whilst also treating metallurgical off gas from MIM's copper smelter. The copper smelter consists of a primary smelting facility -the proprietary Isasmelt bath furnace producing copper matte - and secondary smelting of the matte, which takes place in four Pierce Smith converters. The design/construction contractor for the job was Lurgi Australia in conjunction with its parent company Lurgi Metallurgie/Lurgi Umwelt. The project was executed via a lump sum turnkey basis. There were numerous challenges to this job. This was the largest metallurgical acid plant ever built and only the second time that separate companies intended to operate a smelter and the downstream acid plant. The design was based on design data provided by Mt Isa Mines Limited (MIM), WMCF validated all design inputs. The plant was built within 180 m of the local community. Mt Isa is a small town with a population of some 24,000 people. A decision had to be made about what to do with the waste heat (export or internal use) and a cost effective transport solution was required to transport the large volumes of acid to Phosphate Hill. The process The sulphuric acid plant comprises five main areas: * Primary gas cleaning * Secondary gas cleaning * Oxidation plant * Acid storage * Sulphuric acid loading and transport Primary gas cleaning

Primary gas cleaning, located at the base of MIM's copper smelter, is divided into two sections: gas from the copper Isasmelt waste gas scrubbing section and gas from the copper converter off-gas scrubbing section. In the first section, copper Isasmelt waste gas, containing sulphur dioxide passes through an electrostatic precipitator which partially removes dust contained in the gas. The gas then enters a two-stage scrubbing system. The first stage is a quench tower where the gas is cooled from a temperature in the range of approximately 220300[degrees]C to approximately 68[degrees]C by a spray system, while also being partially cleaned of impurities. During the second stage a radial flow scrubber, a Lurgi proprietary design, further cleans the gas where it exits with a final temperature of approximately 66[degrees]C. The gases are drafted through the scrubbers by an TD fan. In the second section, there are four MIM copper converters, each with a separate radial flow scrubber. The gas is cooled from approximately 450-550[degrees]C to approximately 68[degrees]C by a spray system, while also being cleaned of dust and other impurities. The four gas streams merge to a single duct. Each radial flow scrubber has an ID fan at the outlet to draft the gases. The gas streams from both sections are then combined before entering the secondary gas cleaning section. Secondary gas cleaning Secondary gas cleaning removes the remaining gaseous, liquid and solid impurities, leaving purified sulphur dioxide gas in a wet state. The gases first pass through two gas cooling towers which operate in parallel and cool the gas from approximately 67[degrees]C to approximately 40[degrees]C by condensing water from the gas phase and further removing impurities. The next stage cleans the gas using electrostatic mist precipitators (EMPs). This area has four primary and four secondary EMPs. Oxidation plant The oxidation plant consists of an acid circuit, catalytic conversion system integrated with sulphur preparation (melting, filtration and storage) and burning. A waste heat boiler system is also incorporated in the plant. The wet [SO.sub.2]-bearing gas is taken from the secondary gas cleaning section and is passed through a drying tower which is irrigated with 95% sulphuric acid to remove the water from the gas.

The dry sulphur dioxide gas is then passed through a three pass catalytic converter where the sulphur dioxide reacts with oxygen in the presence of a catalyst and is converted to sulphur trioxide. Prior to entering the catalytic converter, the gas is combined with sulphur dioxide produced from sulphur burning. Initially the sulphur (pastille form) is melted and filtered to remove impurities. The molten sulphur is then fed to a furnace where the sulphur reacts with oxygen to produce sulphur dioxide. The sulphur dioxide produced is combined with the gas from the exit of the drying tower. The sulphur dioxide from sulphur burning provides supplementary acid for the plant. Finally, the sulphur trioxide passes through the absorption tower which is irrigated with 98.5% sulphuric acid. The sulphur trioxide is absorbed into the acid by reacting with the water content to produce the final product, 98.5% sulphuric acid in a liquid state. The heat generated from the catalytic conversion reaction and from the sulphur burning is used to raise steam. The plant incorporates a waste heat boiler and superheaters for this function. The steam raised is used to drive a turbo-alternator set for the production of power. Power produced by the turbo-alternator set will deliver +65% of the site's internal requirements. Sulphuric acid storage Acid from the sulphuric acid plant is delivered via a 200-mm stainless steel pipeline to two 10,000 tonne mild steel storage tanks and a 450 tonne stainless steel scavenge tank. Acid loading and transport Acid from the storage tanks is pumped in two 250-mm mild steel pipelines (including leak detection systems) to the rail loading station. Queensland Rail transports the sulphuric acid to WMCF operations at Phosphate Hill by acid tank cars designed by American transport company, GATX. Each trainload will be between 22 to 26 tank cars, each holding 58 tonnes. A rail siding has been constructed providing two lines for acid loading plus a line for the locomotive to bypass parked acid tank cars. The advantage of the GATX system is that the number of filling points is greatly reduced. WMCF will have only two filling points. The GATX tank cars are interconnected by hoses so that once a car is filled, acid will then pass through the car and into the next and so on. Malfunction of equipment and/or process condition will initiate an emergency stop of the sequence. The displaced vapour is returned to the storage tanks so they are kept in equilibrium.

Reduced emissions The introduction of the sulphuric acid plant by WMC Fertilizers Ltd at Mount Isa will substantially reduce levels of sulphur dioxide emissions from the smelter operations. In the past, sulphur dioxide gases were emitted from the 270-m lead smelter stack and the 153-in copper smelter stack. The sulphuric acid plant has been designed to capture 80% or more of the sulphur dioxide emissions from the copper smelter. The guaranteed conversion efficiency is 97.4% at the nominal capacity. Although performance testing has not been fully completed as yet, data collected to date indicates in excess of 97.4% for acid production rates less than the nominal rate of 3700 t/d. Following the removal of the majority of the sulphur dioxide component, the tail gas from the sulphuric acid plant is exhausted to the atmosphere via a 110m stack. The tail gas consists of a minor component of sulphur dioxide, some oxygen and carbon dioxide, the majority balance being nitrogen. Technical aspects of the project The sulphuric acid plant is designed for a dry gas flow of 91.7 [Nm.sup.3]/s at 10.1% [SO.sub.2] at the inlet of the oxidation section. This is comprised of gas from the Isasmelt, a large Pierce Smith converter on a copper blow, a small PS converter on a copper blow, minimum sulphur combustion and dilution air. Although it is currently a single absorption plant, tie-ins and space have been provided in the acid plant design to facilitate a retrofit to double absorption if required. The off gases will provide of the order of 800,000 t/y equivalent of sulphuric acid. To make up the shortfall, a 25 t/h sulphur furnace consisting of 2 x 12.5 t/h Luro burners has been installed. The intention will be to run the sulphur burning train continuously but at low turn down rates. This allows continued acid production in the case the smelter is shutdown. The presence of the sulphur burner also meant that a dedicated preheater was not required. Primary gas cleaning consists of five proprietary Lurgi radial flow scrubbers similar to those installed at Magma, Arizona. Due to the fact there are no hot gas precipitators in between the converters and the gas scrubbers, these radial flow scrubbers were the preferred choice due to previous operating experience. The stainless steel scrubbers were manufactured by NDA Engineering (NZ) with the variable speed ID fans on each of the gas scrubbers being supplied by Rothemulle. A brick-lined mild steel quench tower is installed downstream of the Isasmelt hot gas precipitator. The counter current flow of gas to weak acid spray allows the arsenic to crystallise in the gas phase and be removed from the weak acid circuit via bleed control.

The EMPs were sourced out of Chemical Process Equipment Limited (India). The drying and absorption towers were supplied by Evans Deakin Industries (EDI). There are 2 KKK blowers with electric drives rated at 4.9 MW each and have installed soft starters to limit the starting current. The boiler system was supplied by Bertsch (Austria) with the SS 3-pass converter with an internal hot heat exchanger supplied by EDI. The converter is 20m high and 16m in diameter. Conventional vanadium catalyst was used for the first two passes with caesium impregnated catalyst used in the 3rd pass for higher recoveries. The pipework around the drying tower is anodically protected 316L SS, the absorption tower pipe work is Sandvik SX, and the distributor is constructed of Superferrit. Lurgi's proprietary [NO.sub.x] removal system has also been installed. The sulphur filter was supplied by AMA Filters. Waste heat is recovered and sent to a 9.7MW steam turbine supplied by Shin Nippon; the alternator was supplied by ABB. Simon Carves Australia won the installation contract worth $5M AUD for these works. The acid storage tanks and rail loadout facility were constructed by Stork ICM. The storage tanks are mild steel with anodic protection supplied by Kvaerner Chemetics. Impact of the community Measures that were taken to alleviate community concern due to the proximity of residences included: * A 5 metre noise mitigation barrier running the length of the site. This alone cost $1.8 million. * A commitment to provide an extensive vegetation barrier so as to minimise any visual affects. * Containment measures that would cater for the catastrophic failure of both acid storage tanks. * An acid resistant impermeable liner under the rail loadout facility designed to contain and collect any spillages. * Dedicated noise mitigation wall around the steam turbine/dump condenser. Current status The first sulphuric acid was produced from sulphur on 9 September 1999 and from metallurgical off gas on 28 September 1999. Commissioning commenced during July and ran through until early

October. The nameplate capacity of the plant is 3700 t/d. Although some short term high rates have achieved around 3,500 t/d, performance testing had not been completed at press time and the gas sources had not yet been combined together in order to achieve the maximum rate. COPYRIGHT 2000 CRU Publishing Ltd. This material is published under license from the publisher through the Gale Group, Farmington Hills, Michigan. All inquiries regarding rights should be directed to the Gale Group. Title: Full steam ahead. Date: 9/1/2006; Publication: Sulphur; Author: Rao, V.V. Modern sulphuric acid plants are, in fact, generating stations for electric power. The superheated, high-pressure steam produced in the waste heat recovery system must, therefore, be maximised and its temperature and pressure maintained at optimum values. Dr V.V. Rao of Chemithon Engineers Pvt, Mumbai, discusses how this should be achieved while operating the sulphuric acid plant efficiently with high conversion efficiency and high heat recovery. ********** Sulphuric acid plants based on sulphur burning generate steam as a byproduct. Heat is evolved during sulphur combustion, oxidation of S[O.sub.2] to S[O.sub.3] in the catalyst beds, formation of [H.sub.2]S[O.sub.4] from S[O.sub.3] and [H.sub.2]O in absorption towers, compression of air and cooling of hot gases prior to absorption. Heat is also released in sulphuric acid plants based on metallurgical gases during S[O.sub.2] oxidation and it can be recovered to generate steam. As the capacity of sulphur based and metallurgical gas based plants are increasing and power costs have been rising in recent times, the generation of superheated steam in sulphuric acid plants and its use for electric power generation have gained tremendous importance. It is interesting to note that power is generated without C[O.sub.2] emissions and therefore, sulphuric acid plants can claim carbon credits. A modern sulphuric acid plant can generate 1.3 tonnes of superheated steam at 40 kg/[cm.sup.2]g and 400[degrees]C per tonne of sulphuric acid produced. It can also generate 0.3 to 0.5 tonne of low-pressure saturated steam at about 10 kg/[cm.sup.2]g. High-pressure superheated steam is utilised to run condensing turbines and generate electric power. Low-pressure steam is used in the plant for sulphur melting, deaeration and process heating. Superheated steam generation

Unlike a fuel based power plant where combustion gases generate superheated steam by continuously cooling the gases from the furnace outlet temperature to the air preheater outlet, the combustion gases in a sulphuric acid plant are cooled in discrete steps. The gases from the furnace at 1100[degrees]C are first cooled to about 420[degrees]C before they enter the first catalyst bed (pass) of the 4 or 5 pass converter, which oxidises S[O.sub.2] to S[O.sub.3]. The gases are cooled after the first bed to about 440[degrees]C. The composition of the gas leaving the bed, the outlet temperature and the conversion efficiency depend on various factors such as the activity of the catalyst, inlet temperature, rate of reaction and gas distribution. The process involves the conversion of S[O.sub.2] to S[O.sub.3] in four or five (mostly four) stages with intermediate cooling and absorption of S[O.sub.3] to produce 98% [H.sub.2]S[O.sub.4]. Heat evolved during gas cooling before absorption steps is used to preheat boiler feed water. The heat evolved during the high temperature process steps such as sulphur burning and oxidation of S[O.sub.2] to S[O.sub.3] in the first catalyst bed, is used for evaporation and superheating. Table 1 gives the gas temperature range and the type of steam generation equipment that can be located after or between the processes steps in a sulphuric acid plant. In a typical double contact double absorption sulphuric acid plant, boiler feed water consisting of condensate and make-up demineralised water is heated in a deaerator tank to a temperature above 100[degrees]C. Preheating of feedwater may be done in acid coolers before it enters the deaerator. Acid coolers operated at higher temperature may also be used to generate low-pressure steam (MECS's HRS/Outokumpu Technology's HERO systems). High-pressure steam may be generated by one of the following schemes: * Water from the deaerator is passed through two economisers located after beds 3 and 4/5 where it is heated to saturation temperature and converted to saturated steam in a boiler located after the sulphur burner. The steam is superheated in superheaters located after bed 1 and after bed 4/5. * Water from the deaerator is heated to saturation in an economiser located after bed 4/5 and converted to saturated steam in a boiler after sulphur burner and superheated in superheaters located after beds 1 and 2. Other alternatives used by plant designers include location of a superheater after bed 1, a second boiler after bed 1 or 2, superheater after second and fourth pass, economisers after third and fourth passes and an economiser after third pass only. Designs allow for location of interpass gas-gas heat exchangers after second pass, third pass and after fourth/fifth passes. High-pressure steam is generated at 40 kg. [cm.sup.2]g/400[degrees]C or 60kg/[cm.sup.2]g/480[degrees]C in large

capacity sulphuric acid plants (1000 t/d and above) to generate electric power in condensing type generators. Power generation from superheated steam For a 2000 t/d sulphuric acid plant superheated steam generation at 40 kg/[cm.sup.2]g and 400[degrees]C can typically be 1.3 tonnes per tonne of 100 % [H.sub.2]S[O.sub.4] or 108.3 tonnes/hour. At 60 kg/ [cm.sup.2]g and 480[degrees]C it will be typically 1.23 tonnes/tonne of 100% [H.sub.2]S[O.sub.4] or 102.5 tonnes/hour. In this case heat recovered from acid cooling system is not considered as the lowpressure steam generated in these systems is best used for process heating. 108.3 tonne/hour of 40 kg/[cm.sub.2]g & 400[degrees]C steam can generate 21.9 MW of power with exhaust at 50 mm Hg. However, 102.5 tonnes/hour of 60 kg/[cm.sup.2]g and 480[degrees]C steam can generate 23.4 MW, which is 6.8 % higher assuming 65% efficiency for both alternatives. In both cases, the heat recovery is the same, about 74.6 million kcal/hour. Flow diagrams in Figs. 1 and 2 illustrate Schemes 1 and 2 to generate 40 kg/[cm.sup.2]g/400[degrees]C and 60kg/[cm.sup.2]g/480[degrees]C in sulphur burning acid plants. It is evident that for efficient operation and optimum performance of the turbogenerating system, the pressure and temperature of the superheated steam in the sulphuric acid plant must be maintained at the design values. While the pressure of steam can be easily maintained at the design level in the plant operating at 60-100 % capacity, it is difficult to maintain the temperature of the superheated steam. The temperature of superheated steam is dependent on the process temperatures. It is often observed in practice that the actual temperature of superheated steam is lower than the design value (400/480 [degrees]C) and this results in lower power generation. This is a loss of revenue to the sulphuric acid plant. In view of its economic value, the factors, which affect superheated steam temperature, must be carefully examined. This paper is a modest attempt in this direction. Factors affecting superheated steam generation The most important factor that affects the superheated steam generation and its temperature is the converter. The catalyst in the first bed requires a design inlet temperature of about 415[degrees]C for 11.5% inlet S[O.sub.2] in a sulphur burning plant. Ideally, a conversion of about 62 % is achieved in the first pass with an outlet temperature of 615[degrees]C. This is achievable in a plant with new catalyst or with catalyst whose activity is equivalent to new catalyst. This is unfortunately not the case in most operating plants. Even with screened and topped up first bed catalyst, a conversion of 62% and a

temperature rise of 200[degrees]C in the first bed are not generally achieved in plants after one or two years of operation. Consequently, the plant operator maintains higher inlet temperatures of 430[degrees]C to 450[degrees]C in order to reach an outlet of 615[degrees]C after the first bed. The waste heat boiler after the sulphur burner will now generate less steam due to lower drop in gas temperatures across it. Quite often the outlet temperature of the first pass does not reach 615[degrees]C due to an increase in pressure drop and loss in activity. The operator has to maintain the second pass inlet temperature at 440[degrees]C or higher to get the return gas from the first absorber as close to 425[degrees]C as possible. This may prove to be a futile exercise if the gas-gas heat exchangers are fouled. The obvious effects of the drop in first pass conversion on the waste heat recovery system are: * heat recovered in the boiler after the burner decreases, and * heat available in the superheater between 1st and 2nd passes is also reduced. It is well known that a loss in conversion efficiency in the first bed is made up partially in the second and third beds in a sulphuric acid plant. The operator adjusts the inlet/outlet temperatures of the second bed so that the inter-pass heat exchanger outlet gas is as close as possible to 420[degrees]C at the inlet to the fourth bed. This is again dependent on the performance of the inter-pass heat exchangers. The heat exchangers, therefore, also play an important role in the acid plant waste heat recovery system. A temperature lower than 420[degrees]C at the inlet of the 4th pass reduces the conversion and results in high stack S[O.sub.2] emissions. The low gas temperature at the outlet of the fourth/fifth pass reduces the heat recovery in the economiser located after the fourth/fifth pass. The recovery of heat in the economiser after the third pass depends on the actual conversion in three passes, the performance of the heat exchangers and gas temperature at the inlet to the economiser. All these plant problems can result in a significant reduction of steam generation, which can be 5 % or more. Ideally, the feed water to the boiler should be at the saturation temperature with no steaming and the boiler should produce dry saturated steam. The superheater should increase the temperature of dry steam and provide the superheat by sensible heating. Unfortunately, such ideal conditions do not exist in a sulphuric acid plant. At any plant capacity where the sulphur and airflows are fixed, only the furnace outlet temperature is maintained at the design value of 1100[degrees]C for 11.5% S[O.sub.2]. The other temperatures depend on the activity of the catalyst beds and on the fouling (internal & external) of heat exchangers and the waste heat recovery system

itself. The quantity of steam generated and its final temperature (for superheated steam) are not independent variables, which can be adjusted in a sulphuric acid plant. They are slaves to the plant parameters, which are set to achieve the target production of sulphuric acid and not generally for steam and power generation. This situation should be avoided and both sulphuric acid production and steam/power generation must be operated at the highest possible efficiency. Reasons for low steam generation Some of the possible reasons for low steam generation can be summarised as follows: * boiler tube fouling; * lower conversion in first pass; * fouling of economisers; * fouling of gas/gas heat exchangers. Reasons for low superheated steam temperature Low superheated steam temperatures may be due to the following reasons: * hot gas temperature drop is lower in the superheater after first pass; * fouling of gas-gas heat exchangers; high steaming in economisers; * high wetness fraction in saturated steam at the outlet of the boiler; * inefficient removal of saturated liquid droplets in cyclones/mesh pad in boiler drum/shell. If steam, at 40 kg/[cm.sup.2]g, at the outlet of the boiler has 1 wt-% water, the superheated steam outlet temperature will be reduced by about 16[degrees]C. In some sulphuric acid plants, the degree of superheat in steam at the outlet of the superheater is hardly 20[degrees]C indicating that there is about 8% moisture in steam. The total heat recovery is not reduced due to the low superheat in steam. On the contrary, a higher quantity of steam is generated. However, the quality of steam is below the norms for power generation. Achieving rated superheated steam generation and temperature It must be ensured at the design stage that the pressure, and water and superheated steam temperatures for the waste heat recovery system are chosen such that no steaming takes place in the economiser. The boiler feed water line from the economiser to the

boiler should not have sharp downward and upward bends and should slope gently upwards to avoid hammering. Sufficient space should be provided for steam and water separation in the steam drum. Efficient internal and external cyclones to separate water droplets must be provided to generate dry saturated steam with less than 0.05% moisture and less than 0.05 ppm total dissolved solids. Apart from the proper mechanical and process design of piping from economiser to boiler and internal and external cyclone/mesh separators, it is necessary to ensure that the economiser does not steam during operation. A simple way to ensure it is to provide a superheater to control the temperature of gas at the inlet to the economiser so that water at the outlet is just at the saturation temperature. This secondary superheater acts as the pinch heater, which reduces the wetness of steam and provides superheat before steam enters the main superheater located after the first pass. Boiler feed water can be added and the steam desuperheated at an intermediate location in the main superheater to control and maintain the final temperature of the superheater steam. Figure 3 shows modified Scheme No. 1 to generate 40 kg/[cm.sup.2]g/400[degrees]C superheated steam with a pinch superheater before the economiser. It is also important to maintain the boiler pressure at a sufficiently higher than the desired export steam pressure so that the saturation temperature is higher and the steaming is lower in the water which enters the boiler.
Table 1: Steam generation equipment in a sulphuric acid plant Process step After sulphur burning Between beds 1 and 2 Between beds 2 and 3 Between beds 3 and 1 Between beds 4 / 5 and absorber 2 Cooling of acid in absorber 1 Temp. range [degrees]C 1100-420 610-440 520-440 320-180 450-130 220-190 Type of equipment boiler, superheater boiler, superheater superheater economiser superheater, economiser LP boiler/water heater

COPYRIGHT 2006 CRU Publishing Ltd. This material is published under license from the publisher through the Gale Group, Farmington Hills, Michigan. All inquiries regarding rights should be directed to the Gale Group.

Title: Maximizing energy savings in sulphuric acid plants.(heat recovery systems)

Date: 5/1/1999; Publication: Sulphur; Author: Connock, Lisa Since the late 1980s, the highly exothermic sulphuric acid manufacturing process has been an ever increasing net exporter of energy. As energy prices have risen, the role of the modern sulphuric acid plant as a thermal power station has taken on increasing importance. Lisa Connock reports on Monsanto's and Lurgi's latest heat recovery systems for sulphuric acid plants. Since the 1980s leading sulphuric acid plant designers such as Monsanto Enviro-Chem Systems in the USA and Lurgi Metallurgie in Germany have introduced several new technologies for improved heat recovery in new and existing sulphuric acid plants. When retrofitting sulphuric acid plants for maximum energy savings, each plant must be evaluated based on its existing equipment and value of power to determine the best selection of energy recovery options. Monsanto heat recovery options The Heat Recovery System (trademark HRS) process developed by Monsanto in the 1980s permits the recovery of intermediate pressure (IP) steam from the absorption stage. This became practical following the recognition that when acid absorption takes place at higher temperatures, the hot acid is less corrosive if the acid concentration in the absorber is controlled within close limits. Common stainless steel alloys become virtually corrosion resistant at (205 [degrees] C) 400 [degrees] F and higher when the acid concentration in the absorber is increased by less than 1%. A more recent Monsanto development is the Monarch process which elevates the grade of some of the absorption heat to the production of higher pressure steam. Where there is a significantly greater need for electrical power than heating steam, Monsanto offers the Super HRS process using gas turbines exhaust to superheat the intermediate pressure HRS steam for steam turbine power generation. The Monarch process The Monarch process is a wet gas process which combines HRS, steam injection and a condensing economizer to increase the amount of recoverable energy from a sulphuric acid plant. Two key features of this technology are the recovery of essentially all the process heat as steam, which eliminates the need for cooling water in the acid plant, and a heat shift from the production of medium pressure (MP) steam to the production of high pressure (HP) steam.)(1)

The processing of gases containing water, sulphur dioxide (S[O.sub.2]) and sulphur trioxide (S[O.sub.3]) to produce sulphuric acid is a well established and proven technology, sometimes referred to as the wet catalytic or wet gas process. Plants using this technology typically operate on feedstocks which produce water when burned, e.g. hydrogen sulphide. The wet catalytic process can be characterized as an acid plant without a drying tower. Cooled combustion gases are taken directly to the converter, thus eliminating the capital cost associated with drying. Conventional vanadium catalysts have worked very successfully under these conditions. The dew point of the gas stream after pass three of the converter ranges from about 210 [degrees] C (410 [degrees] F) to about 270 [degrees] C (520 [degrees] F). The lower end of this range is typical for a plant where ambient air is the main source of moisture. The upper end of the range is typical for a plant where steam injection is used to produce a nearly equimolar mixture of sulphur trioxide and water. Wet S[O.sub.3]-containing gas can be handled in carbon steel equipment provided the gas temperature is kept above the dew point. The relatively high dew point generally limits cooling equipment to boilers and super-heaters. Equipment operated below the dew point must be constructed of alloys or other corrosion resistant material. A flow diagram for the Monarch process is shown in Figure 1. Moist ambient air is drawn through a filter by the main blower. The compressed air is preheated before entering the sulphur burner. The air heater uses 10 barg (150 psig) steam from the HRS to heat combustion air, which shifts additional heat to HP steam production. The gas exiting the sulphur burner is cooled by a waste heat boiler and superheater before entering the first converter pass. A superheater after the first pass and a hot heat exchanger after the second pass are standard gas cooling equipment for these locations.
Table 1: Sulphur burning Monarch vs a conventional plant Conventional High pressure steam Pressure, psig Temperature, [degrees]F Production, klb/h Production, lb/lb Medium pressure steam Production, klb/h Production, lb/lb Electric power 0 0 46.4 0.33 900 900 375 1.20 900 925 461 1.48 Monarch

Gross, MW Internal use, MW Net export, MW

45 9 36

69.5 9 60.5

Dilution water, in the form of 0.3 barg (5 psig) saturated steam, is added to the gas leaving the third pass. As the gas is cooled in waste heat boiler no. 2 and condensing economizer 3B, some of the sulphur trioxide reacts with the water vapour to form sulphuric acid vapour. About one-fourth of this reaction heat is recovered in waste heat boiler no. 2 and three-fourths is recovered in economizer 3B. Some acid is condensed in the economizer which is designed using materials that are proven in HRS service to have very low corrosion rates for similar conditions. This heat of reaction and condensation is recovered as HP steam. The gas leaving the economizer goes to a conventional HRS. From the HRS, the gas is heated in the cold and hot interpass heat exchangers before entering the fourth converter pass. The cold interpass heat exchanger is located after the fourth pass, so it is only exposed to dry gases with a low dew point. The cold gas leaving the cold interpass exchanger enters the hot interpass exchanger at a temperature above the dew point of the hot gas entering the hot interpass exchanger. The gas leaving the fourth pass is cooled in the cold interpass exchanger and economizer 4A before entering the final absorption tower (FAT). From there it is vented to the atmosphere through the plant stack. The acid from the FAT is pumped through the FAT acid cooler, which uses demineralized water to cool the acid. The cooled acid is then distributed to the final absorption tower and the upper stage of the heat recovery tower (HRT). The water leaving the FAT cooler is further heated in the HRS preheater before going to the deaerator. The deaerator is operated at a pressure high enough to allow all the acid heat to be recovered. The product acid cooler and the compressor lube oil cooler are the only cooling water requirements in the acid plant area. The only need for a cooling tower is for the steam condenser in the turbine generator area. The most cost effective steam generating equipment tends to be the economizers, superheaters, and boilers, in that order. Ultimately, the type of equipment and extent of heat recovery from a wet gas stream is an economic decision based on balancing the incremental cost of heat transfer area against the value of the additional power generated. A condensing economizer can provide a cost effective means for increasing the production of HP steam. Subsequent optimization of the Monarch process in 1995 led to increased power generation. Table 1 shows a comparison of Monarch with a conventional design based on a 3750 short ton/day sulphur burning plant with 11.5% S[O.sub.2] (dry basis).

The results in the table are based on generating maximum power. No low pressure steam export has been considered and internal power usage includes a motor driven compressor. In both the conventional and the Monarch cases, the net power will be reduced in a fertilizer plant by the amount of steam used for phosphoric acid evaporation and ejectors. If 163,000 lb/h of 40 psig (3 barg) steam is extracted for the evaporators and 17,700 lb/h of 150 psig (10 barg) steam is used for the ejectors, sulphur melting etc., the net power shown in Table I would be reduced by about 10 MW. Compared to 1990, the optimized Monarch process has increased the estimated incremental cost of the Monarch plant over the conventional plant due to the higher costs of stainless steel. However, a series of incremental changes in the flow sheet has increased the gross production by more than 12%. As a result, the total plant investment equivalent ($/kW) has actually been reduced. The major changes can be summarized as follows: * A 900 psig (62 barg) boiler has been added after pass 3. * The 900 psig (62 barg) trim superheater has been moved to the exit of the main WHB. * 150 psig (10 barg) steam from the HRS is superheated to 750 [degrees] F (400 [degrees] C). * A 900 psig (62 barg) boiler feedwater is preheated with 150 psig (10 barg) steam before going to the condensing economizer. * All boiler feedwater is preheated in the economizer by gas from the fourth pass and in the HRS system by hot 440 [degrees] F (227 [degrees] C) acid. Heat Recovery System (HRS) The HRS, a key element of the Monarch process, has flourished in the past ten years. The number of HRS units installed now totals 19. Individual plant capacities range from 260 s.t/d to over 4850 s.t/d and the total installed capacity is over 39,500 s.t/d. With the exception of a few excursions, these plants have experienced very low corrosion rates, less than 2 mil/year (0.05 mm/y), handling concentrated acid at temperatures well over 400 [degrees] F (200 [degrees] C).
Table 2: HRS retrofit HRS short ton/day HP steam, klb/h HRS steam, klb/h 2600 244 108 Steam Injection 2600 244 121 Condensing economizer 2600 277 103

30 psig steam, klb/h stage 1 flow, gal/min stage 1 concentration, % Acid temperature, [degrees] F Power increase, kW

0 5100 98.64 433 base

12 5200 99.0 440 375

26 5200 99.0-99.3 429 1645

Since its conception, the basic process has remained unchanged. The Heat Recovery System is basically an absorber that operates at about 400 [degrees] F and uses a boiler to remove the absorption heat as steam (at up to 150 psig), instead of acid coolers (where heat is wasted by rejecting it to the cooling tower). The gas from the economizer enters the first of two stages in the Heat Recovery Tower (HRT). High temperature absorption and condensation occur in the lower stage. The upper stage is a cooler-condenser, where the gas is contacted with cool sulphuric acid to reduce sulphur trioxide and sulphuric acid vapour to normal levels. The gas is slowly cooled in the upper stage to minimize mist formation. Gas conditions leaving the tower are essentially the same as gas leaving a conventional interpass tower. Acid circulation through the tower absorbs heat from acid condensation and sensible gas cooling. The circulating acid is cooled in the HRS boiler. The cooled acid stream flows to the diluter where it is mixed with boiler feedwater for trim concentration control, before returning to the HRT stage. The overflow from the HRT flow to the HRS heater where it is cooled by feedwater to the HRS boiler and HP boiler. The acid stream is further cooled in the HRS preheater before flowing to the final tower pump tank. Like Monarch, HRS has been optimized to increase power production. A similar system is employed where both HRS and HP boiler feed water is heated in the HRS heater by hot acid and in economizer 4A by hot gas. Then HRS steam is used to preheat just HP boiler feed water in a carbon steel vessel. Effectively, the HRS continues to act as a heat pump by transferring energy from the MP system to the HP system where more power is produced. For HRS in a standard dry gas plant, there are numerous options with decreasing energy such as increasing water circulation through the HRS heater and flashing it back in the deaerator. The added heat recovery depends on the power cost versus the cost of added surface and additional equipment. Steam injection This concept involves injecting steam into the process gas upstream of the HRS tower. The advantage is to react S[O.sub.3] with the water vapour before entering the tower, thus reducing the acid concentration rise across the lower stage. A lower concentration rise allows for a higher inlet concentration at the same circulation rate. One of the benefits of this scheme is that it can be used to upgrade LP steam to

150 psig steam (provided the steam pressure is higher than the process gas pressure), by means of chemical reaction. Condensing economizer The function of the condensing economizer is to shift hydration heat from the medium pressure HRS system to the HP steam system. S[O.sub.3](g) + [H.sub.2]O(g) [right arrow] [H.sub.2]S[O.sub.4](g/l) The gas phase reaction is approximately 60% complete at the economizer exit. Since the tube wall temperatures are below the dewpoint, some condensation heat is also recovered. The economizer is constructed of the same corrosion resistant alloy materials that have been proven in HRS service. The mole ratio of water to sulphur trioxide is kept below 1.05 which corresponds approximately to the concentration of the sulphuric acid azeotrope. This ensures that the condensation product will have a concentration greater than the sulphuric acid azeotrope which is approximately 99%. The condensate concentration is not very sensitive to water vapour content. If there are excursions in the steam addition rate, the condensate film is maintained at a relatively high acid strength, where the corrosion rate is low. In fact, 140% of the stoichiometric water can be added without decreasing the condensate concentration below 98%. The excess water vapour passes to the HRT, where the large hold-up of acid prevents the concentration from dropping rapidly. As the decreasing concentration is detected, the steam valve is throttled. Other applications Although the condensing economizer was developed for application in the new Monarch process, there are also applications for existing plants already retrofitted with HRS. Steam injection in conjunction with the condensing economizer can be installed to shift the production of MP steam to high pressure. Even though existing plants are the typical dry gas process, many of the benefits of Monarch can be attained by creating the wet gas directly before the HRS tower by using the steam injection vessel. The amount of steam injected is increased to make up for the water removed in the existing dry tower. Table 2 shows a comparison for a 2600 s.t/d plant with the base case as HRS. Steam injection alone increases the medium steam production by 12% which results in a 375 kW increase in power. With steam injection followed by the condensing economizer there is a 5% reduction in MP steam but an increase of 13% of HP steam. The net result is an increase in power production of 1645 kW. Additional benefits include maximizing the acid concentration to stage 1 of the HRT and lowering the acid temperature to the HRS boiler.

This application is particularly advantageous in existing HRS plants where the turbine generator is at its maximum admission of MP steam, but has additional HP steam capacity. Because the addition of steam injection with a condensing economizer reduces the heat load on the HRS, the plant capacity may be increased. On retrofit plants where HRS is being added, steam injection and the condensing economizer reduce the cost of the HRS. Lurgi heat recovery designs Lurgi's heat recovery system for maximizing energy savings from sulphuric acid plants was developed with particular emphasis on simple and safe operation. The key element of Lurgi's HEat RecOvery System (HEROS)[2] is a Venturi absorber with a dedicated acid circulation system that is installed upstream of the intermediate absorption tower. Heat generated in this system is transformed into LP steam in a specially designed boiler. The corrosion resistance of the materials of construction does not rely on extremely close control of operating parameters. The design permits the shutdown of the HEROS while the intermediate absorption tower remains in full operation. The design can be applied to both new and existing plants. The first HEROS was commissioned in 1989. The existing intermediate absorption tower in this plant was already equipped with two circuits one for the Venturi scrubber and a second one for the downstream packed tower. Therefore, only the steam generator had to be tied into the Venturi circuit. The acid circulation pump and the acid piping were replaced to adapt them to withstand the higher temperatures. The S[O.sub.3]-containing gases enter the Venturi at a temperature of approx. 300 [degrees] C (570 [degrees] F). The acid temperature at the Venturi scrubber inlet is 172 [degrees] C (340 [degrees] F) and rises to 195 [degrees] C (380 [degrees] F) in the Venturi due to S[O.sub.3] absorption. About 95% of the S[O.sub.3] contained in the gas is absorbed in the Venturi section, which means that the sulphuric acid concentration has to be monitored and controlled in the Venturi circuit. The hot acid flows by gravity into a pump tank from which it is pumped via a vertical pump through the steam generator and then back to the Venturi. The steam generator produces 4.5 t/h of saturated steam at 0.5 MPa (73 psig) which is directly put to use in the plant. The LP steam was injected into the Venturi top, primarily because, in this specific case, the gas was already wet. This arrangement was expected to provide a favourable mixture of sulphur trioxide and water. At some point during operation, the steam injection system failed due to mechanical problems and it became necessary to add dilution water to the Venturi sump. It turned out that monitoring and control are just

as simple and immediate as when adding steam. For this reason, the plant now operates with direct injection of water. The dimensions of the acid-cooling system have been designed to also enable operation of the sulphuric acid plant without the Venturi and energy recovery system. In this mode, the steam generator is bypassed and all of the sulphur trioxide is absorbed in the intermediate absorption tower. While the downstream packed tower is a conventional absorption tower in most respects, it does require a high-efficiency (Brownian diffusion) mist eliminator to remove the fine mist resulting from condensation of sulphuric acid vapours. This system is particularly suited for retrofitting existing plants, without losing their flexibility and their reliability of operation. The only prerequisite is that there should be sufficient space available to locate the Venturi section as close as possible to the absorber. The space required for the pump tank and the boiler section must also be taken into account. Retrofitting will have virtually no effect on plant operation when the Energy Recovery System is out of service. Another example of retrofitting Lurgi's HEROS into an existing plant is shown in Figure 2. The plant incorporates both an entirely new construction and a retrofit. The sulphuric acid plant downstream of a pyrite roasting plant has been adapted to sulphur burning, the plant capacity has been increased by 60% and the energy recovery system has been installed. The existing acid coolers have been adapted. Due to space restrictions, the new steam system was located to the side and the former gas dryer has been used as an air dryer. The rest of the acid system remains unchanged. Two failures have occurred since the original start-up of the plant. The first was clearly identified as a faulty weld seam. The second failure occurred a few days after a pipe rupture in one of the superheaters upstream of the intermediate absorption tower. As a consequence of the superheater damage, large quantities of steam together with preconverted gas flowed into the intermediate absorption unit generating an extremely large amount of heat, at the same time diluting the circulating acid. The customer would only accept the energy recovery system subject to the following provisions:

* Operation of the sulphuric acid plant must not become more complicated. * The sulphuric acid plant must be able to continue operation even if the energy recovery system does not work properly. These requirements have been met. Only three parameters are monitored and controlled: the acid concentration of the Venturi circuit, the steam pressure of the LP steam system and the pump tank level. All the other temperatures follow automatically, the sulphuric acid circulation rate remains constant and the steam production rate is only dependent on the capacity of the plant. The amount of steam produced can, however, be influenced by allowing a smaller or larger quantity of hot acid to pass from the Venturi section into the tower section. Acid piping and the heat exchanger of the LP steam generator are constructed of material 1.4575. All other plant items in contact with acid are made of brick-lined mild steel. For reasons of absorption efficiency, the acid concentration should be kept at 98.5%. Safety devices Apart from the acid concentration control already mentioned, a second measuring device for concentration incorporating an alarm is installed. Further measurements include: * Continuous measurement of the corrosion rate, * leak monitoring with acoustic alarm, * measurement of boiler water conductivity and pH including the corresponding interlocking systems. New plants In 1996 Lurgi commissioned its first plant specifically designed for this system. The plant has now been operating trouble free for more than two years [ILLUSTRATION FOR FIGURE 3 OMITTED]. The energy recovery system consists of a Venturi and the closecoupled conventional absorption tower. Both vessels are made of material No. 1.4575. The conventional tower has a packed section and candle-type high-efficiency mist eliminators. Each vessel has an independent pump tank and acid circulating system with one or more vertical acid pumps. The conventional tower acid circuit has a standard acid cooler. To prevent production losses due to the energy recovery system, the acid cooling system is sized to remove 60% of the primary absorption heat when the energy recovery system is not in service. The steam

generation section consists of a typical kettle-type evaporator to which a tube bundle heat exchanger is flange-mounted [ILLUSTRATION FOR FIGURE 4 OMITTED]. Hot sulphuric acid is pumped through the tubes which are surrounded by boiler water. In this heat exchanger, the sulphuric acid is cooled down and then injected into the Venturi top via a number of nozzles. The strength of the sulphuric acid is controlled by adding water to the Venturi sump. In the conventional section, the water is added via the tower. The excess hot acid produced in the Venturi circuit passes finally into the pump tank of the tower circuit before it is used to preheat boiler feed water. The start-up principle of the heat recovery system is just as simple as that for normal acid circuits. After switching on the Venturi circuit pump, the water in the tube-bundles is heated up and evaporated. Process conditions To date, the maximum achievable steam pressure has been 1 MPa. This upper limit depends only on the rate of corrosion of Superferrit at acid temperatures above 200 [degrees] C, which has not been tested so far. However, superheating of the saturated steam to higher temperatures somewhere else in the plant is possible. For example, starting from boiler feed water at 105 [degrees] C, a standard double catalysis system with a 3 + 1 circuit, can additionally recover up to 0.5 t/t of acid as LP steam. The precise amount depends on different factors, which are illustrated in Figure 5. The water which is introduced into the system by the humidity of the air passing through the drying tower has to be distributed to the absorption towers in order to maintain the necessary acid concentration. With increasing water content of the gases, the amount of cold diluted acid that has to be added to the hot Venturi circuit will increase, too. As a result, the production rate of LP steam will decrease. Another important influence is the quantity of sulphur dioxide which has been converted to sulphur trioxide by the time the gas enters the Venturi absorber. In the 3 + 1 configuration more of the total quantity of sulphur trioxide is removed than in the 2+2 configuration, thus improving the production of LP steam. The amount of LP steam depends also on the temperature of the gas coming from the intermediate absorber. Reducing this temperature, for example by the installation of an economizer, reduces the amount of LP steam, while increasing the amount of HP steam.

In cases where part of the LP steam is used for deaeration of the boiler feed water, the net amount may be increased by preheating the boiler feed water in the acid coolers of the final absorbers. The combined amount of HP steam and LP steam can be fed into a turbine generator plant. This utilization of steam enables a power output at the generator terminals of approx. 430 kW per tonne of sulphuric acid. A two thousand tonnes 'sulphuric acid power station' for example, will generate nearly 36 MW without producing any greenhouse gases. HEROS Advantages The main advantages of the Lurgi heat recovery system HEROS may be summarized as follows: * Saturated steam is produced up to 1 MPa: * The acid piping and heat exchanger are constructed of a ferritic alloy which features corrosion rates of less 0.1 mm (0,004 inch)/year when used in a temperature range of up to 200 [degrees] C and in a concentration range of 95 to 100%. This feature provides the operator with additional safety in normal operation. * The other components are made of conventional construction materials (brick-lined tower) and are therefore not subject to corrosion even under the most extreme circumstances. * Control of the acid concentration in both the Venturi section and in the conventional section is straight forward and simple. * The sulphuric acid plant can continue operation even when the energy recovery system and, in particular, the steam section, is out of operation (i.e. when the plant is operating according to the standard mode). * The system can be retrofitted to existing plants provided that there is sufficient space available in the area of the absorption section. References 1. Randolph D. L., Walser J. P., Horne J. R. and Weiss W. M.: "Monarch(TM) HRS retrofit: A technology update". Regional Central Florida AIChE Meeting (May 1997). 2. Rauser W. C. and Ludtke P.: "HEROS: The Lurgi heat recovery system in sulphuric acid plants". Sulphur 98, Tucson, Arizona (Nov 1998). COPYRIGHT 1999 CRU Publishing Ltd.

This material is published under license from the publisher through the Gale Group, Farmington Hills, Michigan. All inquiries regarding rights should be directed to the Gale Group.

Title: A low-bite sulphuric acid catalyst proves its worth. Date: 5/1/1991; Publication: Sulphur; The point of the catalyst in the sulphuric acid plant is to allow the oxidation of sulphur dioxide to take place at the lowest possible temperature. Three years ago Haldor Topsoe introduced a new catalyst with superior performance at tures 20-40 deg C below the normal operating temperatures of conventional catalysts. It has now been successfully installed in a considerable number of sulphuric acid plants. This short article explains the circumstances under which the new catalyst can be of greatest benefit. The main factor limiting the efficiency of a contact sulphuric acid plant is the extent which sulphur dioxide is sulphur trioxide on the catalyst. From the thermodynamic point of view, the lower the temperature the more efficient this reaction can be; the catalyst is needed to make the reaction proceed at temperatures at which it would otherwise be too slow. For decades sulphuric acid catalysts have comprised vanadium pentoxide doped with minor proportions of alkali metal (chiefly potassium) salts, known as "promoters", on a refractory silica carrier. Most sulphuric acid catalysts only begin to operate reliably at a temperature of 400-420 deg C. That is because they will only function when the vanadium pentoxide is in a molten condition. The chief purpose of the alkali metal promoter is to lower the fusion point of the vanadium pentoxide. Sulphuric acid reactors are traditionally adiabatic; in other words, there is no means of removing heat from the gas while it is passing through the catalyst mass. The gas therefore gets progressively hotter as it passes through the catalyst. If an infinite mass of catalyst was provided, the temperature would go on increasing until the equilibrium balance of sulphur dioxide and sulphur trioxide in the gas was established, but with feed gases of the usual concentration (911% (SO.sub.2)the temperature corresponding to equilibrium lies above the practical maximum for the catalyst and materials of construction, which is about 640 deg C. The catalyst mass therefore has to be divided into separate beds, the first containing no more catalyst than is needed to allow the process gas temperature to rise to about 620 deg C; the hot gas from its outlet is cooled before being introduced to the next bed. In successive beds the temperature rises close to the equilibrium temperature, as the concentrations of the reacting species (SO 2 and 0 2) are declining and that of the product, sulphur trioxide, is

rising. There may be four or five catalyst beds altogether, and as regards the final(SO.sub.2)/(SO.sub.3) conversion efficiency, the temperature in the last of these is the most important. Having a catalyst with a low initiation temperature is thus a special advantage there. In 1988 Haldor Topsoe A/S introduced a new type of vanadium catalyst, VK58, for sulphuric acid plants. Whereas the well-established Topsoe VK38 catalyst has been optimized for operation over the full range of conditions normally experienced in sulphuric acid plants, VK58 has been developed specially for operation at low temperatures. It incorporates a caesium promoter, which has boosted its lowtemperature activity and has reduced its "strike" (initiation) temperature 20-400C below that of conventional catalysts. Today, VK58 is installed in more than 20 contact converters world wide, and feedback from its users has clearly delineated the advantages of using it. These are: * Overall conversion in single absorption plants has been improved. * Throughput: can be increased owing to better conversion. * Operation of double-absorption plants with inadequate interpass heat exchanger capacity to maintain the original design inlet temperature of the succeeding bed is vastly improved. * Start-up time is reduced. * The period during which the plant can be restarted without recourse to the start-up heater is extended. * Operational flexibility is increased. Improving conversion efficiency

VK58 was installed for the first time in the last pass of a single absorption plant treating off-gases from two copper roasters. In this case, the sulphur dioxide conversion has been improved from about 98% to more than 99%: in other words, sulphur dioxide emissions have been reduced by approximately 50%. Since then, the fourth passes of several other single-absorption plants have been recharged with the new catalyst; in each case, improving the conversion efficiency was the principal goal. Operating experience appears to have been very satisfactory so far, and high conversions have been reported. Solving inadequate reheat problem In a number of cases VK58 has been installed in the fourth passes of 3 + 1 double-absorption plants where it was difficult to maintain the fourth pass inlet temperature above 400'C owing to limitations in the intermediate heat exchanger. As a result, these plants had to be operated at reduced capacity and at higher than optimum temperatures in the upper passes. Installing VK58 has made it possible to operate the fourth pass with the inlet gas temperature at an easily attainable level of 390'C; this has removed all the former constraints on production. As there is a temperature rise of 20-30 deg C across the final pass, it was not necessary to use VK58 throughout the whole bed; instead it was installed in the upper (cooler) part of the bed only. Based on one year of good experience, the operator of one of these plants decided to load VK58 in the fourth pass of a second plant as well. Moderating first-bed temperature rise VK58 is also of potential benefit to plants where very high feed gas sulphur dioxide concentrations threaten to take the first-pass exit temperature above the temperature limit for the materials of construction. For example, at a Canadian copper smelter operating on oxygen enriched air, the feed to the converter contains up to 14% sulphur dioxide and 15% oxygen. At a normal first-pass inlet temperature of 410-420 deg C, this very reactive gas would take the exit temperature to 6600C. The installation of VK58 has enabled the plant to be operated at an inlet temperature as low as 380'C, which limits the exit gas temperature to 635 deg C. Reducing start-up time In a large number of instances, VK58 has been installed in the upper part of the first pass for the purpose of reducing start-up time. (Again, it is pointless to use it for the whole of the pass, since any catalyst of good quality will work as well at the much higher temperatures further down the bed). Many metal sulphide ore roasters dispose of their sulphur dioxide-containing waste gases into a sulphuric acid plant. Ore roasters are a notoriously bad source of sulphur dioxide, as the flow and composition of the off-gases fluctuate as a matter of course. Sometimes the acid plant's feed supply is interrupted altogether, forcing an unscheduled shut-down. Since it is not permissible in most

cases for the roaster to operate without the sulphuric acid plant, it is crucially important to be able to restart the acid plant quickly after such an interruption so that the roaster can get back into full production as soon as possible. Experience in these first-pass installations of VK58 has been extremely satisfactory; restart temperatures as low as 340'C have been reported, and often as a result it has been possible to restart without using the start-up preheater, saving fuel as well as time. Where VK58 is also installed in the last pass, sulphur dioxide emissions during start-up can be significantly reduced. In addition to the well-known 10-mm ring shape known from Topsoe's widely used VK38 catalyst, VK58 is offered as 14-mm rings, which are specially designed for first pass installations, where good dust tolerance and pressure drop characteristics are important. TECHNICAL TRENDS SULPHURIC ACID USES US gasoline rules give boost to sulphuric acid alkylation Environmental concern in recent years has dealt more than one blow to the old order of gasoline formulation. Tetra-ethyl lead (TEL) - added to gasoline for decades to improve its octane rating - is rapidly being phased out, partly because it inactivates catalytic exhaust converters and also because it is itself toxic. Its replacement, methyl tert-butyl ether (MTBE) is only partly effective, so gasoline has had to be modified to reduce the proportion of rough-burning straight-chain paraffin hydrocarbons (n-alkanes) and increase the proportion of other, smoother-burning hydrocarbons, especially branched-chain alkanes. One route to branched-chain hydrocarbons, which has been particularly successful in the United States, is alkylation. In this process, isobutane is made to react with olefins, particarly butylenes, in an acidic environment. Two acids have been used industrially for this purpose: hydrogen fluoride and sulphuric acid. For a time it looked as if HF alkylation might eventually supersede the sulphuric acid route because the volatile hydrogen fluoride could be

recovered easily after use, while the contaminated sulphuric acid from the sulphuric acid route had to be disposed of or subjected to elaborate reprocessing. However, concern over the environmental and health effects of hydrogen fluoride have dented the outlook for HF alkylation and given sulphuric acid alkylation a new lease of life. Alkylation in the United States has now received an extra boost because of new rules governing volatile emissions of certain components of gasoline introduced under the 1990 Clean Air Act, as alkylate contains none of the volatiles specified for control. Recently, the US oil giant Exxon has announced that it has entered into an agreement with the M. W. Kellogg Co., a leading engineering and contracting company serving the oil industry, under which Kellogg will provide process design, start-up training and a follow-up service in support of Exxon's process marketing effort. Kellogg is not licensed to market the process itself.

Exxon described its latest alkylation technology at a recent meeting of the National Petroleum Refiners' Association in San Antonio, Texas. The process comprises an optimized reactor design in which particular attention has been given to acid-hydrocarbon phase mixing, space velocity, simplicity and temperature control. As regards the last, the optimum of about 4.50C is by deliberately allowing some of the isobutane to remove reaction heat by evaporation. The process is stated to be cheap to build and run and produces a high-quality alkylate with good octane rating. COPYRIGHT 1991 CRU Publishing Ltd. This material is published under license from the publisher through the Gale Group, Farmington Hills, Michigan. All inquiries regarding rights should be directed to the Gale Group.

Title: Aluminizing stands the test of time. Date: 1/1/1996; Publication: Sulphur; Author: Bayer, George T. Following a review of the latest literature and recent discussions with sulphuric acid plant owners, Kim Wynns and George Bayer reaffirm the benefits of aluminizing 304H to combat high-temperature sulphidation and polythionic stress corrosion cracking. Aluminized austenitic stainless steel is still the material of choice by many designers for combating high-temperature sulphidation seen in sulphuric acid plants as well as in gas processing and refineries. In the last decade, bare 304H emerged as the front runner in sulphuric acid plant design when the price of stainless steels dropped and the higher design temperatures became a factor. Recent discussions with sulphuric acid plant owners who changed from the carbon steel design to the stainless steel design indicate that, for the most part, they are pleased with the choice. Unfortunately, as sulphuric acid plants and sulphur recovery units have matured over the years, and as rates and yields have been driven higher and higher, pressure on the operating regime has resulted in higher than expected sulphidation corrosion, flaking of the protective oxide film, and increased fouling of the catalyst. A review of recent literature(1,2) about the performance of the new Claus converter and heat exchanger designs has raised concerns about an inordinate amount of black sulphidic oxide scaling observed during equipment outages. This unpredictable condition has been viewed in most instances as merely a nuisance. However, the flaking of the black oxide film has, to one degree or another, caused reductions in operational capacities via fouling of the catalyst and subsequent control problems. This condition is not all that surprising because the

sulphidation corrosion rates for bare stainless steels double in the temperature range of 1,100 [degrees] F (590 [degrees] C) to 1,200 [degrees] F (650 [degrees] C). Aluminized stainless steel, on the other hand, exhibits a 1-2 order of magnitude decrease in corrosion rates over the bare alloys. Earlier studies by Morris [ILLUSTRATION FOR FIGURE 1 OMITTED] clearly demonstrate the superior sulphidation resistance of aluminized austenitic stainless steels over the bare material. The areas within the sulphuric acid plants that have experienced more formation and subsequent flaking and fouling of the black sulphidic oxide film are the catalyst screens, the first (hot) catalyst support beds, the exchanger tubes, and the converter tubes. The screens are being replaced by some owners during their annual inspection and repair downtime because of corrosion and plugging with oxide scale and slag. This plugging is attributed to an inordinate amount of the black sulphidic oxide film flaking off the 304H material, travelling downstream to the catalyst screens, and building up on the screens. The presence of N[O.sub.x] in the process stream also contributes to the flaking of the protective oxide films as well. This black sulphidic oxide scale, in concert with the slag generated from the low melt constituents (V, Na, K), more prevalent in metallurgical plants, are believed to be responsible for the extremely short life of the screens. The first (hot) catalyst support bed also seems more prone to the forming and flaking of the protective oxide film, thus contributing to the short life of the beds and screens. The exchanger tubes and the converter tubes, depending on the design, also contribute to the generation of the black sulphidic oxide scaling, probably due to the massive surface area exposed directly to the process flow. These problem areas of the 304H design in sulphuric acid plants are candidates for the use of surface alloying by aluminizing, which is one of the many surface modification techniques performed at Alon Processing, Inc. Aluminizing is the solid state diffusion of aluminum into the metal surface using either the packed cementation process or other technologies which apply pure aluminum or aluminum alloys, followed by controlled diffusion. In the case of aluminizing 304H for protection against sulphidation and oxidation, the diffusion zone ranges from 3 to 5 mils in depth and results in a combination of iron+nickel aluminide and iron aluminide. Aluminizing 304H presents a material solution on the surface by modifying the 304H alloy, forming iron and iron-nickel aluminides without changing the strength or creep characteristics from the original design criteria, and maintaining the same heat transfer rates. Hence, a mechanical re-design is not required when aluminizing 304H.

The alloys considered to replace the 304H in solving the hightemperature problem are 309H and 310 stainless steel. However, these materials are predicted to be only marginally better than 304H, since the solution to the above-described problems involves the masking and tying up of the iron and nickel in the austenitic stainless steel. Both 309H and 310 stainless steels are austenitic and have iron as the main constituent. Also, both have nickel which has proven to be deleterious at these temperature ranges and total sulphur content in an oxidizing environment. When higher temperatures are reached and the low melt metals start to become molten, there will be a breakdown of the protective oxide scale, and the slag will tend to adhere to the austenitic stainless. This action effectively causes the protective oxide scales to spall which then collectively plug the screens with the scaling and slag. Not only are 309H and 310 more costly for the material and fabrication than 304H, but neither will appreciably negate the effects of the high-temperature corrosion. The use of aluminizing, however, greatly improves the performance of the 304H base material by reducing sulphidation and oxidation. It also provides a tenacious protective oxide film which minimizes adherence and the eventual plugging of the low melt metals. This oxide film is greatly enhanced over the normal [Cr.sub.2][O.sub.3] by supporting it with complex aluminum oxide scales which have been proven to reduce the sulphidation and oxidation experienced in environments such as those found in sulphuric acid plants. Aluminizing has been used by Alon Processing with great success in over 300 sulphuric acid plants worldwide due to quality processing and assisting clients with fabrication expertise. Alon has written and qualified 11 welding procedures covering the welding of over 21 base materials with 10 different fillers in accordance with ASME Section IX. This effort was completed in order to support clients with answers to their questions about fabrication and to alleviate concerns about the effects of welding and corrosion resistance of the weld. Clients can select from the welding data base a procedure(s) most suited for their application. Clients, however, cannot use Alon's welding procedures as a stand-alone because of certain Code restrictions. They must re-write the procedure, in these cases, and qualify it for themselves. Alon's procedures do provide all of the essential variables for clients, thereby allowing them to bypass the development of a procedure and move directly to qualification of their own procedure. Quality assurance of the diffusion process is paramount at Alon. Every retort heat is carefully studied and the heat cycle is appropriately designed and programmed. Samples are removed after each heat and metallurgically examined for depth and quality of diffusion. This information is forwarded to the client on each order as requested. One question that seems to come up, however, when discussing the heating cycles is the propensity of austenitic stainless steel to sensitize because it is cooled through the sensitizing range (800-1,200 [degrees]

F/430-650 [degrees] C). There has been no sensitization seen on any heats sampled at Alon. Review of the heating cycles has determined that the rate of cooling through this temperature range is probably too fast for the formation of the deleterious [Cr.sub.23][C.sub.6] chromium carbide. Sensitization of austenitic stainless steels, 304H for example, is expected with the standard operating conditions in sulphuric acid plants. Another concern with 304H is the potential for polythionic stress corrosion cracking(3). Published characterization of the "black oxide film" seen during various down-time inspections noted the presence of iron sulphides in the corrosion products. Laboratory analysis of this 'black box film' shows its basic chemistry to be iron, sulphur, and oxygen. The data shows quite plainly that the corrosion/oxide flakes are predominately in the form of iron oxides and sulphides. On a positive note, end users have noted measurable but not appreciable wall loss of the 304H material during inspection and repair downtimes. Flaking of this black sulphidic oxide scale continues to take place although minor compared to the excessive flaking seen in older designs using carbon steel. This flaking is still believed to be aggravated by the step-up in operating conditions, the presence of N[O.sub.x], and the cool-down and heat-up thermal and mechanical stresses locally induced which cause the oxide film to break away from the substrate. The film, however, is quickly renewed with no appreciable wall loss. The chromium oxide layer underneath the iron oxide/sulphide scale is thought to be more resilient and less prone to brittle cracking and flaking. It is, however, a concern that the chemistry and morphology of this "black oxide film" is prone to a very deleterious stress corrosion cracking phenomena: polythionic stress corrosion cracking (PSCC). That refineries have experienced the effects of polythionic stress corrosion cracking is evidenced by the NACE publication recommending practices in protecting equipment from this cracking phenomena (RP0170-85)[4]. Refineries characteristically have been processing heavier and more sour crudes characteristic of today's marketplace, hence the requirement to be more versatile in handling variable feed stocks. The higher the sulphur constituents in the feed stocks, the greater the possibility for polythionic stress corrosion cracking to occur. Polythionic stress corrosion cracking normally takes place when sensitized austenitic stainless steels are exposed to air (oxygen) and water (condensation) during the shutdown of equipment. Austenitic stainless steels can become sensitized either during manufacture of the steel, weld fabrication, or normal operations when allowed to precipitate chromium carbides ([Cr.sub.23][C.sub.6])[5] as they are heated and held in the temperature range of 800F (430 [degrees] C) to

1,500 [degrees] F (820 [degrees] C). Carbide precipitation in the grain boundaries depletes chromium in the surrounding regions, thereby allowing the polythionic acids to corrode and stress crack the stainless. First, there are [H.sub.2]S and S[O.sub.x] gas-steel reaction products that are formed on the surfaces of the stainless steel in the form of oxide and sulphide scales. When the equipment is shut down and opened to the atmosphere, air (oxygen) and moisture (humidity/water wash) put the [H.sub.2]S and S[O.sub.x] into solution, and the corrosion process is started. As the acids are formed, the pH drops and pressure and thermal stresses occur. The corrosion then takes place where the weak acids are formed, and the SCC occurs where the stainless is most susceptible, in sensitized regions. Aluminum diffusion procedures used in the original low-cost carbon steel designs have proven successful over the last 25 years with very low corrosion rates. Alon was instrumental in assisting in the original sulphuric acid plant designs with specifications of the aluminum diffusion technology and materials, as well as fabrication instructions[6]. The advent of the newer Claus design, however, required the use of 304H, in lieu of carbon steel, due mostly to the higher operating conditions (1,200 [degrees] F/650 [degrees] C) in the converter. Carbon steel does not have the strength at these temperatures, hence the use of 304H, a material with the mechanical strength, creep strength, and corrosion resistance needed to operate at these high temperatures. While the "improved" design change to 304H has looked good from the performance and production data, undocumented reports of cracking with this new design raises immediate concern about polythionic stress corrosion cracking. The single greatest concern about PSCC is that once cracking has started, arresting the cracks is virtually impossible while repair by welding is out of the question because the welder will chase cracks forever. Aluminum diffused austenitic stainless steels (304H), however, have proven successful in mitigating the effects of polythionic environments because of their inherent sulphidation resistance, corrosion resistance to mild acids, and ability to resist hydrogen permeation. The reduction of hydrogen permeation of approximately 1,000 times less than bare 304H is especially helpful to those refineries using the new converter technology with 304H as a base material. Aluminum diffusion of 304H, therefore, is a long-term solution to the oxide flaking phenomena, even for the more aggressive metallurgical sulphuric acid plants. References

1. "Getting the details right", Sulphur No. 239, pp. 41-52 (Jul-Aug 1995). 2. Shaw, D. and Harding, G.: "Stainless Steel Converter Performance", Chemetics International Company Ltd. Clearwater Convention, Central Florida Section, American Institute of Chemical Engineers (May 1995). 3. Samans, C. H.: "Stress Corrosion Cracking Susceptibility of Stainless Steels and Nickel-Based Alloys in Polythionic Acids and Acid-Copper Sulphate Solution". NACE 20th Annual Conference (Mar 1964). 4. "Protection of Austenitic Stainless Steel from Polythionic Acid Stress Corrosion Cracking During Shutdown of Refinery Equipment", NACE Publication RP0170-85. 5. Samans, C. H., Kinoshita, K. and Matsushima, I.: "Further Observations on Sensitization of Chemically Stabilized Stainless Steels". Corrosion/76 (Mar 1976). 6. Weinbaum M. J. and McGill, W. A.: "Alonizing to Prevent Corrosion in the HPI Sulphur Recovery Plant". Sulphur 87, Houston, Texas (Apr 1987). 7. "Protecting equipment in sulphuric acid plants", Sulphur No. 179 pp. 27-32 (Jul-Aug 1985). Kim A. Wynns is Director of Technical Marketing and George T. Bayer is Manager of Research & Development at Alon Processing, Inc., Tarentum, Pennsylvania. COPYRIGHT 1996 CRU Publishing Ltd. This material is published under license from the publisher through the Gale Group, Farmington Hills, Michigan. All inquiries regarding rights should be directed to the Gale Group.

Title: Acid plant revitalisation: large or small, a plant revamp may be just the revitalisation your plant needs to continue its success in today's competitive marketplace. Motives for retrofit projects include energy recovery, utility expansion, plant capacity increase, emissions reduction, and equipment replacement. Lisa Connock reports on a selection of recent projects.(RETROFIT PROJECTS)

Date: 3/1/2006; Publication: Sulphur; Author: Connock, Lisa MECS projects MECS, Inc., formerly Monsanto Enviro-Chem Systems, has completed over 100 retrofit projects for sulphuric acid plants. Some recent examples, covering a wide range of projects, are presented below. Case 1 In a recent challenging retrofit project, decreasing emissions while improving process control with varying gas strength was the goal at a sulphuric acid plant at a metal roasting complex. The gas strength to this 730 t/d sulphuric acid plant varied from a maximum of 10% S[O.sub.2] down to 0-1% S[O.sub.2], which made the ability to maintain the heat balance and S[O.sub.2] conversion very difficult. The existing plant could not maintain the converter at the optimum temperatures, and hence the overall conversion of S[O.sub.2] often fell short of the target. MECS modelled the different gas conditions, studied the current plant operation and design, and determined that the entire contact section must be addressed in order to meet the 99.92% conversion requirement over the wide range of operating conditions. An AspenTech process simulation was used to model and optimise the converter, towers, and heat exchangers. The existing oleum tower was converted into an intermediate absorption tower, changing the plant to a 3-1 double absorption scheme. MECS incorporated an indirect fired preheater to provide supplemental heat when the gas strength was lower than the autothermal point. In addition, a number of discreet bypasses at the converter and gas heat exchangers allowed for better balance and conservation of the available process heat and minimised the use of the fired preheater. This new design allowed the system to operate at much more of a steady state condition than previously. The project included a new stainless steel converter, all new MECS catalyst, new MECS mist eliminators, and all new gas heat exchangers. Modifications to the existing main compressor, acid coolers, and acid towers were made in order to support the overall goals. The plant was recently started up and early feedback has been very positive. Case 2 Revamp projects do not need to be complicated; they simply require analysing the problem and finding the most appropriate solution. A 3-1 double absorption sulphur burning sulphuric acid plant wanted to increase production capacity from 2110 to 2360 t/d.

To analyse catalyst and converter performance, MECS uses the PeGASyS Portable Gas Analysis System. The PeGASyS system analyses the S[O.sub.2] and [O.sub.2] converter gas streams, detects leaks in gas-to-gas heat exchangers, identifies S[O.sub.2] gas bypassing, and measures overall plant conversion performance. Measurements with the PeGASyS system showed that first pass catalyst should be replaced with 100% new MECS XLP-220 ribbed ring catalyst to improve conversion efficiency. Calculations showed that to improve conversion and increase plant capacity, the fourth pass standard catalyst should be replaced with 100% new MECS SCX-2000 caesium-promoted catalyst. These catalyst changes resulted in a pressure drop reduction of 76 mm w.c. in the first pass and 25 mm w.c. in the fourth pass even at the increased plant rate and the higher catalyst loading in the fourth pass. By replacing the first and fourth pass catalyst and increasing the inlet S[O.sub.2] from 11.4% to 12.1%, this client was able to increase their plant rate by 10% and keep their S[O.sub.2] stack emissions the same. Case 3 As oil and energy prices continue to increase, energy recovery becomes more important in the economics of a sulphuric acid plant. MECS provides engineering and equipment that not only lower corrosion and minimise mist generation, but also dramatically increase energy recovery. The patented Heat Recovery System (HRS) recovers the heat generated by the absorption of S[O.sub.3] and reaction with water to form sulphuric acid and uses the heat to produce mediumpressure steam. Ten years ago when a metallurgical double absorption sulphuric acid plant was constructed, the economics of the HRS process were not viable. However, the client did recognise that an HRS may be profitable in the future and the new intermediate absorption tower purchased for the plant was designed for future use as an HRS tower and made of ZeCor[R]-310M. This client studied the economic impact of adding an HRS again when an MECS debottlenecking study increased the plant capacity to 2720 t/d, but they could not find economic merit with producing steam for a turbogenerator and selling the power. However, with the high oil prices, this client recently found a near-by company that was interested in purchasing medium-pressure steam at a price that was highly profitable. The sulphuric acid plant was retrofitted with MECS' standard HRS equipment including an HRS boiler, diluter, steam injection vessel, heater, and preheater. The intermediate absorption tower was converted to an HRS tower with the addition of a 2nd stage UniFLO[TM] Distributor, 2nd stage packing, and an HRS pump boot. Because HRS towers have considerably more mist generation than intermediate

absorption towers, new mist eliminator elements were necessary for the HRS retrofit project. Custom-designed concentric Energy Saver (ES) mist eliminator elements replaced the existing ES elements, thus increasing the element surface area without increasing the mist eliminator housing diameter or changing the tubesheet. As is now standard in MECS' Heat Recovery Systems, this HRS retrofit included steam injection, which increases the amount of medium-pressure steam produced, reduces diluter vibration, and reduces HRS tower corrosion. This client is now realising the economic benefits from generating 10 barg HRS steam. Case 4 Replacing old, worn-out equipment is a common driver for a retrofit project. However, with the right engineering and technology, replacing equipment can also be an opportunity for process improvements. A 270 t/d sulphur burning single absorption sulphuric acid plant needed to replace its carbon steel converter after 50+ years of service. On a turnkey basis, MECS designed and supplied a robust, efficient, stainless steel converter with internal superheaters after passes two and three. The design incorporated the layout of the original converter with the benefits of new superheaters, new catalyst, and the capacity for expansion in the future. MECS optimised the catalyst performance for low pressure drop and low emissions resulting in a conversion increase from 98% to a guaranteed 98.43%. Emissions testing by the plant, confirmed by MECS PeGASyS analysis, determined that the new converter was operating at 98.75% conversion with 9.3% S[O.sub.2], which is an outstanding level of conversion for a single absorption plant. Haldor Topsoe projects In 1996, Topsoe responded to the demands for lower S[O.sub.2] emissions by developing a new catalyst, VK69. The second generation, caesium-promoted catalyst VK69 was designed specifically for operation in the final passes of double absorption plants. The high activity of VK69 provides the opportunity for more than 50% reduction in S[O.sub.2] emissions from existing double absorption plants. It can also be used to increase production rates without increasing S[O.sub.2] emissions. VK69 can be used for the design of new or revamped plants with S[O.sub.2] emissions of 40 ppm or less. Over the past decade, VK69 has partly or fully replaced catalyst in the last pass(es) in more than 50 sulphuric acid plants, representing different plant designs and operating on different sources of sulphur dioxide.

The following case study demonstrates how VK69 has been used to increase production rate and reduce S[O.sub.2] emissions. A phosphate fertilizer manufacturer located in Florida was faced with the need to increase the sulphuric acid production in order to keep up with the consumption from the phosphoric acid plant. This facility has four large sulphuric acid plants based on sulphur burning. The plant chosen for debottlenecking was originally built in the mid-70s with a design capacity of 1361 t/d and an S[O.sub.2] emission permit of 2 kg/t. The plant has a 3-1 layout, i.e. the intermediate absorption tower is located after the third pass. Over the years, the plant has been debottlenecked to a design capacity of 2359 t/d but could only produce approximately 2223 t/d even after a turnaround. During a turnaround cycle, the production would slowly drop from 2223 t/d to 1996 t/d. The production rate of the plant is airflow limited. The main air blower is a steam turbine driven unit. Any major airflow increases would require replacement of both the turbine and the blower, which would be an expensive proposition. To gain some additional airflow, the plant implemented several minor pressure drop saving projects, such as repacking absorption towers and replacing a gas-to-gas heat exchanger. However, the major increase in production rate would have to come from an increase in the S[O.sub.2] gas strength. The plant was typically operating at approximately 11% S[O.sub.2] feed gas strength. By increasing the gas strength from 11 to 12% S[O.sub.2], the plant could increase production rate by around 10%. However, the increase in gas strength from 11% to 12% S[O.sub.2] decreases the [O.sub.2]/S[O.sub.2] ratio from 0.91 to 0.75. The reduction in [O.sub.2]/S[O.sub.2] ratio provides less favourable gas conditions at the inlet of the converter and thereby increases the load on the catalyst. In 2004, the plant applied to the State of Florida to increase the sulphuric acid production permit to 2495 t/d. This was approved but at the same time, the S[O.sub.2] emission permit was reduced from 2 kg/t to 1.75 kg/t. The debottlenecking placed three demands on the catalyst: * Increased production rate without the ability to substantially increase the catalyst volume; * Less favourable [O.sub.2]/S[O.sub.2] ratio due to the increase in S[O.sub.2] gas strength; * Reduced allowable S[O.sub.2] emission.

The plant requested a guarantee from the catalyst vendor to produce 2359 t/d at a 12% S[O.sub.2] gas strength as well as a pressure drop guarantee of 254 mm WC at 2359 t/d. The previous catalyst loadings with standard potassium promoted catalyst in each bed are shown in Table 1. The top three beds of the converter were already completely full with catalyst. The fourth bed had room to install additionally 7,000 litres of catalyst. It was determined that the only way to achieve the increased production rate at a higher S[O.sub.2] gas strength, the reduced S[O.sub.2] emission and at the lowest possible pressure drop was to install the caesium promoted VK69 catalyst from Topsoe in the fourth bed. The requested conversion and pressure drop guarantees could have been met with a short loading of 130,000 litres of VK69 in the shape of 9 mm Daisy. However, the plant was not interested in a short loading with the 9 mm Daisy shape. Instead, Topsoe produced VK69 in the wellknown 12 mm Daisy shape in order to meet the conversion and pressure drop guarantee with a full loading of 165,000 litres of catalyst in bed 4. The catalyst loadings after the debottlenecking are shown in Table 2. The total loading of 406,000 litres corresponds to 172.1 litres/t/d at 2359 t/d or 162.7 litres/t/d at 2495 t/d. During a shutdown in June 2004, the 165,000 litres of VK69 in the shape of 12-mm Daisy catalyst was installed in the fourth bed. When the plant started up after the turnaround, it averaged 2424 t/d and an S[O.sub.2] emission of 1.65 kg/t. The plant could have produced more if there was more airflow available. Catalyst performance can be closely monitored by Topgun analyses carried out by Topsoe's experienced engineers. Topgun is a precision portable gas analyser for measurement of S[O.sub.2] and [O.sub.2]. The gas analyses results are utilised in computer simulations to provide accurate and reliable evaluation of the actual plant performance. A Topgun test performed in August 2004 showed S[O.sub.2] emission below the guaranteed level at a production rate of 2391 t/d and a feed gas S[O.sub.2] strength of 12.1 to 12.2%. It should be noted that the month of August is the worst production month in Florida for a plant that is airflow limited due to the high temperatures and humidity. In March 2005, 9 months after start-up, on

a cold, dry day, the plant produced 2481 t/d with S[O.sub.2] emissions below the guaranteed level (Table 3). The pressure drop guarantee was also met. During the Topgun test in August 2004, the pressure drop was 208 mm WC at a production rate of 2391 t/d. Subsequent monthly pressure drop testing by plant personnel has shown the pressure drop to be in the range of 180-230 mm WC at a production rate >2359 t/d. It is observed that after installation of the VK69 catalyst in bed 4, an 11% increase in the production rate has been obtained and at the same time the S[O.sub.2] emission has been reduced from 2.0 kg/t to 1.75 kg/t. Noram Engineers and Constructors Computational Fluid Dynamics (CFD) is a powerful tool, which allows examination of the detailed flow, pressure and temperature patterns inside sulphuric acid equipment. At Sulphur 2005, Alfred Guenkel of Noram Engineering and Constructors discussed how CFD can be used to troubleshoot problem areas in an acid plant and test the merits of plant modifications and upgrades before committing to major capital expenditures. It can also become a powerful aid to the designer by providing the necessary insight to avoid pitfalls. One of the case studies highlighted referred to gas distribution in a gas bypass duct of a hot exchanger inside a converter and is presented below. Noram recently completed a project to replace a converter in a 1000 t/d acid plant. The stainless steel converter was shop fabricated in sections and included an internal hot exchanger. All sections were shipped to the site and assembled at a location adjacent to the existing converter. Removal of the old converter and tie-in of the new converter were completed in less than three weeks. Over the last eight years, Noram has replaced essentially all the original equipment of the acid plant, while expanding the plant by about 30%. Figure 1 shows the converter including the internal hot exchanger and the gas flow arrows through the converter. The coloured area in the core was modelled through CFD. The design challenge was the by-pass duct around the hot exchanger that is required to control the bed 4 inlet temperature. Two process options had to be considered. The first was that of reusing existing conventional catalyst at a design inlet temperature of 425[degrees]C. The second was for a future case where caesium catalyst will be used at a lower inlet temperature of 390[degrees]C. The latter will require significantly more bypassing.

There were a number of design issues. First, the relatively cool bypass S[O.sub.2] gas from the cold exchanger had to be blended with the hot S[O.sub.2] gas leaving the internal hot exchanger to result in a uniform inlet temperature to catalyst bed 4. The CFD boundary conditions for these two cases are as follows:
Conventional catalyst Bypass flow/temp: 0.6 kg/s / 305[degrees]C Hot exchanger exit flow/temp: 19 kg/s /429[degrees]C Caesium catalyst Bypass flow/temp: 5.2 kg/s / 270[degrees]C Hot exchanger exit flow/temp: 14.3 kg/s /433[degrees]C

Figure 1 shows the results of the CFD work for six cases, three geometries for the high flow case and three geometries for the low flow case. As a general observation it was noted that in low flow cases the bed 4 inlet temperature was uniform for all geometries. There was, however, a significant temperature variation of up to 70[degrees]C in the vestibule wall area above the hot exchanger for the case of the simple elbow. In the high flow cases, there were variations in the bed 4 inlet temperature of up to 10[degrees]C in all cases, which is acceptable. Evidently mixing of the two larger gas streams of different temperature is more difficult. The extended elbow gave by far study case shows that very small changes in duct geometry can have significant effects on the temperature patterns in critical areas. Begg Cousland and Jiangsu New Hongda The sulphuric acid industry in China has undergone a huge change in the last five years. Many of the pyrite-based plants that predominated and were notoriously dirty and prone to problems have been closed due to environmental concerns. They are being replaced or augmented by a new generation of larger capacity plants, incorporating at least a few key components from outside China, often copying a few components and design features from outside China and mostly changing to sulphur burning or non-ferrous metals off-gas as the source of sulphur dioxide. The desire is to build smelters, sulphuric acid and phosphate fertilizer plants along western lines. In most cases, Chinese design institutes such as the Nanjing Design Institute or ENFI are contracted to do the engineering and construction of the plants. Occasionally the technology is supplied to the institute from outside China, but it is relatively rare

nowadays for a contract to be signed directly with a recognised western organisation in this field. Jiangsu New Hongda Petrochemical Machinery Co. Ltd (New Hongda) has been a leader for some time in China in developing bigger and better locally made equipment for chemical process plants. In 2002, a first collaboration was made between Jiangsu New Hongda and Begg Cousland to commence the marketing and production of Begg Cousland's range of 'Becofil' candle filter mist eliminators in China. As an existing manufacturer of knitted mesh pad demisters, the addition of candle filters completed the mist elimination range New Honda could supply. A full contractual industrial collaboration between Begg Cousland and Jiangsu New Hongda has now been implemented in the field of key equipment and technology worldwide. In 2005, Begg Cousland carried out a sulphuric acid tower revamp project in Russia, equipping three towers (DT, IAT and FAT) at Metakhim, Volkhov, St Petersburg region, with self-supporting ceramic domes, saddle random packing (both from China), acid distributors and mist eliminators. The project engineering was done in Russia, with Russian vessel shells and internal brickwork. The ceramic domes were 4754 mm diameter and were levelled out with cross partition rings and supported mainly 2-inch saddles. High-efficiency Browninan Diffusiontype mist eliminators were installed in the intermediate and final absorption towers. The drying tower was fitted with a single-stage wire mesh demister and SMART[R] acid distributors were used. The plant started up in September 2005. The contractual guarantees (Table 4) have all been met.
Table 1: Catalyst loadings with standard catalyst before debottlenecking Bed No. Catalyst volume, litres 1 70,000 2 77,000 3 94,000 4 158,000

The total loading of 399,000 litres corresponds to 179.5 litres/t/d at 2223 t/d. Table 2: Catalyst loadings after debottlenecking Bed No. Catalyst volume, litres Catalyst type 1 70,000 existing 2 77,000 existing 3 94,000 existing 4 165,000 new VK69

Table 3: Acid plant performance before and after installation of VK69 in the fourth pass Before installation of VK69 After installation of VK69

Acid production, t/d S[O.sub.2] strength, mole % S[O.sub.2] emission, kg/t Catalyst loading, litres/t/d Table 4: Contractual guarantees met Drying tower: single stage demister Exit: Pressure loss: Pressure loss: 5 microns.

2223 11.0 2.0 179.5

2481 12-12.2 1.75 163.6

3 microns, 98% removal of particles < 3 microns. < 180 mm [H.sub.2]O.

Second absorption tower: candle filters Exit: Pressure loss: 3 microns, 98% removal of particles < 3 microns. < 180 mm [H.sub.2]O.

Drying and absorption: minimum 99.9% efficiency.

COPYRIGHT 2006 CRU Publishing Ltd. This material is published under license from the publisher through the Gale Group, Farmington Hills, Michigan. All inquiries regarding rights should be directed to the Gale Group.

Title: Lurgi takes contract for Altonorte acid plant.(Lurgi Metallurgie) (Brief Article) Date: 9/1/2001; Publication: Sulphur; Noranda's local subsidiary has contracted Lurgi Metallurgie to supply the sulphuric acid plant for a major expansion of its Altonorte copper smelter in Antofagasta (Region II). The lump sum, turnkey contract to supply the acid plant is valued at $40 million, out of a total $170 million spend on the upgrade. In addition to the new sulphuric acid plant,

Noranda is upgrading an existing unit for a total acid output of 700,000 t/y. Current production is 250,000 t/y. The new Lurgi unit will have a nameplate capacity of 2,200 t/d, based on treatment of 175,000 [Nm.sup.3]/h of off-gases. The acid plant supplier will work with Outokumpu's Chilean subsidiary on the project, hence this is the first instance since Outokumpu's acquisition of Lurgi for the two companies to work together on a contract. The first phase of the smelter's expansion is expected to be finished by the end of this year, when new equipment is expected to provide more cost-effective production. A second stage of the upgrade, scheduled for completion in 2003 when the Lurgi plant will be installed, will see Noranda ramp up output. The upgraded copper production will involve installing a new rotary concentrate dryer and feed system, replacing a reverberatory furnace with a continuous reactor, and replacing three Pierce-Smith converters with larger versions. Altonorte is being expanded to produce up to 290,000tpy of copper anodes from a current 160,000tpy. COPYRIGHT 2001 CRU Publishing Ltd. This material is published under license from the publisher through the Gale Group, Farmington Hills, Michigan. All inquiries regarding rights should be directed to the Gale Group.

Title: Mitigating corrosion in sulphuric acid production.(Statistical Data Included) Date: 11/1/2001; Publication: Sulphur; Author: Connock, Lisa A number of highly corrosion resistant materials are available today for use in the production of concentrated sulphuric acid. Provided they are properly selected for the operating conditions, these alloys provide the benefits of long operating life under harsh operating conditions, extended periods of uninterrupted production cycle and a lower incidence of catastrophic equipment failure. Modern sulphuric acid plants handle acid strengths normally in the range 93% to 99.5% and, in some plants various concentrations of oleum. The corrosion resistance of alloys within this relatively small concentration range can vary widely and can be difficult to predict. The corrosiveness of sulphuric acid depends upon many factors, particularly temperature and concentration. However, whereas increases in temperature generally give a corresponding increase in

corrosion rate, increasing the acid concentration can increase or decrease the corrosion rate depending upon the actual concentration. This effect is attributed to the fact that the hydrogen ion concentration in sulphuric acid increases with concentration, but at higher levels decreases again (Fig. 1). The hydrogen ion concentration directly affects the rate of the cathodic reaction and thereby the rate of anodic dissolution. Additionally, corrosion rates can also be critically affected by other variables. The presence of oxidising or reducing impurities, the presence of chlorides, velocity effects and galvanic effects may alter the serviceability of a particular material of construction. These influences can make predicting actual corrosion rates for a given material problematic. The corrosion of metals in sulphuric acid is complex. However, the electrical behaviour of most metal alloys falls into three categories: active, passive, or active-passive (Fig. 2).[1] For active behaviour (case I), the corrosion potential is in the active region and a wide range of corrosion rates is possible. For passive behaviour (case III), the corrosion potential is in the passive region; these alloys generally passivate spontaneously and exhibit low corrosion rates. For activepassive behaviour (case II), both active and passive behaviour is possible. This can lead to the possibility of unpredictable and erratic corrosion rates, depending on the environment. Cast irons Cast iron has been used for many years in the construction of pumps, piping and other components in the manufacture of concentrated sulphuric acid. Today, gray iron, ductile iron, and a number of speciality irons continue to be used with good success in this service. Like carbon steel which is used in handling concentrated sulphuric acid at ambient temperatures under static and low velocity conditions, cast iron derives its corrosion resistance primarily from the formation of an iron-sulphate film. This sulphate film is highly protective, unless physically disturbed. The actual corrosion rate depends on the temperature, acid concentration, iron content and flow, because these parameters determine the rate of dissolution of the protective sulphate film. However, compared to carbon steel, the higher carbon and silicon content of cast irons leads to conditions favouring superior resistance at higher velocities and elevated temperature. Gray cast iron normally should not be used in the oleum range because of a tendency toward catastrophic cracking caused by a reaction between the free [SO.sub.3] and the graphite flakes in the iron. Chas. S. Lewis' L-14(R) iron, introduced in 1980 is used extensively in larger acid pumps and gate valve products for principal body

components where high dimensional requirements are not of paramount concern for hydraulic performance (volutes, elbows, discharge pipes, shaft columns and valve bodies). Alloying elements control the microstructure of the iron matrix in such a way as to provide favourable graphite dispersion. This iron resists "oleum cracking" and used in heavy-walled sections provides good service life in concentrated acid to temperatures approaching 135[degrees]C (Fig. 3). A number of speciality ductile irons have been used extensively in piping around acid towers. Furnished in very heavy-walled sections, they have good ductility, and form a tough sulphate film that resists corrosion. Sizing the piping so that fluid velocities do not exceed 1-2 m/s generally precludes erosive wear in acid piping. Acid Piping Technology's Mondi[TM] piping is a special alloy of ductile iron with unique metallurgy developed to handle 92-99% sulphuric acid at temperatures up to 149[degrees]C. Ductile iron by nature is much safer than its cast iron predecessor as it has yield and elongation in addition to being approximately four times stronger. The most unique feature is its corrosion resistant metallurgy that yields a life expectancy four times longer than cast iron. Since its introduction in 1983, Mondi piping has demonstrated excellent performance in recirculation piping for drying and absorbing towers, product transfer lines and tower distribution systems. In operation, a tough sulphate film is formed on the surface. The initial corrosion of Mondi is higher in forming the film. After formation, this sulphate film remains to protect the surface and corrosion rate is greatly reduced. The low corrosion rate continues over the years of plant operation. Measured corrosion rates from many years of actual plant operation are the true measure of Mondi performance. The curve in Fig. 4 shows reported corrosion rates after 2-8 years of plant operation for 93% and 98% acid in drying and absorbing tower piping system. At some point during the operation of an acid plant, the acid concentration in the drying or absorbing systems will likely experience a weaker acid excursion due to process upset or equipment malfunction. Weaker acid excursions below 96% will accelerate corrosion of austenitic stainless steel piping and decrease its service life. Many plants have reported that their Mondi piping systems with 93-99% have operated through weaker acid excursions. These plants also reported that the Mondi piping did not show significant corrosion after the excursions. Mondi piping is very forgiving and provides reliable performance with long service life at reduced cost compared to austenitic stainless steel piping systems. Stainless steels and nickel based alloys

The corrosion resistance of stainless steels and most nickel-based alloys is complex due to the active-passive nature of the alloys. Resistance to corrosion depends upon achieving electrochemical passivity - case III behaviour. Passivity is achieved by the surface formation of tightly adhering, crack-free, complex oxide films that protect the underlying metal. The formation and maintenance of these oxide films requires oxidising conditions. Therefore, highly aerated solutions are much more suitable than air-free ones. Similarly, the presence of oxidising impurities stabilises the passive film, markedly improving the corrosion resistance. Essentially, chromium and silicon are the two elements that promote the formation and adherence of these films. In addition, corrosion resistance can be often enhanced in mildly oxidising environments, and those reducing impurities, by the addition of nickel, molybdenum, and copper to the alloy. Other alloying elements are then added in order to adjust the metallurgical and m echanical properties of the final alloy. Generally, for austenitic stainless steels (304, 316 types), stable passivity is achieved at ambient temperatures in the very low and very high concentrations and oleum. Higher austenitic stainless steels (the 20-type alloys) are usually the first considered when the sulphuric acid environment is too corrosive for 300-series stainless steel, or cast iron. The nickel base alloys have superior resistance up to 95% concentration because of their high alloy content. Frequently, low corrosion rates occur in both the active and the passive corrosion states. Thus reliable corrosion behaviour is achieved over a wide range of concentrations, temperatures and impurity levels. Krupp VDM's Nicrofer 3127 hMo - alloy 31 - is an iron-nickel-chromiummolybdenum alloy with a nitrogen addition. It was designed to fill the gap between existing super austenitic stainless steels and the nickel base alloys. Nicrofer 3127 hMo is characterised by outstanding resistance to sulphuric acid, even highly concentrated acid. Typical applications include sulphuric acid coolers and waste sulphuric acid recovery. Other alloys from Krupp VDM for sulphuric acid applications include Cronifer(R) 1925 hMo - alloy 926, a super austenitic stainless steel used for sulphuric acid distribution systems and coolers; and Nicrofer(R) 5923 - alloy 59, a nickel-chromium-molybdenum alloy with an extra-low carbon and silicon content, also used for sulphuric acid coolers. Chromium alloy metals are selected for use in high temperature heat recovery service with 98.0 to 99.5% sulphuric acid to 200[degrees]C. These alloys include austenitic and duplex stainless steels having high chromium content. However, a minor decrease in concentration at these high operating temperatures will cause high corrosion rates for these alloys, especially if exposed to high velocity conditions. Lewmet(R) 15, a proprietary high chromium duplex stainless steel of Lewis Pumps, has exhibited excellent corrosion resistance in heat recovery applications. It can be hardened to approximately 375 BHN

(40 Rc) and has shown superior resistance to weak acid corrosion as evidenced in process variable excursions in existing heat recovery systems. Nicrofer 3033 - alloy 33 is a high chromium austenitic alloy developed by Krupp VDM. [2] It exhibits outstanding resistance to corrosion in highly oxidising media, such as concentrated sulphuric acid, and its copper content facilitates passivation in sulphuric acid. Typical applications of alloy 33 (W. Nr. 1.4591, UNS R20033) include heat exchangers, vessels, tubes and other equipment for sulphuric acid production plants, sulphuric acid heat recovery and distribution systems. Table 1 gives the results of field tests under flowing conditions in which alloy 33 was tested in 99.1% sulphuric acid at 150[degrees]C and a flow velocity of [greater than or equal to] 1 m/s over 134 days. Under these plant conditions the stainless steel AISI 316 Ti and the nickel based alloy 825 failed but alloy 33 performed even better than the chromium-rich nickel base alloy 690. In another sulphuric acid plant alloy 33 was tested in 98.5% sulphuric acid with some fluctuations down to 96% at a temperature of 135140[degrees]C. The acid flow rate was [greater than or equal to] 1 m/s. Table 2 lists the test results in comparison with two stainless steels 316 Ti and 304, the chromium-rich nickel based alloy G-30, and a special silicon-containing steel A611. Lewis pumps has recently introduced two new materials to its alloy range: Lewmet(R) 70 and Zeron 100. Lewmet 70 is the product of a five-year research project in conjunction with the University of Missouri-Rolla. It is a high silicon nickel based alloy specifically designed to resist high temperature weak acid conditions. Extensive corrosion testing in the laboratory has shown excellent corrosion resistance in sulphuric acid concentrations as low as 70% to the boiling point. With significantly more ductility than high silicon iron alternatives, this material could prove to be a viable option for difficult "weak acid" applications. Plant evaluations are continuing. Zeron 100 is a super duplex stainless steel for use in aggressive corrosive environments. It is considered to be the original super duplex stainless steel, characterised by its high molybdenum and nitrogen content and having a pitting resistance equivalent number (PREN) greater than 40. In an agreement between Lewis Pumps and Weir Materials Ltd, UK, Lewis will market Zeron 100 to its traditional markets, sulphuric acid and phosphoric acid production. Zeron 100 will provide solutions for high temperature sulphuric acid energy recovery systems where traditional alloys have not been providing adequate service life. High silicon stainless steel alloys

High silicon stainless steel alloys were developed in the mid 1980s. Nominally Fe-l8Gr-l8Ni-5Si, these alloys possess outstanding corrosion resistance in 98% sulphuric acid to 140[degrees]C. However, the corrosion rates can increase dramatically with decreasing acid concentrations and with acid concentrations in excess of 99.5% through the oleum range. Corrosion protection is obtained by the formation of a tenacious siliconrich film formed on the surface during the initial days of corrosion. Prior to the introduction of silicon-containing stainless steels, critical applications such as drying and absorbing towers and pump tanks were traditionally made of acid brick-lined carbon steel, and acid piping and distributors were made of cast iron. The main advantages of silicon stainless steels in these applications are their extremely high corrosion resistance for concentrated sulphuric acid, reduced maintenance, and improved reliability and safety. Sandvik SX sulphuric acid steel The Sandvik SX sulphuric acid steel (UNS S 32615) is a high silicon containing austenitic stainless steel. It was developed by Sandvik some 20 years ago, exclusively for the use in concentrated sulphuric acid. The SX steel is characterised by an excellent corrosion resistance over a wide concentration range at high temperatures, in both static and dynamic conditions. Its corrosion rate at normal sulphuric acid plant operating conditions is well below 0.1 mm/year (4 mils/year). Furthermore, the SX steel is easy to work, weld and install, and does not require anodic protection. The properties of SX steel make it a suitable material of construction for all components in the absorption part of a sulphuric acid plant. The SX steel is covered by ASME code case 2029-2. The Edmeston SX System is based on the application of the SX steel. Edmeston AB, a fully-owned subsidiary of Sandvik, Sweden, introduced it to the market in 1985. Edmeston has marketed the SX steel and equipment ever since through its licensees, agent and representatives. The Edmeston SX system has been applied to nearly all components in the absorption and drying loops with numerous references in successful operation all over the world. A total of more than 3000 tons of SX equipment is now in operation worldwide. The number of plants installing SX piping has increased rapidly over the last few years. Since 1990 more than 450 tons or 16,000 m (10 miles) of SX piping have been installed at over 100 plants worldwide. [4] Monsanto Enviro-Chem Systems The Engineered Alloy Product Group of Monsanto Enviro-Chem Systems is committed and focused on providing solutions to corrosion problems

in the sulphuric acid industry. Enivro-Chem's portfolio of acids for strong sulphuric acid includes materials such as SX and 310M, and ZeCor [TM] sulphuric acid stainless steel a relative newcomer, available exclusively from Enviro-Chem. ZeCor [TM] was developed in response to the need for a material that exhibited extreme corrosion resistance in 93%-99% sulphuric acid with a cost structure that would allow it to be competitive with traditional materials of construction such as cast iron and brick-lined carbon steel. ZeCor [TM] was introduced commercially in December 1998 and has been widely accepted by the industry. To date, more than 50 ZeCor [TM] distributors, as well as numerous piping systems, towers and other sulphuric acid equipment have been installed worldwide. SARAMET alloys SARAMET is family of silicon stainless steel alloys introduced to the sulphuric acid industry by Kvaerner Chemetics, Inc. (KCI). The original material, known as SARAMET 23, was introduced in 1982 and quickly proved it self to have outstanding corrosion resistance in turbulent, hot, concentrated sulphuric acid. In addition, it possessed mechanical properties superior to, and weldability similar to, common 300 series stainless steels. The performance of SARAMET 23 decreases with decreasing concentration. For this reason KCI limits its application to sulphuric acid concentrations greater than or equal to 92%. Two additional SARAMET alloys and cast versions are now also available. [3] SARAMET 35 has excellent corrosion resistance to both oxidising/ concentrated and reducing/dilute strengths of sulphuric acid. Because of its performance and versatility it is regarded as the premium material in the alloy family. Weak sulphuric acid resistance is advantageous in applications where process upsets, air/ atmospheric moisture ingress and dilute acid formation from strong acid water addition are concerns. Practical examples of these are drying acid circuits in certain smelter acid plants, where acid strength excursions can occur, gas inlet regions in sulphur burner air drying towers, and strong acid pump tanks under suction and with tip entry dip tube style water dilution. Certain metallic materials commonly used in concentrated sulphuric acid service, such as ductile and cast iron, and carbon steel are susceptible to velocity induced erosion corrosion. SARAMET 35 has been erosion corrosion tested in 98% sulphuric acid at 120[degrees]C with acid velocities of 9 and 25 ft/sec. At both velocities no detectable corrosion was observed over a 14-day test period.

In sulphuric acid plant heat exchangers, the water/coolant side corrosion resistance of an alloy can at times be as important as the acid side corrosion resistance, due to episodes of poor water quality. Both SARAMET 35 and SARAMET 23 have been tested in accordance with ASTM CT61 procedure and found to have a relative chloride pitting resistance at leas equivalent to 316L stainless steel, the industry standard for shell and tube heat exchanger tubing. In addition, SARAMET 35 possesses high strength and toughness when compared to workhorse 300 series stainless steels, good forming and welding characteristics and physical properties comparable to other stainless alloys. SARAMET 21 is the least costly member of the SARAMET family, with the narrowest concentration/ temperature window. The material offers all welded construction, improved economy and acceptable corrosion performance in certain acid plant areas. SARAMET castings are advantageous when heavy sections, intricate shapes or small production quantities are required. Cast alloy formulations and processing routes have been developed to yield materials with equivalent corrosion resistance and similar mechanical properties, when compared to their wrought counterparts. The corrosion performance of all SARAMET alloys is significantly enhanced by ANOTROL [R], anodic protection. Combining the properties of ANATROL and SARAMET makes it possible to extend the range of metallic equipment in terms of acid concentration and temperature. Anodic protection As mentioned above, most metals will corrode within a certain range of electrical solution potential and solution pH. At potentials more negative than this range, corrosion ceases (cathodic protection). At potentials more positive than this range, several metals become passive. For these metals the potential can be shifted electropositively into the passive range through anodic protection. Anodic protection is especially applicable to sulphuric acid environments. It often enables a designer to make overall cost savings by permitting the use of a low alloy rather than a corrosion-resistant metal. For example, a tank used to store concentrated sulphuric acid can be fabricated from carbon steel with anodic protection as opposed to more expensive stainless steel or carbon steel with an organic lining. The most commonly utilised non-proprietary stainless steels for hot concentration sulphuric acid are S30400 (T304), S31600 (T316) and their low carbon variants S30403 (T304L) and S31603 (T316L). At ambient temperature, these austenitic stainless steels are immune to corrosion in high concentration ([greater than]90%) sulphuric acid.

Corrosion becomes a concern with increasing temperature. As the operating temperature rises above 75[degrees]C, the electrochemical potentials of stainless steels exhibit an oscillation where the potential alternates between active and passive potentials. This results in corrosion rates of 316SS as high as 495 mils per year in 93% sulphuric acid at 100[degrees]. [5] Corrosion Service Company Limited (CSCL) has used Anotection [R] (anodic protection) to protect stainless steel in hot concentrated sulphuric acid for two decades. The corrosion rate of either steel or stainless steel in sulphuric acid service is a function of both temperature and acid concentration. Table 3 indicates the typical corrosion rate reduction that can occur on 316 SS in two concentrations of sulphuric acid by the application of anodic protection. Figure 5 shows an anodic polarisation curve for 316 SS in 93% [H.sub.2][SO.sub.4] at 70[degrees]C. Note that the current density required to achieve passivation is almost [10.sup.4] [micro]A/ [cm.sub.2] This potentiodynamically derived polarisation curve indicates that an impractically large current capacity power supply would be required to exceed the active-passive transition point. Fortunately, smaller capacity units are feasible when operated galvanostatically to take advantage of the coulombic effect. Current densities to maintain passivation are normally an order of magnitude lower than the primary transition current. An interesting application of electrochemical protection involves the combined use of anodic protection and cathodic protection for corrosion mitigation in acid coolers (Fig. 6). The shell and tubes, made of 316 SS and exposed to the acid, are anodically protected where two Hastelloy rods, inserted in the place of two tubes, act as the cathodes. In addition, the carbon steel head boxes expo sed to cooling water are protected with galvanic anodes. Piping carrying sulphuric acid can also be protected anodically. Anodic protection can be installed in conjunction with new and existing structures. The economic benefits are attractive in both cases. The cost effectiveness of anodic protection is a function of vessel surface area. In general, protecting a larger vessel translates into a significantly reduced price per unit surface area. As a result of the large differences in corrosion rates between vessels in the active and passive state, it is imperative that anodic protection systems operate correctly. Therefore, virtually all systems are supplied with a remote monitoring unit. This computer-based unit allows offsite experts to review and analyse operational data and recommend changes. Pumps and valves Pumps, valves and piping, respectively, pressurise, control and direct process fluids. In the production of concentrated sulphuric acid, pumps,

valves and piping are subjected to a media that is hot, corrosive and often abrasive (due to the presence of solid impurities). In order to maintain performance throughout a reasonable service life, the designers of such equipment must select materials that are suitable for these fluid properties, especially for those critical components subject to high fluid velocities and turbulence that can cause wear by erosion. Pump designs require that close dimensional tolerances be maintained in order to ensure maximum hydraulic efficiency and performance, particularly between impeller/casing rings and sleeve bearing components. Valves require the same maintenance of dimensional tolerances between discs/plugs and their seating surfaces, in order to provide precise control and/or tight shut-off according to their function. The perfect material of construction for these critical components therefore, is one that resists corrosion over a usable range of acid concentration and operating temperatures, is hard enough to offer abrasion resistance when required, and has non-galling characteristics. The selection of materials for the principal "body" components of pumps and valves (i.e. volutes and valve bodies) and piping must take into account not only the potential effects of abrasion and corrosion, but must have sufficient mechanical strength to contain the fluid pressure over a reasonable lifetime. Therefore, to build a useful -- but cost effective product -- the design and choice of materials must be optimised according to the nature of the fluid and the required conditions of service. The lifetime of a pump or valve is not only dependent on the material used, but also on the way they are operated. For instance, throttled valves increase the velocity of the acid, which usually results in a sharp increase in corrosion. By choosing a suitable material, the attack of erosion corrosion can be reduced. Cost effective pumps, valves and piping can be designed and supplied to meet flow sheet requirements in sulphuric acid plants and will yield good service provided they are operated within the specific ranges. However, even the best-designed equipment will fail if process conditions are violated. The four primary causes of (unexpected) corrosion are: acid leaks, acid strength out of range, acid temperature too high, and acid flows that are too high. Lewis Pumps The use of highly corrosion-resistant nickel based alloys used in the critical components of Lewis sulphuric acid pumps dates back to 1925, about the time these alloys became commercially available. The nickel base permitted higher additions of the desired alloying elements as compared to iron based alloys. The early alloy, Ni-22Cr-7Mo-6.5Cu exhibited a corrosion rate of less than 0.25 mm/y in 98% acid to 90[degrees]C with operating velocities to 30 m/s. However, this alloy,

which was fully austenitic, could not be hardened and was only available in cast form. In 1940 Alloy 20, Fe-20Cr-3Oni-3Mo-3.5Cu was introduced. While offering utility in 98% acid to 90[degrees]C operating temperature, the resistance to corrosion-erosion decelerates rapidly above this temperature. Alloy 20 is a fully austenitic alloy available in both cast and wrought form, and cannot be hardened. Lewmet(R) 55, Ni-3lCr-3Si-3Mo-3Cu, was introduced by Lewis Pumps in the early 1970s. The corrosion rate of this alloy is presented in Fig. 7. This alloy also exhibits excellent corrosion resistance in 93-98% sulphuric acid and all concentrations of oleum. There is virtually no increase in the corrosion rate due to erosive wear at velocities to 30 m/s. This alloy is hardened to 400 BHN (45Rc) to provide excellent galling and abrasion resistance with no detectable loss in the corrosion rate. These characteristics make Lewmet the ideal material for use in manufacturing close clearance critical components for pump sleeve bearings and impeller/casing rings and for valve discs/plugs and seats. Subsequent to the introduction of Lewmet(R) 55, a wrought version of this alloy was developed. Introduced as Lewmet(R) 66, this modification has the same corrosion resistance as its parent alloy, is available in both cast and wrought forms, but cannot be hardened. Using a typical Lewis pump as an example, the materials of construction chosen for a given service vary according to the specific requirements of the component parts: Lewmet(R) 55 is chosen for the impeller, impeller nut, wear rings, bearings and journals. These components require a high degree of dimensional stability, are subject to high velocity and wear conditions. Lewmet(R) 55 was specifically designed for this service. Readily available in wrought bar form, Alloy 20 provides good general corrosion resistance for the pump shaft and bolting below the cover plate. To prolong serviceability, especially in larger pumps, a Teflon shaft cover is also utilised and a Cap-Nut fastening system provided with O-Ring seals. The pump body, which includes the volute, discharge elbow, pump boot, and discharge pipe, must have good overall corrosion resistance and maintain sufficient mechanical strength to contain fluid pressure. Speciality cast iron L-14[R] is an ideal cost effective candidate for these large cast components. Friatec-Rheinhutte Friatec-Rheinhutte possesses many years of experience in the practical application of corrosion- and wear-resistant materials in sulphuric acid

pumps and valves. Table 4 shows the range of materials on offer. The company also supplies vertical and horizontal centrifugal pumps for sulphuric acid plants. References (1.) Cooke, M.J. (Chas S. Lewis & Co. Inc.): Materials of construction for pumps, valves and piping used in the production of sulphuric acid". (2.) "Nicrofer 3033 -- alloy 33: A new corrosion-resistant austenitic material for many applications. VDM Report No. 24 (June 1998). (3.) Harding G (Kvaerner Chemetics): "Developments in sulphuric Acid Metal (SARAMET) Technology", Sulphur 98, Tucson, Arizona (Nov 1998). (4.) Kodeda F. and Berglund G (Edmeston): "Edmeston SX System & Sandvik SX Stainless Steel: Review of 15 years experience in the sulphuric acid business". (5.) Munro, J.I and Shim, W.W. (Corrosion Service Co. Ltd): "Anodic protection -- Its operations and applications". Materials Performance, (May 2001). [Graph omitted] [Graph omitted] [Graph omitted] [Graph omitted] [Graph omitted] [Graph omitted]
Table 1 Corrosion resistance of alloy 33 and other materials tested in a sulphuric acid plant. (99.1% [H.sub.2][SO.sub.4]. velocity flow [greater than or equal to] 1.2 m/s, 150[degrees]C, test duration 134) Alloy 825 316 Ti 690 33 Table 2 Corrosion rate (mm/y) 1.46 0.81 0.09 [less than]0.01

Corrosion resistance of alloy 33 and other materials tested in a sulphuric acid plant. (96-98.5% [H.sub.2][SO.sub.4], velocity flow [greater than or equal to] 1 m/s, 135-140[degrees]C, test duration 14

days) Alloy 316 Ti 304 G-30 A611 33 Table 3 Corrosion rate (mm/y) 0.24 0.18 0.08 0.03 [less than]0.01

Corrosion rate of 316 SS (mpy) in [H.sub.2] [SO.sub.4] 93% [H.sub.2][SO.sub.4] Temperature 70[degrees]C 100[degrees]C Unprotected 29 495 Protected [less than]2 25 98% [H.sub.2][SO.sub.4] Unprotected 41

Temperature 70[degrees]C 100[degrees]C Table 4

98% [H.sub.2][SO.sub.4] Protected [less than]2

Friatec-Rheinhutte materials for pumps and valves Material 1.4136S DIN G-X 50 CrMo 29 2 Properties and application Corrosion- and erosion-resistant high alloy ferritic cast steel. Typical applications are highly concentrated sulphuric acid up to 180[degrees]C, oleum, fertilizer production, crude phosphoric acid containing solids. Austenitic stainless steel with high silicon content. Provides excellent resistance to erosion-corrosion resistance in the dryer, intermediate and absorber stage of sulphuric acid plants. Special high-alloyed material for pumps operating in absorber acid (99% [H.sub.2][SO.sub.4]) in sulphuric acid plants with heat recovery in the temperature range of 180-240[degrees]C. Highly corrosion resistant chrome alloy silicon cast iron with good resistance to wear and increased chemical resistance. This material is chemically resistant to sulphuric acid at all

RHSX

RHRS

Sigu[beta] DIN G-X 90 SiCr 15 5

concentrations up to boiling point, therefore for all sulphuric acid applications including the evaporation of waste sulphuric acid.

COPYRIGHT 2001 CRU Publishing Ltd. This material is published under license from the publisher through the Gale Group, Farmington Hills, Michigan. All inquiries regarding rights should be directed to the Gale Group.

Title: Fighting corrosion in sulphuric acid plants. Date: 9/1/1991; Publication: Sulphur; The product efficiency of the contact sulphuric acid process is already very high, but there is still scope for increasing reliability and thermal efficiency. The key to both is better materials of construction, especially in the parts of the plant which handle liquid acid. The contact sulphuric acid process is one of the most mature technologies in the chemical industry. Considering that its central feature is an equilibrium reaction which has to be assisted catalytically - the oxidation of sulphur dioxide to sulphur trioxide - its inherent efficiency is quite remarkable. It has fundamentally changed very little over the years - it hasn't needed to. The most radical improvement was the introduction in 1963 of the double-absorption or double-catalysis concept, in which the equilibrium SO.sub.2/SO.sub.3, conversion was shifted artificially by dividing the sequence of catalytic conversion stages into two and passing the gas through an intermediate absorption stage to remove the bulk of the sulphur trioxide. Tbis development raised the theoretical maximum efficiency from about 98.5% to almost 100% and practical conversion efficiencies from around 98% to 99.5-99.8%. Since then there have, of course, been useful and significant improvements, but they have mostly been concerned with individual areas of the process, rather than with the overall concept, and with generally improving energy-efficiency and reliability. The latter expedient is, of course, a permanent aspiration of the plant operator, but it has been lent new importance in many areas by the introduction of environmental regulations. While the contact process has always scored highly on product efficiency, the same cannot be said of energy-efficiency. However, because the reactions involved are all exothermic, the only energy it has ever needed to import is the power for the main blower for driving acid and water pumps. Plants which obtain their sulphur dioxide feed by burning elemental sulphur or pyrites actually enjoy a very large

bonus in the form of surplus high-level reaction heat which is easily recovered in the form of high-pressure steam in waste heat boilers on the sulphur furnace or the pyrites roaster. This is serious steam: up to 1.4 tonnes of steam per tonne H.sub.2,SO.sub.4. However, one third of the total quantity of reaction heat in such plants is generated in the acid circuits, and in old plants it was at such a low temperature level that it was effectively useless and was merely rejected into cooling water or air. Metallurgical sulphuric acid plants, where the feed gas, often containing less than ideal concentrations of sulphur dioxide, is received over the fence from metal ore roasting and smelting operations which have usually recovered most of the high-level heat for their own use, are even more disfavoured: the gas must first be cleaned and dried, during which it has to be cooled to near ambient temperature, and all the high- and medium-grade heat produced in the conversion section is used up in reheating the cold feed gas to the catalyst strike point. In these plants, therefore, effectively all of the reaction heat is rejected at low grade through the acid circuits. Originally the acid in the absorption and drying circuits had to be kept well cooled for two reasons. One was the need to avoid acid mist formation, which was temperature-dependent. The other was that no existing metallic material of construction could stand up to concentrated sulphuric acid at temperatures above about 70 deg C. Acid absorption towers could be lined with acid-resistant bricks and other non-metallic materials and be filled with ceramic packing, but those materials were obviously out of the question for piping and coolers, which were normally made of cast iron, but the corrosion rate even at fairly low temperatures was high enough to demand a very generous corrosion allowance in wall thicknesses. Heat transfer through the thick cast iron cooler tubes was lamentably low, and sulphuric acid coolers had to be very massive to compensate. In the socalled cascade cooler design, serpentine tubes were horizontally mounted in outdoor racks and were cooled partly by natural convection and partly by evaporation of cooling water with which they were constantly irrigated. In an alternative design the tubes were finned and cooled, with or without irrigation, by a forced air draught. Such coolers had a limited life; maintenance costs were high and leaks an all-toofrequent occurrence. Other critical items included the acid distributors at the top of the absorption and drying towers. Tbe operational disadvantages of old-fashioned cascade coolers were sufficient cause to seek alternatives, and in the 1960s and early 1970s compact stainless steel plate and spiral heat exchangers cooled by water began to replace them. When, in the early 1970s, energy prices began to leap upwards, it very much sharpened awareness of the potential value of the prodigious amount of low-level heat at that time being wasted. By that time satisfactory means had been devised to suppress acid mist, making it possible to contemplate raising the temperature at which the heat was rejected. By various means, that has progressively been achieved, allowing the heat to be used first in

district heating schemes or on-site boiler feed water or process stream preheating, later in concentration of phosphoric acid or reconcentration of used sulphuric acid, and most recently in generating steam at temperatures of up to I 0 bar. This last attainment necessitated some modifications to the detail of the process, but neither it nor any of the earlier advances would have been possible without significant improvements in the protection of acid circuit equipment against corrosion, both by passivation treatment and by developments in the materials themselves. The feasibility of running an acid circuit at elevated temperature clearly depends on solving materials corrosion problems in every equipment component that is in contact with the acid and not just pipework and coolers. Pumps, valves, acid distributors and tower components must all reliably resist corrosion over a predetermined design life. In comparison with the acid handling parts of the plant, materials selection in most the parts of the plant which handle process gases above the dewpoint is fairly straightforward. Mostly ordinary carbon steel can be used, although special corrosion treatment of heat exchanger components has been shown to increase their life dramatically. This two-part article outlines how materials of construction for sulphuric acid plant service have developed and are continuing to develop. In this part it surveys metallic materials of construction for use in the "wet" parts of the plant handling liquid acid or acid mist and then looks at the special requirements of specific individual acid-handling equipment items. Tbe concluding portion, to be published in the next edition of Sulphur, will comment on some solutions to problems in dry parts of the plant and, finally, survey available ceramic materials and their applications. How sulphuric acid corrodes Although sulphuric acid is the most frequently encountered industrial corrosive, its complex corrosive behaviour has remained poorly understood until relatively recently. It corrodes by different mechanisms at different concentrations, and its behaviour is influenced by temperature and dissolved impurities and, of course, by the composition of the material being corroded. Tbe selection of materials, therefore, requires a thorough knowledge of the operating conditions as well as the mechanical design details. At concentrations below about 85 wt-% at room temperature (65 wt-% at higher temperatures), sulphuric acid is highly dissociated into hydrated hydrogen ions and sulphate ions and behaves as any other normal strong mineral acid. The mechanism of metallic corrosion is represented by the following equation. H.sub.2, SO.sub.4 + 2M->M.sub.2,SO.sub.4 + H.sub.2

At higher concentrations and temperatures hydrogen ion corrosion becomes progressively less important (in industrial-strength 98% sulphuric acid there are very few hydrogen ions); sulphuric acid behaves instead as an oxidizing agent 2H.sub.2, SO.sub.4, + SO.sub.2 + 2H.sub.2 O Metallic materials which resist one type of corrosion do not usually resist the other. Selection of a metal or alloy for a particular application therefore depends critically on accurate knowledge of the reducing or oxidizing nature of the acid, which as mentioned - depends not simply on knowing its concentration but also all other variables, such as temperature and impurity content, which might affect it. Metallic construction materials Historically, lead and cast iron were the metals of choice for components in the acid circulation system. Steel, where used, was lined with non-metallic materials. Lead Lead is resistant to normal acid corrosion but is susceptible to attack under oxidizing conditions. It was, in fact, the first special material of construction to be used in sulphuric acid manufacture, giving its name to the "lead chamber" process - the standard production method until the contact process was developed. Because modem plants mostly produce sulphuric acid outside its safe concentration range, lead today is little used in sulphuric acid plants except those of the wet-catalysis type, which produce acid of 78% H.sub.2,SO.sub. 4 or less, but it is still quite common in feed gas cleaning equipment such as scrubbers, electrostatic precipitators, shell-and-tube coolers, piping, valves and pumps. Cast iron As remarked earlier, cast iron is out of fashion in applications such as acid coolers or heat recovery equipment, but it is still in use in "lowtech" applications where heavy wall sections providing large corrosion allowances fit the process requirements and offer important economic and safety advantages. It performs best at fairly high acid concentrations. Iron resists sulphuric acid attack by forming an insoluble iron sulphate film. This film is the result of the initial corrosion reaction between the acid and the exposed metal. As the iron corrodes, the thickness of the film increases, which has the effect of impeding further acid attack. Tbe sulphate film itself is of limited solubility in concentrated sulphuric acid, but it is rather easily eroded away from the base material if the acid flow rate is too brisk. It is also more likely to be damaged by elevated pressure and low acid concentration, both of which increase the solubility of the film and hasten its breakdown'.

Tbe limiting safe values of acid flow velocity and acid temperature for ordinary cast iron are well known. As a general rule, the acid velocity should not exceed 1 m/s and the temperature 90'C. Provided that these rules are observed and adequate corrosion margins are allowed in fabrication, cast iron has a life expectancy of at least ten years. As previously mentioned, cast iron remained the sole material for concentrated hot acid until the end of the 1960s, when stainless steel and other high alloy materials first started to replace cast iron in coolers. Modem cast iron grades, alloyed with up to 1% of chromium or copper, are standard materials for concentrated sulphuric acid of 90-99% H 2so 4 and at temperatures of up to 1200C. Cast iron is mainly used for acid piping, acid irrigation systems in packed acid towers and (where they have not been replaced by something else) irrigation (cascade) coolers. Although these cast iron grades have a very high erosion-abrasion resistance, they are quite sensitive to stress corrosion cracking, which is induced by the formation of sulphate along the graphite lamellae. Alloy 20 The first stainless steel alloy developed for sulphuric acid, Alloy 20, was first introduced in the mid 1930s. Type 20 alloys were originally developed by Fontana, and it is understood that the 20 in the designation of many alloys in this group resulted from the fact that the cast ACI CN-7M composition, typical of these alloys, was the twentieth modification tested by Dr Fontana. All of the alloys in this category are iron-based nickel-chromium-coppermolybdenum alloys. The group contains both cast and wrought alloys, which are roughly equivalent in corrosion resistance. Alloys in this category include: Durimet ahoy 20," Aloyco alloy 20, Worthite and Carpenter alloy 2OCb-3. Developed in 1947, Carpenter 201, was a wrought counterpart to cast ACI CN-7M. Since then the alloy has undergone several improvements. In 1948, columbium was added to stablize it against chromium carbide precipitation; in 1963, the nickel content was increased to about 3335%, primarily to give greater resistance to stress-corrosion cracking and improved resistance to boiling sulphuric acid under heat-transfer conditions. Minor processing changes have been made subsequently to give even greater resistance to intergranular corrosion. Me current version, Carpenter 2OCb-3, is commonly used in concentrated acid service for valve stems or pump shafts that have to go through packing. Tbe cast Alloy 20 types are used mainly for valve bodies and pump casings 2. Nickel-base alloys During the 1930s and 1940s, nickel-base corrosion-resistant alloys, most notably Illium nickel-base chromium-molybdenum-copper alloys, were developed and introduced into sulphuric acid service. Illium alloy G is a cast alloy which was originally developed to resist mixtures of

sulphuric and nitric acids, as encountered in the Chamber process for sulphuric acid. Illium alloy 9811 is a weldable, machinable cast alloy that was originally designed to withstand hot 98% sulphuric acid at temperatures up to about 100'C. Illium alloy B", another cast alloy, is a modification of Illium alloy 98 which extends the useful service range in 98% sulphuric acid up to temperatures of about 125 deg C. One of the first of the present generation materials was Lewis Pumps' Lewmet 55 alloy, introduced in the 1970s. This cast nickelbase alloy is capable of extended service in 98% sulphuric acid at temperatures up to 140'C. Tbe alloy is used extensively in pumping applications and has demonstrated exceptional erosion/corrosion resistance with operating velocities up to 30 m/s. Additionally, Lewmet" is age hardenable to 42 R.sub.c without losing its corrosion resistance. Hardenability is an important consideration in sulphuric acid tower circulation systems, since the circulating acid often contains abrasive brick chips and saddle packing fragments suspended as solids in the tower acid. More recently, Lewmet 66 alloy has been introduced. This alloy is the wrought counterpart of Lewmet 5511 and is available in bar and wire forms, as well as in cast form. As with Lewmet 55, the alloy exhibits excellent erosion-corrosion resistance to 98% sulphuric acid at temperatures up to 1400C. Materials falling into the category of nickel-base ironchromiummolybdenum-copper alloys for sulphuric acid include Incoloy alloy 825 and Hastelloy G and G-3. Incoloy alloy 825, has very good resistance to sulphuric acid at concentrations up to 40% H.sub.2,SO.sub. 4 at boiling temperature, at concentrations up to 60% H 2so 4at 800C, and at all concentrations at temperatures under 65'C (see Fig. 1). This alloy is stabilized against carbide precipitation by a titanium addition so that it can be used in the as-welded condition. Hastelloy G is a modification of the obsolete Hastelloy F. It is a lowcarbon, nickel-base alloy containing significant amounts of chromium, molybdenum and copper and is stabilized against carbide precipitation with columbium. This alloy has improved resistance to sulphuric acid and can withstand the effects of both oxidizing and reducing media. A further attribute of Hastelloy G is its excellent resistance to chloride stress-corrosion cracking. Hastelloy G-31, is a modified version of Hastelloy G with a similar general corrosion-resistance. This modification was developed to be resistant to the formation of grain boundary precipitates during prolonged heating, such as might occur during stress-relief of a carbon steel vessel clad with the alloy. Anodic protection for stainless steel In the 1970s, the Canadian company Chemetics International introduced an electrolytic method of enhancing the corrosionresistance of standard grades of austenitic stainless steel in acid

coolers and piping which allowed the maximum temperature under which they could operate to be extended from about 11O deg C to as high as 140 deg C without suffering excessive corrosion, even under turbulent acid flow conditions. The method comprised passing a low-voltage direct current through the acid between the carcase of the cooler as anode and special cathodes installed inside the cooler. The current density was set to optimize the stability of the passive film formed on the stainless steel surfaces exposed to the acid in the cooler. Chemetics applied the technique to shell-and-tube acid coolers with the acid running on the shell side, since it was easy to install electrodes running the full length of the cooler among the tubes and thus ensure a reasonably uniform electric field in all parts of the cooler. Other companies applied the technique to different patterns of cooler with varying degrees of success. Anodic passivation can only be successful if the system is kept completely filled with acid. Anywhere that air accumulates will not be protected, as the air acts an insulator, preventing current from flowing through the affected area of the steel surface. It is also important to maintain the electric potential over the entire surface within the effective range. Below its lower limit the potential is too low to create and maintain the passive layer, while above the upper limit the electric current actually destroys the passive layer and increases, rather than restricts, the rate of corrosion. As the temperature and corrosivity of the acid increase, the difference between the minimum and maximum effective anode potentials diminishes until it becomes impracticable to maintain a reliable state of passivation. Both Lurgi and Monsanto Enviro-Chem (MEC) have done extensive research and development on anodic protection of stainless steel in sulphuric acid. MEC has supplied over 120 acid coolers with anodic protection since 1978. These include units operating on cooling water as well as units used for a modest degree of heat recovery - boiler feedwater preheating or district heating schemes, for example. Corrosion rates for anodically protected stainless steel coolers are typically less than 0.03 mm/a. Because of the low corrosion rate, compact size and low maintenance, these coolers have been readily accepted in the sulphuric acid industry. High-silicon stainless steel alloys More recently, high-silicon stainless steel alloys, such as Chemetics' Saramet and Sandvik's SX, have been introduced. These alloys exhibit good corrosion resistance in 98% sulphuric acid at temperatures up to 1400C without anodic protection. However, at lower acid concentrations the corrosion rate is reported to increase significantly. They also do not withstand corrosion by oleum.

Until now high-silicon alloys have mainly been used in wrought products: tubes, pipes, sheet and plate. Specialized welding techniques have been developed. The corrosion resistance of components fabricated from them has been confirmed by plant experience under normal operating conditions. Silicon austenitic stainless steels were originally developed for strong nitric acid service, but over the last 15 years Chemetics has developed, tested and proved this material in sulphuric acid distributors, acid piping systems, pump tanks, absorber towers, drying towers, acid pumps, tower packings, acid coolers, acid strainers, nozzle liners and boiling acid reactors. The newest acid plant application for Saramet is in acid tower mist eliminators. The Otto York Co. markets Saramet mist eliminators. The use of high silicon stainless steel in sulphuric acid manufacturing and concentration plants is covered by Chemetics'patents in many countries, including the United States and Canada. Edmeston/Sandvik have entered into a licence agreement with Chemetics under which they have a non-exclusive right to sell these materials for sulphuric acid applications. If the combination of temperature and acid concentration is correctly maintained, Saramet, corrodes only very slowly (0.5 mils/year), but outside its passive range it can corrode rapidly, though in an unpredictable manner. Figure 2 indicates the acid strength and temperature window where Saramet corrosion will be virtually nonexistent passive condition) under plant operating conditions. The graph is based on field experience and a large laboratory-generated database. Saramet is a very strong and ductile material and its mechanical properties and processing characteristics are similar to those of standard 304L stainless steel. Tensile test elongations of approximately 30% are typical and, as a piping material, it will deform to a large degree before failure. This feature enables early detection of mechanical faults and avoids catastrophic failure. It is fully weldable and can be repaired, if need be, by butt-welding. It is therefore not necessary to stock spare components. Components made of Saramet as of any stainless steel or high alloy - weigh very much less than the equivalent cast iron parts. Up to now a wholly-owned subsidiary of Chemetics has fabricated Saramet almost exclusively, thus ensuring high standards of quality and favourable deliveries. Sandvik SX sulphuric acid steel was introduced in 1984 by Edmeston AB, a Sandvik subsidiary. This austenitic stainless steel was developed exclusively for sulphuric acid service. Sandvik SX has excellent corrosion resistance in concentrated sulphuric acid at temperatures up

to about 1500C (see Fig. 3). It is currently being used in a variety of applications, including towers, distributors, pump tanks, heat exchangers, mist eliminators, mesh pads, piping and nozzle sleeves. In 1986, MEC acquired a licence to manufacture and market equipment fabricated from SX. Since then NIEC has built four strong acid towers and numerous distributor systems of SX. In one plant the three towers, acid distribution systems, and strong acid piping were all fabricated of SX. An alloy tower usually costs more than one of brick-lined carbon steel; however, this extra cost is often offset by the reduced maintenance and shorter installation time. Alloy distributors are much less unwieldy than their cast iron counterparts and can be designed for high efficiency. The fine-diameter wire used in mesh pad mist filters makes them particularly susceptible to corrosion. SX mesh pads have so far been installed in 12 sulphuric acid towers. Tbe first was in a drying tower and has been operating for three years without problems where alloy 20 mesh pads were failing in 10 months. New iron alloys As with stainless steels and nickel-base alloys, new irons have also been introduced over the last ten to fifteen years. Ductile iron pipe has replaced a large proportion of the grey cast iron pipe. A number of corrosion-resistant iron alloys developed specifically for sulphuric acid service includes Monsanto's Mondi (Monsanto ductile iron) and Lewis Pumps' L-14 Iron. In strong sulphuric acid tower circulation duty, L-14 iron alloy exhibits up to 60% greater corrosion resistance than Process Iron", a cast iron material which has been an industry standard since its development by Lewis and DuPont in the early 1940s. Steel alloys Several steel alloys am now being used in high-temperature "heat recovery" applications; operating conditions are generally limited to 98.599.5% H.sub.2,SO.sub. 4 at temperatures up to 220 deg C. Examples of these high-performance alloys include Superferrit 1.4575 and Rheinhiitte's high chrome semi-austenitic cast material for pumps known as 1.4136HRS. Reports indicate that alloys with high chromium contents and little or no molybdenum content provide optimum performance in these environments. Tower applications Brick-lined carbon steel has been and still is the industry standard for absorber towers and pump tanks. However, installation times and labour costs for such units are excessive where "fast track" construction is called for.

As mentioned above, a relatively recent development in tower design is the use of an unlined vessel fabricated of high-silicon stainless steel. Preliminary reports indicate satisfactory performance; however, the long term effectiveness of this design still remains to be proved. High-silicon stainless steels have been used successfully for a variety of tower accessories, including distributors, saddle packing and wire mesh mist elimination equipment. For absorption and drying tower systems fabricated of SX without brick lining, Edmeston provides a complete tower with acid distributor (in most cases a pipe type with a special thread for quick assembly), packing support and all the necessary details for a complete installation. The SX-towers are designed to be lifted into place already filled with ceramic packing. Tbe demolition of the existing tower and the installation of a new tower takes approximately 10-12 days. To date 12 SX-towers have been installedd, comprimising all types drying absorption, stripping and sulphur dioxide cooling towers. The next step will be to replace the ceramic packing with structured metallic packing made of SX. Tbe potential advantages of this include low weight, reduced tower size and lower pressure drop. Lewmet alloy has also been used for a number of tower accessories, including gas inlet thimbles and acid outlet nozzles which have been in service since the late 1970s. Recently, Lewmet alloy has been used to fabricate pipe-type distributors and wire mesh pads for sulphuric acid mist elimination. Pump tank designs include brick-lined steel cylindrical vessels in both vertical and horizontal configurations. While used occasionally in the past, the horizontal pump tank design has become more widely accepted in recent years. Unlike vertical tanks, the tops of which are unlined, horizontal tanks are brick-lined over all their interior surfaces. More recently, as in other areas of the circulation system, unlined highsilicon austenitic stainless steel has been used for pump tanks. However, for reasons of both economy and safety, this practice has not been widely adopted. One pump tank component which has stood out over the years as a persistent problem is the water dilution pipe, or injection quill. Silicon iron used in the past was liable to break under mechanical or high temperature shock, leading to stratification of the diluted acid. Lewmet alloy is much less likely to fail because it is both ductile and resistant to corrosion at the high temperatures produced by acid dilution, and the service life of this highly-stressed component has in consequence been considerably extended. Piping/valves

Cast iron is used primarily for strong acid piping and corrodes constantly during its 4-10 year plant lifetime. The use of cast iron typically adds 10-25 ppm of iron to the product acid, which is of concern to the more quality-conscious clients. Prudent operators feel obliged to hold an extensive inventory of spare pipe spools, elbows and tees since failures are frequent in a cast iron piping system and custom-sized components may take a long time to obtain. The largest single deficiency of cast iron is its mechanical properties. It is very brittle and fractures instead of deforming when overstressed, making it a safety liability for workers. Heavy-wall cast iron pipe was used extensively in the USA until the early 1970s, when municipal water distribution systems switched from using cast iron pipe to ductile iron pipe. The decline in volume business eliminated many foundry sources for grey iron pipe and there was concern in the sulphuric acid industry that cast iron pipe would cease to be available at a reasonable cost. So the US acid industry followed suit and switched from grey cast iron to ductile iron. But in other countries where grey cast iron is still readily available it is still used extensively because of its superior corrosion resistance. Although, in the 1970s, ductile iron pipe was known to have superior mechanical properties, its corrosion resistance was not well established. Monsanto, therefore, conducted tests to compare the corrosion resistance of cast and ductile iron. Initial tests showed significant variations in the corrosion rate of ductile iron, which were later traced to variations in the silicon content of test coupons. This finding led to the development of Mondi ductile iron. The composition of Mondi is controlled to maintain superior mechanical properties while maximizing corrosion resistance. A comprehensive comparison of various cast and ductile irons revealed more than a 600% variation in corrosion rate. In general, cast irons have a lower corrosion rate than ductile iron. However, Mondi's corrosion resistance is superior to many cast irons, and its improved mechanical properties confer a significant safety advantage over cast iron pipe. Use of Mondi has increased steadily since its introduction in 1984. Last year, annual sales of Mondi pipe and fittings approached 1,000 tonnes. FEP-lined carbon steel is also used for strong acid piping; however, although the FEP liner itself is 100% corrosion-resistant, it becomes very soft and permeable to sulphuric acid and sulphur trioxide at temperatures in the range of 75-100'C. Spool pieces of FEP-lined piping in diameters greater than 12 inches >30.5 cm) are not readily available commercially and custom spares are required to replace damaged piping components. Acid and gas permeation vent holes are required in

the carbon steel shells, and this seriously compromises the integrity of the piping. More recently, a number of circulating systems have been retrofitted with anodically-protected 300 series stainless steels. Thinner-walled pipe can be used to keep costs competitive. Of course, care must be taken to provide adequate support for the thin-wall piping for the static and dynamic loads encountered. High-silicon stainless alloy piping systems are also now being installed. The main advantage of using this construction material for piping is that there is no risk of erosion-corrosion at higher acid velocities. The acid velocity inside cast iron was limited to 1 m/s. For SX piping there are no such limitations, so smaller-diameter piping can be used. The limit is set by the maximum acceptable pressure drop. Furthermore, SX is so workable that it is easy to make modifications to the piping system. Cast iron and stainless steel flow control valves, primarily 316 and Alloy 20, are still in use for lower temperature applications in strong acid tower circulation systems. But in modem systems running at higher temperatures more resistant materials are advisable. Valves fitted with Lewmet alloy gained rapid acceptance in the late 1970s. Lewis gate and globe valves provide consistent tight shutoff and the butterfly valves have demonstrated reliable, repeatable control characteristics. Valves from 15 mm to 150 mm in which all wetted components are of Lewmet have been furnished in a variety of applications, including sampling lines, and have outlived valves constructed of other alloys at operating temperatures up to 132'C. Acid coolers Absorption and drying acids are recycled and cooled in coolers of various designs. Traditionally, cast iron serpentine cascade coolers have been used and are still installed in many plants world wide. However, in plants where seawater is used as a coolant, frequent maintenance is required with this type of cooler because of excessive external corrosion. This is due in part to direct corrosion by seawater and also to corrosion by diluted acid from leaking flanges. Normally such coolers have to be replaced every 1.54 years. Another major drawback of this type of cooler is its inferior thermal efficiency, thus requiring large areas for installation. In the USA and in plants engineered by Western sulphuric acid process designers, anodically-protected stainless steel shell-and-tube coolers are now virtually standard. Until recently, anodically protected coolers provided the only really reliable economic way of recovering acid waste heat at a useful grade. Shell-and-tube heat exchangers have dramatically reduced acid leakage and associated safety risks for operating personnel. Their one inherent disadvantage is that they do

not remain passive for very long if the electrical passivation system fails or goes out of adjustment. In the 1970s and early 1980s, FEP tank-coil ("spaghetti") coolers were used for a brief time, but a number of technical problems became evident. The narrow-diameter tubes were liable to fouling by impurities in the cooling water and were susceptible to mechanical damage, especially if there was any vibration. More seriously, the tube material was permeable to sulphuric add, which meant that in a closed circuit heat recovery system acidity built up in the cooling water. Industry surveys indicate that tank-coil coolers are no longer being installed in new sulphuric acid plants, while most of the original installations have been replaced by other types of coolers, notably, anodically protected stainless steel shell-and-tube design. More recently, high-silicon austenitic stainless steel coolers without anodic protection have been installed. To date, for example, more than 30 SX coolers have been successfully installed in plants around the world. They can operate at temperatures up to 150 deg C, according to the acid concentration. SX coolers have also been used in clean acid applications - for cooling acid that must not be contaminated with iron. The absence of metal loss in one particular case was assessed to be less than 0.004 mm/ year, corresponding to an iron contamination of less d= 0.1 ppm iron. In the same plant, six SX coolers were installed under cover, adjacent to the towers, thus replacing the complete battery of old outdoor cast iron cascade coolers. Special precautions have to be taken in specifying materials for coolers intended for use with brackish cooling water or sea water on account of chloride-induced corrosion effects. A careful assessment of the service parameters is done in each case. Seawater has been successfully used as a coolant in some SX coolers, but in other cases Edmeston might use SX for uncooled surfaces and a chloride-resistant stainless steel for the tubes. Bimetallic tubes have also been suggested for an installation using acid heat for desalination of seawater. Plate-type heat exchangers have also been applied in sulphuric acid plants to recover waste heat. However, the sealing materials place limitations on the material's acid inlet temperature. Alfa-Laval offers plate and spiral heat exchangers in a wide range of metallic materials for sulphuric acid plants. They include the basic austenitic stainless steels such as types 304 and 316, super alloy stainless steels and nickel alloys such as Hastelloy C276. Anodic protection permits the use of intermediary stainless steels such as 254 SMO for temperatures in excess of 100 deg C without the fear of chloride ion attack from the water side. The conventional gasket material is Viton-G; however, advances have been made by Alfa-Laval

in the development of a high-temperature ethylene propylene polymer for use in acid strengths up to 80% and temperatures up to 100 deg C at lower concentrations. Newer metallic materials finding fresh applications in the industry are those based on chromium and silicon alloying. Haynes' G30, VDM's 3127 and Sanicro 28 alloys are all being used increasingly in spent acid regeneration and scrubbing applications, especially where halide ions are present. For example, AJfa-laval has supplied plate exchangers in G30 material to BASF, Germany, where graphite had previously been used. Welded units in G30 are also being used in Germany in spent acid regeneration. Further afield, Alfa-Laval has supplied units to Chile using G30 for 80% acid and Nicrofer 3127 with EPDM gaskets on weak acid cooling. Pumps In the acid circulation system, the pumps are the only pieces of rotating equipment. Internal acid velocities within the pump casing can reach thirty times the design velocity encountered in the acid piping. Careful attention to materials selection is critical to achieving suitable pump service life. With a corrosive medium such as sulphuric acid, it is obviously of great importance from the point of view of both safety and damage to avoid any design with shaft seals that will leak. Submerged centrifugal sump pumps driven through vertical shafts from remote motors are ideal because they have no seals. Horizontal pumps with hydrodynamic (glandless) seals are also used with satisfactory results. Materials used for pump components exposed to high velocity and turbulence include stainless steels, such as Alloy 20, and nickel-base alloys, such as Lewmet 55 alloy. A wide variety of other materials have been used for pump components which are subject to lower operating velocities. These include Process Iron, cast iron alloys and stainless steels. Recently, Lewis introduced L- 14, iron, which is suitable for use in 98% sulphuric acid at temperatures up to 132'C. The requirement to operate the acid circulation system at higher temperatures has also resulted in the need for pumps and valves able to withstand these more aggressive conditions. In general, cast materials are more corrosion-resistant for pump internals than other fabrications. Pump and valve manufacturers such as Rheinhutte and Chas. S. Lewis & Co. have developed new designs with fewer moving parts, made either from silicon cast iron or various high-performance high-alloy steels to meet the new demands. Rheinhutte's most widely used material for sulphuric acid is its 15% silicon iron (Siguss), which is used for horizontal pumps. This material is unique compared with other alloys in that it exhibits excellent corrosion resistance to sulphuric acid at all temperatures and acid concentrations. Its unique corrosion resistance is basically due to two

factors the natural resistance of the iron silicide matrix structure, and the silica formed on the surface of the material in contact with the medium. It is, however, brittle and susceptible to thermal shock. Hightemperature heat recovery systems Heat energy has been recovered from acid circulation systems for a number of years and has been used for process and local town heating. Normally, however, this heat has been recovered at the relatively low circulating acid temperatures common during the 1970s. In the mid 1980s, new technology was introduced which increased acid temperatures above 200 deg C, which now enables recovery of energy from the acid circulation in the form of 10-bar steam. Monsanto's Heat Recovery System (HRS) was developed as a result not so much of the introduction of new materials as of the discovery that old materials could be used at much higher temperatures if the acid concentration was carefully controlled. Commercially available stainless steel alloys which work well when process operating parameters are followed closely have been selected for these systems. Several full-scale plants have now been constructed and a number of additional plants are in the design stage. The first HRS started up in South Korea in 1987 and continues to meet design expectations. This plant, which uses Lewis pumps and valves for circulation of the very high temperature acid, is generating about 9 MW of power using the heat recovered from 2 x 1,350 t/d acid plants. Corrosion rates on type 310 stainless boiler tubes are typically less than 0.04 mm/a, and no anodic protection is required. Corrosion-resistance in strong sulphuric acid at high temperatures can be characterized in terms of alloy composition. The best corrosion resistance generally results from alloys with chromium and low molybdenum content. The 300 series stainless steels in order of decreasing preference are: 310, 309, 304, 316, 317. Austenitic alloys containing both high nickel and high molybdenum, for example B2 and C276, are the worst performers in this service. Molybdenum-containing ferritic and duplex alloys which contain no nickel or low nickel work well provided the chromium content is relatively high >25%). In the early 1980s Metallgesellschaft made a breakthrough in materials technology with the development of ferritic chromium-molybdenum steels, available for the first time in plate thicknesses above 10 mm. This material (DIN No. 1.4575) is known commercially as Remanit

4575, Cronifer 2803 Mo and Superferrit 1.4575. Its composition is shown in Table 1. Before the introduction of this material, Metallgesellschaft had conducted tests with high-chromium ferritic steel in the bypass of a sulphur burning system at an elevated flow velocity of 3 m/s. The results of these tests confirmed the favourable corrosion properties of this type of steel at high temperatures. However at that time the material was only available commercially as thin sheeting. Material 1.4575 has been tested in the laboratory at temperatures up to 200'C and in pilot plants, for example, the Lurgi-designed pilot RuhrZink plant in Datteln, operated by Metallgeseflschaft, and in a pilot plant where the material was used for the venturi part in the intermediate absorber circuit of a sulphur-burning system. Figure 4 shows the range of application for Superferrit 1.4575 in concentrated sulphuric acid based on the results of these laboratory and field tests. In 1989, the first evaporator made of material 1.4575 was put into operation in the low-pressure steam energy recovery system of a sulphuric acid plant (Fig. 5). The venturi concept has proved to be advantageous when producing low-pressure steam in a heat exchanger with hot sulphuric acid (about 200 deg C). The intermediate absorber has two separate acid systems. In the venturi part, about 90% of the sulphur trioxide contained in the gas is absorbed, the circulating sulphuric acid is heated to between 170 and 200 deg C, the upper limit. ne cylindrical tower part operates at conventional acid temperatures to ensure complete absorption and effective droplet separation. References 1. McClain, G. E.: "Materials and technology considerations in sulphuric acid plant energy recovery". In "Making the Most of Sulphuric Acid", pp. 207-225. British Sulphur, London (1982). 2. "The Corrosion-Resistance of Nickel-Containing Alloys in Sulfuric Acid and Related Compounds",

pp. 2542. Corrosion Engineering Bulletin No. 1, International Nickel Company, Inc. (1983). n COPYRIGHT 1991 CRU Publishing Ltd. This material is published under license from the publisher through the Gale Group, Farmington Hills, Michigan. All inquiries regarding rights should be directed to the Gale Group.

Title: Forward looking at SPCC.(includes related articles on smelting process and on suppliers of smelter acids)(Southern Peru Copper Corp.) Date: 11/1/1998; Publication: Sulphur; Author: More, Alexander Southern Peru Copper Corporation is in the process of expanding its mines and modernizing its smelter at Ilo to improve efficiency and, especially, environmental performance. A 100% capacity expansion of the Kvaerner Chemetics single-absorption sulphuric acid plants feeding on off-gas was completed earlier this year, and future plans will give SPCC one of the best sulphur capture rates in the world. Alexander More reports. SPCC - an outline Copper mining and smelting operations tend to be in remote and inhospitable areas, and Southern Peru Copper Corporation (SPCC) is no exception. The Southern Peru Copper Corporation was set up around 1950 to exploit ore deposits developed during an exploration campaign by Northern Peru Copper (a subsidiary of ASARCO, Inc.). The project did not come into operation until 1960. Southern Peru had to install extensive infrastructure in the area, including a new port, townsites, maintenance shops and a railroad. SPCC has two mines on the east side of the Cordillera de la Costa (the coastal mountain range): the original mine at Toquepala and a second one at Cuajone, which began operations in the mid 1970s. A tortuous 200-km private railroad links the Toquepala mine to a smelter, copper refinery and port facility on the coast at Ilo, which is as far up the coast as the Coastal Highway has yet reached. The nearest commercial airport is two hours' drive south at Tacna, close to the Chilean frontier. The only land access to northern Peru is by a link road running up through the mountains to the PanAmerican Highway. The terrain surrounding Ilo is at the northern tip of the Atacama Desert and is commensurately barren and arid. There is precious little agriculture in the area, and apart from the small fishing fleet that operates out of the town's harbour and a couple of local fish

meal factories, the fortunes of which are at the mercy of the muchpublicized climatic phenomenon known as El Nino, the local economy is underpinned almost entirely by SPCC. In view of the predominantly south-westerly prevailing wind, the smelter and its associated power plant were established about 12 miles north of the town, on a terrace sandwiched between the shoreline and the coastal mountains, which beyond that point rise almost straight out of the sea. The copper refinery, which includes furnaces for remelting blister copper ingots and recasting as anode plates as well as the electrolytic tankhouse and cathode blank facilities and a precious metals recovery area, is between the smelter and the town. The refinery is a remarkably modern facility, allowing the tankhouse to be maintained in absolutely pristine condition. SPCC's port facility is close to the town on the south side of the municipal port. After installation of a new 40-MW generating set, the power plant, which supplies both the Ilo facilities and the mines, was sold in 1997 to a subsidiary of a Belgian-owned utility but will continue to take steam from the smelter and to supply power to SPCC under a 20-year contract. The agreement includes a commitment by the power company to provide the capital needed to expand the Ilo power plant to accommodate SPCC's expansion plans. The sulphide ore from the Cuajone and Toquepala mines is milled and concentrated by flotation on site; the concentrate, which contains about 27-28% Cu, is shipped to Ilo over the company's own railroad. A capacity expansion of the Cuajone mine by 65,000 stpy of copper is due for completion early in 1999, and a possible further larger expansion is contemplated. Sulphur capture at Ilo The smelting technology of the original installation was conventional, comprising two reverberatory furnaces and four Peirce-Smith converters, along with a blister-copper ingot casting facility, ancillaries and utilities. Two further reverberatory furnaces, three more PeirceSmith converters and a further blister casting facility were added in 1976 to handle the additional material from the new Cuajone mine. Subsequently one of the original reverberatory furnaces was taken out of service and demolished. On account of the high volume and low sulphur dioxide content of reverberatory furnace off-gases and the low sulphur dioxide content and highly intermittent nature of the gases from Peirce-Smith converters, economic sulphuric acid production was not practical at Ilo, and for over 30 years no sulphur capture of any kind was practised. In 1989 the company began to evaluate ways of collecting smelter gases to allow sulphur abatement, and in 1991 it made an agreement

with the Government to install a 150,000-mtpy sulphuric acid plant (which would arrest about 100,000 mtpy of sulphur dioxide). The key to the project was the installation of an El Teniente Modified Converter (CMT). Originally developed by Codelco in Chile as a means of upgrading low-grade matte by direct addition of concentrate and blowing with oxygen-enriched air, the CMT is now recognized as a primary smelting process in its own right. It produces an off-gas with a much higher sulphur dioxide concentration than a reverberatory furnace, and unlike a Peirce-Smith converter, it does not have to be rotated for discharge at any part of the cycle, so much more efficient fume containment and collection is possible. Fig. 1 is an outline flow diagram of the present arrangement of the smelter (See box for outline description). The next stage of modernization at the smelter was given the go-ahead in September. It comprises building a new single-line Outokumpu flash furnace with a capacity of 1.25 million stpy of concentrate and a Kennecott-Outokumpu flash converting furnace to replace the old Peirce-Smith converters. The reverberatory furnaces will be demolished. The sulphur dioxide off-gases from these devices are much more concentrated than from reverberatory furnaces, which will enable SPCC to raise its sulphur capture rate in the mid-90% range. A new double-absorption sulphuric acid plant with a capacity of 4,700 stpd will be built on a part of the site currently occupied by the workshops. This programme should be completed in 2003. The estimated cost is $875 million. The sulphuric acid plant The contract for the original sulphuric acid project was awarded to Davy (now Kvaerner) International; process design and engineering for the gas cleaning plant and sulphuric acid plant were handled by its Chemetics affiliate (now Kvaerner Chemetics). The 300 stpd oxygen plant was supplied by Air Products. The new facilities were commissioned in September 1995 and officially opened on 19 January 1996 by Peruvian President Alberto Fujimori. After the CMT had been proved in a period of stable operation at full capacity, the second of the two original reverberatory furnaces was closed down and demolished. The specified nameplate capacity of the new sulphuric acid plant was 578 stpd, representing a sulphur capture of 18% of the site's total sulphur emissions. It was designed to a single-absorption flowsheet with a three-bed converter and an overall conversion of 96.5-98%, giving a residual tail gas content of 2,000-2,500 ppm or 0.5 tph of sulphur under normal operating conditions. The first plant arrested 18% of the total sulphur dioxide emissions from the site. Realizing that the acid plant would consume just half the sulphur dioxide output of the El Teniente converter, SPCC instructed the

contractor to design the converter and mass transfer devices for double the plant capacity and to provide site space, connections and a certain number of equipment foundations for building and tying in a second gas cleaning line and duplicate heat exchangers. The overall cost of the original acid plant and CMT project was $104 million. The sulphide deposits at the Cuajone mine are overlain by an oxide ore layer with a rather better copper content (a shade under 1%). This ore had been disturbed to get at the sulphide ore body and was being held in stockpiles at the mine. The availability of a captive supply of sulphuric acid enabled SPCC to exploit this ore by heap leaching. Leachate from the Cuajone mine is piped to a solvent extraction/electrowinning (SX/EW) plant at Toquepala, where it is combined with leachate from the biologically-assisted leaching of low grade sulphide martial-and processed to produce LME Grade A cathodes. This project, also completed in 1995, produced over 45,000 st of low-cost copper in 1996, its first full year of operation, increasing the company's output of cathode copper by 15%, equivalent to 9% of Peruvian national production at the time, and surpassed that level in 1997 by another 2,500 st. A $45 million expansion due for completion by the end of 1999 will raise electrowon copper output to 62,000 stpy. Even as the first plant was being built, SPCC was evaluating its options for the second phase of the acid project. These were, essentially: * to duplicate the existing plant (with the exception of the drying tower, converter and absorber, which would be common to both plants); * to convert the plant to a 2 + 1 double-absorption configuration, connecting the intermediate absorption system between the second and third beds of the existing converter; * to convert the plant to a 3 + 1 double-absorption configuration, which would entail adding a separate converter vessel to contain the final catalyst bed. The first of these options would exactly double the plant's capacity to 1,156 stpd, maintaining the same S[O.sub.2] conversion efficiency overall at a cost of about $35 million. The second would raise capacity to 1,175 stpd and the S[O.sub.2] conversion efficiency to 99.7% when processing 8.5% S[O.sub.2] feed gas or 99.5% when processing 9% S[O.sub.2] feed gas (equivalent to 450 ppm S[O.sub.2] in the stack) at a marginal cost over the single-absorption option of about $6 million. The third would raise the capacity by the same amount and would achieve 99.7% efficiency with 9% S[O.sub.2] feed gas (350 ppm S[O.sub.2] in the stack) and would cost about $8 million more than the single-absorption option.

Converting the existing plant to double absorption would have increased the downtime needed for expansion. SPCC therefore elected for the single absorption. The company specified that connections and site space should be provided to allow later addition of a second absorption tower and further heat exchangers to convert the installation to a 2 + 1 double-absorption plant. Construction of the second line began in July 1997 and the new equipment was tied-in during February 1998 and started operation in March 1998. As before, the project was managed by Kvaerner Metals, and Kvaerner Chemetics undertook the process design and engineering for the gas cleaning system and the acid plant. At the same time as the new sulphuric acid plant was being built, an enlarged and upgraded effluent treatment facility was installed. Opening the new plant raised SPCC's sulphur capture rate from 18% to 30%. Gas cleaning Apart from arsenic, the CMT gas which is received from the smelter partly dedusted and cooled (320-375 [Delta] C) - does not contain any problem constituents requiring special treatment (mercury, for example), and the gas cleaning system is relatively simple [ILLUSTRATION FOR FIGURE 2 OMITTED]. The down-draft venturi contactor quenches the incoming CMT gas by intensive contact with weak (1-2% [H.sub.2]S[O.sub.4]) acid sprays, which also remove fine particulates. The humidifier section - a void spray chamber at the base of the adjoining gas cooling tower - ensures that the gas is cool enough (69 [degrees] C) for downstream equipment and ducting to be fabricated in low-cost FRP. In the packed cooling tower its temperature is further reduced to 35 [degrees] C, at which temperature its water vapour content is low enough for the correct water balance to be maintained in the plant. Volatile impurities (principally arsenic) condense at this stage. Finally, two wet electrostatic precipitators arranged in cascade remove acid mist and any remaining traces of dust. The weak acid circulates through a stripper - the air from which carries any desorbed sulphur dioxide back into the process gas stream upstream of the precipitators - and through plate heat exchangers directly cooled by seawater. The level of impurities in the weak acid is controlled by withdrawing a purge stream to the effluent treatment plant. Contact plant Figure 3 is a flow diagram of the sulphuric acid plant proper. The drying tower, which handles the total gas flow from the two gas cleaning trains, lowers its moisture content to below 50 mg/N[m.sup.3] by contact with 93% acid on ceramic saddles. Kvaerner Chemetics's

design is constructed of carbon steel with an acid-resistant brick lining. The bottom is dished to prevent heave. A fibre-bed mist eliminator at the outlet of the tower arrests aspirated spray and mist. Two main blowers running in parallel drive the gas through the plant. The original machine is rated at 1,200 kW, but the second one added when the plant was expanded was more powerful (1,500-kW) to allow for the possible future conversion of the plant to double-absorption. The gas-gas heat exchangers, which recover heat from the process gas from the catalyst beds and raise the feed gas to the reaction temperature (420 [degrees] C), are of a Kvaemer Chemetics lowpressure drop shell-and-tube design, in which the gas flows radially through the tubes. The two exchangers for each stage are connected in parallel. The feed gas is divided and part is passed through the cold exchangers, which cool the gas leaving the final catalyst pass, while the remainder passes through the interstage heat exchangers, which cool the gas between the second and third catalyst passes. The two streams are then reunited to pass through the twin hot exchangers, where the gas picks up heat from the first catalyst pass. In a normal plant Kvaerner Chemetics would build the hot heat exchanger into the centre of the converter, but to install additional tubes in an internal exchanger during the expansion of SPCC's plant would have taken up too much time, so in this case the hot exchangers are external. To allow for extra loading if and when the plant is converted to double absorption, the second cold heat exchanger added during the expansion is larger than the original one. The converter is of Kvaerner Chemetics's proprietary all-welded stainless steel design, in which the bed compartments are completely gas-tight. Haldor Topsoe ribbed ("daisy") catalyst (VK-38 in beds 1 and 2, VK-48 in bed 3) has been used on account of its good pressure drop characteristics.
Who supplied what? Quench venturi, humidifier, cooling tower Weak acid stripper, distributor quench tank, cooling pump tankESP vacuum breaker loop pot Original wet ESPs New wet ESPs Quench pumps Weak acid stripper pump Water coolers, weak acid cooler Cold + hot heat exchangers, acid coolers Converter Preheater, dilution air fan, combustion air fan Stack Drying and absorbing towers, Swemco Fabco Joy Technologies FLS Miljo Wilfley Gould Alfa-Laval Fromson Heat Transfer Ellett Biglow Liptak Warren

product stripper, pump tanks, absorber tanks, etc Tower distributors Product stripper distributor Mist eliminator Dryer acid pumps, strong acid valves Most other acid pumps Strong acid sump pump Packing, acid-proof vessel linings Catalyst Silica quartz Metal ductwork spools FRP ductwork General piping Piping etc supports Expansion joints Dampers

Eaton Metal Products Acid Piping Technology Norton Koch Lewis Wilfley Gould Anchorite Topsoe Southern Products and Silica Dowa Fabrication Inc. Fabricated Plastics Vandervell Piping and Tubing Grinnell Supply Sales Hi-Span Precision Products, Papco Shanrod

The absorption tower is of broadly similar design to the drying tower, except that candle filter elements are used in the top of the tower for arresting acid mist rather than the simpler fibre pad used in the drying tower. Cooling and heat recovery All high-grade process heat produced in a smelter acid plant is utilized internally in preheating the process feed gas. There is, however, a substantial amount of low-grade process heat. At SPCC this is all transferred to seawater, which is drawn from an intake at the northern end of the site and is subsequently fed to a desalination plant in the power station. The weak acid and the blower lubricating oil are cooled directly against seawater, but the strong acid coolers on the product, drying tower and absorber acid circuits and the process gas economizer upstream of the absorber are cooled sequentially (in that order) by demineralized water in an intermediate circuit. This water is circulated through seawater coolers, which reduce its temperature from about 138 [degrees] C to 24 [degrees] C, raising the temperature of the sea water to 88 [degrees] C. All seawater heat exchangers are plate heat exchangers with titanium plates. SPCC standardized on AlfaLaval plate heat exchangers of only two sizes in the interests of minimizing the number of different spare parts to be held in stock. The acid coolers are anodically-protected shell-and-tube heat exchangers. It was the advent of this technique, pioneered by Chemetics over 25 years ago, that permitted the operating temperature of the absorber acid circuits of sulphuric acid plants to be raised to a point at which heat of a useful grade could be recovered. Effluent treatment

Apart from possible acid leaks and spills in the plant and loading area, the only effluent is the weak acid purge. As mentioned, arsenic is the only noxious impurity, and the effluent treatment comprises a twostage neutralization/precipitation treatment with milk of lime (made from calcined seashells mined locally) and thickening followed by treatment with ferric sulphate to precipitate ferric arsenate. The stream from the arsenic precipitation section is laundered to the second neutralization reactor, and underflow pumped to the neutralization thicker. The underflow from the neutralization thickener is pumped by pneumatically-operated diaphragm pumps (the only design found to be reliable in such an application) to a holding tank and thence to a filter press. Cake from the filter press is discharged directly into side-dump railcars, which haul it to the company's disposal site, where it is encapsulated in slag. The liquid overflow from the arsenic reactor thickener is back-neutralized with sulphuric acid and discharged into the sea. The site By its very nature, and however well it is run, any smelter is a dark, forbidding, mephilical place, illuminated by awe-inspiring pyrotechnic displays of sparks and incandescent rivulets of molten slag and metal flowing into huge glowing crucibles. The sulphuric acid plant at SPCC is in striking contrast. The equipment is very neatly laid out and, in spite of the various changes in the course of the project, everything appears to be easily accessible for maintenance or modification. All sorts of details demonstrate the meticulous note taken of every aspect of the company's experience with the original plant. For example, the cladding of the original plant and the steel grid used for steps, catwalks and drain grilles are already showing signs of corrosion on account of the combination of acid fumes and salt spray in the atmosphere. So the steel cladding of the new plant is coated with an ochre-coloured epoxy resin, and non-corrodible FRP grid has been used for the catwalks, etc. SPCC is evaluating various different kinds of acid-resistant coating on the concrete apron under the gas cleaning section to protect it from damage by spilt acid (not that there was any evidence of that), and the one finally selected will be applied to the complete area. Instruments around the plant are enclosed in plastic boxes with weather seals to protect them from acidic and saline fumes. A great deal of careful thought has gone into this project, and the experience will undoubtedly be invaluable in the next phase of the project. That really will be "The Big One"! RELATED ARTICLE: Smelting process outline The reverberatory furnace receives concentrate and return slag from the converters, which still contains 3-5% Cu. In the high temperature and generally oxygen-deficient conditions, iron sulphide reacts with

any copper oxide present in the concentrate to iron oxide and copper sulphide: FeS + [Cu.sub.2]O [right arrow] FeO + [Cu.sub.2]S Much of the iron oxide reacts with gangue materials (silicates, aluminates and calcium) and extra silica added as a flux to form slag, containing not more than about 0.7% Cu, which floats on top of the socalled copper "matte". It is withdrawn periodically and dumped after quenching. The matte, a mixture of ferrous and cuprous sulphides comprising about 35% Cu and 26-28% S, is tapped off periodically and conveyed to the converters. Here further silica flux is added to the matte and air is blown through. Initially the residual iron content of the matte is oxidized and reacts with the silica flux to form iron silicate slag (the "slag blowing" stage). The molten mass remaining after removal of slag, known as "white metal", is predominantly cuprous sulphide and contains about 75% Cu. Further air blowing in the "copper blowing" stage oxidizes the sulphide to sulphur dioxide, but almost none of the copper is oxidized until there is very little residual sulphur. [Cu.sub.2]S + [O.sub.2] [right arrow] 2Cu + S[O.sub.2] The crude "blister copper" (99.3% Cu) is stored in a molten state in holding furnaces until it is cast into ingots. In the CMT the smelting and slag blowing stages are combined by introducing both concentrate and matte and blowing with 30% oxygenenriched air. The white metal is passed to the Peirce-Smith converters for copper blowing. COPYRIGHT 1998 CRU Publishing Ltd. This material is published under license from the publisher through the Gale Group, Farmington Hills, Michigan. All inquiries regarding rights should be directed to the Gale Group.

Title: [H.sub.2]S[O.sub.4] + [H.sub.3]P[O.sub.4] [right arrow] Clearwater: the central Florida Section of AIChE met in June for the 28th year in Clearwater to examine current issues in sulphuric and phosphoric acid operations and technology.(Meeting Report) Date: 11/1/2004; Publication: Fertilizer International; Over the years "The Clearwater" has grown from its original concept of an informal Saturday morning get-together of a few Florida phosphoric acid plant engineers who happened to be spending Memorial Day weekend with their families at Clearwater Beach into something much bigger. The scope of the program has expanded to include sulphuric

acid as well as phosphoric acid and phosphate topics, and the Saturday sessions have been supplemented by workshop sessions on the afternoon of the preceding day. It regularly attracts 250-300 delegates, including strong participation from the contractors and equipment suppliers, many of whom also help the event to survive on a sound footing by providing welcome sponsorship. And, happily, although it has now moved away from Memorial Day weekend, the venue remains the same, the families are still very much in evidence, and the atmosphere is as relaxed and informal as ever. Not bad for an event that is essentially all done in 24 hours! Held on 4 and 5 June, this year's conference, the 28th in the series, was no exception, with around 280 delegates. Not surprisingly for a meeting of that length, they were almost all from North America, predominantly the United States. Workshops This year the phosphate workshop was dedicated to the UCEGO rotarytable phosphoric acid filter. It was conducted by members of RPA Process Technologies, the owners of the technology, and presented a number of perspectives and case histories on economic and technical aspects of the revamping or enlarging of existing UCEGO filters or complete replacement of existing rotary filters with new UCEGO filters. Your reporter, meanwhile, was in the next room in the sulphuric acid workshop, which was considering enhanced control systems for sulphuric acid plants. Under the joint chairmanship of Rick Davis, of Davis & Associates, and Jim Dougherty, of IMC Phosphates, it comprised a number of short presentations or statements followed by an extended discussion from the floor. David Randolph, of Monsanto Enviro-Chem, spoke about Aspen Plus Web Models, Mark Martin, of Koch Knight LLC, about the T-Econ model for optimising tower performance and economics, Louis Haevner, of Emerson Process management, on the thesis that eliminating variability in any kind of continuous process is the key to operating closer to process limits and, therefore, maximising profitability, and Chris Davis of Davis & Associates about the next step for control systems. Phosphate session The formal sessions on Saturday morning, which ran in parallel, may only have lasted half a day, but plenty was packed in, by dint of starting at 8 a.m. D. C. Agarwal, of Thyssen Krupp VDM USA, presented a portrait of Alloy 31 (UNS N08031)--a fully austenitic development of Alloy 28 with additional molybdenum and nitrogen--and its applications in phosphoric acid plants. This alloy has a favourable track record in early application in a number of phosphoric acid plants both in and outside the United

States and is apparently less expensive than existing alloys with comparable performance. In a presentation copiously illustrated with graphs and, especially, bar charts, Louis Irwin, of Arr-Maz Custom Chemicals, reported on the influence of variables such as the specific gravity of the slurry and that of the filtrate on the filtration rate in a number industrial phosphoric acid plants and the effect of adding polymeric filtration aids. As Florida phosphate mining moves southwards into lower-grade and lowerquality deposits, the need for filtration aids will increase. Faustino Prado, of Prado & Associates, outlined a project that his company is undertaking for a food company in Turkey for producing purified phosphoric acid for use in food processing and polyphosphate production. The plant will initially operate on imported phosphoric acid, but eventually the client intends to generate his acid requirements from indigenous phosphate rock. Therefore it is designed to accommodate phosphoric acids of varying provenance. It is also designed to use as much Turkish-made equipment as possible, and that determined the choice of mixer-settlers, which could be fabricated locally in FRP, rather than columns, which would have had to be imported. Resin-impregnated graphite has all the desirable properties as a material for making heat exchangers for phosphoric acid evaporators bar one: compared with metallic materials it is brittle and, therefore, heat exchanger tubes made out of it are easily damaged. Loic Bernard, of SGL Acotec, explained how his company has dramatically reduced the incidence of burst or broken tubes by reinforcing them with highly pretensioned carbon fibre. The fibre is fully elastic and therefore remains under tension even under fluctuating loads or in stress surges. As it has a negative coefficient of thermal expansion, the tube bursting pressure actually increases with temperature. Even if a tube fails, the carbon fibre holds it together and can even prevent it from leaking under pressure differentials of up to 5 bar until the next planned shutdown. Currently agricultural production in Brazil is spiralling and, after presenting a fair amount of statistical data on it, Paul Smith, of P. Smith & Associates, representing Bunge Fertilizantes, gave sketches of the phosphoric acid expansion projects (Fosfertil-Ultrafertil, Uberaba; Bunge, Cajati; and Copebras, Cubatao and Catalao) that have been or are being implemented in response to it, as well as surveying the technology that they are using to maximise the utilisation of indigenous phosphate resources. Herman Purutyan, of Jenike & Johanson, set out the adverse effects of particle segregation on the handling characteristics and product quality of particulate products such as granular fertilizers, and most especially blends, whose performance may be so badly impaired that the product

has to be rejected and reworked. He explained the mechanisms of segregation (sifting, particle entrainment and fluidisation) and finally outlined methods of solving or preventing segregation, beginning with tests to determine the mechanism. Options include modifying the material properties (for example, narrowing the particle size range), modifying the process (for example, locating a blending operation as close as possible to the point where it is to be packed or used), and modifying equipment such as hoppers to promote mass flow rather than funnel flow or using a distributor at the inlet to a silo. Tony Brown, of GranuTec, and Keith Leong, of WMC Fertilizers, described how capacity-limiting problems at WMC's phosphate complex in Queensland, Australia, were solved. The design capacity of 135t/h of granular ammonium phosphates depends on producing both MAP and DAP. Satisfactory MAP production by the backward titration method was impossible because of the high iron content of the phosphoric acid, which caused gelling in the preneutraliser. The additional water needed to keep the slurry pumpable caused higher than acceptable residual moisture in the product, impairing its handling and storage characteristics. Changing to forward titration enabled nameplate capacity to be achieved, but limitations on strong acid output necessitated very careful control of the water balance in both the preneutraliser and the granulator as well as tight control of the recycle. An article based on the paper presented by E. Papaconstantinou, of PFI, and S. Kurowski, of Profile, on the replacement of PFI's Prayon 24B tilting-pan filter by a more modern 24-75 TDI filter has appeared recently in this magazine. (1) Sulphuric acid session Most phosphate operations have their own captive sulphuric acid facilities, and most of those are based on burning elemental sulphur. At older complexes, in particular, it is likely that past expansions or debottle-necking of the phosphoric acid will have used up any spare capacity in the sulphuric acid plant. The only options open to a producer wishing for a modest further increase in [P.sub.2][O.sub.5] capacity without embarking on a disproportionately expensive refit of the sulphuric acid plant are to buy in merchant sulphuric acid or to use oxygen enrichment. Derek Miller, of Air Products & Chemicals, set out the technical limitations on oxygen enrichment, especially raised temperatures in the sulphur burner and waste heat boilers, pressure drop, catalyst loading limits, overall cooling capacity, and materials compatibility. The economics depend on the relative cost of oxygen, which depends on the supply, itself very largely determined by the requirement, and on the price of merchant acid, which is more variable.

To enlarge the output of a 2,000-t/d plant by 5% to 2,100 t/d by oxygen enrichment requires about 56 t/d of oxygen. Up to a daily oxygen requirement of about 50 tonnes, especially if this is a variable, intermittent or temporary demand, liquid oxygen delivered by road or rail is usually recommended. Although the price of the oxygen is high, the required additional facilities cost very little. Above 50 t/d, some kind of on-site generation facility is, in general, preferable. For capacities up to about 120 t/d a vacuum swing adsorber (VSA) is suitable if the oxygen requirement is fairly constant. Above that level, a cryogenic air separation unit is required. In either case the plant is likely to be owned by an industrial gas supplier and the operator has a long-term supply contract. As a less expensive alternative to the traditional turn-key contract for sulphuric acid plant construction, Roll Fleck, of Fleck Chemical Industries, postulated the idea of engineering package contracts between specialist engineering companies and operating companies with the available resources to co-ordinate the work and fulfil the procurement function for main equipment items. The specialist engineers would undertake detailed engineering for the complete project, including any amendments within battery limits. The owner would take responsibility for procurement, though with full assistance and technical advice from the specialist engineers, who would also monitor the fabricator's execution of the contract and the performance of the field contractor during the erection phase and provide a representative to be on hand during commissioning. This approach is most appropriate for revamp projects, and several case instances of such projects that Fleck Chemical has undertaken were cited. From the jungle of safety regulations administered by OSHA and EPA for the protection of workers on site and the public outside from toxic and explosive chemicals, Farrokh Ollia and Richard Collins, of IMC Phosphates, presented IMC's interpretation of two features for which the agencies have provided no guidance: Facility Siting and Human Factors. Facility Siting may be defined as a site-wide evaluation with a mitigation plan to protect each building's occupants in the event of a release of a hazardous chemical. Human Factors analysis can best be described as the systematic evaluation of factors that influence the performance of operators, maintenance staff, technicians and other plant personnel. Steven Ziebold, of Monsanto EnviroChem Systems, presented a status report on fibre bed entrainment filters, which are crucial in arresting acid droplets and mist leaving the absorbers of any sulphuric acid plant. The continuing challenge for manufacturers of fibre bed filters, driven by the ever-increasing size of sulphuric acid plants, is to get the same or better performance from a smaller filter. Monsanto has adopted two alternative approaches. One is to reduce the diameter of the elements in a candle filter--for example, from 24 inches (61 cm) to 8 inches (20.3cm); the other is concentric filters with one element

mounted inside another. The latest development is the SuperMat, which will be available from 2005. This uses engineered multi-layered glass fibre mats wrapped round a fibre bed cage and test runs in both absorption towers of a 1,000-t/d sulphuric acid plant have confirmed that they are as efficient as existing types but for a lower pressure drop. It is easy to take the compressed air system in a plant for granted, but compressed air is the most expensive utility: 85% of the electrical energy used to produce it is dissipated as heat and, after other inevitable losses, 11% at best is left to do work. But some systems may be only 5% efficient. Bob Laine, of Southern Corporation, set out the criteria for a perfectly operating system and what deficiencies an audit of the system might be expected to detect. Gordon Cameron and David Hodgson, of Cecebe Technologies, pointed to some of the reasons why problems occur in packed drying and absorption towers in today's large plants, which operate with high gas flows and high acid temperatures and are increasingly made of materials that are very corrosion-resistant under normal operating conditions but can be damaged or destroyed very quickly if there are excursions outside their temperature and acid concentration limits. In particular, it can be risky to use laboratory corrosion test results which do not take account of impurities present under actual plant conditions. Some pertinent thoughts on materials selection were given. Although anodically-protected acid coolers in standard stainless steel grades such as 304L and 316L stand up well to corrosion, they depend on the proper functioning of an electrical system which adds to maintenance requirements. Nick Bhambri, of Monsanto Enviro Chem Systems, presented the benefits and value proposition for coolers made of ZeCor[TM], an alloy already familiar to the industry in over 200 installations of distributors, towers, pump tanks and other equipment. The final presentation, given by C. P. Ganatra, of W. L. Gore & Associates, set out the benefits of standardising gaskets in chemical plants and presented the very promising results of tests devised by the PVRC and other standards-setting authorities for properties such as bolt load retention, sealability, blow-out resistance and hightemperature aged leakage relaxation which have been carried out at third-party laboratories on Gore Universal Pipe Gasket (Style 800) ePTFE material. Gore TriGuard[TM] gaskets in this material are claimed to be the most creep- and blowout-resistant yet. Field trials are now in progress. Extramural attractions Nine hospitality suites--a well-established tradition of the Clearwater-were open on the Friday and Saturday evenings, courtesy of companies

supplying equipment, engineering and chemicals to the phosphate industry. In addition, in what has become another tradition, Arr-Maz Custom Chemical hosted a poolside lunch for delegates after the close of the conference on Saturday, and Monsanto Enviro-Chem laid on a lavish buffet dinner with live music and prizes in the evening. References (1.) Papaconstantinou, E.; Kurowski, S.: "Filter replacement pays dividends". Fertilizer International 401 (Jul-Aug 2004), 34-37. COPYRIGHT 2004 CRU Publishing Ltd. This material is published under license from the publisher through the Gale Group, Farmington Hills, Michigan. All inquiries regarding rights should be directed to the Gale Group.

Title: Towers and converters: technology review; Sulphur magazine provides a comprehensive overview of the key technologies available for acid towers and converters, with contributions from leading companies in the field. Technologies covered include mist elimators, acid distributors, tower shells, packing, packing support and converter internals.(SULPHURIC ACID TECHNOLOGY) Date: 9/1/2005; Publication: Sulphur; Acid Piping Technology, Inc. Tower distributors APT supplies Mondi[TM] ductile iron distributors of trough and downcomer design and drilled piped design by various engineering companies. The trough and downcomer design has been widely used since the 1960s. This design has 2-inch to 2.5-inch square open area downcomers, which are not subject to pluggage by packing or brick chips. Both the troughs and downcomers have ample wall thickness for long service life. Earlier trough and downcomer distributors were made of gray cast iron. Typical life was about six years for downcomers and ten years for troughs. In the mid 1990s APT improved the materials supplying these distributors with Mondi. Today, Mondi downcomers have operated for ten years with little measurable wear and more years of life expected. Mondi troughs are providing much longer service life based on measured wear.

Mondi distributors have improved reliability and long service life. They have good corrosion resistance to lower acid concentrations, which can occur from process upsets, other equipment malfunctions and plant outages. Tower packing APT's ceramic products are made of chemical porcelain, which has high mechanical strength, low porosity and superior performance to chemical stoneware. This minimises chips that can damage pumps and plug some distributors. APT supplies 1/2-inch through 3-inch standard saddles, grid blocks, cross partition rings and heat recovery system saddles. If lower pressure drop is needed 2-inch and 3-inch super saddles providing 1015% lower pressure drop than conventional saddles can be supplied. Converter internals Significant improvements in materials and design have been made in converter internals to minimise heat scaling, warping and distortion. Material improvements include pass 1 grids and all support columns made of HS Meehanite[TM], which has high strength to 981[degrees]C. Pass 2, 3 and 4 grids and division plates are made of GE-30 Meehanite, which is an improvement over gray cast iron. Design improvements for pass 1 grids include cross sections from 3inch to 5 1/2-inch thick and increased support columns to 3 1/2-inch diameter from an earlier design of 2-inch diameter. Today's design and Meehanite materials are providing long service life with the ability to handle higher temperature conditions in the converter. Many converters with grid and column design are still operating after 25+ years of service. Aker Kvaerner Chemetics Acid tower internals Chemetics offers acid towers either as a traditional brick-lined design or in Saramet[R] Austenitic Stainless Steel. While process design parameters are similar for both options the towers differ in a few areas. Chemetics brick-lined towers feature a proprietary self supporting ceramic dome. The elements of the dome operate under compression from the weight of the packing above providing a reliable and stable support. Use of the dome also eliminates the need for arches or piers in the bottom of the tower, thereby simplifying installation of the brick lining and removing point loadings from the floor.

Chemetics metallic acid towers feature a high voidage injection packing support fabricated in Saramet[R]. The open area in the packing support exceeds 100% of the tower cross-section area and eliminates the potential of flooding as the gas and acid respectively enter and leave the packed bed. The support is custom designed to match tower diameter and is supported on a number of Saramet[R] beams and a circumferential support ring. Acid distribution in both tower design options can be either with a Saramet[R] trough or pipe distribution system. Saramet[R] pipe distributors have been in service since 1982 when the first commercial application of silicon stainless was installed in a tower at Boliden Skelleftehamn in Sweden. Saramet[R] pipe distributors are simple to install and easy to maintain, are insensitive to levelling, are relatively low cost and offer a long trouble free life as evidenced by the first unit which is still in service after 23 years. Many plant operators have a personal preference for trough distributors. Saramet[R] trough distributors are available where the number of distribution points can be increased from around 2.2 to 4 points/[ft.sup.2]. [23 to 44 points/ [m.sup.2]] giving a better performance in the top section of packing. Chemetics trough design uses a submerged orifice to control the flow of acid into the down comer tubes. The orifices are readily accessible for removal of packing chips and the acid head over the orifices minimises flow variation due to any errors in levelling or flow disturbances. Converter internals When first introduced in 1979, the Chemetics all stainless steel converter ushered in a new standard of performance and expectations within the sulphuric acid industry. Chemetics philosophy for converter design was simple. First the vessel had to reliably support the catalyst mass. The converter had to contain the gases within the vessel and avoid leakage between the passes to achieve good conversion. The converter had to provide good access for maintenance for screening of catalyst and most importantly with the increasing use of high voidage catalyst, had to provide good, uniform distribution of gas within the catalyst beds to ensure optimum catalyst performance to achieve high conversion efficiencies. It was also obvious to Chemetics that eliminating or simplifying gas ducting and eliminating awkward transitions [oval, rectangular or mouthorgan] in gas ducting would increase the overall reliability of the acid plant; hence Chemetics designs featured internal heat exchangers for gas cooling/reheating and steam superheating. These principles remain the cornerstones of Chemetics converter design. The converter is an all stainless steel all welded vessel. Catalyst is supported on perforated diaphragms, which are welded to the shell and core of the vessel, providing open and uncluttered access for maintenance. At every possible level gas is introduced radially into the catalyst beds at low velocity from multiple distribution ports to ensure uniform distribution for optimum catalyst

performance. Gas heat exchangers are incorporated into the core of the vessel eliminating external gas ducting, saving pressure drop, cost of installation and maintenance and plot space. Begg Cousland Begg Cousland has extensive experience in the manufacture of both knitted wire, mesh pad type demisters and fibre bed candle filters. Acid coalescer options The Becoil demisting unit is a high efficiency, low pressure loss device for removing liquid particles > 5 microns. To help the collection efficiency below 5 microns, the Becone coalescer has been developed. This unit is made from composite/coknitted monofilaments and staple fibre yarn exhibiting along its length the ends of the staple fibres which compose it. These fibres are much smaller in diameter than either the yarn into which they are spun or the monofilaments, consequently forming a more efficient filter. The multitude of fibrous ends presented to the gas flow reduces the streamline effect, trapping the fine droplets within the coalescer, and any coarse droplets so formed are reentrained in the gas stream leaving the coalescer. They are then removed by a Becoil demister. The combined Becone and Becoil installation increases collection efficiency to > 98% in the 2-5 micron range. Fibre materials are glass, PTFE, polypropylene and Dacron. Pressure loss is increased but not dramatically since the Becone coalescer still has considerable free volume even allowing for the introduction of the fibrous yarn. For similar performance in a single stage, a combination coalescer and demister is available in flat or coned form, depending on vessel design. For drying towers, co-knitted wire and fibre (metal or PTFE wire + glass or Teflon fibre), either as a combined single stage with a wire only layer, usually below a co-knit layer, or as a separate first stage, can be used for optimum effectiveness and for higher liquid loads. Candle filter options The four most common glass fibre options for sulphuric acid plants are TGW 15, B 14, B 12 and G 25. TGW 15 is selected for highest efficiency mist removal (100% > 1 micron, 98% < 1 micron), invisible stack emission < 20 mg/N[m.sup.3] and maximum corrosion protection. It is available as a hanging or standing type.

B 14 is selected for very high effciency mist removal (100% > 3 micron, > 98% < 3 micron), limit of installation space and limited pressure loss. It is available as hanging or standing type. B 12 is selected for high effciency mist removal (100% > 3 micron, 95% 1-3 micron, 80% 0.5-1 micron), limit of installation space and little fine mist content. It is available as standing type only. G 25 is selected for high gas volume per filter (mist removal: 100% > 3 micron, 90% 1-3 micron, 70% 0.5-1 micron), limited installation space and mainly droplet removal. It is available as standing type only. For high liquid loads Star type candle filters are available. The Star type has integral rings for enhancing drainage from the fibre beds (> 2 times quicker drainage), thus increasing the filter's ability to handle high liquid loads without reentrainment of droplets and decreasing the filter's pressure loss, since the filter's total resistance includes the liquid load factor. CECO Filters CECO Filters has been a leader and innovator in the field of sub-micron mist elimination for more than 30 years. After patenting the first fibre bed filters utilising the diffusion theory of Brownian motion of submicron particles, ICI of the UK licensed CECO to market the filters world-wide. Originally designed to prevent acid mist carry-over in ICI's sulphuric acid absorption towers, CECO has applied fibre bed filter technology to a myriad of industries ranging from asphalt manufacturing to ammonium nitrate production to general chemical processing and others. For sulphuric acid manufacture, whether sulphur burning or metallurgical off gas-based, CECO Filters provides the latest technology in fibre bed mist eliminators and mesh pads for sulphuric acid mist capture in sulphuric acid drying and absorption towers. Using a combination of its proprietary hand-wrapped blanket and machinewound roving medias, candle filter designs are optimised to each application. In 1990, CECO Filters introduced the patented Twin-Pak[TM] design. The Twin-Pak[TM] is the original concentric nested filter design that provides up to 60% greater surface area in the same space as a single candle. Capable of being retrofitted into existing candles, the TwinPak[TM] offers benefits in terms of increased absorber through-put, reduced pressure drop, and reduced installation cost. In 2005, CECO Filters became a licensee of the VKR Enhanced[TM] mesh pad. Originally introduced in 1995, it remains a leader in high flow/high efficiency mesh pad technology. VKR[TM] technology can be

provided via new mesh pads or retrofitted to existing pads increasing liquid handling capacity up to 300% and vapour capacity up to 20%. CECO's latest innovation is its proprietary graded bed filter. The graded bed concept incorporates multiple layers of low-, medium-, and highdensity media to maximise sub-micron collection efficiency while improving liquid drainage and, where insoluble sulphates are collected, extending filter life. The graded bed media can be provided via new filter elements or re-packed onto existing element cages. CECO has always been active with existing acid manufacturers such as Kidd Creek Mines, and with users of sulphuric acid such as surfactant and sulphated nitrate fertilizer producers, and has placed a new focus on sulphuric acid manufacturing. The CECO graded filter has been selected for installation in the absorption towers of new sulphuric acid plants under construction for Southern Peru Copper, Balkash Kazadhstan, and Lucite International. CECO has also been selected to provide new replacement filters and to repack existing filters for producers such as Honeywell, Lucite International, PCS Phosphate, and General Chemical. Canal Engineers Canal Engineers manufactures high performance mist eliminators for both drying and absorption towers. The shells of the mist eliminators are made in either stainless steel grades or in advanced high nickel alloys, and for WSA they are made in glass reinforced polyester. Canal can advise the most suitable material for each specific application and, if required, recommend the number and type of candles needed, as well as the installation design. The quality of Canal's mist eliminators has been evidenced recently. Extensive sampling made on a drying tower where 14 candles CFM 76 X 165 BCCO-ST are installed, showed that the retention capacity remained almost unchanged after 23 months of operation without any maintenance:
Particle size > 1 micron < 1 micron < 0.5 micron Efficiency 100% 82% 71%

Edmeston Edmeston is the exclusive supplier of Sandvik SX stainless steel and has supplied equipment manufactured in Sandvik SX for over 20 years. The SX alloy and weld filler material is well proven since 1984. In fact,

its features and corrosion properties has become a standard of comparison for all other materials being introduced for use in strong sulphuric acid applications in the concentration range 93-99%. Even though the SX material offers best available corrosion properties, the correct process and mechanical design is equally important. Equipment design is subject to continuous improvement with feedback from thousands of references. Tower internals are of particular interest since this is an area where SX equipment can offer substantial benefits in comparison with use of traditional materials and designs. Acid distributors Edmeston offers three types of distributors. All are tailor made to fit the intended application. The distributor type can be suggested by Edmeston, based on process conditions, or chosen according to the clients' preferences. The trough-type distributor is normally chosen for high performance towers or when a high density of irrigation points is required. The distributor is typically designed with up to 44 points/[m.sup.2]. A recent development in design is the reduced number of troughs in combination with an improved irrigation point pattern. The spacing between the troughs has been increased leading to a more cost effective design and lower tower pressure drop, maintaining a very uniform acid distribution pattern. The new design has been implemented in several projects and Edmeston recently delivered two absorption tower distributors, with 7 m diameter and an acid flow of 1300 [m.sup.3]/h to a client in North Africa. The pipe-type distributor is a cost efficient choice for new installations or replacements. Even though it is available for any tower size, the simple design is particularly suitable for mid-size (5 m) or smaller towers. The special patented threaded coupling of the branch pipes to the header allows a very quick and easy installation. The coupling has recently been further improved and new designs of pipe type distributors do not require any o-ring seals. The flarp-type distributor is a variety of the plane pipe type, only the orifices are directed upwards, spraying acid on a deflection plate, the flarp, thus distributing the acid in a fan-shaped stream on top of the packing. The flarp-type distributor is often used for replacements of similar cast iron designs but it is also a preferred design for new installations by some clients. Packing supports SX packing supports are used for both alloy and brick-lined towers. The design has constantly been improved with apparently small but very

significant changes in design, targeting to eliminate possibilities for local corrosion attacks. The packing is supported directly by the SX grating, eliminating grid bars and partition rings. The open surface of the grating is typically in the vicinity of 85%, reducing the pressure drop compared to conventional designs. Strainers, inserts and various internals In addition to the larger internals many smaller components are fabricated in SX including outlet strainers, vortex breakers, and nozzle sleeves. The strainers are manufactured from SX mesh, allowing flexibility in design. The possibilities to utilise SX for tower internals are many. An unusual application is the tower bottom protection. Insufficient curing of the mortar led to erosion that threatened to destroy a brick bottom. The bottom was shielded from the impact of the falling acid by SX plates that were assembled, with SX bolts and nuts, to a protective dish. Koch Knight LLC Today, sulphuric acid plants must reduce costs while simultaneously improving production and operating standards. In particular, rising energy costs make a tremendous impact on the operational curves describing equipment performance. What could have been optimal in the past might have become inefficient nowadays. Higher capacity and higher efficiency are the two most used terms for defining an item of equipment. What constitutes higher capacity depends on the performance of the particular equipment. For sulphuric acid and chemical production towers, the optimum performance point reflects the minimum use of energy providing the maximum production output. Traditional tower and equipment design is based on models and equations established 20-30 years ago. Sulphuric acid towers in particular are designed based on the 3-inch ceramic saddle capacities. However, surging energy costs and prices, as well as today's construction and operating costs make tower design a more complex matter. To help operators determine the optimal performance available from a tower, Koch Knight offers the T-ECON[TM] economic analysis model for sulphuric acid mass transfer media. The two main factors involving tower performance are its technological and economical performance. Technological performance relates to the total throughput of the equipment. An increase in throughput with a higher capacity will provide benefits translated into more production, with the corresponding economical return.

A proper economical return involves the increase in the tower efficiency. The proper usage of the tower resources, particularly the amount of energy and the total performance of the tower as it processes raw materials, provide for more efficient equipment. A complete view of the equipment is provided in order to analyse its behaviour. While designing a new piece of equipment, or the revamp of an existing one, the mass transfer capacity of the packing must fit the technical, operational, and budgetary needs of the facility. The lowest first cost packing option may be attractive when it fits the approved budget for a tower. However, buying the lowest cost packing option available may not maximise the tower's value over the life of the plant. A more in-depth analysis of the best financial option is required. Koch Knight combines excellent technical resources for mass transfer applications with a complete array of available packing products. The T-ECON[TM] model provides plant operators with a method to study the range of Knight packings, including economical imported materials, Flexisaddle[TM] standard and low pressure drop Flexisaddle[TM] LPD[TM] random tower packing, and high performance Flexeramic[R] ceramic structured packing. The T-ECON[TM] tower analysis model simulates the tower performance with various packing options to determine the net present value, that is, the true value in today's currency of the money invested by the company in the packed bed during the life of the mass transfer media. Since a sulphuric acid tower media charge should last more than ten years, the model conservatively assumes a ten year packing life and shows the cost effects of all the available tower packing options. An interesting result from a past study concluded for an Asian metallurgical plant is shown in the graph, which was generated by the T-ECON[TM] model to show a summary of the net cash flow over a life of ten years. The graph visually compares lifetime costs of each packing option, and reveals that a higher investment today represents the most economical long term packing solution. The T-ECON[TM] model shows that Flexeramic[R] Type 88 ceramic structured packing provides the highest net present value over the ten year term. Knight-Ware[R] Flexisaddle[TM] 3-inch LPD (low pressure drop) packing offers a more rapid payback time due to its lower net present value. Standard Knight-Ware[R] Flexisaddle[TM] ceramic 3-inch saddles are a good initial cost value, but the lower initial investment does not represent the best long term choice for the plant.

In this case the client selected the Flexisaddle[TM] 3-inch. LPD[R] packing option as the best Knight product choice to meet their needs today. As the plant demands more production from the equipment, the option for installation of Flexeramic[R] packing will be available for a furture repack installation. In summary, the Knight T-ECON[TM] economic modelling tool can give operators a method to know that a tower is running with the optimised mass transfer package available in the market, at the lowest life cycle cost to provide the highest long-term profit. Maximising tower performance and the useful life of the equipment provides reliability to the process as a whole. Koch-Otto York Koch-Glitsch, LP, through its Koch-Otto York business group, offers several mist elimination products to improve the reliability and economics of sulphuric acid plants. Sulphuric acid plants Each type of sulphuric acid plant has unique design requirements. Sulphur burning, spent acid regeneration, and metallurgical acid plants all work on a similar catalytic conversion of S[O.sub.2] to S[O.sub.3] to make sulphuric acid, but require different mist eliminator designs to work reliably. Koch-Otto York supplies a complete line of mist eliminators to assure optimal design. Fibre bed elements are the most commonly used mist eliminator in sulphuric acid production. Flexifiber[R] mist eliminators are customdesigned and have proven ideal for use in all three major towers (drying tower, interpass tower and final absorption tower) in a sulphuric acid plant. The two types of Flexifiber[R] elements typically used are Brownian Diffusion (BD) and Impaction Cylinder (IC). Brownian diffusion elements offer the ultimate separation, removing up to 99.9% of all submicron mist. The "fibre" type used in fibre beds includes glass, carbon, polyester, polypropylene, and ceramic depending on process conditions. Koch-Otto York has been very successful using carbon fibre for applications involving fluorides, which typically dissolve the glass fibres. New designs using drainage layers significantly increase the capacity and reduce pressure drop of sulphuric acid absorption towers. Impaction Cylinders can be used when large housings are not practical or the Brownian diffusion mechanism is not required. IC elements are smaller in size and operate at higher bed velocities to separate entrained liquid by an impaction mechanism. Recent R & D tests have improved IC technology by

combining Koch-Glitsch's Flexifiber[R] and Yorkmesh[TM] technologies. IC-M elements have helped debottleneck absorption towers and IC-K elements stay cleaner and wash easier when used in drying towers. The Demister[R] wire mesh mist eliminator is commonly used when other design requirements exist, such as a low pressure drop specification, fouling solids, or simply a limited plant budget. The Koch-Otto York Safety Scrubber[TM] housing allows the best combination of cost, pressure drop, efficiency, serviceability and, most importantly, safety. Mist eliminators are maintained and changed without entering the tower. Demister[R] mist eliminators in sulphuric acid service have historically been supplied in Alloy 20 and plastics including Teflon[R] and Halar[R], but Alloy 66 is now widely used because it demonstrates excellent corrosion resistance in sulphuric acid. Acid plant gas cleaning systems Efficient gas cleaning is essential to metallurgical acid plants with dirty feed gas. Gas cleaning units located upstream of the acid plant typically use wet scrubbers and electrostatic precipitators to prepare the gas entering the acid plant. Poor acid mist removal in the gas cleaning unit will lead to down-stream corrosion along with high acid consumption and high maintenance cost in the drying tower. Koch-Otto York offers a family of Flexichevron[R] mist eliminators that offer excellent mist elimination combined with low pressure drop and fouling resistance. Materials of construction include metal, polypropylene, FRP, polysulphone and other plastics. Retrofits can be added to systems struggling with high operating design capacities. MECS Inc. Formerly known as Monsanto Enviro-Chem Systems (see news p. 8), MECS, Inc. is a leading provider of engineering, products and services to the sulphuric acid industry. Sulphuric acid towers and internals Productive, safe and cost effective sulphuric acid plant operations pose many challenges, and corrosion ranks near the top of the list. MECS' Engineered Alloy Products group offers a number of products and technologies to meet these challenges. Chief among these is ZeCor[R], a corrosion-resistant alloy available exclusively from them. MECS has improved on the traditional approach to provide today's industry standard in the design, fabrication and operation of ZeCor[R] acid towers. When comparing the costs of a standard brick-lined carbon

steel tower to a ZeCor tower, the gap in pricing is narrow when considering installation total delivered "all in" costs. There is a nominal premium for ZeCor over brick lining, however, this is abundantly off set compared to the added value, enhanced efficiencies and life cycle costs. For example, ZeCor acid towers offer the following benefits: * Where soil conditions require even deeper piling for heavier loads, ZeCor foundation cost could be about half of that for brick lined. * Avoidance of joint failures and leaks; brick quality is getting lower as moulds become old and worn. * Reject rate for bricks is high, this spoilage is in subcontract costs. Labour pool for skilled brick masons is dwindling and may affect quality and schedule. * Eliminate loose brick or chips from damaging strong acid pumps. * Acid quality is enhanced by lowering iron content. * Less sulphates in strong acid circuit for cleaner more efficient towers. * With MECS alloy packing supports, up to 80% open area for best gas distribution vs. 37% for self supporting dome or 48% for Aludur beams. * Lower engineering costs. * Shorter schedules due to minimal field work. * Less dependence on a larger number of suppliers and subcontractors. * Less on-site construction time and overhead costs. * Greater project control. UniFlo acid distributors The UniFlo[TM] design by MECS provides customers all the advantages of a conventional trough-style distributor with many added benefits. The gate assemblies in each trough afford easy flow adjustment that is made in minutes--without changing out orifice plates. The result is accurate and uniform acid distribution and maximum performance. The UniFlo[TM] distributor is offered in ZeCor[R] alloy, one of the toughest corrosion-resistant materials on the market. MECS also uses a variety of other alloys to meet specific needs. The UniFlo[TM] distributor gives many years dependable service. Considering life cycle costs, UniFlo[TM] distributors save more than 25% over conventional cast iron designs for initial capital costs and maintenance. The added

value provided by long-term reliability and plant on-stream time is a plus. Tower packing--WavePak[TM] Reducing pressure drop not only enhances the performance of sulphuric acid towers, it also leads to big savings. MECS developed WavePak[TM] ceramic porcelain packing to provide both performance and savings. WavePak[TM] ceramic packing offers major advantages over other traditional packing materials. It delivers with superior internal gas distribution, higher capacities, and optimum mass transfer efficiencies. Equally important, the WavePak[TM] unique construction pays back by providing significant pressure drop savings over conventional saddles. A plant can save as much as $10,000 in operating costs for each inch of pressure drop that is reclaimed with WavePak[TM] when replacing 3inch standard ceramic saddles. Maintenance and spares MECS offers a complete line of products that provide performance in shoring up weak links. These engineered alloy products can be retrofitted into brick-lined carbon steel vessels or other equipment fabricated from conventional materials. A plant maintenance engineer can choose from alloy nozzle assemblies or sleeves to repair damage and eliminate the safety hazards of acid leaks. Offered for inline as well as side and bottom outlet nozzles with Vortex breakers, MECS strainers are ruggedly built for long life. Engineered alloy packing support grids uses a unique design to replace ceramic grid bars and blocks. Prefabricated alloy grating makes handling and installation easier, while providing enhanced performance over ceramic systems. MECS spare parts and replacement products give acid plants the solutions needed to avoid costly, time-consuming repairs, and enable maintenance departments to strengthen weak links that cause repeated problems. Compact MECS Brink[R] diffusion fibre beds Two strategies to significantly increase fibre bed area in an existing tower are concentric elements and small diameter elements. MECS has successfully used both of these diffusion fibre bed designs in strong sulphuric acid plants to reduce operating pressure drop or increase plant rate when production is blower limited. Concentric fibre beds

The concentric design was developed by Monsanto/Brink in the 1960s with concentric HV fibre bed installations. Due to the increase in energy costs and a frequent need to debottleneck operations, the concentric design is becoming more popular today. The concentric design replaces conventional mist eliminators with what is an element inside an element, or concentric design. Concentric elements have an element in the normally void volume in the center of a conventional mist eliminator. The internal element is in opposite orientation to the main mist eliminator. There are distinct advantages to this approach because use of concentric beds increases bed area while using the existing conventional bolting making retrofitting possible. The use of concentric elements can lead to lower pressure drop by as much as 30 to 40+% depending upon element style and application. There are tradeoffs with the concentric design. The elements are heavier, so in some cases additional tubesheet re-enforcement is required. Also the additional weight makes it somewhat harder for maintenance crews to handle so extra rigging and installation care are required. In the case of standing style, seal legs are used for the internal forward flow elements. When retrofitting, extra provisions may be needed to prevent the additional seal legs from interfering with existing tower internals below the tubesheet. Small diameter fibre beds Another method of achieving higher capacity and/or lower pressure drop it to use small diameter fibre beds. These beds have a smaller outer diameter than conventional beds and provide upwards of 45% increase in capacity over an installation of conventional sized fibre beds. This advantage is due to the dramatic increase in fiber area that is achieved by having a larger number of individual fiberbeds in a specific tower volume. The small diameter fibre beds are much lighter and easier to handle than conventional or concentric beds. Although more small diameter elements are used compared to conventional elements, the number of bolts to install elements are reduced by over 75% using a unique clamp arrangement. One sulphuric acid client in Finland has been successfully using small diameter Brink fibre beds in IPAT service since 1996. MECS sulphuric acid catalysts

MECS provides two relatively new catalysts that both offer pressure drop decrease compared to standard rings. The XLP is a six-lobed, ribbed-shaped sulphuric acid catalyst specifically designed for pressure drop reduction in all beds of the converter. It is available in both of the proven LP-120 and LP-110 catalyst formulations. These new products are designated XLP-220 (upper beds) and XLP-110 (lower beds). Installation of the XLP catalyst will result in a pressure drop decrease in excess of 25% compared to the standard LP-110 rings and approximately a 10% reduction in pressure drop relative to the standard LP-120 rings. The higher void area of the ribbed shape improves its dust-handling capabilities, resulting in a lower rate of pressure drop build-up. Litre for litre, the user will continue to realise the same conversion performance experienced with the traditional LP catalyst formulations while maintaining the same low screening losses. The SCX-2000 is an extremely active, newly formulated caesium catalyst designed for the lower beds of the converter. This catalyst is formulated specifically for lower pass applications with or without interpass absorption. The enhanced catalyst support structure of the SCX-2000 generates the greatest conversion possible from the caesium-promoted catalyst while maintaining the same low screening losses that are experienced with the traditional Cs-110 ring catalyst. The optimised formulation of vanadium with alkali-metal promoters results in a catalyst with exceptional conversion efficiency available throughout the entire operating temperature range. The user will experience lower S[O.sub.2] emissions at reduced catalyst volumes with the SCX-2000 relative to the more conventional ring catalysts. The SCX-2000 also has a six-lobed, ribbed-shaped ring structure that provides increased void area resulting in a lower rate of pressure drop build-up; approximately 25% reduction in pressure drop relative to the standard Cs-110 rings will be realised. Rauschert Verfahrenstechnik Rauschert Verfahrenstechnik has been designing and manufacturing mass transfer equipment for more than 30 years. Besides engineering and contracting companies, its main customers are based in the chemical, petrochemical and refining industries worldwide. Rauschert offers all kinds of tower packing, tower internals and fractionation trays for absorption, distillation and heat exchanging processes, covering a complete range of materials (metal, plastic and ceramic) and all commonly used shapes and types of tower packing. Packing is manufactured in Europe as well as Asia. Tower internals (e.g. liquid distributors, liquid collectors, support grids and mist eliminators) as well as fractionation trays (e.g. sieve trays, valve trays, bubble cup

trays and dual flow trays) are designed drawn by the engineering department using AutoCAD and Solidworks. Special designs tailored to customer's demands can also be made. The equipment made from metal and plastic materials are manufactured in Rauschert's workshop in Germany and certified according to ISO 9001. As a sideline product for the European market, Rauschert also provides package units for recovery of ammonia from process waters as well as flue gas scrubbing systems. Besides ceramic tower packing and internals, Rauschert also provides FRP internals to the sulphuric acid industry. A Kombielement[R] combines the function of a support plate and a liquid collector in one space saving arrangement. In this case, the special requirement of the customer was to realise a very low weeping rate (< 70 l/[m.sup.2]h) which was verified during the test run. Rauschert is also a licensee of the Carola technology patented by the German Research Center Karlsruhe. Carola is a highly efficient but cost effective separator for fine particulate matter in gases including S[O.sub.3] aerosols. The separator works in saturated gas streams by electrostatic charging of the particles, which are later separated on a grounded surface collector. Particles with diameters smaller than 100 nm are still separated with efficiencies greater than 80%. A second industrial unit has been installed at an exhaust gas cleaning plant for gases from ceramic kilns. In addition to sulphur dioxide, the gas contains sulphur trioxide with concentrations up to 1000 mg/ [m.sup.3]. Carola separates this aerosol to an emission level below 30 mg/[m.sup.3]. The unit is designed for a gas flow rate of 15,000 [m.sup.3]/h. The pressure loss over the total unit is below 2 mbar, the total energy demand is below 4 kW. The Carola unit is integrated in the top of the S[O.sub.2] scrubbing unit with a diameter of 2000 mm. Noram Engineers and Constructors Many maintenance and operating problems in sulphuric acid plants can be traced back to poorly performing acid towers. The cause of poor performance may be process related, for example, high gas temperatures or inadequate acid circulation rates. The cause may also be related to mechanical defects, fouled packing, plugged distributors, leaky mist eliminators or failure of the tower shell. Process issues

The role of acid towers in sulphuric acid plants is to provide mass transfer from a gas phase to the acid phase. This is achieved by filling the acid tower with packing and irrigating the packing with acid. In drying towers, moisture in the process air or S[O.sub.2] gas is transferred, while in absorption towers, S[O.sub.3] is absorbed by the acid. The required residual concentrations of [H.sub.2] or S[O.sub.3] have been firmly established through good industry practice or environmental legislation. Typically absorption efficiencies of about 99.98% must be achieved in acid towers. Mass transfer in acid towers is always gas side controlled. For such systems the progress of mass transfer through an acid tower can be characterised by the "Number of Transfer Units (NOG)", NOG = ln(Yin/Y), where Y is the molar gas phase concentration. For the required absorption efficiency of 99.98%, NOG is 8.5. The actual physical "Height of one Transfer Unit (HOG)" for specific packing must be determined experimentally. For the standard 3-inch ceramic saddle currently most commonly used by industry, HOG is about 0.4 m, which results in a total required tower packing height (H = NOG X HOG) of about 3-3.5 m (10-12 ft). This packing height has become an industry standard. More packing height offers no benefit; less packing height invariably causes serious degradation in performance. HOG is primarily a function of the size and shape of packing, of the acid irrigation rate and uniformity of acid distribution, and of the uniformity of gas distribution. The superficial gas velocity has only a minor effect on HOG unless flooding conditions are approached. While the promotion of mass transfer is the primary role of packing, gas phase pressure drop or gas flow capacity is the second important parameter of packing performance. Mechanical Issues The key mechanical components in an acid tower required to meet the process performance objectives are the following: * Tower shell; * Packing support; * Packing; * Acid distributor; * Mist eliminator. Noram will always recommend the use of brick-lined towers over alloy towers because brick-lined towers will tolerate excursions in acid strength and temperature, while alloy towers are vulnerable to such excursion. Over the life of a tower, excursions will invariably happen

and failure of an alloy tower can be rapid. Noram prefers a dome packing support system to the arch and beam support. The dome is inherently stronger, no dome has every failed while, beams and arches have failed quite often. Further, the arch design puts mechanical stress on the tower bottom and causes gas maldistribution as the incoming gas channels through the arches to the opposite side of the tower. Noram will always use a dished tower bottom since ceramic components are strongest in compression. Noram supplies proprietary Cecebe HP[TM] packing. This high strength packing is made through a slip casting process. The proven saddle shape is kept, which will ensure true random packing arrangement and will prevent gas and acid channelling. However, the HP[TM] saddle shape is modified to lower pressure drop while maintaining absorption efficiency. HP[TM] packing has about half the pressure drop of conventional 3-inch ceramic saddles and a gas handling capacity about 25% higher. Pressure drop correlations used in Noram's acid tower designs for HP[TM] packing are based on actual acid plant operating data in over 35 installations. Without having even acid distribution, an acid tower will not meet its performance objectives. Noram offers the proprietary Smart[TM] distributor, a pipe distributor located above the packing, which uses downcomers to direct the acid at low velocity some depth into the packing. Even acid distribution is achieved through suitable sizing of the distributor nozzles. A key feature of the Smart[TM] distributor is external clean-out ports, which allow cleaning the distributor without requiring tower entry by maintenance staff. The radial arms of the Smart[TM] distributor are set into nozzles in the tower shell allowing full access. The Smart[TM] distributor can be cleaned during a plant shutdown lasting only a few hours. A further important feature of the Smart[TM] distributor is that it generates almost no acid spray, which could overload the mist eliminator. The acid discharge velocity, in the Smart[TM] distributor, is less than 1 m/s vs the 3-4 m/s of trough type distributors. The spray generation rate varies in proportion to the square of the discharge velocity. Over 40 Smart[TM] distributors have been supplied by Noram. To further enhance acid tower performance. Noram offers the Flow Correction ring (FC[TM]). By placing smaller packing in an annulus near the top of the packing and by selectively placing downcomers of the SMART[TM] distributors in this area, compensation is made for gas and acid channelling at the tower wall caused by the lower void fraction in the wall region. Gas velocities at the wall can be 20% higher than in the core of the tower and may be responsible, in some plants, for poor tower performance. COPYRIGHT 2005 CRU Publishing Ltd.

This material is published under license from the publisher through the Gale Group, Farmington Hills, Michigan. All inquiries regarding rights should be directed to the Gale Group.

Title: Acid plants address environmental issues.(SULPHURIC ACID TECHNOLOGY) Date: 5/1/2005; Publication: Sulphur; The sulphuric acid industry can no longer be viewed as a significant contributor to sulphur dioxide pollution. Due to recent developments, for example, in design, simulation packages, catalyst, and mist eliminators, acid plant emissions of sulphur dioxide to the environment are minimal. Other environmental issues such as the conservation of water are also being addressed. ********** Modern sulphuric acid plants are based on the contact process using a vanadium pentoxide catalyst and are designed and built with reliability as a key factor. The use of computer based design, simulation packages and improved materials developed over the past few years have led to more reliable acid plants. The process technology for the manufacture of sulphuric acid differs depending upon the source of sulphur dioxide gas. Basically there are two types of acid plants: * Those that use dry sulphur dioxide gas e.g. from elemental sulphur. In these plants the air is dried before use in the sulphur burner; * Those that use wet gas as in the case of copper, zinc, and lead roasters or from hydrogen sulphide plants. In these plants wet gas is required to be cleaned and cooled in a series of scrubbers and electrostatic precipitators and finally dried before entering the contact plants. Pollution awareness and steps to control S[O.sub.2] emission In recent times there has been increasing concern about the pollution caused by sulphur dioxide and acid mist emissions and the public awareness of air pollution has increased considerably. It has become a very sensitive issue. The appearance of an acid plant stack is an indication to the general public of how well a plant is being operated. The expectation is that the stack should be clear without any visible emissions. Anything being emitted from a stack automatically gives the perception that a pollutant is being emitted to the environment. The appearance of the

acid plant stack is one of the key factors in maintaining good public relations. Any visibility from the stack or smell in the surrounding area may be considered as a problem in the operation of the plant well upstream in the process. Pollutants emitted from sulphuric acid plants include S[O.sub.2], S[O.sub.3] and acid mist. The amount of S[O.sub.2] emitted is inversely proportional to the conversion efficiency. The conversion is affected by the following: * number of stages in the catalytic converter; * amount of catalyst used; * temperature and pressure; * concentration of reactants (S[O.sub.2] and [O.sub.2]); * catalyst bed temperatures during start-up. In the conventional process, the fourth pass, which operates at 410430[degrees]C, is found to be inadequate to convert the last traces of sulphur dioxide to sulphur trioxide owing to thermodynamic and equilibrium restrictions. The new modified DCDA system employs a fifth pass. With an extra stage of cooling between the fourth and fifth passes and introduction of additional air to cool gases to 380[degrees]C, the approach to chemical equilibrium is favoured. (1) In addition, the use of low bite catalyst will guarantee the stack analysis below 100 ppm. A wide variety of sulphuric acid catalysts are available to meet different conditions. For example, Monsanto offers eight different types of catalyst for various applications and situations. The most commonly specified catalysts are the LP (Low Pressure Drop) ring type catalyst. The caesium-promoted CS type catalysts were introduced in 1990, which have higher activity and lower strike temperatures (low kindling temperature) than standard catalysts. This catalyst when used in first pass, due to lower first pass inlet temperature requirement allows a greater recovery in the boiler placed after furnace. This catalyst also allows high strength sulphur dioxide to be used, thereby reducing the power required to drive the gas through the plant. LP (Low Pressure Drop) ring type catalyst is primarily used in the first and second passes of a converter where low pressure drop and high activity are required. The large ring provides a high void volume permitting greater dust penetration and more uniform dust distribution. This translates to less pressure build-up over time and less frequent screenings.

During any sulphuric acid plant start up, stack emissions are higher than during normal operation. In the past, concessions have been granted to sulphuric acid manufacturers on technical grounds for sulphur dioxide pollution during a start up period of 72 hours. However, pollution control authorities have now withdrawn this on the grounds that, due to adverse affects on the local population, high levels of sulphur dioxide can no longer be tolerated even for a short period. With the increased pressure from authorities, existing sulphuric acid plants are required to install an alkali scrubbing system. A well designed alkali scrubber has to be able to accommodate the high load on the system during unsteady early stages of the start up operations, both after short stoppage (for example, power failure or maintenance) and after prolonged annual stoppage for tower inspection and routine maintenance However, alkali scrubbers are not economically viable on a continuous basis, a modified DCDA system using five passes instead of the conventional four is found to be more attractive Control of emissions Reduction of undesired gas constituents Greater attention and emphasis is being placed on the reduction of total plant emissions by improved design, selection of the proper quality and quantity of catalyst in converter passes and efficient operation of the plant according to written procedures. This ensures that plant emissions stay well within the prescribed limits and prolongs the life of the plant. Recovery of undesirable components Sulphur dioxide abatement by scrubbing consists of a chemical reaction between S[O.sub.2] and a basic liquid solution. This operation is achieved generally in a gas/liquid contact packed tower or a scrubber. A liquid circulation loop is operated from the bottom to the top of the tower, where the liquid is distributed above the packing. The gases enter the bottom part of the tower, contact and react with the basic liquid solution on the packing. The S[O.sub.2] content in the outlet gases is achieved by controlling the pH of the solution and by adding more or less basic concentrated solution into the liquid circulation loop. One or two reaction steps may be needed depending on the inlet and outlet S[O.sub.2] content and the basic product used (ammonia, caustic soda, magnesium or calcium hydroxides, etc.). The resulting by-products (ammonium-, sodium-, magnesium-, or calcium-, sulphate, sulphite and bisulphate) can be sold or may have to be disposed of. For example, S[O.sub.2] is absorbed in a recirculating

solution of ammonia giving ammonium sulphite/bisulphate. A part of the sulphite/bisulphate liquor is neutralised with 98% [H.sub.2]S[O.sub.4] to form ammonium sulphate solution and S[O.sub.2] gas. This liberated gas is dried and compressed to give liquefied sulphur dioxide. This dried gas can also be recycled to boost acid production. Proper dispersion of the gas Dispersion is the simplest of all three methods as all that is required is an adequately designed stack. Stacks are used to reduce the ground level concentration of a pollutant by emitting the process gas at great heights. The ground level concentration depends on the pollutant emitted, the gas temperature and velocity of emission, the actual stack height, wind velocity, the terrain and the atmospheric conditions. At low wind velocities, the rise of the gas due to its temperature is likely to carry the gas to great heights. At high wind velocities, turbulence quickly disperses the gas. Thus at moderate wind speed the highest ground level concentrations are likely to occur. The sample points for determination of plant emissions (S[O.sub.2] and acid mist) are generally located on the stack. The S[O.sub.2] concentration measurements are often done in a number of locations throughout an acid plant. The most common S[O.sub.2] measurement is in the stack allowing the plant operator to stay within the permitted emissions limits. The S[O.sub.2] concentration can range from 0 to 250 ppm S[O.sub.2] for double absorption plants to as high as 0 to 3000 ppm S[O.sub.2] in single absorption plants. Measurements of S[O.sub.2] may also be done at the inlet of a gas cleaning system. This measurement tells the acid plant operator the gas strength that is coming from the metallurgical operation. Another common location for S[O.sub.2] measurements is at the blower discharge in metallurgical or regeneration acid plants. After gas cleaning, the S[O.sub.2] concentration is unknown as well as the [O.sub.2]:S[O.sub.2] ratio. Air dilution may be required to achieve the desired conversion in the converter. On-line continuous measurement of S[O.sub.2] and [O.sub.2] may be required to control the amount of dilution air being added to the process. Recent projects Some recent examples of sulphuric acid projects and their targets for S[O.sub.2] emissions are detailed: * Coromandel Fertiliser Limited (CFL) is one of the biggest manufacturers of phosphatic fertilizer in India. CFL has awarded a contract to Monsanto-DMCC Enviro-Tech and Engineering Limited

(MDEEL) for the execution of a 300 t/d sulphur-based sulphuric acid plant on a turnkey basis at Visa-khapatanam in their fertilizer complex. The plant is scheduled for commissioning in November 2005. MDEEL will guarantee S[O.sub.2] emission of 0.6 kg per ton of acid in this plant. * Philippine Batteries Incorporated (PBI) located at Bo-Bulac, St. Maria, Bulacan in the Philippines, is the largest and most modern battery manufacturing facility in Southeast Asia. It produces acid batteries by the name Motolite (ranking no. 1 in Philippines). These batteries are exported to many countries including the US and Australia. PBI requires acid of battery quality (i.e. less than 10 ppm Fe.). PBI invited MDEEL to set up a 70 t/d sulphuric acid plant to produce battery quality acid. MDEEL supplied the basic engineering for this plant along with proprietary supplies. The plant guarantee trial was given at 75 t/d battery quality acid of 2-3 ppm Fe and with emissions of 33-40 ppm S[O.sub.2]. * JSC Kazakhmys Corporation, the world's 9th largest copper producer, is committed to reducing S[O.sub.2] emissions from its Balkhash copper smelter by almost 2.5 million kg/day. Chemetics has been contracted to build a 3850 t/d single train metallurgical sulphuric acid plant in Balkhash Kazakhstan. The S[O.sub.2] emissions from the plant will be less than 300 ppm. * Southern Peru Copper Corporation (SPCC) has contracted Chemetics to build a new 3,760 t/d sulphuric acid plant at its copper smelter in Ilo Peru. The plant will capture the off-gasses from the smelter, which is also being modernised as part of the Ilo site's overall environmental compliance with Peruvian plant emission regulations. The S[O.sub.2] emissions from the plant will be less than 300 ppm. Acid plant improvements for water conservation As in many parts of the world, fresh water in southern India is a valuable and increasingly expensive resource. For a large industrial complex like a copper smelter, which consumes substantial quantities, this can become a significant operating cost. Sterlite Industries operates a copper smelter at Tuticorin in Tamil Nadu State in Southern India. Production at the smelter began in 1997. Sterlite has recently expanded its copper production capacity from 175,000 to 300,000 t/a. As part of the expansion a new 1,600 t/d acid plant was built in addition to the existing 2,100 t/d acid plant giving a combined acid plant capacity of 3,700 t/d. (2) When operation of the first acid plant started in 1997, the waste heat from the strong acid cooling systems, which comprised two absorber acid coolers, one drying acid cooler and a product acid cooler, was

rejected via a classical water cooling tower arrangement that operated with 7,500 m 3/hr flow cooled from 40 to 30[degrees]C. By 2000 when Sterlite began to develop plans to expand the Tuticorin smelter the cost of water consumption was already rising, a study was commissioned to examine options to reduce water consumption at the plant. Heat rejection from the acid plant was identified as one of the major freshwater consumers and of this, the absorption acid cooling accounted for close to 1,700 [m.sup.3]/day, made up from evaporation losses, wind losses and blowdown. With assistance from Chemetics, various options of reducing water consumption were examined. The total quantity of heat rejected from the acid plant and its relevant level is shown in Table 1. As an alternative to operating a water cooling tower, indirect cooling using air-cooled heat exchangers was examined. Tuticorin is situated 8[degrees] 45' north of the Equator and ambient daytime temperature throughout most of the year is in the 30-35[degrees]C range. Removal of the lower grade heat by indirect air cooling was shown to be uneconomical and impractical, therefore, the focus was put on the absorber cooler heat duty. The original absorber acid coolers utilised 3,300 [m.sup.3]/hr of cooling water at 30[degrees]C at a pump discharge pressure of 45 m as shown in Fig 1. An optimum design case was developed balancing the size and cost of the acid coolers with that of the air coolers for the ambient summer conditions. For this application 55[degrees]C water into the acid coolers with a 30[degrees] temperature rise gave an optimum design as shown in the adjacent Fig. 2. Design of the new acid coolers and the air coolers was also optimised to reduce pressure drop. For the revised operating conditions the absorber coolers were designed to operate on a separate closed demineralised water loop where heat is be rejected via air coolers. Water flow through the new absorber acid coolers was reduced to 1,380 [m.sup.3]/hr., at an operating head of 20 m on the water pump, representing a substantial power saving in pumping costs. The two new acid coolers were designed to directly replace the existing coolers with only minor modification required to the acid and water piping. Both of the new coolers were larger in diameter at 1.3 m, with a combined heat transfer area of 1,636 [m.sup.2]. Materials of construction were Chemetics standard for energy recovery hot water service and both coolers were supplied with Anotrol[R]2000, Chemetics latest proprietary anodic protection system. Design of the cooling water loop and air coolers was performed in house by Sterlite with assistance from Chemetics and the local air

cooler supplier. The cooling water loop consisted of the acid coolers producing the heat, two new lower capacity cooling water pumps, a bank of twelve air cooler modules, demineralised water tank and interconnecting carbon steel water piping as shown in Fig. 3. An area adjacent to the acid plant was identified as the location for the air coolers. Foundations were designed and installed and the modules were lifted directly into position upon delivery to site. The air coolers, which were designed and supplied by Coil Company India Limited of New Delhi, consisted of twelve modular bays, each bay containing two bundles with 336 X 16 mm diameter X 7.365 m long, aluminium fined copper tubes arranged in a 'V' frame structure. Each module includes 3 X 15 kW induced draft cooling fans. Modified water piping was pre installed and the system was ready for the switchover during a scheduled plant shutdown. During a 36 hour plant shutdown, the two existing acid coolers were removed and replaced by the new larger coolers. The two original coolers were uncoupled from the piping, which was then modified to reduce the diameter of the water pipe and shortened slightly to accommodate the larger diameter coolers. The modified piping was tied in and the system readied for commissioning. The new anodic protection system was installed and pre-commissioning checks performed. Upon restarting the acid plant it was immediately evident that the air coolers were not performing to specification as the 55[degrees]C design water outlet temperature was not being achieved. Investigation of the problem ultimately led to the conclusion that hot air was being recycled around the coolers causing the drop off in performance. The reason for this was attributed to the space below the coolers which appeared to be restricting the flow of cold ambient air. The problem was overcome by installing shutters on top of the air coolers to channel the hot air upwards and away from the intake area. With the shutters installed the air coolers are now performing to design at full plant load. Plant performance With the new cooling system in place all of the project objectives have been realised. Water consumption at the cooling tower has been reduced by 1,519.2 [m.sup.3]/day representing a substantial saving plus, power consumption on the new system has been reduced by over 5.5 MW per day adding further to the savings (Table 2). The modifications made to the acid plant in 2003, have already more than paid for the investments in the new equipment.

In May 2004, a routine turnaround inspection for the new cooling system was performed. There was no measurable corrosion in the acid coolers from the high temperature operation and of course no blockage to the tubes or debris as was the past experience when operating with the open cooling tower system. Concurrent with this retrofit project, Sterlite has built a second acid plant at Tuticorin and has duplicated the modified acid cooling system on the new plant. One modification to the system is that the new air coolers are installed at a higher elevation above grade to eliminate the hot air recycle problem.
Table 1: Acid plant heat rejection Source Gas cleaning and cooling Gas drying Absorption Product cooling Total Level 30[degrees]C 45[degrees]C 75[degrees]C 40[degrees]C Quantity [G cal/hr] 30.0 10.2 40.9 0.8 81.9 % 36.63 12.45 49.94 0.98 100.00

Table 2: Modified cooling system savings consumption Original cooling system Cooling water flow Pumping requirement Cooling tower fans Total electrical requirement Makeup water to cooling tower Modified cooling system Cooling water flow Pumping requirement Air cooler fans Total electrical requirement Makeup water to cooling tower [for other duties] Savings: Electrical power Makeup water to cooling tower Total annual savings Flow Power

3,300 [m.sup.3]/hr [measured] 1,699.2 [m.sup.3]/day 1,380 [m.sup.3]/hr installed actual summer usage [measured] 180.0 [m.sup.3]/day

674 kW/hr 80 kW/hr 18,096 kW/day

150 kW/hr 540 kW/hr 517.5 kW/hr 12,420 kW/day

5,676 kW/day 1,519.2 [m.sup.3]/day [330 operating days]

present value 22,704 Rs 68,364 Rs 30,052,440 Rs [650,000 US$]

Note: The 180 [m.sup.3]/day shown as make up to the cooling tower is not shown under savings as the blow-down water was used for process dilution.

References

1. Savant P.B. and Shukla S.P. (Monsanto DMCC Enviro-Tech and Engineering Limited): "Emissions in sulphuric acid plants--A critical issue", (Mar 2005). 2. Kumar S. (Sterlite Industries) and Miller G. (Chemetics): "Acid plant operating improvements from conservation of an often overlooked and precious resource--Fresh Water". Paper presented at Sulphur 2004, Barcelona, Spain (24-27 Oct 2004). COPYRIGHT 2005 CRU Publishing Ltd. This material is published under license from the publisher through the Gale Group, Farmington Hills, Michigan. All inquiries regarding rights should be directed to the Gale Group.

Title: Delivering safety.(includes related articles)(transportation of sulphuric acid) Date: 3/1/1999; Publication: Sulphur; Author: Stevens, Jason The safe transportation of sulphuric acid, spent acid and oleum continues to be a key concern for the international sulphuric acid industries. While industry players have broadly embraced the Responsible Care[R](*) initiative, a foundation of any sound safety strategy, there is the ever-present danger of becoming complacent. Jason Stevens highlights some of the key challenges and innovations attached to this important industry. Characteristics of sulphuric acid The harmful effects of sulphuric acid, oleums, sulphur trioxide and spent acid on human beings are well-known. On direct contact with the skin sulphuric acid eats away at tissues, may produce burns and be accompanied by shock and collapse. Contact with the eyes may result in severe damage or even loss of eyesight. Sulphuric acid vapours cause a host of respiratory problems and also effect eyes and teeth. These effects are primarily the result of its dehydrating and corrosive properties. International regulations Consequently, international regulations exist for the safe handling and conduct of acid between the producer and the customer. Although legislation differs slightly from country to country, the United Nations Complete Hazard Classification governing the transportation of hazardous goods usually features strongly in individual nation's

regulations (please see box on page 25 for expanded account of the UN Complete Hazard Classification which designates various characteristics of sulphuric acid, oleums and sulphur trioxide and the necessary actions to take in the case of exposure).[1] Championing self-regulation The introduction of ISO 9000 standards of operation and the growing adoption of the principles of Responsible Care reflect a self-awareness on the part of industry to changing expectations of the term 'safety'. There is a growing expectation that through education, inquiry and evaluation the upstream supplier will exercise due diligence in determining that the product being sold is passing into hands that are familiar with its properties and capable of maintaining the high standards of safety which have applied to that point in the chain of production and distribution.[2] The principles of both ISO 9000 and Responsible Care require that there be a free flow of information along the entire production and sales line. The Material Safety Data Sheet (MSDS) provides an effective vehicle for this information. The contents could typically include: * Product information; * Hazardous or regulated ingredients; * Physical and chemical data; * Fire/explosion hazard; * Reactivity data; * Preventative measures; * First aid measures; * Special alerts; * Preparation information. The MSDS recognizes the importance of full and clear language warning/informing of properties and potential behaviour that may be associated with materials as they pass from seasoned producers to "lay consumers". It is worth noting that most companies engaged in the transportation of acid often take measures to improve their safety performance well

before the heavy regulatory hand of government appears. These measures often exceed statutory requirements. For example, Noranda DuPont LLC provides specialized sulfuric acid handling videos and a technical manual that provide practical information beyond that provided via the MSDS. However, it also evident that many smaller companies often do not have the economic muscle to fully match those of their larger competitors, and consequently lag behind in certain areas of safety. The fact that these companies still meet the necessary legal requirements is no reason for complacency and a vigilant eye must be kept out for offenders who purposely side-step an opportunity to improve their safety record. A history of innovation A technological milestone in the transportation of acid by rail was the development of the unit train which allowed a greater number of tank cars to be moved at the same time thereby improving efficiency and arguably safety. The number of spill causing accidents by this method of transportation are very rare. For instance in North America, accidents involving rail movement have a recurrence interval of about 600 years per tank car. This translates into a single car travelling 7.3 million miles between accidents, or more than 250 times around the world.[3] The tank car Of crucial importance in maintaining and improving this safety record is the tank car which over the past few years has undergone a high degree of innovation. Research & Development continues with government departments, carriers and tank car manufacturers to further improve the safety and reliability of tank cars, thus ensuring that this mode of transportation which is essential to the economics of bulk movement remains acceptable from a safety and environmental aspect.[4] Working with regulatory authorities A prime example of this dynamic occurred in the United States in the late 1980s. DuPont, with their long safety tradition, who even have a safety business (SEMS) which provides safety consulting and training services to companies worldwide, worked with other suppliers in industry to build support for the Department of Transportation's (DOT) initiative to improve safety standards for Poison Inhalation Hazard (PIH) Liquids, which included oleum at 30% and greater strength.

Following the approval of the H-181 standard for PIH railcars, DuPont proceeded to upgrade its rail fleet for 30% or greater oleum, CSA (Chlorosulfonic Acid), sulphur trioxide liquid and DMS (Dimethyl Sulfate) to meet or exceed all HM-181 structural standards by the time the standard was put into full effect. According to DuPont, the new DOT design incorporated a combination of features that were similar to those employed for many years by itself to ensure railcars transporting very hazardous substances could be handled safely and would not leak in a rail accident. In the late 1980s a train travelling 65 miles per hour derailed near a federal facility in Terre Haute. The incident involved a pre HM-181 DuPont railcar with pressure design and rollover protection similar to those later adopted in HM-181. The train was subsequently raised by a crane, placed back on the rail tracks and returned to DuPont for unloading without spilling a drop. By 1995, DuPont had shifted it's focus towards oleums under 30% strength. While not legally defined as PIH substances, "low-strength" oleum presents the same hazards as the PIH acids to a lesser degree. Recognizing the gap between the protection provided by specials cars and that provided by regular acid cars used exclusively in the industry for non-fuming acids and weaker oleum, DuPont announced, effective 1 January 1997, that it would no longer ship any fuming acid in ordinary, non-pressure railcars. DuPont also recognized that customers who needed smaller size shipments also needed containers that were designed with the same attention to container integrity and safe handling as railcars. DuPont developed special tank truck, ISO tank and portable container designs for its fuming acids and for Dimethyl Sulfate (DMS). DuPont told Sulphur that it had stopped supplying such acids in drums at that time because a drum design cannot meet DuPont's standards of Responsible Care in using and transporting these acids. Meanwhile, Noranda DuPont LLC, the sulfuric acid joint venture company between Noranda, Inc. and DuPont, has confirmed that it will take delivery of four double-hull 2,200 tonne barges for use in the distribution of sulphuric acid along the Gulf Coast, in the first quarter of this year. These carbon steel barges will exceed United States coast Guard regulatory requirements for barges of this design and for sulphuric acid service.

The design includes personnel and environmental safety features such as a vapour recovery system, gauging system, overfill protection equipment, automatic cargo shut down devices and double-hull construction. Noranda DuPont said the four new barges reflect its commitment to safety and reliable growth with their customers, who count on their logistics capabilities and infrastructure to do this. The barges will complement a new terminal agreement with Odfjell ASA and its affiliate Baytank. See separate box later on in article for more details. Improving existing regulations It was noted by Mr H. Nevatia at Sulphur 96 in Vancouver,[4] that a large number of truck/lorry accidents in India could perhaps be attributed to defective motor vehicles. Mr Nevatia declared the immediate need to formulate a new code dealing exclusively with construction of vehicles for carriage of hazardous goods and then to ensure that these rules are actually complied with.[5] He said although the Static and Mobile Pressure Vessels (Unfired) Rules lay down guidelines for including the design stresses arising from shock during transportation these rules do not go into the quantitative aspects of design and do not cover other aspects of hazards. Some of the practical aspects that need to be considered during this exercise include: * Choosing a suitable corrosion allowance for the tank car design; * Considering the variance in vapour pressures combined with temperature fluctuation; * Ensuring that exposed valves are of the same structural integrity as the tank. Valves: attention to detail Over the last decade the configuration of the valve has been modified in a variety of ways to prevent it being sheared off during an accident, thus discharging the contents of the car. These are usually the weakest points of any tank truck or rail tank car, and care should be taken to ensure that they are of the proper material, type and pressure rating. Modified designs include incorporating skid protection, the use of lower profile valves and provision of additional shear sections.

A large number of users prefer unloading by connecting a pump to the bottom drain valve. Any leakage from this valve poses the danger of the entire tank being emptied out. Compromise is consequently not a suggested solution. The valve should at all times be supported from the bottom to avoid cantilever load and be protected by enclosing it in a framework of structural steel or in a steel box so that there is no direct impact in case of an accident. Even these precautions will not always be enough and leaks have still be known to occur. Consequently, some companies in North America have broken with tradition and now employ top unloading valves. For instance, Canadian-based Marsulex which offers a broad range of environmental services (See Sulphur No. 258: p 30) and distribution system consisting of 2,000 leased rail cars, 11 distribution centres and four intermodal transfer facilities in North America, is using pumps to force the acid up a special induction pipe and out the top of the tank car. This method has been so successful that the DOT is considering instituting regulations to order all companies involved in the transportation of hazardous goods to switch to top unloading of the tank car. However, generally speaking, unloading from the top requires a high degree of infrastructure and skill and is not always available with smaller companies. Thus, it seems likely that in the short-term, operators will choose the unloading method most suited to them. Achieving quick, safe turnarounds Loading rates are crucial to quick turnaround times on the transportation equipment involved in moving the acid. There is no point in achieving good transit times and then losing this advantage by poor turnarounds. Speed has to be balanced with safety, and it would be worthwhile to examine a few international examples that reflect this need. Nacozari, Mexico The world-renowned sulphuric acid production plant at Nacozari, Sonora, built by Mexicana de Cobre recognized the need for enhanced efficiency by upgrading its loading facilities from six to twelve railcar loading arms and adding two additional truck loading facilities. With a rated capacity of 2,625 t/d of sulphuric acid, this plant also has the capacity to load 620 cubic metres per hour. It has also enlarged its

tank car fleet by 144 cars to 250 tank cars. The company is using 10 unit trains of 24 tank cars in each unit. Each unit train delivers around 1900 tonnes. On average, 36 tank cars are loaded each day, while another 36 tank cars are unloaded at the Pacific Ocean port of Guayamas for export to the world markets. About 1,200 tonnes of acid is loaded onto a ship each hour from both tank and rail cars. Each car is thoroughly checked by a safety team and the operator before going back to the plant. There are five storage tanks at the port; one is located at the bottom of a hill while the other four tanks are located a the top of the hill.[5] These five tanks are filled through pipelines fitted with 100-MM Lewis Gate Valves. These valves are fitted with proximity switches to indicate which tank is "on-line" and to ensure that 96% and 98% product acids are not inadvertently switched. The elevation of the tanks above the surrounding port provides ample pressure head for the loading of ships. One important development in the area of safety, was Mexicana de Cobre's decision to bypass the tank at the bottom of the hill due to recently discovered leaks. It is now possible to send the acid directly from the tank cars to the storage tanks located at the top of the hill.[6] Copper Cliff, Canada Simon-Carves Fenco used its extensive experience from the Mexicana de Cobre project to upgrade and modernize Inco Limited's nickel/copper smelting facilities at the Copper Cliff smelter in Sudbury, Ontario - the largest single stream sulphuric acid plant in the world at one time. The plant, with an ultimate capacity of almost 2,900 t/d of acid, was fitted with new storage and loading facilities capable of loading up to twelve, 100 tonne rail cars in one hour with any of the three products (i.e. two sulphuric acid strengths of 93%, 98%; 25% oleum) stored on site. These tank cars can be loaded simultaneously in one hour. A second parallel loading track is also available.[7] Caproleuna, Germany The Caproleuna plant in Germany designed and built by Lurgi, has a combined loading and unloading station for sulphuric acid and liquid sulphur, allowing loading and unloading of trucks or railway tank cars.

Each loading arm has a capacity of 60 [m.sup.3]/h each; two sulphuric acid pumps situated in the unloading area, one of which remains on standby. Key safety features of the distribution point include a signal lights system which only allows trucks or tank cars to move if the loading arms are positioned in the resting position. Lurgi loads tank cars and trucks using flowmeters which are programmed to stop flow at a predetermined tonnage. An automatic system to empty loading arms is also available. Companies on both sides of the Atlantic will typically employ secondary containment sites for both storage tanks and loading/unloading areas. Both Marsulex and Lurgi use a combination of acid resistant tiles, membranes and coatings to contain spills which are then directed to the neutralization pits. Lurgi also ensures a ventilation system is connected to the scrubber. A good maintenance program In many accidents involving loss of contents, product loss occurs through fittings. Some of these occurrences are obviously unavoidable, but it does stress the importance of good maintenance programs on fittings. Surge protectors According to Marsulex, one of the reoccurring problems facing the industry is the frequent small release of acid from ruptured pressure relief disks. Due to the rupture, splashing acid can find its way out the top of the car and spill down the sides. The consequences of this can be severe - especially if it occurs in the shunting yard. A car that is accelerated too quickly from a starting position can often result in a disk being ruptured and personnel being splashed by the escaping acid. Consequently Marsulex and others introduced surge protectors underneath the pressure disks which immediately solved the problem. Recently, higher disk bursting pressures of 165 psi are now permitted on tank cars to help avoid this problem. Fighting corrosion North America differs from the EU in that the tank container is considered part of the structural frame of the tank car. Consequently the corrosive properties of typical 93%-transported sulphuric acid represents a threat to the structural integrity of the tank car.

By the mid-1970s it had become apparent that the outer shells of a large number of tank cars were in a poor state. External corrosion, a typical problem, is unrelated to internal corrosion in railcars. This led CIL, Industrial Chemicals and other industry players to introduce the use of phenolic coated resins, which, when applied to the interior of the shell with a spray gun produced a protective coating which lasted up to a period of 10 years. The coating prevented corrosion thereby ensuring that iron from the corrosion process did not contaminate the acid and reduce its commercial saleability. Today, almost all acid is transported in lined cars. Long sweep elbows to the rescue Since installing long sweep elbows or bends to the pipeline running between the Equilon (formerly Texaco) and Tesoro (formerly Shell) refineries in Anacortes, Washington, General Chemical reports a remarkable success in alleviating corrosion failures at the welds. General Chemical Anacortes Works, located between the two refineries ship both virgin sulphuric acid (99%) and spent sulphuric acid (90%) via pipeline to/from both refineries. Several years ago corrosion was identified as a key concern, especially as one section of the 4 inch diameter pipeline, which was common to both refineries, handled the entire volume of acid - sometimes experiencing a transfer rate of 209 gpm. Many of the factory elbow failures resulted in emergency unit shutdowns which disrupted operations and were a threat to safety. Built 10 years ago with standard off the shelf long radius fittings, regular corrosion failures were occurring near the welds, at the elbows and on the side of the tees. Mr John Thomas, Maintenance Foreman, identified two factors contributing towards the severe corrosion on the fitting. The first was a swirling action which produced deep swirl marks; the second was turbulence at the weld. A swirling action is created at the turn because of the acids resistance to compression. As the volume of liquid passes through the turn, the liquid on the outside radius has farther distance to travel than the acid on the inside radius. Since this entire volume needs to travel at the same speed, a motion is created through the turn allowing the liquid on the inside and outside radius to travel together without being compressed or expanded.

The liquid rotates to compensate for the difference in distance. This rotation is evidenced by the swirling marks that are created inside the fitting. After much deliberation and considering many alternatives, Mr Thomas decided to stay with the 4 inch line size. A local fabrication shop was able to successfully cold bend some pipe to form an elbow with a 20-rich radius for 4-inch pipe without it being deformed The shop required a little extra length on each end for the pipe bender to attach. Rather than have the pieces trimmed, the bends were ordered with 18-inch long straight sections at each end. This length helped to reduce the second problem by moving the weld away from the turn. "This method has been very successful. In 1990 this line was replaced, and the leaks that have occurred after this revision have been at reducers and tees," said Mr Thomas. "These isolated problems help to highlight the effectiveness of the long sweep bends". As a result, the same method was implemented throughout the spent acid feed and system, with all the factory elbows being replaced by long sweep bends. Since completing the work several years ago, there have been no failures. However, this design does require some ingenuity in routing as there are considerable differences in space requirements at the turns. Lots of care has to be taken to avoid interferences and all the routes have to carefully checked. Mr Thomas admits that in some instances the design will not work. "When using this design, try to keep the number of turns to a minimum; you may have to change the routing several times during the design phase but the benefit is in the reliability of the system once installed". Emergency Response (ER) Even though acid containers today are more reliable, with larger volumes being moved there is a greater risk of an accident taking place. There is thus the need to maintain the ability to respond to an accident.

Emergency response capability, whilst being an old concept amongst the chemical community, has become a "buzzword" over the last decade. This has been caused by concentrated media coverage of a number of major incidents.[8] The introduction of stricter legislation regarding the transportation of dangerous goods has provided the necessary impetus to make all facets of the industry acutely aware of the responsibilities associated with chemical shipping. The complicating factor in this case is the fact that the shipper has a responsibility during the entire period the product is in transit. This could cover movements across a couple of provinces, states or in fact from country to country. This presents a number of logistical and organizational challenges to the shipper in terms of maintaining the necessary systems to respond directly to any accident. Often, surrounding communities need to be involved in the process.[9] Consequently a number of sulphuric acid producers will often go beyond regulatory requirements to ensure that acid reaches the customer safely. For instance, Mexicana de Cobre provides ER training to civil authorities and red cross firemen in those areas that the acid passes through. To further increase efficiency and to further improve their safety performance, Mexicana de Cobre bought 80% of the train route between El Tajo and Guayamas. The ability to respond quickly and effectively has also not been lost on North American companies. For instance, Marsulex has developed an extensive ER network with the objective of having resources on site within 6 hours of an incident occurring anywhere within US and Canada. Also, Noranda DuPont LLC, in conjunction with its parent companies, has the largest sulfuric acid response system in North America. In India, the Indian Link Chain Manufacturers (ILCM) has noted two suggestions that could make ER quicker and more effective in the area of road hauliers.[10] The first is to equip the tank lorries with wireless systems so that communication of an emergency is immediate. The second is to

establish emergency control centres at specific locations on the highways which would be manned continually. Since the extent and nature of a emergency can vary considerably, the response required would also vary and often require ingenuity along with standard skills. They would provide medical services and towing services. These centres would also have to cater for all hazardous goods to make the centres economically viable. ILCM also notes that there should exist a mechanism for accident reporting in prescribed formats so that accidents can be analyzed and the findings incorporated in future ER procedures. More important than having the ability to respond, is a system geared to the prevention of incidents. This can be achieved by the implementation of extensive tank car inspection and maintenance programs, as well as by ensuring that loading and unloading crews are well-trained. For example Noranda DuPont LLC has a team of experienced technical representatives who provide customers with on-site technical support in the areas of safe handling and prevention. Acid handling seminars, hosted by producers or marketers are also a useful tool for improving the overall safety awareness in industry.[11] The computer revolution Computer technology has become a vital tool in improving efficiency and consequently safety in the sulphuric acid arena. Unless the cars can be accurately tracked and the data continually updated, efficient movement is not possible. Computer technology can be used in the following areas: Linear program for optimising distribution patterns, and financial forecasting. * On-line rail car management system * On-line order entry inventory control system for invoicing, accounts payable and accounts receivable * On-line freight rating system which is tied into the order entry system. It is expected that with the improved efficiencies resulting from the implementation of on-line rail car management systems, it is expected that the bulk movement of sulphuric acid will continue to improve.[12]

Conclusion A large proportion of the world's 155 million-plus t/y of sulphuric acid production must be moved great distances from the point of production to the point of consumption; the distance travelled increases with each passing year. Continued economic innovation, with the aid of computer technology, has pushed the transportation radius of manufactured acid to over 2000 miles in some cases.[13] Any company involved in this exercise needs to display a long-term commitment towards ensuring the acid reaches its customer safely, quickly with minimal or zero impact to the environment. Those companies that practice prevention rather than cure will ultimately display a better safety and environmental record. They will also probably outperform their rivals in the economic arena. Of crucial importance to any shipper/road haulier of acid is the structural integrity of the tank car. Maintenance, regular inspections along with forward thinking on how to improve its reliability will ensure a company's safety performance improves over time. The sulphuric acid industries have thus far demonstrated a proud safety record. However, under the constant eye of a hungry media and a suspicious public, it must continue to adhere to the Principles of Responsible Care and demonstrate further its innovative capabilities. Continued commitment from source point to end use will ensure the bulk movement of acid becomes even more safer and economical in the next millennium. The United Nations acid test Sulphuric acid, oleums, and liquid sulphur trioxide are considered corrosive materials which have resulted in various international regulations governing their safe transportation being formulated. Corrosive materials are defined as those which cause visible destruction or irreversible alteration in human skin tissues at the site of contact and/or those that severely corrode steel. The three grades of acid fall under the UN Complete Hazard Classification seen in Table 1.

The UN number is a unique four-digit number for each substance, which simplifies retrieval of emergency response information from computerized databases. [TABULAR DATA FOR TABLE 1 OMITTED] The characters of the emergency action code specify the following procedures. "4" indicates that water must not be allowed to come into contact with substance whereas "2" indicates that a fog or fine spray must be used in the case of fire or spillage. "W" indicates that the basic action should be one of containment, full protective clothing with breathing apparatus attached; the substance is violently reactive. "P" indicates that the basic action should be one of dilution, full protective clothing with breathing apparatus attached; the substance is violently reactive. In the UN Hazard class '8' indicates corrosive and '6.1' indicates toxic i.e. liable either to cause death or serious injury or harm to human health if swallowed or inhaled or by skin contact. The ADR hazard identification number system was devised by The European Agreement Concerning the International Carriage of Dangerous Goods by Road. "80" indicates corrosive substance. "x88" indicates highly corrosive substance which reacts dangerously with water. "x886" indicates highly corrosive substance, toxic, which reacts dangerously with water. This system is based on the UN Hazard class but indicates the reactivity with water and the intensity of the hazard as well.[13] The safe handling of spent acid Spent alkylation acid is particularly unstable, noxious and unpleasant material which must be handled with extreme caution. Rail cars and trucks must be carefully opened using spark-proof tools, sampled with a thief, tested for acidity with a hydrometer, and then unloaded under an inert gas. If the gravity indicates an acidity below 87-88%, the car/truck should be incinerated directly and not unloaded into a tank of spent acid - the entire tank could "run away". Storage tanks must be kept sealed and vented with strictly no smoking or open flames permitted. Transportation of the waste acid from the refinery to the sulphuric acid plant can require several days or even weeks, especially if rail is used. During this time, the acid may heat, especially during the summer. The colour of the acid will darken as colloidal carbon forms. The colloidal carbon content sometimes increases to 3-4%, but even higher carbon contents have been observed if the acid is stored for extended periods.

The sulphur dioxide produced both dissolves in the acid and collects in the gas phase above the acid. The evolution of sulphur dioxide and noxious fumes and odours from the used acid continues with storage at the acid plant. Tanks should be vented to caustic scrubbers to remove the sulphur dioxide before it is released to the atmosphere. The hydrocarbon vapours that pass through the caustic scrubbers can either be flared with an independent flare or exhausted to the refinery flare system. If the sulphuric acid plant is adjacent o the refinery, the storage tanks can be vented through water seals to the decomposition furnace using caustic scrubbers and flares as back-ups. This is preferred, as the economic loss of sulphur can be significant.[14] New sulphuric acid terminal agreement Noranda DuPont LLC announced recently that it has contracted with Odfjell ASA and its affiliate Baytank (Houston) to transport and terminal sulphuric acid from Noranda's Gaspe, Quebec smelter to Baytank's terminal in Bayport, Texas. Noranda DuPont LLC plans to barge, rail and truck acid to customers from Baytank. From a safety viewpoint, the agreement takes on greater significance when one considers that Baytank is the first and only public terminal in the United States to be named a Responsible Care Partner by the Chemical Manufacturer's Association. Odfjell Tankers and Baytank hold the attraction of a "total logistics package" for Noranda DuPont LLC, including both shipping and storage services. "We find the location of Baytank's terminal operations in Bayport to be an excellent fit," said Mark E. Myers, product manager, Noranda DuPont LLC. The agreement follows the acquisition of four new 2,200 tonne sulphuric barges by Noranda and DuPont which will come into service sometime in the first quarter of this year. Noranda DuPont LLC formed in 1998, as a joint venture company between Noranda and DuPont, markets and distributes sulphuric acid from 12 North American production facilities using a distribution fleet of about 2,200 railcars, 10 barges, a 7,000 tonne ship and an expanding network of terminals. Many thanks to Chas S. Lewis, USA, for their help in putting together this article -Ed.

* A registered trademark in the US of the Chemical Manufacturers Association. References 1. Nevatia, H.: "Key Issues Affecting Safety in the Bulk Transportation of Sulphuric Acid, Oleums and Liquid Sulphur Trioxide in India", British Sulphur, Sulphur 1996 Conference, Vancouver, October 1996. 2. "Accepting the challenge", Sulphur No. 52, pp21-32 (Jan-Feb 1996) 3. Trickett, A. A., Young, D. W.: "Transportation and Handling of Sulphuric Acid", British Sulphur, Sulphur 1985 Conference, London, November 1985. 4. Trickett, A. A., Young, D. W.: "Transportation and Handling of Sulphuric Acid", British Sulphur, Sulphur 1985 Conference, London, November 1985. 5. Nevatia, H.: "Key Issues Affecting Safety in the Bulk Transportation of Sulphuric Acid, Oleums and Liquid Sulphur Trioxide in India", British Sulphur, Sulphur 1996 Conference, Vancouver, October 1996. 6. Ortega, J. L., Rocha, O. G.: "Mexicana de Cobre Completes New Sulphur Acid Plant and Shipping Terminal", British Sulphur, Sulphur 1990 Conference, Cancun, April 1990. 7. Longo, A., Boyd, W. K, Boillat, R. E.: "Inco Limited - World's Largest Single Stream Metallurgical Gas [H.sub.2]S[O.sub.4] Plant", British Sulphur, Sulphur 1993 Conference, Hamburg, April 1993. 8. Trickett, A. A., Young, D. W.: "Transportation and Handling of Sulphuric Acid", British Sulphur, Sulphur 1985 Conference, London, November 1985. 9. Ortega, J. L., Rocha, O. G.: "Mexicana de Cobre Completes New Sulphur Acid Plant and Shipping Terminal", British sulphur, Sulphur 1990 Conference, Cancun, April 1990. 10. Nevatia, H.: "Key Issues Affecting Safety in the Bulk Transportation of Sulphuric Acid, Oleums and Liquid Sulphur Trioxide in India", British Sulphur, Sulphur 1996 Conference, Vancouver, October 1996. 11. TrickeR, A. A., Young, D. W.: "Transportation and Handling of Sulphuric Acid", British Sulphur, Sulphur 1985 Conference, London, November 1985. 12. Trickett, A. A., Young, D. W.: "Transportation and Handling of Sulphuric Acid", British Sulphur Sulphur 1985 Conference, London, November 1985.

13. Nevatia, H.: "Key Issues Affecting Safety in the Bulk Transportation of Sulphuric Acid, Oleums and Liquid Sulphur Trioxide in India", British Sulphur, Sulphur 1996 Conference, Vancouver, October 1996. 14. Lang, E.G., Albright, L. F.: "The Genesis, Storage, Transport and Regeneration of Alkylation Waste Acid", British Sulphur Sulphur 1996 Conference, Vancouver, October 1996. COPYRIGHT 1999 CRU Publishing Ltd. This material is published under license from the publisher through the Gale Group, Farmington Hills, Michigan. All inquiries regarding rights should be directed to the Gale Group.

Title: The contact process. (250 years of vitriol, part 2) Date: 7/1/1996; Publication: Sulphur; Continuing our historical survey of sulphuric acid technology. As mentioned in the first part of this article, the contact process for manufacturing sulphuric acid was not developed into a workable embodiment for 40 years after it was first proposed. One reason for the long gestation period was partly that there was already a tried and tested procedure - the chamber/tower process which could provide sulphuric acid suitable for all the purposes that demanded it at the time, so why change to something untried? The other was the rather inadequate state of scientific understanding of the physical chemistry of equilibrium reactions and catalysis. As was the case with the processes for manufacturing many basic industrial chemicals, most of the development work on the contact sulphuric acid process was done in northern Europe, especially Germany, the United States and pre-revolution Russia. The detailed course of its early development in each of these areas was to some extent coloured by the nature of the most readily available raw materials. The United States, whose newly-established Frasch sulphur industry in the southern states made it by far the largest producer of elemental sulphur in the world, concentrated on sulphur-burning processes. Elsewhere pyrites was the predominant local source of sulphur, and process development was therefore centred round ore roasters as the source of sulphur dioxide. Ironically, in later years Europe made more use of sulphur-burning technology as elemental sulphur became more plentiful and cheap, while North America has made greater use of roaster-based acid plant technology to harness the vast volumes of waste sulphur dioxide from large metal smelting operations.

Basic problems of S[O.sub.2] conversion The contact process is in principle the simplest imaginable route for producing sulphuric acid. It comprises converting sulphur dioxide and oxygen into sulphur trioxide (equation 1) and then combining the sulphur trioxide with water to form sulphuric acid (equation 2). 2S[O.sub.2] + [O.sub.2] [equilibrium] 2S[O.sub.3] (1) S[O.sub.3] + [H.sub.2]O [approaches] [H.sub.2]S[O.sub.4] (2) The "fly in the ointment" is the little "equilibrium" symbol in equation 1, which indicates that equation 1 represents an equilibrium between the two reactions represented by equations 1a and 1b. 2S[O.sub.2] + [O.sub.2] [approaches] 2S[O.sub.3] + heat (1a) 2S[O.sub.3] + heat [approaches] 2S[O.sub.2] + [O.sub.2] (1b) The rearward reaction, denoted by equation 1b, is favoured by supplying heat, whereas the forward reaction (equation 1a) is favoured by taking it away. That means that at high temperature the system reaches equilibrium at a lower concentration of sulphur trioxide than it does at lower temperature. The unfortunate thing is that it is necessary to heat the system to a fairly elevated temperature before anything significant happens at all, because both reactions (i.e. equations 1a and 1b) are what is termed "kinetically inhibited". The reason for that is that the "activation energy" - the energy needed to excite the reacting species into a state from which a chemical reaction will result - is substantial, and effectively none of the molecules in the system possess this energy at ambient temperature. The most straightforward way of providing it is by heating. On a molecular basis, what happens is that the kinetic energy of the individual molecules is increased so that they collide more frequently and more energetically. This happens in a Gaussian or random fashion, as some molecules acquire more than the average energy, and others less, which is why the reaction begins gradually and increases in speed as the temperature is raised. The activation energy for the forward reaction (equation 1a) is lower than that for the rearward reaction, but by the time sufficient molecules of sulphur dioxide and oxygen have acquired the necessary energy to give a good rate of reaction an already appreciable proportion of the sulphur trioxide molecules have become activated as well, allowing the reverse reaction to take place. So a system which starts off with just sulphur dioxide and oxygen appears to stop reacting well before all the sulphur dioxide has been converted to sulphur trioxide. A partial answer to the problem is to use a catalyst. This is a substance that has the ability to enhance the rate of reaction in a chemical

system at a given temperature but itself ends up in exactly the same chemical state as it started off. What is in effect happening is that the intervention of the catalyst modifies the energy profile of the reaction, either by providing an alternative reaction route which has a lower activation energy but the same eventual result or by capturing the molecules in such a way as to increase the frequency of potentially reactive encounters at lower overall energy levels. Early ideas We know that today, Peregrine Phillips, the vinegar manufacturer from Bristol who first proposed the contact process in 1831, and the other early workers who followed him arrived at practical answer to the problem empirically, without ever really understanding why or how it worked. Phillips used platinized asbestos for his catalyst, though others reported some experimental success with pumice (with and without an addition of manganese dioxide), chromium and copper oxides, pyrites cinders, copper sulphate, silica, and platinized metal sulphates. In fact, no-one really understood much about it until Knietsch, of BASF in Germany, presented a lecture to the German Chemical Society in 1901. This dispelled some misconceptions that had been propagated some years before about the stoichiometry of the reaction, offered workable solutions to the problems of using pyrites as a raw material, and acknowledged the importance of withdrawing heat from the catalyst mass. In short, it opened the door to the development of the contact process on an industrial scale, and with it the prospect of the economically-priced concentrated sulphuric acid needed for the emergent alizarin dyestuffs industry. Platinum-containing catalysts, in one form or another, were to remain the basis of practically all commercial production from the beginnings of the contact acid industry until the advent of vanadium-based catalyst - another BASF innovation - in 1915. Though over the following years BASF adopted vanadium-based catalyst in all its plants, the United States industry continued to be almost completely dependent on platinum catalysts until the end of the 1920s, when American manufacturers developed durable vanadium catalysts with the aid of former BASF scientists. From then on these catalysts, which were both less expensive than platinum and more resistant to poisoning, progressively supplanted platinum. Figure 1 is a generalized flow diagram of a sulphur-burning contact plant from around the turn of the century. In comparison with a contact process flow diagram from later years, the most immediately evident difference is the use of a gas cleaning train. This was necessary to prevent poisoning of the sensitive platinum catalysts of the period. No attempt was made to make use of the prodigious amount of heat produced in the sulphur combustion, which was dissipated in a series of coolers - cast iron coolers to handle the hottest gas and lead coolers to resist corrosion from acid condensation at lower temperatures. This

meant that the feed gas had to be reheated to the initiation temperature of the catalytic conversion reaction in the same way as in a metallurgical acid plant. Heat exchangers were, however, provided to recover the heat of reaction from the conversion section (a feature disclosed in a Hoechst patent of 1888); at start-up all the reheat had to be provided in a fired heater. Because of restrictions imposed by the available materials of construction in the acid circuit, the process gas had to be subjected to a final stage of cooling in an air-cooled heat exchanger before admission to the absorption stage. In the arrangement shown in Fig. 1 the catalyst is divided into two masses in separate reactor shells, but that was not always the case. All the methods of regulating the temperature in the catalyst mass which are familiar today had been patented by 1899. Four main proprietary variants of the process were developed at that time: the BASF process, the Grillo-Schroeder process, the Mannheim process and the Tentelew process. The BASF process used a platinized asbestos catalyst. In the earliest plants, this was held in a cluster of parallel tubes which could be heated by gas jets at start-up and then, when the full operating temperature was attained, could be cooled with air to regulate the temperature. As the pressure drop across this device was too high, later plants used a single lagged cylindrical steel shell with up to 50 cast iron catalyst shelves, on which the platinized asbestos was spread in thin layers. The gas flowed downwards through the beds to prevent entertainment. Temperature control in this case was provided by external heat exchangers of a shell-and-tube design not unlike that used in modern sulphuric acid plants. The Grillo-Schroeder process, also developed in Germany, used platinized magnesium sulphate catalyst. In the original converter design, the catalyst was laid on five or six perforated trays horizontal trays in a vertical cylindrical shell, fed at the bottom with gas preheated in tubular heat exchangers to the inlet temperature (around 385 [degrees] C). A later converter design [ILLUSTRATION FOR FIGURE 2 OMITTED] comprised five beds in a double-walled cylindrical shell. Incoming feed gas at 200-250 [degrees] C passed upwards through the jacket space, picking up additional heat through the inner wall, and then passed downwards through the catalyst beds. Between the beds it was deflected outwards by a circular baffle so as to make contact with the inner shell wall. Yet another German development, the Mannheim process (not to be confused with the Mannheim kiln process used for making alkali metal sulphates from their chlorides), was developed at Verein Chemischer Fabriken, of Mannheim. Though it was one of the first contact processes to become obsolete, it is interesting for two reasons: one was that it introduced the concept of using pre-dried air, though for pyrite roasting, not for sulphur burning. The other was that it used the

principle of double absorption, which - as shown below - was to revolutionize the conversion efficiency and pollution control performance of contact plants many decades later. Conversion was conducted in two completely separate stages, the first - unusually employing a ferric oxide mass (actually pyrites cinders) in a shaft reactor and the second platinized mats of asbestos rope lying on wire netting. Because the ferric oxide operated at temperatures up to 750 [degrees] C it did not achieve a particularly high degree of conversion (30-45%), but it served as a guard bed, reducing the amount of arsenic and other poisons reaching the platinum catalyst. To attain the necessary high temperature, the incoming feed gas was first passed through a tubular heat exchanger, where it acquired heat from the exhaust from the platinum catalyst converter, then through cast iron pipes in the ferric oxide catalyst mass, and finally through a small fired heater. After passing out through the cinder catalyst the gas was cooled and contacted with concentrated sulphuric acid in an intermediate absorption stage, then reheated and passed through the platinum mass. With fresh catalyst it required an inlet temperature of 400 [degrees] C, giving an overall conversion of 90-92%, but as the activity of the catalyst fell the inlet temperature had to be raised and the efficiency fell in proportion, to around 83-86% at an inlet temperature of 500 [degrees] C. The process was therefore more elaborate and less efficient than either BASF or Grillo-Schroeder. Another early process, which proved also to be an early casualty in the race between contact processes, although it did enjoy a fair run of successful use for about two decades, was the Russian Tentelew process, which was in use in Russia by about 1894 but not generally published until around 1902. The converter in this process was designed with an empty upper chamber surmounting a tube bundle containing the platinized asbestos catalyst. Feed gas, partially preheated to about 220 [degrees] C in a tubular heat exchanger against a portion of the converter exhaust, acquired heat by backward transfer from the catalyst mass to bring its temperature to about 380 [degrees] C as it entered the catalyst. Enter vanadium catalyst Although BASF was the first to make industrial use of a catalyst based on vanadium in about 1915, the use of this material had been proposed at least as far back as 1899. The large-scale commercial history of vanadium catalyst, however, dates from 1926 when the first Monsanto vanadium catalyst appeared. The active constituent was a complex sodium-vanadium silicate which was precipitated in the form of a gel from a solution containing sodium vanadate and water-glass. The gel was then pounded with a powdered siliceous carrier, formed into pellets and dried.

This catalyst was developed by two expatriate former employees of BASF, who promptly parted company with Monsanto after a disagreement about royalties. One of them - A. O. Jaeger - joined a rival company, Selden Co., and in 1928 was awarded two patents for a catalyst made by impregnating a siliceous carrier with a mixture of potassium vanadite and vanadyl sulphate. In a lawsuit brought by Monsanto in 1927, the two catalysts were ruled to be distinct inventions and Monsanto's claim to ownership of the Selden catalyst was dismissed. A second lawsuit brought against Selden by the General Chemical Co. (holder of the rights to the BASF patents in the USA) also failed. The Selden catalyst and a converter designed by Jaeger were embodied in a complete sulphuric acid process marketed from 1928 onwards by Chemical Construction Corporation (Chemico), while Monsanto, which began constructing sulphuric acid plants at about the same time, used its own catalyst. In Germany, where Lurgi was the preeminent constructor for contact acid plants, BASF catalyst predominated. There were differences in philosophy at that time about how to control the temperature in the catalyst mass. The early vanadium catalysts were said to be able to withstand temperatures up to 600 [degrees] C, and even today, in fact, the maximum desirable temperature in a vanadium catalyst mass is about 620 [degrees] C. The substantial heat of reaction means that under adiabatic conditions the temperature in single bed of catalyst will easily exceed this unless the sulphur dioxide concentration of the feed gas is severely restricted. With plant capacities generally on the increase, there was a continuing incentive to process feed gases at the highest possible concentration in the interests of keeping gas volumes, and thus equipment sizes, to the minimum. Some means was therefore needed to control the temperature of the gas as it passed through the catalyst mass. Also, since the theoretical conversion efficiency, dictated by the thermodynamic equilibrium in the sulphur dioxide/trioxide conversion, is best at the lowest practical operating temperature, careful temperature profile control would raise the conversion efficiency while at the same time reducing the volume of catalyst needed. The Jaeger converter [ILLUSTRATION FOR FIGURE 3 OMITTED] was a two-bed design comprising an internal heat removal system based on bayonet tubes. In the first bed the heat of reaction was given up to the incoming feed gas, which was preheated to the initiation temperature as a result. The second bed was air-cooled. BASF and Monsanto, on the other hand, divided the catalyst into a series of five horizontal beds operating essentially adiabatically, though cooling (by incoming feed gas) was initially provided only between the second and third beds. Originally separate reactor shells were used, one to house beds 1 and 2 and the other beds 3-5. Later designs placed all the catalyst beds in a single shell and provided inter-bed cooling between every bed, which brought the sulphur trioxide conversion in the later stages closer to the

theoretical equilibrium value and incidentally allowed satisfactory performance to be obtained from only four beds overall. Because of the availability of elemental sulphur in the United States, most contact plants built there were designed to burn it. Features of modern contact plants which already appeared in plants of that time include an air drying tower, instead of a feed gas dryer, which dispensed with the need to cool the combustion gas to low temperatures and then reheat it to the initiation temperature; a liquid sulphur spray burner; and a waste heat boiler to recover the heat of combustion of the sulphur. It was usual practice to pass the combustion gas from the sulphur furnace through a so-called "hot-gas filter" to remove the small amount of ash that is always present in sulphur from native deposits. Filtering of the liquid sulphur, which eliminated the need for a hot-gas filter, was a later development. The availability of by-product steam, which could be used for driving machinery such as the main blower, had a distinctly beneficial effect on the process economics. Over the years the steam system in the contact section itself (i.e. associated with the converter) became progressively more sophisticated so as to maximize the degree of high-level heat recovery. Alternative raw materials As already mentioned, the United States was in the uniquely privileged position of having a plentiful source of good-quality elemental sulphur in the Frasch industry in Texas and Louisiana. Apart from the volcanic sulphur deposits in Sicily (historically unreliable as a source of sulphur for political reasons) and the native sulphur deposits in Poland, which were rather remote, until the 1950s no potential source of elemental sulphur within Europe was known. The European and Russian industries therefore grew up more on the basis of so-called "metallurgical" plants, which operated either on the gases produced by roasting pyrites, deposits of varying sizes being available in most countries, especially Spain, Portugal, Italy, Germany, Norway, Sweden and Finland, or on waste gases from the roasting of non-ferrous metal sulphide ores. Pyrites may contain 45% or more sulphur by weight and yields sulphur dioxide by a self-sustaining autothermal reaction when roasted in the presence of air. Although it is possible to recover some high-grade heat from the roaster itself and from the roaster gas, there is no opportunity for high-grade heat recovery from the contact section itself, because the raw roaster gas has to be subjected to elaborate purification treatment to remove the many solid, volatile and gaseous impurities, which necessitates cooling the gas down completely. Virtually all the reaction heat generated in the converter therefore has to be recovered for preheating the feed gas. Pyrites-based sulphuric acid processes therefore have two obvious disadvantages in comparison with sulphurburning processes: the sulphur dioxide generation facilities are far

more elaborate and expensive, and the energy economics are inferior. Against this has to be balanced the strategic, logistical and economic advantages of having a locally-available raw material. Even more disadvantageous as a source of sulphur dioxide is the exhaust gas from non-ferrous ore roasting and smelting, since here the needs of the sulphuric acid plant are subordinate to those of another process, which tends to be intermittent and variable in operation, and it is impossible to optimize the feed gas conditions to suit the contact plant. High-level heat from the roasting operation, if recovered, is not necessarily available to the sulphuric acid plant operator. Because of the great preponderance of metallurgical sulphuric acid projects in Europe, the accumulated experience of Lurgi in this field is probably second to none. Figure 4 presents a flow diagram of a modern Lurgi conventional contact process, revealing the elaborate heat recovery measures needed to maintain autothermal operation. Metallurgical gases often contain volatile impurities which, if allowed to pass through a normal gas cleaning system, are harmful because they either damage the catalyst or the fabric of the plant (for example, chlorides) or contaminate the product acid (mercury, especially). Boliden has developed most of the technology used for removing mercury from metallurgical feed gas. Available methods include introducing selenium into the wet scrubber of the gas cleaning system, separately scrubbing with mercuric chloride or concentrated sulphuric acid, or passing the gas through a bed of supported selenium or activated carbon. Surely the most extreme example of the trade-off between sulphuric acid production economics and the convenience and security of raw material supply must be the Mueller-Kuehne process, which generated sulphur dioxide by reductive calcination of anhydrite (calcium sulphate) in a rotary kiln. This must have been the dirtiest and most energyintensive sulphuric acid process ever, conceived in the desperate conditions of war-time Germany and subsequently adopted with enthusiasm by the UK fertilizer industry, which lacked any other indigenous sulphureous raw material. A mixture of coke, anhydrite and sand was introduced into the upper end of a gigantic inclined rotary kiln, in which it met a countercurrent flow of hot combustion gas from furnace burners introduced at the lower end. A clinker emerged from the lower end which was crushed and milled for cement production. A raw gas stream containing sulphur dioxide, carbon dioxide and a fair measure of dust was then led through a gas cleaning system somewhat similar to that of a metallurgical acid plant. It was impossible to prevent pollution from such a mechanism, and in 1972, even before the first "energy crisis" of 1973/4 ICI, a major UK user of the process, abandoned the process in favour of a new twin-stream Lurgi-built sulphuric acid plant at its Billingham site, which was frequently shrouded in ammonium sulphate fog formed from sulphur dioxide

emissions from the old plant and escapes of ammonia from antiquated coal-based ammonia facilities. The Chief Alkali Inspector - the UK Government's chief pollution control officer - declared the ceremonial shut-down of the last plant as the fulfillment of a lifetime ambition. Some years ago, when the price of elemental sulphur showed signs of rising, the Florida Institute of Phosphate Research and Freeport McMoran Inc. did some development work aimed at improving the energy economics of reductive pyrolysis of calcium sulphate to the point where it could be used as a means of recycling "phosphogypsum" (the by-product calcium sulphate from phosphoric acid manufacture), but the conditions on the sulphur market in the past few years have been hardly propitious. "Wet catalysis" Although the Claus process for converting hydrogen sulphide to sulphur by partial oxidation was patented in the 1880s, the gigantic amount of development work which has been done on it mostly dates from the post-Second World War period, when there was a vast push to develop oil and gas resources around the world. In the 1930s, waste gas streams containing the exceedingly toxic (and offensive) hydrogen sulphide were a real problem, because on combustion they produce water vapour, which instantly combines with any sulphur trioxide formed during its passage through the plant to form sulphuric acid vapour. Acid mist can condense anywhere the temperature falls to or below the sulphuric acid dewpoint, wreaking havoc on any exposed metal surfaces and catalyst particles with which it subsequently comes into contact. Lurgi developed the solution to this problem in the form of the so-called "wet-catalysis" process by simply eliminating heat exchangers between the first catalyst bed and the final absorption stage. The hot, moist gas formed by combustion of hydrogen sulphide with a smaller than usual excess of air was cooled in a waste heat boiler to about 440 [degrees] C and then passed sequentially over several passes of normal sulphuric acid catalyst. After all but the last catalyst stage the gas was cooled by quenching with additional air. From the final catalyst pass the gas passed directly at exit temperature (420-430 [degrees] C) to a "condensation tower" - a contact cooler irrigated with cooled sulphuric acid at about 50 [degrees] C - with which the combining sulphur trioxide and moisture coalesced before they could form the much more intractable sulphuric acid mist. Because of the [H.sub.2]O:S[O.sub.2] stoichiometry of hydrogen sulphide combustion products, the maximum attainable acid concentration from the conventional wet-catalysis process was 90%, and because of the corrosion characteristics of sulphuric acid that, in effect, meant that the acid strength had to be kept down to 78-80%. In its Concat process, Lurgi raised the capability of the process to produce 93% acid by dividing the acid condensation into two stages. The first is a venturi stage, in which the majority of the sulphuric acid vapour but

very little free water vapour is condensed at 180-230 [degrees] C. In the second stage, the gas, considerably diluted with additional air, is scrubbed with relatively dilute sulphuric acid, which removes any remaining sulphur trioxide/sulphuric acid vapour, at the same time losing moisture to the tail gas. A portion of the circulating acid is passed into the venturi scrubber stage to maintain the 93% concentration. The principles of Haldor Topsoe's WSA and WSA-2 processes are similar. The latter process has, however, been targeted particularly at recovering sulphuric acid from S[O.sub.2]-containing combustion and roaster gases. And, as shown later, Monsanto has proposed a universal sulphuric acid process running on wet-catalysis principles. The impact of the environment For many years the S[O.sub.2] conversion efficiency of the contact process remained about the same, at around 98%, which was considered satisfactory from both the economic and the environmental point of view. Two hideous smoke pollution episodes (which had nothing to do with sulphuric acid plants) in London (1951) and Donora, Pennsylvania (1952) aroused public and government concern about atmospheric sulphur emissions in all the industrial countries and heralded the start of the current era of general environmental awareness. Though minor contributors in comparison with the myriad sources of sulphur-containing combustion gases, sulphuric acid plants were among the most obvious targets and came under pressure to cut emissions, especially after the development of the double-absorption concept in the 1960s, which substantially improved the inherent conversion efficiency. The USA and Japan led the way in introducing regulations which made the use of this process virtually obligatory in new plants, and they were followed soon after by the majority of European countries. Existing plants in the most environmentally sensitive areas began to "clean up their act", either by conversion to double absorption (a favoured option when coupled to a capacity expansion) or by retrofitting with one of a number of tail gas treatment systems. These are too numerous to list, and some remained little or no more than concepts on paper. The main contenders included ammonia scrubbing (which produced ammonium sulphate as a by-product), regenerative alkali sulphite scrubbing such as the Wellman-Lord process (which produces concentrated sulphur dioxide either as a product or for recycle back into the acid plant) or catalytic absorption on wet activated carbon in systems such as Lurgi's Sulfacid process (which produces a dilute sulphuric acid stream of little utility other than to feed back into the main acid plant). Double absorption: nothing new under the sun

As already mentioned in connection with the Mannheim process, the concept of double absorption, whereby an intermediate absorption stage is interposed after part of the sulphur dioxide has been converted to sulphur trioxide, in fact goes back to the very early days of sulphuric acid manufacture. But it was not until 1963 that the idea, which is based on a rock-solid principle of physical chemistry, was revived. In any chemically reversible system, of which the S[O.sub.2]/S[O.sub.3] conversion is a prime example, the eventual position of equilibrium in the reaction corresponds to a fixed ratio between the concentrations of the reactants and the products. Remove any one of the participant species, and the system will react in such a way as to restore the overall ratio to the equilibrium value. Thus by absorbing sulphur trioxide after two or three catalyst beds, at which stage the majority of the sulphur dioxide in the process gas has already been converted, it is possible to improve the conversion achieved in the final one or two catalyst beds. The earliest double-absorption plants achieved an overall S[O.sub.2] conversion efficiency of 99.5%, and nowadays refinements have boosted its capability to 99.85% or more. Under the name "Double Catalysis" the idea was reintroduced in 1963 by the German chemicals producer Bayer AG, in collaboration with Lurgi. Chemico and the other major process designers quickly followed suit with their own systems: Monsanto with "Interabsorption" and The Ralph M. Parsons Co. with "DC/DA" (double contact/double absorption). (Chemico went bust in the early 1970s; its sulphuric acid process technology has continued to be developed by Siry Chamon Impianti of Italy. Also in the 1970s Parsons more or less dropped out of the sulphuric acid business and its former chief engineer on sulphuric acid, Tim Browder, set up his own company. However, Parsons has since proposed a non-catalytic sulphuric acid process.) Operation under pressure Traditionally sulphuric acid plants have been essentially atmosphericpressure plants, the blower creating just sufficient positive pressure to drive the gas through the plant. For that reason gas ducts and process vessels are relatively massive and, with their additional layers of thermal lagging, give sulphuric acid plants their characteristic lumpy appearance. Since the conversion of sulphur dioxide to sulphur trioxide entails a reduction in volume, the equilibrium point is favourably affected by the application of pressure, which also reduces the necessary size of the equipment. Nevertheless, the idea has never really got beyond the prototype stage. There are two probable reasons, the first being that the double-absorption technique takes care of the efficiency considerations, the other being that most countries demand certification of equipment running at anything over 5 bar. Of the two systems ever offered commercially, one - developed in France by PCUK, now Atochem - was, in fact, also a double-absorption system and boasted an efficiency of 99.85% at a time when "atmospheric" doubleabsorption processes had only been designed for 99.5%. The other

system, developed in Canada by Chemetics International Co., sought to exploit the benefits of modest pressure operation to attain performance in a simplified single-absorption plant (only three beds in the converter, for example) equivalent to that of contemporary doubleabsorption designs. The quest for energy recovery A "conventional" sulphur-burning double-absorption plant recovers all the surplus heat content of the process gases in the form of 1.1-1.2 tonnes of high-pressure steam per tonne of [H.sub.2]S[O.sub.4] produced, but that only accounts for 60% of the total energy input. The remaining 40% is lost, mainly as the low-level waste heat rejected in the acid coolers. In a "cold gas" plant receiving a cooled sulphur dioxide stream from a gas cleaning system, all the high-level heat is recycled internally, which means that essentially the entire energy input is lost. This is a very substantial amount of heat, and in the wake of the "energy crises" of 1973/4 and 1979 a great deal of interest was awakened in recovering this heat for some useful purpose. That would have been a complete impossibility in the early days of the contact process because the only material available at an economic cost for making acid coolers was cast iron, and the absolute top limit for its operation was about 100 [degrees] C. Were a sufficiently compact heat exchanger design available, the recovered heat would have been of very low grade. As we shall see in the third instalment of this article, to be published in a future edition, it is thanks to a progressive improvement in materials of construction and acid-circuit equipment design that it became possible to raise the operating temperature of the acid absorption circuits in proportion, first to a level at which the waste heat could be recovered as hot water for district heating schemes or use in another process, then to a level where it could be used for boiler feed water preheating or phosphoric acid concentration, and finally to a high enough level to raise low- or medium-pressure steam. The culmination of this evolutionary process is Monsanto's HRS (Heat Recovery System), in which 99% acid at about 165 [degrees] C is fed into a specially-designed packed intermediate absorber, leaving at 200220 [degrees] C and about 100% concentration, and is circulated through a boiler, raising steam of up to 10 bar directly. Because S[O.sub.3] absorption takes place under conditions where mist formation is much less of a problem, in a further development of the concept - the Monarch [TM] process [ILLUSTRATION FOR FIGURE 5 OMITTED] - Monsanto has dispensed with the drying tower completely, and with it the requirement for handling and cooling 93% acid in the 60-70 [degrees] C range. Because of limitations on space, it was not possible to provide a list of literature references here. A bibliography will be published in a

forthcoming issue with the third instalment of this article, which will outline the history of critical equipment items and materials of construction which have made the high performance of the modern sulphuric acid plant possible. COPYRIGHT 1996 CRU Publishing Ltd. This material is published under license from the publisher through the Gale Group, Farmington Hills, Michigan. All inquiries regarding rights should be directed to the Gale Group.

Title: Improving plant operation between turnarounds.(sulphuric acid plants) Date: 1/1/1999; Publication: Sulphur; Author: Pillai, K.A. The main process steps in the manufacture of sulphuric acid by the DCDA (double contact double absorption) route using solid sulphur are well known and can be summarized as follows: * Melting the solid sulphur with steam coils, followed by filtration, if required, to obtain clean sulphur containing less than 10 ppm ash; * Burning the molten sulphur in air to produce gas containing sulphur dioxide; * Cooling the gas in a waste heat boiler system which produces superheated or saturated steam at conditions fixed, based on requirements; * Catalytic oxidation of nearly 9597% S[O.sub.2] to S[O.sub.3] in three consecutive passes of converter containing vanadium pentexide catalyst with intercooling of gas in between. The exothermic heat of reaction is utilized to produce steam in the waste heat boiler system and to reheat the gas going to it in the fourth pass from the intermediate absorber. * Absorption of S[O.sub.3] formed in the gas stream in 98.4% acid in an intermediate absorption tower producing sulphuric acid. * Catalytic oxidation of the remaining S[O.sub.2] to S[O.sub.3] in the fourth pass of the converter to get a conversion efficiency of more than 99.7%. The exothermic heat is also utilized as in the previous passes. * Absorption of the S[O.sub.3] formed in the fourth pass of the converter in the final absorption tower to produce sulphuric acid.

* A low grade heat recovery system can be considered instead of the intermediate absorber, which will produce additional steam at low pressure. In the remainder of this article, typical problems in the manufacture of sulphuric acid will be outlined together with solutions that have been effectively adopted to remedy them. Sulphur melting and filtration section Sulphur from storage is fed to sulphur melting pits equipped with steam coils. The steam coils are usually fed with steam at 7.0 bar(g). The molten sulphur overflows to the mixing pit and from there to the precoat pit by under flow. Steam coils using steam at 4.5 bar(g) are also provided to ensure completeness of the melting process as well as to keep the sulphur in molten condition. Precoating agent is added in the precoat pit, from where dirty sulphur is pumped by a precoat pump to the sulphur filter to obtain a clean sulphur filtrate containing less than 10 ppm ash. Precoat pump bottom bush bearing failure is a common occurrence because dirty sulphur is taken from the pump discharge for the lubrication of the bush bearing. This has been reduced considerably by providing a coarse mesh upstream of the pump to remove the dirt from the molten sulphur which is the main cause of the bearing failure. The failure of sulphur lines can be reduced to a great extent by providing a tangential steam connection to the jacketed sulphur lines. This avoids direct impingement of steam on the inner pipe of the jacketed sulphur lines. The ash carried over from the sulphur filters of acid plants is the main cause of dust problems and the consequent increase in pressure drop in the catalyst bed in the converter. The major portion of pressure drop in a sulphuric acid plant is contributed by the pressure drop in the converter and this has a direct effect on the power requirement. Long shutdowns of sulphuric acid plants are mainly intended for sieving the catalyst for dust removal. The performance of the catalyst after sieving will deteriorate to some extent as mixing of catalyst occurs. The ash carry over can be contained to a great extent if the ash carry over from the sulphur filter is controlled. Often, not enough attention is paid to this. Carry over can be controlled by properly maintaining the sulphur filter as well as the quality of the sulphur fed to the filters. Pressure leaf filters are normally used for filtering the ash in sulphur. Every time the filter is cleaned, the leaves should be inspected for damage. If any damage is found on the leaves, they should be replaced without delay. The major factor affecting the life of filter leaves is the corrosion problem due to acidity in the sulphur. The acidity of sulphur

has to be checked and neutralized on a continuous bases to ensure proper functioning of the filter and long life of the filter leaves. Gas to gas heat exchangers The conversion efficiency of a sulphuric acid plant depends to a great extent on the performance of the gas to gas exchangers. Tube leaks due to corrosion is the major factor affecting the exchanger performance. Tube leaks can contribute to mixing of converted gas with unconverted gas. The analysis of gas at the inlet and outlet of the heat exchanger should be taken when the S[O.sub.2] content is found to be high. One of the possible reasons for deviation of the in temperature from design figures is due to tube leaks in exchangers. During major shutdowns the tube to tubesheet joints and tubes have to be replaced or plugged. During short shutdowns, visual inspection of tubes and tube to tubesheet joints have to be carried out. Converter During normal operation, the performance of the converter is observed with respect to the temperature rise in each bed and the pressure drop across each bed. The most important factor to be controlled is the inlet temperature to the catalyst bed of the converter. The lower the inlet temperature to each bed, the better is the conversion efficiency. The inlet temperature to each bed should be maintained just above the biting temperature, which is the temperature at which the catalyst is active. Prolonged operation of the converter at higher inlet temperatures than required will have an adverse affect on the activity of the catalyst. The catalyst will no longer be active at the lower temperatures at which it was operated. This damage is irreparable and hence the inlet temperature to the catalyst beds should be maintained at the optimum level. The pressure drop across the converter catalyst beds should be checked regularly to ensure no channelling or dust build up in the catalyst bed. Leakage across partition plates should also be checked by gas analysis. During major plant shutdowns, the brick lining on the sides of the converter may also be checked. After sieving, it should be ensured that the catalyst is filled to the required quantity. Waste heat boiler system

The gas from the sulphur combustion furnace, which is at around 10001,200 [degrees] C, will normally be cooled to the required temperature in the waste heat boiler system. As furnace gas contains small quantities of S[O.sub.3], it is possible for occlusion in between the tubes to ferrule area, which can lead to corrosion and subsequent damage of the tube to tubesheet joints in the case of a fire tube boiler. Refractory work at the inlet to the waste heat boiler system should therefore be done properly during erection of the waste heat boiler system itself. The gas outlet temperature from the economizer/final heat exchanger upstream of the intermediate absorption tower/final absorption tower should not be allowed to go below the dew point of S[O.sub.3] which is in the range 180 to 220 [degrees] C. The temperature of the inlet gas to the intermediate absorption tower, i.e. the outlet gas from the economizer, should be in the range 180 to 220 [degrees] C, whereas for the final absorption tower, the range is 150 to 200 [degrees] C. If these temperatures are not maintained, S[O.sub.3] condenses and there is a consequent risk of corrosion and damage of equipment upstream of the absorption tower. Absorption section Many of the problems associated with sulphuric acid plants is due to the corrosive nature of sulphuric acid, especially when it becomes dilute. Emission of mist and its control The functioning of the air drying tower and absorption towers forms one of the critical areas of concern. The moisture, if carried away from the air drying tower, forms acid/acid mist when it reacts with S[O.sub.3], which is carried to the catalyst beds and downstream equipment. The acid mist settles on catalyst beds as well as equipment during shutdowns of the plant if proper purging is not carried out and can adversely affect the catalyst life and activity as well as causing corrosion of equipment. The moisture carry over from the air drying tower can be controlled within tolerable limits if the drying tower is properly inspected and operated. In the case of the intermediate and final absorption towers, high efficiency mist eliminators are required to eliminate the mist carry over. Mist carry over from the intermediate absorption tower damages the catalyst in the fourth bed and causes corrosion of downstream equipment, whereas in the case of the final absorption tower it leads to pollution of the atmosphere. Possible reasons for high mist carry over are: * bypassing of mist eliminators

* improper acid distribution resulting in high mist loading of mist eliminators and thereby carry over of mist from the mist eliminator * low acid circulation rate * variation in the acid concentration maintained in the tower. Bypassing of mist eliminators Bypassing problems can occur if the mist eliminator is not properly installed. There can be gaps between the main structural part of the mist eliminator and the mist eliminator itself. Whenever maintenance work on mist eliminators is carried out, it should be ensured that no passage is given for air/gas channelling through the mist eliminator. In candle type (standing) mist eliminators where the liquid seals are extended to channels, gas channelling can occur if the gaskets are not fixed properly. For candle-type (hanging) mist eliminators, gas channelling can occur if the liquid seal at the bottom of the mist eliminator breaks. Damage such as shrinking can occur to mist eliminators made of PTFE or equivalent material, if hot gas backing occurs from the furnace when the drying tower is located after the blower. Corrosion of the mist eliminator and subsequent channelling can also occur if a demister pad of SS 316 or such materials are used, which are corroded by dilute acid. The pressure drop across the mist eliminator will be low compared to normal figures if channelling is there, hence this is a good indication of channelling. The pressure drop across the mist eliminator should be taken at least once a day and if the pressure drop falls suddenly, inspection should be carried out and any necessary repairs/replacements made. Poor acid distribution Proper acid distribution is one of the most important parameters for efficient tower performance and for controlling mist carry over. During erection of the tower, it should be ensured that the acid distribution channels, if the distribution is via channels, are properly levelled. Improper levelling of the acid distribution channels can contribute to poor acid distribution. Acid distribution can also be adversely affected if distribution pipes from the channels are not properly fixed. It should also be ensured during erection itself that the size of the orifices installed in the acid distribution pipes are correct to ensure proper distribution.

Improper connection at joints between channels and distribution pipes can lead to splashing of acid from distribution pipes/channels and subsequent high mist carry over. Low acid circulation rate The acid circulation rate should be sufficient to ensure proper drying/absorption. Low acid circulation rate due to blockage in the pump suction/discharge lines can contribute to low circulation rate which would adversely affect the drying/absorption efficiency which may lead to high mist carry over. A low motor load indicates low acid circulation rate. Wear and tear of impellers can also contribute to low circulation rate which is a gradual phenomenon. Acid concentration Acid concentration maintained in the tower plays a vital role in controlling mist especially in the absorption tower. This is due to the peculiar vapour pressure property of sulphuric acid against temperature. The vapour pressure of sulphuric acid is at its lowest at about 98.4 to 98.7%. The vapour pressure of sulphuric acid is greater at any concentration above or below this range. The vapour formed on the liquid surface forms mist in combination with S[O.sub.3] which is very fine in nature and very difficult to separate, even with high efficiency mist eliminators. High acid concentration will lead to carry over of unabsorbed S[O.sub.3], leading to lower efficiency. Continuous monitoring of acid concentration with control arrangement is required for maintaining the concentration of acid within limits. Channelling of packed bed Packed bed support failure and consequent collapse of packings can contribute to channelling of air/gas flow. A sudden reduction in pressure drop is an indication of channelling in the packed bed. Sometimes the collapse of packings can block the entire passage of air/gas flow, in which case the pressure drop in the bed becomes extremely high. The pressure drop across the packed section of the tower should be checked at regular intervals. A fall in pressure drop across the packed bed is an indication of channelling. Whenever a fall in pressure drop across the tower occurs and high mist carry over is noticed, the tower should be inspected at the earliest opportunity. Unconventional but successful maintenance practices

Maintenance problems are dealt with to minimize production loss. Some unconventional but successful methods adopted for maintenance which may be of interest to readers are given below. A tower bottom acid leak was rectified by inserting a plate at the bottom and welding it to the tower to enable continued production until the long planned shutdown. The entire tower was lifted using jacks for inserting the plate. This was successfully implemented in a 1000 t/d sulphuric acid plant. Expansion bellow leaks on the gas ducts were stopped by making a gas box around the bellow. This arrangement required shutdown for a short period only. FRP coating was provided to contain the leakage of gases with a temperature of less than 200 [degrees] C. This arrangement required a shutdown for a short period. To reduce down time, acid leaks at flange joints were rectified effectively by providing a box filled with acid proof mortar at the flange joint, especially at equipment nozzle flanges. To avoid maintenance and operation of two pumps, i.e. the sulphur precoat pump and filter feed pump, these two pumps were combined in a single pump to carry out both duties. This arrangement has been working successfully in two 1000 t/d sulphuric acid plants. COPYRIGHT 1999 CRU Publishing Ltd. This material is published under license from the publisher through the Gale Group, Farmington Hills, Michigan. All inquiries regarding rights should be directed to the Gale Group.

Title: Plants get clean and lean: sulphuric acid producers around the world are operating at full capacity in response to buoyant global demand. The industry is also increasing its efficiencies while addressing major concerns about its contribution to the environment. Some of the key issues and technological advances are described here. (SULPHURIC ACID TECHNOLOGY) Date: 5/1/2006; Publication: Fertilizer International; The production of sulphuric acid accounts for around 90% of world sulphur-in-all-forms use, the vast majority being produced on site for captive use. The main component of internationally traded sulphuric acid is by-product material from base metals smelters, produced as a means of reducing sulphur dioxide emissions. (World Sulphuric Acid Situation, Mike Kitto, British Sulphur Consultants. Paper presented at

Sulphur 2005, October 2005.) Out of a total world output of 185.0 million tonnes [H.sub.2]S[O.sub.4] in 2004, world production of smelter acid totalled 46.3 million tonnes [H.sub.2]S[O.sub.4], representing 25% of total new acid production. Fig. 1 gives a breakdown of world sulphuric acid production by raw material. World smelter acid production rose from 29.0 million tonnes [H.sub.2]S[O.sub.4] in 1994 to 46.3 million tonnes [H.sub.2]S[O.sub.4] in 2004, an increase of 17.4 million t/a at a compound growth rate of 4.7%/year. This far exceeded the rate of output growth of base metals during this period and reflected the added pressure on smelter operators to improve their sulphur capture efficiency. Further substantial increases in smelter acid production are expected during the next ten years, to reach a forecast 70.3 million tonnes [H.sub.2]S[O.sub.4] by 2014--an increase of 23.9 million tonnes at a compound growth rate of 4.2%/year. This is a lower rate of growth than the 4.7%/year recorded between 1994 and 2004. One reason is that more and more smelters are achieving satisfactory levels of sulphur capture of above 90%. The rate of increase of acid production is therefore becoming more of a function of base metals demand. The sulphuric acid industry has inaugurated a wholesale range of improvements across the entire production spectrum, and sulphuric acid process and equipment technologies have had to adapt in response to several factors: * Economies of scale have resulted in the construction of ever-larger plants. * Advances in metallurgical smelting technology have led to higher sulphur dioxide (S[O.sub.2]) concentrations in smelter off-gases. * The use of caesium-promoted catalysts has resulted in changes in converter process constraints. * More stringent environmental standards have required the adoption of the double absorption process. The industry has paid particular attention to environmental issues. Indeed, the sulphuric acid industry can no longer be viewed as a significant contributor to sulphur dioxide pollution, and following recent developments in design, simulation packages and mist eliminators, acid plant emissions of S[O.sub.2] to the environment are minimal. Other environmental issues such as the conservation of water are also being addressed. Modern sulphuric acid plants are based on the contact process using a vanadium pentoxide catalyst and are designed and built with reliability as a key factor. (Acid Plants Address Environmental Issues, Sulphur, No. 298, May/June 2005, p33.) Computer aided design technology (CAD),

simulation packages and improved materials developed in recent years have led to more reliable acid plants. The process technology for the manufacture of sulphuric acid varies according to the source of S[O.sub.2] gas. Basically, there are two types of acid plant: * Those that use dry S[O.sub.2] gas, for example, from elemental sulphur. In these plants, the air is dried before use in the sulphur burner. * Those that use wet gas as in the case of copper, zinc and lead roasters or from hydrogen sulphide plants. In these plants, wet gas is required to be cleaned and cooled in a series of scrubbers and electrostatic precipitators and finally dried before entering the contact plants. The production of sulphuric acid became increasingly the subject of public concern because of S[O.sub.2], S[O.sub.3] and acid mist emissions, and in order to foster better public relations, acid producers have endeavoured to eliminate such emissions. A polluting plant is also an inefficient plant, as the amount of S[O.sub.2] emitted is inversely proportional to the conversion efficiency. The conversion is affected by the following factors: * Number of stages in the catalytic converter * Amount of catalyst used * Temperature and pressure * Concentration of reactants (S[O.sub.2] and [O.sub.2]) * Catalyst bed temperatures during start-up. In the conventional process, the fourth pass, which operates at 410430[degrees]C, was found to be inadequate to convert the last traces of S[O.sub.2] to S[O.sub.3], as a result of thermodynamic and equilibrium restrictions. The DCDA (double catalyst, double absorption) system was devised to employ a fifth pass. The new DCDA system also provided an extra stage of cooling between the fourth and fifth passes and introduced additional air to cool gases to 380 [degrees]C. Another innovation has been to employ a low bite catalyst, which can guarantee a stack analysis of below 100 ppm. A wide variety of sulphuric acid catalysts are available to meet different conditions. For example, MECS, Inc. (formerly known as Monsanto Enviro-Chem Systems) offers eight different types of catalyst for various applications and systems. The most commonly specified catalysts are the LP (Low Pressure Drop) ring type catalyst. Caesium-promoted CS type catalysts were introduced in 1990. These have higher activity and lower strike temperatures (low kindling temperatures) than standard catalysts. This

catalyst allows high strength S[O.sub.2] to be used, thereby reducing the power required to drive the gas through the plant. The recently introduced MECS XLP catalyst has been specifically designed for pressure drop reduction in all beds of the converter and is available for use in both upper and lower beds. Installation of the XLP catalyst will result in a pressure drop decrease of 25% or more and approximately a 10% reduction in pressure drop relative to the standard rings. MECS has also devised the SCX-2000 catalyst, which is an extremely active, newly formulated caesium catalyst designed for the lower beds of the converter. It has been formulated specifically for lower pass applications with or without interpass absorption. The enhanced support structure of the SCX-2000 catalyst generates the maximum conversion while maintaining low screening losses. During any sulphuric acid plant startup, stack emissions are higher than during normal operation. With the increased pressure from regulatory authorities, existing sulphuric acid plants are being required to install an alkali scrubbing system. A well-designed alkali scrubber can accommodate the high lead on the system during the unsteady early stages of the start-up operations. However, alkali scrubbers are not economically viable on a continuous basis, and a modified DCDA system using five passes instead of the conventional four has been found to be more attractive. Tackling the undesirables Greater attention is also being placed on the recovery of undesirable components, in particular S[O.sub.2]. Sulphur dioxide abatement by scrubbing consists of a chemical reaction between S[O.sub.2] and a basic fluid solution. This operation is achieved generally in a gas/liquid contact packed tower or scrubber. A liquid circulation loop is operated from the bottom to the top of the tower, where the liquid is distributed above the packing. The gases enter the bottom part of the tower, contact and react with the basic liquid solution on the packing. The S[O.sub.2] content in the outlet gases is achieved by controlling the pH of the solution and by adding more or less basic concentrated solution into the liquid concentration loop. Various products can be used as scrubbers, including ammonia, caustic soda, magnesium and calcium hydroxide. The Koch-Otto York division of Koch-Glitsch LP has developed a patented Safety Scrubber[TM] safety housing, which provides an excellent combination of cost, pressure drop, efficiency, ease of servicing and safety. Mist eliminators can be maintained and changed without entering the tower. Koch-Otto York also markets a comprehensive range of mist eliminators. These have traditionally been

supplied in Alloy 20 and plastics, including Teflon, but Alloy 66 is now widely used: this offers enhanced corrosion resistance in sulphuric acid. Efficient gas cleaning is essential to metallurgical plants with dirty feed gas. (Towers and Converters: Technology Review, Sulphur, No. 300, September/October 2005, p65.) Gas cleaning units located upstream of the acid plant typically use wet scrubbers and electrostatic precipitators to prepare the gas entering the acid plant. Poor acid mist removal in the gas cleaning unit will lead to downstream corrosion along with high acid consumption and higher maintenance cost in the drying tower. Koch-Otto York offers a range of Flexichevron[R] mist eliminators that offer excellent mist elimination combined with low pressure drop. Materials of construction include metal, polypropylene and other plastics. Fibre bed elements are the most commonly used mist eliminators in sulphuric acid production. The two types of elements typically used are Brownian DifFusion (BD) and Impaction Cylinder (IC). BD elements offer the ultimate separation, removing up to 99.9% of all submicron mist. The fibre used in includes glass, carbon, polyester, polypropylene and ceramic, according to process conditions. Koch-Otto York has enjoyed success using carbon fibre for applications involving fluorides, which typically dissolve the glass fibres. New designs using drainage layers significantly increase he capacity and reduce pressure drop of sulphuric acid absorption towers. IC elements are smaller in size and operate at higher bed velocities to separate entrained liquid by an impaction mechanism. MECS markets concentric fibre beds that were developed by Monsanto/Brink in the 1960s. Due to the increase in energy costs and a frequent need to debottleneck operations, the concentric design has gained popularity. This design replaces conventional mist eliminators with what is an element inside an element, or concentric design. The internal element is in opposite orientation to the main mist eliminator. The use of concentric elements can lead to lower pressure drop by as much as 30-40+%. Another method of achieving higher capacity and/or lower pressure drop is to use smaller diameter filter beds. These beds have a smaller outer diameter than conventional beds and provide an increase in capacity of 45 % or more in comparison with an installation of conventional sized fibre beds. The advantage is due to an increase in fibre area that is achieved by having a larger number of individual fibre beds in a specific tower volume. The small diameter fibre beds are lighter and easier to handle than conventional or concentric beds. CECO Filters pioneered the concentric nested filter design, reinforcing the company's role in providing the latest technology in fibre bed mist eliminators and mesh pads for sulphuric acid mist capture in sulphuric acid drying and absorption towers. In 1990, CECO Filters introduced the

patented Twin-Pak[TM]. This provides up to 60 % greater surface area in the same space as a single candle and can also be retrofitted into existing candles. The TwinPak[TM] system offers benefits in terms of increased absorber throughput, reduced pressure drop and lower installation costs. In 2005, CECO Filters became a licensee of the VKR Enhanced[TM] mesh pad. This was originally introduced in 1995 and is an industry leader in terms of high flow/high efficiency mesh pad technology, which can increase liquid handling capacity by up to 300% and vapour capacity by up to 20%. CECO's latest innovation is its proprietary graded bed filter. The graded bed concept incorporates multiple layers of low-, medium- and highdensity media to maximise sub-micron collection efficiency while improving liquid drainage and, where insoluble sulphates are collected, extending filter life. The graded bed media can be provided via new filter elements or re-packed on to existing element cages. Begg Cousland has extensive experience in the manufacture of knitted wire and mesh pad type demisters, and fibre bed candle filters. The Becoil demisting unit is a high efficiency, low-pressure loss device for removing liquid particles of >5 microns. To help the collection efficiency below 5 microns, the Becone coalescer has been devised. The unit is made from composite/ knitted monofilaments and staple fibre yarn. These fibres are much smaller in diameter than either the yarn into which they are spun or the monofilaments, thereby forming a more efficient filter. The multitude of fibrous ends presented to the gas flow traps fine droplets within the coalescer and coarse droplets so formed are re-entrained in the gas stream leaving the coalescer. They are then removed by the Becoil demister. The combined Becone and Becoil installation increases collection efficiency to above 98% in the 25 micron range. Increasing plant capacities As smelters worldwide seek to meet the exceptionally buoyant demand for their products, they are operating at full capacity. Sulphuric acid plant operators are under greater pressure to raise capacity to meet this and forecast increases in demand, and to improve operating efficiencies. Retrofitting new equipment provides an opportunity to raise plant capacity with minimal capital expenditure or long-term disruption to production, and the investment will most likely earn a quick payback in terms of savings through reduced pressure drop or gains via additional heat transfer surface and/or higher volumetric capacity. (Increasing Acid Plant Capacities, Sulphur No. 301, November/December 2005, p35.) There are modern choices of equipment that can be installed in a very short period, helping to minimise a shutdown. For example, modern

radial flow gas- gas exchangers can be beneficial, due to their high efficiency heat transfer surface. This enables the replacement exchanger to be physically smaller than the existing unit, thus assisting with crane access and costs. Another example is the use of stainless steel towers to replace brick-lined units. The lighter steel unit can be lifted into place fully fabricated. MECS, Inc. has completed over 100 retrofit projects for sulphuric acid plants. In one project, the remit was to reduce emissions while improving process control with varying gas strength. The gas strength to this 730 t/d sulphuric acid plant varied from a maximum of 10% S[O.sub.2] down to 0-1% S[O.sub.2], which made the ability to maintain the heat balance and S[O.sub.2] conversion very difficult. The existing plant could not maintain the converter at the optimum temperatures, and so the overall conversion of S[O.sub.2] frequently fell short of target. MECS tackled the problems by converting the existing oleum tower into an intermediate absorption tower, changing the plant to a 3-1 double absorption system (with the intermediate absorption tower located after the third pass). MECS incorporated an indirect fired preheater to provide supplemental heat when the gas strength was lower than the autothermal point. In addition, a number of discreet bypasses at the converter and gas heat exchangers allowed for better balance and conservation of the available process heat while minimising the use of the fired preheater. This new design allowed the system to operate at a much more steady state condition than previously. The project also included a new stainless steel converter, all new MECS catalyst, new MECS mist eliminators, and all new gas heat exchangers. Modifications to the existing main compressor, acid coolers and acid towers were made in order to support the overall goals. The plant was recently started up and is reported to be operating successfully. (Acid Plant Revitalisation, Sulphur No. 303, March/April 2006, p58.) Haldor Topsoe has been involved in debottlenecking various sulphuric acid plants around the world. Many of these revamps have involved the installation of Haldor Topsoe's caesium-promoted catalyst, VK69. This has been designed specifically for operation in the final passes of double absorption plants, reducing S[O.sub.2] emissions by more than 50%. One such installation was in a phosphate fertilizer plant in Florida. This facility has four large sulphuric acid plants based on sulphur burning. The company was faced with the need to increase sulphuric acid production to meet the requirements of the phosphoric acid plant. The sulphuric acid installation dated from the 1970s and was designed with a capacity of 1,361 t/d and an S[O.sub.2] emission permit of 2kg/c The plant has a 3-1 layout, and subsequent debottleneckings have raised the design capacity to 2,359t/d. However, production rarely matched capacity in recent years. The plant was typically operating at around 11% S[O.sub.2] feed gas strength, but by increasing the gas

strength from 11 to 12% S[O.sub.2], the plant could increase production rates by around 10%. On the other hand, the higher gas strength would correspondingly decease the [O.sub.2]/S[O.sub.2] ratio from 0.91 to 0.75, thereby providing less favourable gas conditions at the inlet of the converter and increasing the load on the catalyst. Haldor Topsoe concluded that the only way to achieve the increased production rate at a higher S[O.sub.2] gas strength and with lower emissions and at the lowest possible pressure drop would be by installing the caesium-promoted VK69 catalyst in the fourth bed. This was duly done and when the plant resumed production after turnaround, it averaged 2,424 t/d and an S[O.sub.2] emission of 1.75kg/t. Feed gas S[O.sub.2] strength of 12.2% was also achieved. Noram Engineers and Constructors recently completed a project to replace a converter in a 1,000 t/d sulphuric acid plant. The stainless steel converter was shop fabricated in sections and included an internal heat exchanger. All sections were shipped to the site and assembled at a location adjacent to the existing converter. Removal of the old converter and tie-in of the new converter were completed in less than three weeks. Over the past eight years, Noram has replaced nearly all the original equipment at the facility while expanding the plant capacity by about 30%. The employment of Computational Flow Dynamics (CFD) modelling techniques enabled Noram to plan and test the merits of plant modifications and upgrades before any commitment to major capital expenditures. One design challenge in the above case study was the by-pass duct around the hot exchanger that was required to control the fourth bed inlet temperature. Two process options were considered, the first reusing the existing conventional catalyst at a design inlet temperature of 425[degrees]C, the other for a future case where caesium catalyst would be used at a lower inlet temperature of 390[degrees]C. The latter would require considerably more bypassing. Other design issues also had to be addressed. For example, the relatively cool bypass S[O.sub.2] gas from the cold exchanger had to be blended with the hot S[O.sub.2] gas, leaving the internal hot exchanger to result in a uniform inlet temperature to catalyst bed 4. CFD work looked at six options, and revealed that very small changes in duct geometry could have significant effects on the temperature patterns in critical areas. The above case studies represent just a handful of many recent success stories in the sulphuric acid industry, where producers and the suppliers of technology and specialised equipment have joined forces to forge a global industry that is leaner and cleaner.
Figure 1: World sulphuric acid production 2004

Total 185.0 million tonnes [H.sub.2]S[O.sub.4] Brimstone Smelter gas Pyrites Other 65% 23% 9% 3%

Source: British Sulphur Consulatants Note: Table made from pie chart.

COPYRIGHT 2006 CRU Publishing Ltd. This material is published under license from the publisher through the Gale Group, Farmington Hills, Michigan. All inquiries regarding rights should be directed to the Gale Group.

Title: Chile expands smelter acid production: Chile's domination of smelter acid production in South America is scheduled to accelerate in the coming decade, and so is the country's demand for sulphuric acid to feed northern leaching operations. Date: 9/1/2006; Publication: Sulphur; Production of smelter acid in South America is dominated by Chile, which produces around three-quarters of the continent's output, mainly from smelters operated by the state copper company Codelco. However, and in spite of its status as a world-leading producer of smelter acid, Chile is a net importer. The country's maturing copper industry relies increasingly on leach operations based on copper oxide ores, hence the balance between acid-producing smelters and acid-consuming leach operations increasingly favours the demand side. Additionally, the largest exploitable copper oxide deposits are found in the north of the country whilst the greater part of smelter acid output is significantly further south, so the costs of transporting Chilean smelter acid to leach operations are high. Acid terminals The country has eight acid-handling terminals among its ports, with a combined capacity to store almost 340,000 tonnes of product. Development of these terminals has certainly helped to ease the

movement of sulphuric acid by-product from central Chile to the northern regions where it is needed for leaching operations. However, the expected scale of development in the north's leaching operations is almost certain to demand more and bigger terminals, or significantly higher imports. Chile's copper industry, and therefore the nature and size of its acidproducing and--consuming operations, is set for dramatic changes during the coming 10 years. Codelco has in place a set of plans which are expected to lead to a 60 per cent expansion in output and which include significant growth in its smelting operations. Sulphur burning Less definitely, other copper-producing companies with operations in Chile are looking to expand, from a relatively small base, the amount of acid supplied to leach operations from sulphur-burning plant. The currently heated economics of the copper industry probably do not help any decision regarding capital commitment to new-build sulphur burners. Following a commissioned review of its business in 2005, Codelco outlined its view of future operations. The company expects to produce around 2.7 million t/y of LME grade copper by 2012, eventually 3 million tonnes by 2015, from an output level at the beginning of this year at around 1.8 million t/y. Such a steep rise in output will call for hefty investment by Codelco. For instance the company will expand its Chuquicamata concentrator in the Norte Division to 300,000 t/d output, from a current level of 185,000 t/d, and will expand the output of associated mines. Local smelter capacity would rise from 1.65 million t/y of concentrate to 2 million t/y along with roughly similar extra production of sulphuric acid. Bioleaching In its Andina Division, Codelco wants to expand the capacity of its concentrator from 72,000 t/d to 260,000 t/d. The same division also wants to exploit the parent company's recent investment, along with Japanese mining companies, in bioleach technology by the end of this decade. Bioleaching, in which organisms digest sulphide ores, is effectively acid-neutral. A significant expansion of this technology would, in the long term, have a significant effect on the supply side of sulphuric acid trade in Chile. However, one local attempt to develop a copper business based on biotechnology was recently deemed uneconomic. Another technology which may have a big part to play in the copper industry is atmospheric leaching of low-grade sulphide ores. This too has a limited part to play in acid supply-demand and--as is the case

with a potential project in Botswana (see Industry News, this issue)-can obviate the need for smelter operations. Codelco's El Teniente mining operation wants to develop deeper operations, as part of the company's plan, and the division is also slated to expand its concentrator to an output of 250,000 t/d, from a current 125,000 t/d. The net effect would be the production of 600,000 t/y of LME grade copper (currently 437,000 t/y) by 2020. Gaby project On a similar level of ambition, but on the debit side for Codelco's acid balance, the Gaby Project--some 100 km south of the El Teniente mine and smelter--involves the exploitation of 584 million tons of copper oxide ore through an initial investment of $766 million. Codelco estimates total investment is estimated at $898 million throughout its useful life. With its environmental permits in place, the mining/leaching project started up in February and is expected to be completed at the beginning of 2008. Some 90 per cent of the Gaby mine's reserves are proven, according to a basic engineering study, with a mean grade of 0.41 per cent copper, and an expected useful life of 14 years. Codelco subsequently commissioned mining and plant studies from Aker Kvaerner, SNC-Lavalin and Metalica to support its decision to go ahead with Gaby. The exploitation process will be similar to those used at other Codelco leaching operations, with an annual production of 150,000 tonnes of LME grade copper. Two options The expansion of its existing concentrator and smelter operations was one of two options considered for come time by Codelco with the aim of doubling its value. The company's first plan, now apparently abandoned, was to build a new and very large smelter at Mejillones in the north of Chile. However, according to British Sulphur Consultants*, all of the existing smelters in Chile have achieved marked improvements in their ability to capture sulphur dioxide for the production of sulphuric acid, but stresses that there is still some way to go. Planned and ongoing expansion projects point to strong growth in Chile's production of smelter acid, from 4.6 million tonnes in 2004 to an estimated 6.7 million t/y by 2014. It is worth noting that Chile actually consumed about 4.9 million tonnes of acid during 2004, as good an indication as any of the pressure applied to the country's acid balance by expanding copper oxide leaching operations.

Lion's share Seven copper smelters in Chile account for the lion's share of acid production. However, the country has a history of sulphur-burning, albeit on a far smaller scale. For instance, a sulphur-burning plant in Region I was shut down at the beginning of this decade, re-started two years later, and its operator, Haldeman Mining, is currently producing some 140,000 t/y of sulphuric acid for local leaching operations. The same company may well build a second sulphur-burning plant, with a higher capacity, to serve an expansion of its leach operations in Region I. Meanwhile other companies are examining the possibilities of building large-scale sulphur burners in northern Chile. Sulphur understands that one of these companies is a leading name in international mining. * Sulphuric acid: ten year forecast and market analysis service, annual report to 2014. British Sulphur Consultants Division of CRU COPYRIGHT 2006 CRU Publishing Ltd. This material is published under license from the publisher through the Gale Group, Farmington Hills, Michigan. All inquiries regarding rights should be directed to the Gale Group.

Title: Upgrading virgin acid plants using oxygen: interest is growing in the use of oxygen enrichment to upgrade sulphur burning sulphuric acid plants, to increase production or reduce costs. Derek Miller and Uday Parekh of Air Products and Chemicals Inc. describe oxygen enrichment, its application for acid production and the potential economic benefits.(Oxygen Enrichment) Date: 1/1/2004; Publication: Sulphur; Author: Parekh, Udah The sulphuric acid market has been experiencing severe supply instability in several parts of the world over the past year. This is due to a host of market forces, foremost among them being the reduced supply of smelter acid due to the shutdown of several smelters, at the same time that phosphate fertilizer plants, the largest users of sulphuric acid, are experiencing high operating rates. The situation is further exacerbated by sporadic sulphur shortages, price increases of this key raw material, and increased sulphur demand from China for fertilizer production. The net effect is an increase in the price of merchant acid and increased interest in boosting sulphuric acid production rates for merchant or captive use.

Oxygen enrichment has been used by many industries to economically increase the capacity of air -based processes. Traditional applications include sulphur recovery, fluidised catalytic cracking and sulphuric acid regeneration. Oxygen enrichment is routinely practiced to provide additional capacity without the expense of a new unit or a major facility upgrade. There is increasing interest in the use of oxygen enrichment to upgrade virgin sulphuric acid production. The addition of oxygen enrichment to a sulphuric acid plant can significantly enhance overall profitability when merchant prices are high. Oxygen enrichment for sulphuric acid manufacture Oxygen enrichment may be considered for sulphuric acid plants, on either a short-term or long-term basis. Reasons include: * Cost reduction through displacement of merchant acid consumption. Where acid requirements exceed on-site acid production and merchant acid prices are high, oxygen enrichment can be used to reduce overall operating costs. * Cost reduction through shutting down production capacity. Where multiple sulphuric acid plant trains are in operation, it may prove to be economical to shutdown one train and boost remaining production through oxygen enrichment. * Profit enhancement through incremental acid production. Where acid can be exported to the merchant market and prices are high, it may be attractive to boost acid production through oxygen enrichment and increase export. * Profit enhancement through incremental final product. Where sulphuric acid is used in the production of another product, oxygen enrichment can boost final product rates when merchant acid supplies are tight. A highly simplified process flow diagram for a typical sulphur burning sulphuric acid plant is shown in Figure 1. Molten sulphur and excess dry air are introduced to the furnace where sulphur dioxide is produced. Heat from the exothermic process is removed in the waste heat boiler and then the sulphur dioxide is reacted with the remaining oxygen in a four or five pass converter to make sulphur trioxide. The sulphur trioxide is adsorbed into sulphuric acid in two adsorption towers one between the third and fourth stage of the converter, the other after the last stage. The sulphuric acid is diluted with water to final product concentration and pumped to storage. The process generates a

significant amount of waste heat that is usually used to generate steam and electricity. [FIGURE 1 OMITTED] Process description: oxygen enrichment Typical limitations on combustion processes such as the sulphuric acid process are the amount of available combustion air or process equipment hydraulic limits. When these limits are reached, there are several options that can be considered, if additional capacity is required: * Build a new plant. This is usually the most expensive option and is only considered when all other options save been eliminated and the desired increase in capacity is sufficient to justify the expenditure. * Replace the air blower with larger capacity equipment. This approach typically requires significant capital investment, since there will often need to be additional plant modifications made to accommodate the additional volume of gas to be processed and heat generated. Often pressure drop limitations make this option more expensive than it might first appear. * Add a supplemental blower. This option is similar to blower replacement, but potentially lower cost. One problem with this approach is that as extra air is added, backpressure increases and the capacity of the main blower is reduced, so full benefits are not realised. * Add oxygen. This option tends to be the most economical solution for many applications. Oxygen is added to the discharge of the air blower, through a specially designed diffuser. Adding oxygen increases firing capacity without significant increase in volume of gases to be handled. The addition of oxygen may also enhance process conversions/yields depending on how it is used. The amount of oxygen to be added is dependent on several factors, including: * desired maximum production capacity; * furnace temperature limitations; waste heat boiler limitations; * overall plant cooling limitations; * pressure drop limitations; * materials compatibility with elevated oxygen concentrations (the limit for conventional materials is 28% oxygen).

Typically the amount of oxygen required to make incremental sulphuric acid is about 0.5 tonne oxygen/tonne acid. For example, to get a 5% increase in production from a 2000 t/d acid plant, about 50 t/d of oxygen is required. If pressure drop is limiting, such that the total volume of gas through the process needs to be held constant, this ratio increases a little, since some air will need to be backed out, in order to reduce nitrogen to the process. An oxygen enrichment supply system consists of a source of oxygen, a flow control skid and a diffuser to introduce oxygen into the furnace air. The flow control skid and diffuser are specially designed to ensure safe operation along with excellent control and mixing. Proven systems are used to provide interlocks between the plant and the oxygen supply system to avoid adverse or unsafe conditions arising within the sulphuric acid plant. Technical considerations with oxygen enrichment Whenever oxygen is added to a furnace, certain key operating and safety criteria need to be addressed. Combustion becomes more intense, temperatures increase, more heat is generated and reaction product concentrations can change, based on new kinetic and equilibrium conditions. For sulphuric acid production, furnace temperatures and waste heat boiler loading are of primary importance. In order to be able to predict performance with oxygen enrichment, a process simulation may be prepared and analysed, using plant data and equipment specifications as input. The simulation provides information on furnace conditions, downstream heat recovery, product conversion, product capacity and stack gas conditions. It predicts how much oxygen is required to meet incremental production and the impact on existing process equipment, along with which process limitations, if any, are encountered. Often suggestions can be made to overcome identified plant limitations. The quality of the simulation is a function of available models and thermodynamic property information, matched with practical experience from applying oxygen enrichment at customer sites. Furnace temperatures as a function of oxygen enrichment level, for a typical sulphuric acid furnace, are shown in Fig. 2. [FIGURE 4 OMITTED] Choice of oxygen supply mode The correct choice of oxygen supply is critical in obtaining the best economics and is a function of several different parameters. There are four basic options to be considered.

* Liquid oxygen (LOX). This mode of supply is the most flexible. Oxygen is delivered as liquid by truck, from one of several central manufacturing facilities. A cryogenic LOX storage tank is installed at the site, along with a vaporiser, by the oxygen supplier. Oxygen is withdrawn from the tank and vaporised as required to meet process requirements. The tank is sized to ensure that there is always sufficient capacity to meet demand and is refilled by road tanker, as required according to on-tank volume information, communicated by telemetry to the LOX supplier. Product LOX usage and storage tank/ vaporisation rental fees are invoiced monthly. The major attraction of this mode of supply is that there is minimal up front investment and little in the way of on going commitment. Liquid oxygen can be consumed as required, at varying flow rates, continuously or intermittently. In addition, installation can be rapid (within 1-2 months) and LOX can even be used as a temporary supply until a longer-term solution is installed. The disadvantage of LOX is that it has a higher unit price. Typically LOX is used for volumes between 0-50 t/d and/or where demand is intermittent or not projected to be long term. See Fig. 3 for a typical installation. [FIGURE 3 OMITTED] * Oxygen vacuum swing adsorber (VSA). This mode of supply provides economical oxygen by onsite generation. The process separates out oxygen from the feed air by adsorption and subsequent desorption of nitrogen, moisture and carbon dioxide under vacuum. The oxygen typically has a concentration of around 90 to 95% and is compressed to the desired process requirement. To provide an uninterruptible supply, a backup LOX tank is typically included in the supply configuration. Vacuum swing adsorbers can either be purchased or a long-term supply agreement with the supplier established, where the customer purchases gas and the VSA is owned, operated and maintained by the gas supplier. In such an arrangement a long-term supply contract (10 15 years typically) is established and customers are invoiced a monthly service charge. There is clearly a longer-term commitment required than for LOX. Customer costs are relatively fixed, with the only variations due to changing power consumption with usage (power is typically about 1/3 total price). The advantage is lower oxygen unit pricing. A VSA is attractive where a relatively steady demand for oxygen is anticipated. Typically VSAs are used to supply 20-120 t/d. See Fig. 4 for a typical installation. * Oxygen cryogenic plant. This mode of supply also provides oxygen economically by on-site generation. Air is separated by cryogenic distillation into oxygen and nitrogen. Oxygen purity can vary between 95% and 99.8 % depending on customer need. For oxygen enrichment applications, 95% oxygen purity is often the most economical. Cryogenic plants are most attractive for larger supplies of oxygen. Opportunities for integration exist when co-products can be used, such as high purity nitrogen and clean dry air (CDA) or oxygen for other

applications at the same facility. Such approaches improve economics further. Onsite cryogenic plants typically have LOX backup to ensure 100% supply. The LOX tank inventory is maintained through a small amount of liquid production from the plant. As with a VSA, a cryogenic plant can either be purchased or a long-term supply agreement established to source oxygen from an industrial gas supplier. Typically cryogenic plants are used to supply 100-1,000+ t/d. See Fig. 5 for a typical installation. [FIGURE 5 OMITTED] * Pipeline. Should the customer site be located near an oxygen pipeline, this may be the most attractive mode of supply. Oxygen is generated off-site, by cryogenic plants, and fed to the pipeline. Available volumes will usually be high and prices low and often the supply can be provided with more flexible terms since investment is not entirely dependent on one customer. Typically pipelines supply from 50 t/d--1,000+ t/d. Economics of oxygen enrichment The following economic feasibility assessment for expansion of sulphuric acid production is based on generic published data, using typical industry oxygen prices of $85/t (35 c/100 scf) for LOX and $36/t (15 c/100 scf) for VSA Oxygen. Actual costs for oxygen will be site specific and are a function of volume, distance from liquid plant (for LOX) and cost of power (for onsite production). Calculations are based on the following assumptions: * The customer wishes to expand production of sulphuric acid. Capacity is currently limited and some merchant sulphuric acid is being purchased from external sources at an average $55/t. * For incremental production, only variable costs are to be considered. * It is assumed that there is no additional capital investment and that all other costs (such as maintenance and overheads) are fixed. * For incremental sulphuric acid production, it is assumed that credit can be taken for incremental steam and electricity production. The credit with oxygen is assumed to be the same as for air. In practice it may be slightly better due to enhanced heat recovery due to elevated furnace temperatures. Four cases are analysed: base case (air-based production); base case (merchant); oxygen enrichment using LOX; oxygen enrichment using VSA Oxygen. Results of the analysis are given in Table 1. Conclusions from economic assessment

Usually, the most economical method for producing acid is to load up existing sulphuric acid production to maximum capacity. Once this limit is reached, the choice is between purchasing merchant acid and upgrading the plant through oxygen enrichment or other route. An exception might be where multiple units are currently being operated and there is an opportunity to shut one unit down, by implementing oxygen enrichment on the other units. Both LOX and VSA supply modes can provide incremental sulphuric acid at prices that are competitive with typical merchant prices. For LOX, the breakeven point is around $40-45/t acid. For VSA, the breakeven point is around $20-25/t. Using Oxygen can enhance profitability of incremental production significantly, when merchant sulphuric acid prices are high. Using Oxygen need not require a long-term commitment to be justified. If there are short term concerns regarding the availability or price of merchant sulphuric acid, oxygen should be considered even if only used on a temporary basis (for temporary use, LOX is usually preferred for best overall economics. For a 2,000 t/d sulphuric acid plant, producing an incremental 5% capacity using oxygen can result in annual savings in the range $350,000 to $1,300,000, depending on merchant acid prices and chosen mode of supply for oxygen. Production of additional downstream products, such as phosphoric acid, with this additional sulphuric acid can significantly add to plant profitability. Project execution A staged approach to introducing oxygen enrichment is recommended, since there are a number of issues that need to be adequately addressed if oxygen enrichment is going to be commercially and technically successful. Economic feasibility The first step is to perform a preliminary economic assessment to determine whether the addition of Oxygen is going to be economically attractive when compared to alternatives. The customer and industrial gas supplier work together, to determine the best options for upgrading the plant. For oxygen enrichment, a key issue is the mode of supply. Unless a pipeline is located nearby, the choice is between LOX and an on-site oxygen generator. Factors to be taken into account include: * Continuous vs intermittent oxygen requirement; * The volume of oxygen required;

* Whether any co-product Nitrogen or CDA can be used at the site; * Distance from gas suppliers liquid plant; * Cost and availability of power; * Level of certainty that volumes will be required for long term; * Customer preferences to purchase generation equipment or gas. Often an approach is taken where LOX is used initially--say first year. The customer operates the facility with oxygen enrichment and assesses its effectiveness. At the end of this initial period a decision is made either to continue using LOX or convert to an on-site. Technical feasibility It is important to understand the impact of oxygen addition to the process. A process model of the sulphuric acid plant may be prepared and used to determine critical process parameters such as furnace temperature, waste heat boiler performance and overall heat & material balances around the facility. This information is used to assess technical feasibility and to define critical parameters for the site trial. Site trial Assuming that the project looks economically attractive, the next step is usually to perform a limited period site demonstration. After safety reviews and training, a temporary LOX tank installation is placed at the site, along with a flow control skid. The oxygen diffuser is installed in the air blower dis charge (this is usually hot-tapped, so no shutdown is required). The length of the trial is up to the customer, but is usually at least a week, with increasing amounts of oxygen added until the desired capacity or other limitation is reached. This is the final go / nogo point before implementation. First year operation Assuming that the trial is successful, the customer can immediately start using oxygen enrichment if LOX is to be used. Depending on the nature of the set up for the trial, the LOX system can be left in place or replaced with a permanent installation. If required, the industrial gas company can provide ongoing technical support to resolve any issues and enable trouble-free, efficient operation. It is recommended that audits be carried out at 6 and 12 months to review take patterns, process performance and any changes required to meet ongoing needs. Longer term operation

As part of the ongoing relationship between customer and industrial gas supplier it is suggested that alternative supply modes be reviewed after 12 months of operation to see which option will provide the most effective and economical solution longer term. This will be based on actual use patterns during the first year of operation and projections on future needs. Since operating conditions vary from year to year, it is recommended that ongoing reviews (typically every 6-12 months) takes place between the customer and supplier. In addition, a service contract may be considered where ongoing technical support is made available to help provide safe, reliable and efficient oxygen enrichment operation. Overall conclusions For producers of sulphuric acid looking to increase production or reduce costs, the addition of oxygen can prove to be financially attractive and relatively straightforward to implement. It is important to work closely with an industrial gas supplier with a proven track record in oxygen enrichment, to successfully resolve the technical issues and identify the best implementation strategy and oxygen supply, based on expected use patterns, overall volumes and opportunities for integration.
Table 1: Overall variable cost at economics for incremental sulphuric production using oxygen enrichment Variable costs: Units Consumption/ lb acid Base case with no capacity limit $/1 acid 14.85 0.21 0.00 15.06 1.32 -6.86 0.15 -6.43 -11.83 3.23 Base case with merchant acid $/t acid OE with LOX $/t acid 14.85 0.21 42.50 57.56 OE with VSA $/t acid 14.85 0.21 18.00 33.06

Sulphur Catalyst Oxygen Sub total Cooling water Steam Process water Electricity Subtotal Total variable acid cost Variable costs:

2.25

c/lb lb

0.33 0.50 8.86 -0.60 0.068 -0.08

7.45 5.72 1.10 4.02

c/1000 gal $/1000 lb $/1000 gal c/kwh

Sulphur Catalyst Oxygen Sub total

Cooling water Steam Process water Electricity Subtotal Total variable acid cost 55.00

1.32 -6.86 0.15 -6.43 -11.83 45.73

1.32 -6.86 0.15 -6.43 -11.83 21.23

Generic costs from SRI Consulting PEP yearbook 2000. [O.sub.2] prices are typical industry values.

COPYRIGHT 2004 CRU Publishing Ltd. This material is published under license from the publisher through the Gale Group, Farmington Hills, Michigan. All inquiries regarding rights should be directed to the Gale Group.

Title: An exception to the rule.(cogeneration power plant in the Czech Republic produces sulphuric acid from desulphurization offgases) Date: 5/1/1999; Publication: Sulphur; Author: Vejvoda, Josef Despite the advantages of natural gas as a fuel, coal continues to be an important energy source in many countries. In this article, Petr Buryan and Josef Vejvoda of the Institute of Chemical Technology, Faculty of Environmental Technology, Prague, report on a cogeneration plant in Vresova, Czech Republic which produces sulphuric acid from desulphurization offgases. In the Czech Republic, electricity is generated predominantly by the combustion of pulverised coal. To comply with environmental regulations, power plants are retrofitted with flue gas desulphurization processes, the most widespread technology being wet limestone scrubbing which produces gypsum.[1-3] Almost all power plants use brown coal from local deposits. Sokolovska uhelna Utilities' power plant at Vresova is an exception. It produces electricity from brown coal using integrated steam-gas cycle technology. Formerly a gasworks producing town gas using the Lurgi pressurized moving bed gasifier process, the facility has now been converted to a power plant for the production of electricity and heat for surrounding towns and villages. The gasworks was constructed according to the know-how of Energoprojekt Prague and now covers two units with installed capacity of 185 M[W.sub.e] using Alsthom/General Electric combustion turbines which are fed by gas from Lurgi generators.

The units are used for the production of electricity in semi-peak or peak load regimes. They started operating at full scale production in 1993 and by 1998 had clocked up more than 30,000 hours of power generation. The power plant can be put into operation from cold and reach full operating capacity in 8 minutes. Prior to combustion in the turbines, the gas is desulphurized by the Rectisol process, a physical washing system which uses cold methanol as its solvent. Hydrogen sulphide, carbonyl sulphide and organic sulphur are absorbed in cold methanol at -65 [degrees] C. After solvent regeneration, the sulphur-containing gases are further processed to high quality sulphuric acid. Coal gasification is an upgrading process that converts the carbon content of solid fuel to gas by heterogenic reactions at temperatures of more than 600 [degrees] C. Oxygen and steam are used for gasification. When the gasification takes place at atmospheric pressure, the resulting gas contains carbon monoxide, carbon dioxide and hydrogen. At elevated pressure in the Lurgi gasification plant, the resulting gas contains methane in significant quantity. The combustion of gas with greater heating value is more economical and energy efficient. Gasification technology Coal gasification takes place in two 2.7m diameter Lurgi moving bed gasifiers. Brown coal that has been screened to 10-30mm diameter is gasified by a steam/oxygen mixture at a pressure of 2.5-2.8 MPa. The gasification ratio is 4-8 kg steam/[m.sup.3] of oxygen. Coal moves down the gasifier, passing through several zones, in counter current to the ascending oxygen and steam streams. In the first zone, a layer of hot ash heats the gasification mixture. In the next oxidation zone, strong oxidation reactions take place as a result of the high partial pressure of oxygen. The heat of reaction is utilized in gasification reactions in other zones of the gasifier. The gas stream from the oxidation zone is rich in carbon dioxide and enters a reducing zone in which predominantly heterogenic reactions take place. In the last two zones carbonization and drying take place. In the carbonization zone, tars and oils are formed from the volatilisation of coal. The tars and phenols are removed from the gasifiers in a system of condensers. Water from the gasified coal is evaporated in the drying zone. Figure 1 shows a flowsheet of the power generation technology. Desulphurization of gas

The desulphurization unit is end-of-pipe technology processing expansion gas from the Rectisol cleaning plant. The expansion gas contains 3.6 vol-% [H.sub.2]S and organic sulphur [TABULAR DATA FOR TABLE 1 OMITTED] compounds. The offgas is combusted to sulphur dioxide at a temperature of 1350 [degrees] C. A small quantity of natural gas is added to the low calorific offgas in order to reach the desired temperature. Nitrogen oxides, which are formed as a result of the high temperature, are removed by selective catalytic oxidation. After cooling the flue gas from combustion to 400 [degrees] C, ammonia is added to catalytically convert the nitrogen oxides to nitrogen and water: 6NO + 4NH3 [right arrow] [N.sub.2] + 6[H.sub.2]O 6N[O.sub.2] + 8N[H.sub.3] [right arrow] 7[N.sub.2] + 12[H.sub.2]O After selective catalytic reduction, the gases pass to another reactor where sulphur dioxide is catalytically oxidized to sulphur trioxide: 2S[O.sub.2] + [O.sub.2] [right arrow] 2S[O.sub.3] ([Delta]H = 98 kJ/mol) The reaction is exothermic and the temperature of the gas increases by 19 [degrees] C. Upon gas cooling, 95-97% sulphuric acid is condensed according to the following reaction: S[O.sub.3] + [H.sub.2]O [right arrow] [H.sub.2]S[O.sub.4] ([Delta]H = 101 kJ/mol) In contrast to flue gas desulphurization, no other raw materials are needed. Gas from the sulphuric acid condenser flows through a mist eliminator and is then mixed with hot air, which raises the temperature to 120 [degrees] C, before being dissipated from the stack. The heat recovered from cooling the gas is used to generate saturated steam (3.9 MPa pressure) and to heat combustion air. Table 1 shows basic data for the gases processed. The desulphurization unit is based on WSA and DENOX technologies licensed by Haldor Topsoe. It was constructed between 1990-1992 and came on stream in 1993. The unit is operating at 87-97% of design capacity. The volume of gas processed varies from 8000 to 13,000 [m.sup.3]/h. The quantity of sulphuric acid manufactured usually varies between 0.9 and 3.3 t/h (4.44 t/h [H.sub.2]S[O.sub.4] maximum). During the period 1993 to 1998, 32,000 tonnes of sulphuric acid were produced. To compare with FGD by wet limestone technology, 36,000 tonnes of limestone would have been needed for equivalent S[O.sub.2] capture, resulting in 60,000 tonnes of gypsum to dispose of.

The sulphuric acid produced by the process is of good quality (Tables 2 and 3) and is suitable for the industrial production of many chemicals and fertilizers.
Table 2: Concentration of selected metals in [H.sub.2]S[O.sub.r] from desulphurization Element Concentration (mg/litre) Element Concentration (mg/litre)

Zn [less than]0.15 As 0.18 Mn [less than]0.4 Se 0.49 Ni 1.5 Hg 0.005 Fe 11.4 Cr [less than]1.25 Cu [less than]1.3 Cd [less than]0.2 Pb [less than]2 Co [less than]1.3 Table 3: Comparison of adsorbed organic bound halogens analyzed in sulphuric acid manufactured Adsorbed organic bound halogens ([[micro]gram] Cl/litre) 94 50 230

[H.sub.2]S[O.sub.4] sample Vresova chemical grade technical grade

[TABULAR DATA FOR TABLE 4 OMITTED] References 1. Vejvoda, J., Buryan, P. and Svrcek, P.: "Sulphur dioxide emission control in Czech Republic". Clean Coal Technology Symposium, Ko??? ice (Slovak Republic), Nov 19-21, 1996. 2. Vejvoda, J. and Buryan, P.: "The first experiences in operation of flue gas desulphurization plants". Aprochem '98 Conference, Devet skal (Czech Republic), Oct 19-21, 1998. 3. Vejvoda, J., Buryan, P. and Svrcek, P.: "Flue gas desulphurization in the Czech Republic". Clean Coal Technology Symposium II, Ko???ice (Slovak Republic), Nov 18-20, 1998. 4. Dvorak, K., Slalmonova, A.: "Economical condition of applying advanced energetic technologies in production of energy". Clean Coal Technology Symposium II, Ko???ice (Slovak Republic), Nov 18-20, 1998. This article is an edited version of a paper entitled "Desulphurization of expansion gas from a Rectisol plant in IPPC electricity production in a former gasworks plant in Vresova" by Petr Buryan and Josef Vejvoda, Institute of Chemical Technology, Faculty of Environmental Technology, Prague. COPYRIGHT 1999 CRU Publishing Ltd.

This material is published under license from the publisher through the Gale Group, Farmington Hills, Michigan. All inquiries regarding rights should be directed to the Gale Group.

Title: Kaohsiung plant. (Kaohsiung Monomer Company Ltd.'s spent acid regeneration plant) (Sulphuric Acid Round-up) Date: 1/1/1992; Publication: Fertilizer International; The next step in the evolution of advanced SAR technology came with the start-up towards the end of 1990 of the new SAR facility of Kaohsiung Monomer Co Ltd, Kaohsiung, Taiwan. This company, jointly owned by ICI and China Petrochemical Development Corp, began producing methyl methacrylate monomer in 1978. Initially the 15,000 t/a MMA plant purchased the sulphuric acid and oleum required in the process and discharged the spent acid to waste, but in 1988 the company decided to expand its MMA capacity, and accordingly a plant for recovery of spent acid was deemed a necessity, both from environmental and economic standpoints. Essentially, the Kaohsiung plant bears many similarities in basic design to the Dominguez plant. The technology for the 400 t/d spent acid unit is Rhone-Poulenc (Stauffer)/Chemetics, and again the best available construction materials were used, since monomer production could not be interrupted because of an inability to regenerate spent acid. Minimum emissions and minimized risk of pollution incidents on restart were also important. Figure 8 shows the converter design which incorporates true radical entrance and discharge from all four layers resulting in uniform distribution and resultant improvements in conversion. As has been said, there is a big difference between using spent acid from refinery sources as feed and using spent acid from methyl methacrylate production, the latter containing more water and also significant quantities of ammonium sulphate. Chemical reactions in the combustion chamber include:
H2[SO.sub.4] = [H.sub.2]O+[SO.sub.2] 1/[20.sub.2] ([NH.sub.4])2[SO.sub.4] + [0.sub.2] = [N.sub.2] + [SO.sub.2]+ 4[H.sub.2]0 Organics = [CO.sub.2]+ [H.sub.2]0

Operation conditions in the combustion chamber must be controlled within narrow limits to minimize sulphur trioxide formation, which would represent a process loss. At the same time, complete combustion of hydrocarbons must be ensured while at the same time minimizing the formation of nitrogen oxides.

At the Kaohsiung plant, the spent acid typically contains 45% [H.sub.2] [SO.sub.4] and this is preconcentrated to 65% (salt free basis), maintaining the ammonium sulphate in solution - without charring or polymerizing the organics - by control of temperature and pressure. This is achieved in a Chemetics designed single effect vacuum evaporator, consisting of glass-lined steel vessels and a thermo-syphon reboiler equipped with zirconium tubes. The preconcentrated acid solution is then decomposed in the combustion chamber at around 1000[Degrees]C. Acid is introduced through spray nozzles using high pressure air to improve atomization, and the furnace is fired with fuel oil through separate, tangentially mounted nozzles. Elemental sulphur can also be burned in the furnace as an additional sulphur feed. The chamber must never be allowed to operate under reducing conditions, but excess oxygen in the combustion gases must be controlled to around 1.5% to minimize [SO.sub.3] formation. Heat from the combustion is recovered in a specially designed waste heat boiler and superheater that minimizes the deposition of non-combustibles on the fire side of the tubes. The remainder of the plant design is much the same as that already described above, incorporating the now well-known features of Chemetics plants, with pumps and valves supplied by Chas S. Lewis & Co. COPYRIGHT 1992 CRU Publishing Ltd. This material is published under license from the publisher through the Gale Group, Farmington Hills, Michigan. All inquiries regarding rights should be directed to the Gale Group.

Title: More reliable and efficient towers. (Lurgi drying tower for producing sulphuric acid from sulphur-dioxide containing gases) Date: 11/1/1992; Publication: Sulphur; Although the basic design concept for acid towers has changed very little over the past few decades, a whole host of improvements have been made in all aspects of detailed tower design. In this article we discuss some of the most significant developments. There are four main process steps in the production of sulphuric acid from sulphur dioxide-containing gases by the contact process. They are, gas drying, catalytic conversion of sulphur dioxide to sulphur trioxide, absorption of sulphur trioxide, and acid cooling.

The catalytic conversion of sulphur dioxide to sulphur trioxide was dealt with in detail in an earlier Sulphur article(1). Of the remaining steps, two of them, drying and absorption, require the use of gas-liquid contact devices in the form of packed towers which is the focus of this article. The final step, acid cooling, will be dealt with in a future issue. The design of drying and absorption towers constitutes an important part of the overall design of a sulphuric acid plant. The operating performance, especially the tail gas purity and the service life of the plant depend largely on efficient and reliable drying and absorption systems. Gas drying Gas drying plays an important role in conventional contact plants because it protects the cooler parts of the plant, such as heat exchangers, against corrosion by acid condensation and safeguards against the formation of sulphuric acid mist. It also protects the catalyst from the adverse effects of acid condensation during plant shutdowns. The equipment for gas drying in sulphuric acid plants is similar regardless of whether the acid plant is based on sulphur burning, pyrites roasting or smelter waste gases. In most cases, the gases are dried in countercurrent with fairly concentrated circulated sulphuric acid (96-97% |H.sub.2~S|O.sub.4~) in irrigated packed towers. A typical conventional tower is shown in Fig. 1. The heat of dilution of the sulphuric acid together with the heat of condensation of the water generates a substantial amount of heat in the gas drying stage. For that reason the circulated acid is generally cooled by indirect heat exchange before being recycled to the dryer. The residual water content of the gases after drying corresponds theoretically to the partial pressure of water vapour above the irrigation acid at the prevailing temperature and concentration. In order to achieve a high drying efficiency, the temperature of the irrigation acid is normally maintained at 50-60|degrees~C. The dryer design is determined by a large number of interacting parameters, e.g. surface and geometrical characteristics of the packing material, packing height, gas velocity, irrigation rate, and others. The efficiency of water absorption by sulphuric acid mainly depends on the diffusion resistance of the gas/acid interface. A gas flow velocity kept above the range of laminar flow induces turbulence which not only lowers the diffusion resistance but also improves the liquid distribution. Lurgi drying towers are currently designed for linear gas velocities of 1.2 to 1.5 m/s and above. The lower limit on the irrigation density is set by the minimum acid rate required for uniform wetting of the entire packing surface. The

maximum rate is defined by the flooding limit, which itself is a function of the gas velocity and has to be determined for each packing type. A residual water content of approximately 50 mg/|m.sup.3~ (Vn) after gas drying is considered satisfactory. Absorption of sulphur trioxide The sulphur trioxide formed by the catalytic conversion of sulphur dioxide is absorbed in sulphuric acid of at least 98% concentration, in which it reacts in the liquid phase with existing or added water to form more sulphuric acid. The optimum concentration of the absorber acid corresponds to the azeotrope with the lowest partial pressures of sulphur trioxide, sulphuric acid and water vapour. At lower acid concentrations, the partial pressure of water vapour is higher, and there is a high risk that sulphuric acid mist will form as a result of the direct reaction of sulphur trioxide in the gas phase with the water vapour above the acid. At acid concentrations above the azeotropic point, the off-gas will contain an increased amount of sulphur trioxide and sulphuric acid. The process gas leaving the converter system is cooled in gas-gas heat exchangers or steam generators to a temperature of at least 150| degrees~C (above the acid dew point) before entering the absorber. The process gas temperature entering the absorber in a typical acid plant designed by Iprochim S.A. of Romania varies between 160 and 200|degrees~C, whilst the gas outlet temperature falls in the range 7080|degrees~C. The sulphur trioxide is absorbed in packed towers, usually according to the counter-current principle. The gas flows upwards through the packed bed, which is uniformly irrigated from the top with concentrated sulphuric acid. Efficient sulphur trioxide absorption depends not only on uniform acid and gas distribution in the absorber but also on maintaining the temperature and concentration of the absorber acid at the optimum values. The optimum acid inlet temperature depends on the design conditions, but is usually in the range 60-80|degrees~C and is maintained by indirect cooling. The optimum absorber acid concentration is maintained by adding process water to the acid leaving the absorber. Venturi absorption systems Sulphur trioxide absorption systems based on venturi scrubbers were introduced by Lurgi in the early 1970s. They were developed specifically for the purpose of reducing heat losses during intermediate

absorption so as to permit low-grade smelter off-gases to be processed autothermally in double-absorption plants. As the gas and the absorber acid enter the venturi system in co-current, the gas temperature at the outlet is higher than in conventional countercurrent absorbers with the same acid temperatures. Thus, less heat is transferred from the gas to the absorber acid and has to be dissipated through the acid cooling system. Running the absorber at a higher acid temperature reduces gas heat losses still further. This principle of hot absorption in co-current with acid at temperatures of about 120|degrees~C to 140|degrees~C can be applied not only to process low-grade gases but also to maximize the recovery of heat in double absorption systems, e.g. for the generation of low-pressure steam. The venturi absorption system consists of a vertical venturi scrubber and a packed tower arranged in series. The acid is injected through nozzles at the top of the venturi scrubber. In the downstream packed bed, the droplets entrained by the gases are separated. Depending on the application of the venturi absorber, the packed bed may also be irrigated with uncooled acid in countercurrent. The injected acid and the highly turbulent gas stream in the venturi scrubber provide a uniform, intimate mixing of gas and liquid as well as a large liquid/gas interface and, consequently, favourable mass and heat transfer conditions. The absorption efficiency and the pressure drop of the venturi-type design are similar to those of conventional absorption towers. The pressure drop of both systems is normally approximately 150 to 200 mm WG. This type of venturi system has proved successful in a great number of sulphuric acid plants, particularly in large plants with capacities of more than 2,000 t/d | H.sub.2~S|O.sub.4~. Tower design for dryers and absorbers The essential design characteristics are based on the process conditions mentioned above and the necessity for corrosion-resistant materials to ensure long service life. At first sight, it would seem that there has been little change in the design of modern acid towers compared with towers designed over 40 years ago. The concept of a brick-lined carbon steel shell vessel containing a metal acid distributor, ceramic packing and mist eliminators is just as relevant today as it was when the early towers were designed. However, the similarity between old and new towers ends with these general concepts. In all aspects of detailed tower design there have been significant changes which have occurred as a

result of an improved understanding of the process and mechanical requirements, as well as major advances in materials development. Issues which must be considered when designing new drying and absorption towers include the overall absorption efficiency, capital cost, energy consumption for gas and acid pressure drops, reliabil2ity, maintenance costs, safety and mist generation propensity. At the lowest possible capital investment and operating costs, the plant contractor is required to attain the minimum susceptibility to failures and guarantee the specified operating parameters. For packed towers, the primary design issues are to set the vessel diameter and packing depth based on an optimization of capital cost versus energy consumption. As the size of plants has increased over the years, and improved tower packing has become available, the linear gas velocity has increased from about 0.5 m/s to a maximum of about 2.5 m/s. According to Monsanto's tower design, with typical energy costs, the optimum falls in the range 1.7 to 2.0 m/s. All towers are equipped with mist eliminators. The mist eliminator casings as well as the domes and the gas outlet bends are fabricated in stainless steel to avoid blockage of the filters and the packing by iron sulphate. Construction developments The best designs can be negated by poor construction and inadequate manufacturing quality control. This is especially true of brick-lined acid towers. It is essential to monitor and control the installation of the lining materials very carefully. This includes careful fabrication of the shell to accurate roundness tolerances, cleanliness of the shell surface before lining, even application of mastic or rubber-type lining, consistent mixture of mortar, full coverage of brick joints and surfaces with mortar to prevent voids and even width of mortar joints. Certain brick manufacturers have developed special shapes for nozzles and dished parts of towers. This minimizes the need for brick cutting on site, simplifies installation and generally improves the quality of the finished lining. Chemetics has developed comprehensive quality control standards and procedures to give the highest quality of tower installation, thus ensuring a long tower service life. Construction materials As mentioned above, the drying and absorption towers applied in most cases nowadays are constructed of a carbon steel shell with an acidproof brick lining. Good mechanical design of lined acid towers can only

be achieved by the contractor working closely with the brick suppliers to produce an integrated design. Major repairs that occur in the 10 to 15 year range are often traced back to poor workmanship of the original installation. These repairs are difficult and costly to repair. The two main types of acid brick used for lining acid towers are red shale and fireclay. The difference between these two materials are significant but both materials are excellent for this application. Red shale has a higher density than fireclay, giving it a lower porosity which minimizes the impregnation of the acid through the lining. Although fireclay has a higher porosity than red shale, it has a much lower iron content. This gives red shale its characteristic red colour compared with the pale yellowish colour of fireclay. The iron in the red shale brick reacts with sulphuric acid forming iron sulphate, which, long term, can result in spalling of the brick. Fireclay brick remains free from spalling even after many years of operation. Chemetics has generally specified fireclay brick for its towers, mainly because the Chemetics' self-supporting dome is not available in red shale. A membrane between the brick lining and the metal shell has always been a feature of acid tower design. This membrane provides a "cushion" between brick and shell to assist where differential movement occurs and it also provides a barrier to prevent acid from attacking the shell. Originally, this membrane took the form of asbestos-based sheet impregnated with calcium silicate mortar. Later designs used a bituminous mastic which was applied to the shell with a trowel before brick lining.
Table I Typical Chemical Composition of Brick Lining Used by Iprochim Components Percentage Si|O.sub.2~ 71.30 |Al.sub.2~|O.sub.3~ 23.75 |Fe.sub.2~|O.sub.3~ 1.75 Other oxides 2.45

Modern designs, which are influenced by plant operators' and brick liners' preferences, include mastic coatings covered with PTFE film, sheet rubber-type linings bonded to the metal shell, thermoplastic linings bonded to the shell and ceramic paper linings impregnated with potassium silicate mortar. Chemetics has supplied towers with all the above combinations and believes that they all can give satisfactory life if correctly applied.

Monsanto Enviro-Chem typically uses trowelled asphaltic mastic membranes, and reports an average tower life of about 20 years. FACT Engineering and Design Organisation (FEDO), an Indian contracting company with over 25 years experience in the design of sulphuric acid plants in India, regularly uses a 2-3 mm thick synthetic plastic material such as polyisobutylene sheets. According to FEDO's experience, these synthetic plastic materials cannot withstand being continuously subjected to a temperature of more than 80|degrees~C. The operating temperature of acid in FEDO absorption towers is generally controlled in the range 65-90|degrees~C and the brick lining is usually adequate to prevent excess temperature at the plastic membrane. In certain cases, however, a water jacket using demineralized water as the cooling medium has also been provided at the gas inlet nozzle to prevent overheating of the plastic membrane. Lurgi's design consists of a triple-layer lining to protect the tower sump filled with acid from heavy corrosion. The steel shell in the lower part of the dryer only is further protected from diffusing acid by a polyisobutylene sheeting e.g. Rhepanol. The cylindrical part of the tower is protected by an acid-resistant two-layer lining to a point above the acid irrigation system. The dished bottoms are supported by steel saddles resting on concrete foundations at grate level. This bottom-head and saddle-support design facilitates visual inspection of the bottom. The tower sump is basically provided with dished bottoms and brick lined in the same way as the lower part of the tower. Iprochim acid towers consist of a vertical cylindrical vessel made of carbon steel with a welded tapered top and welded flat bottom. The metal shell is protected on the inside with acid-proof brick. Table I shows the typical composition of the brick lining used. The tower bottom is protected with three layers of brick. From the bottom up, the shell is protected by a triple layer lining up to three metres and a two-layer brick lining thereafter. Above the acid feeding system the shell is coated with stainless steel. A special feature of tower linings is the lining required at the various nozzles. Hot gas inlet nozzles require a combination of acid brick and foam glass to ensure cool metal temperatures. Cold gas inlet nozzles, especially in metallurgical acid plant drying towers require special protection for the metal nozzle against weak acid attack. This protection has traditionally been achieved by the use of lead linings, but recent designs have incorporated rubber-type linings in the nozzle area similar to those used in main tower shells. Acid outlet nozzles were historically installed with a cast iron liner or insert between the brick and the acid. Sealing between the nozzle and the brick was achieved with asbestos rope soaked in mortar. This cast iron insert was a maintenance item requiring regular replacement.

More recently, higher grade metals have been used to replace the cast iron. Although these materials are much better at withstanding attack from hot sulphuric acid than cast iron, the increased thermal expansion co-efficient makes long-term sealing a problem, causing acid weeping between the insert and connection flange resulting in leakage. Chemetics incorporates ceramic inserts and/or specially shaped acid bricks in the acid outlet nozzles of its towers and ensure a high integrity connection with the acid piping by specialized flange sealing techniques. Stainless steel has been applied in acid towers for quite a long time for different components, e.g. gas filter elements, filter casings and acid distribution systems. It was not therefore surprising that the next stage of development was the application of towers entirely made of stainless steel without brick lining. In the early 1980s, Lurgi built an intermediate absorber entirely fabricated of stainless steel to replace a defective brick-lined tower at Norddeutsche Affinerie, Hamburg. The tower has been operating in the conventional temperature range ever since with no upsets. In 1988, Lurgi built a venturi intermediate absorber of stainless steel for the generation of hot water in a sulphuric acid plant. The temperature of the sulphuric acid (98.5% |H.sub.2~S|O.sub.4~) is 140| degrees~C at the absorber outlet, while the gas temperature is 230| degrees~C. As a logical consequence, Lurgi developed a low-pressure steam generator which runs at an acid temperature of about 200|degrees~C. The steam is generated in a kettle-type stainless-steel evaporator combined with a venturi absorber. A final absorber of stainless steel which was recently installed to replace a defective conventional tower is a further typical application. The plant had to be shut down for a few days only for the tower to be exchanged. Towers constructed of speciality alloys can be expected to last for 20 years or more, but the major benefit is the virtual elimination of repairs during that time. Monsanto reports on a plant where the drying and absorption towers were constructed of SX steel. When inspected after operating for nearly 4 years, no visible corrosion effects could be found. Test coupons mounted in the most suspect locations of these towers were in the 0.1 to 0.2 mil/year corrosion range. Only one repair has been required to date, to correct a small area where weak acid could form in the drying tower.

For replacement of old towers, SX towers can be prefabricated. The demolition of the old tower and placement of the new one can be completed during a normal 14-day turn around. Chemetics has pioneered the application of its own patented material called SARAMET|R~ as a material for tower shells and packing supports. To date, one drying tower and two absorption towers have been constructed in SARAMET|R~. The advantage of a simple metal tower compared to a brick-lined tower is self-evident - especially when considering the plant down time required to replace a tower with a simple metal shell versus the time taken to install one that is brick lined. A metal tower is also much simpler to repair than a brick-lined tower. However, despite its excellent corrosion-free performance of SARAMET|R~ in contact with strong sulphuric acid, the performance in the presence of weak acid is no better than conventional 316L. Bricklined towers are not sensitive to upsets in acid strength and therefore are still favoured over a metal tower by most operators. Gas and acid distribution It is essential to ensure that the gas and acid distribution is uniform over the entire tower cross section and that the acid flow rate is high enough to wet the entire packing layer completely. No special device is employed for the distribution of gas inside the tower. Uniform gas distribution is primarily achieved by ensuring that the inlet gas velocity is small in comparison to the pressure drop through the packed bed. Monsanto has observed a few towers with significant gas maldistribution caused by high inlet velocity, but since this is so easily avoided it is seldom a problem. Uniform acid distribution is more difficult to attain and the acid distributors have come in many shapes over the years. The two most common styles are variations on the basic pipe and orifice distributors or trough-type distributors. Pipe distributors are appealing because of their low cost. Early pipetype units of cast iron had problems with limited sizes of castings and with erosion of the distribution orifices. With modern speciality alloys such as C. S. Lewis' Lewmet|R~ alloy or Sandvik's SX Sulphuric Acid Steel|TM~, the orifice erosion problem has been solved. However, the final orifices are relatively small, in the range 10 to 15 mm, and can easily become plugged with brick, mortar, or ceramic packing chips. For these distributors to be successful, good acid strainers must be installed and maintained. Until Chemetics introduced its material SARAMET|R~ in the early 1980s, all acid distributors were made from cast iron. Chemetics pioneered the use of SARAMET|R~ pipe-type distributors which have

two significant advantages, namely, uniform distribution and corrosion resistance. Cast iron trough distributors are difficult to install and maintain at a uniform level, resulting in variations in acid distribution across the tower. Chemetics' pipe distributors are self supporting and, being pressurized, do not depend on accurate levelling for uniform distribution. Cast iron distributors, both the trough and pipe type, require regular replacement due to corrosion. Chemetics SARAMET|R~ distributors are almost corrosion free; distributors have been in continuous operation since 1983 with no measurable corrosion. Chemetics distributors are buried beneath the packing surface unlike trough distributors which sit on the top of the packing. If packing or brick chips are present in the acid and they are carried to the distributor, partial blockage could occur with a pipe-type distributor resulting in a time-consuming maintenance operation to remove and clear the distributor pipes. Troughs are not subject to this problem. To overcome this problem, inline filters can be installed which can be sized to prevent the necessity for cleaning except during planned shutdowns. Chemetics has installed over 70 SARAMET|R~ pipe distributors over the past ten years, only one of which experienced a blockage problem that affected acid distribution. Sulphate build up, which has to be physically removed from trough distributors comes from corrosion of the trough. This is exacerbated by the near stagnant conditions of the acid in the trough. Sulphate can also be transferred to the distributor from cast iron acid piping. All Chemetics acid plants incorporate either SARAMET|R~ or anodicallyprotected stainless steel piping, which avoids the problem of sulphate formation in the acid piping. Monsanto Enviro-Chem and its licensees built about 40 towers in the 1980s using pipe-type distributors, either with cast iron pipes and Lewmet orifice inserts, or all-alloy pipes with drilled orifices. Every tower met its performance requirement initially, but about 20% of them eventually reported poor performance due to distributor pluggage. These were usually traced to strainer failures, strainer bypassing, or strainer removal, but still reflected on the overall plant performance. For that reason, Monsanto has now standardized on all-alloy trough and downcomer acid distributors. About 15 of these are currently in service in drying, interpass absorption and final absorption duty. The first standard distributor has been in operation for four years and none of them have required replacement, repair or cleaning to maintain the expected tower performance. These distributors utilize bent thin-wall

tubing for the downcomers, which allows the designer complete freedom to provide near perfect coverage of the tower cross-section area with uniform acid flow. A number of these have been installed in existing towers to improve performance or to replace worn out cast iron units. Earlier cast iron trough and downcomer distributors were limited to the frequency of distribution points due to the limits of castings. Thus, the packing depth had to be in the range 4 to 5 metres to allow the acid to spread out across the areas between the downcomer points. With alloy tubing, the distribution frequency can be increased to the optimum, considering the cost of the distributor, tower, and pressure drop. The closer packing of the alloy downcomers allows a shorter packing depth, with the benefits of lower capital and lower pressure drop. For more than 15 years, Lurgi has applied acid distribution systems which ensure a large gas inlet opening and optimum acid distribution across the entire tower cross section above the packing layer. Nozzles with inclined upward-pointing lateral orifices made of special cast iron or stainless steel are used. As the acid pressure in the distribution system is almost atmospheric, the acid is distributed smoothly and uniformly over the packing. Conventional tower packing Mass transfer by intimate gas/acid mixing occurs in the area of the packing. Material selection and sizing of the packing substantially influence the mass transfer efficiency and pressure drop. Several different packing types are in successful service in the sulphuric acid industry. However, tower packing in most modern towers consists of 1 1/2", 2" or 3" ceramic saddles, which combine the advantages of long-term resistance to the hot strong acid encountered in the towers, low pressure drop and good absorption efficiency. Monsanto Enviro-Chem has standardized on 75-mm (3") ceramic saddles. With near perfect gas and acid distribution, a depth of 2 metres of this packing will achieve an absorption efficiency of about 99.8%, and to compensate for any maldistribution, an extra 0.3 to 0.6 metres of packing are usually added for either drying or intermediate absorption towers. In the final absorption tower, where a slightly higher absorption efficiency is required, a little more packing is used. Lurgi regularly uses irregularly packed 2" or 3" Intallox saddles of acidproof ceramic material. The packing bed is carried by self-supporting grates which consist of specially-shaped acid-resistant bricks. This ensures an optimum gas distribution and allows any desired arrangement of gas and acid nozzles in the lower part of the tower.

FEDO typically uses Intallox saddles as tower packing, the preferred size being 38 mm (1.5") or 50 mm (2"). The packing load on the supporting structure is usually in the range 3.5 to 4.0 tonnes/|m.sup.2~ under operating conditions. According to FEDO's experience, metallic gratings for packing support have not been successful to date. The company, therefore employs a grating consisting of an assembly of acid-resistant parallel ceramic beams with a flexural tensile strength of at least 12 N/m|m.sup.2~. These beams are supported on arched brick walls built up from the bottom of the tower. The span of the beams is usually limited to 1 metre because of strength limitations. Since the gap between the ceramic beams (approximately 80 mm) is too large to retain the saddles, two or three staggered layers of appropriate fourcell partition rings (size 150 x 150 x 15/120 x 120 x 12/80 x 80 x 8) are carefully stacked above the ceramic beams before filling to the required height with packing. In towers designed by Iprochim, the packing consists of ceramic Raschig rings with sizes ranging between 50 mm and 120 mm, provided with a baffle. Starting from the bottom of the tower, the packing is usually filled as follows: three rows of regularly packed 120mm rings, followed by two rows of regularly packed 80-mm rings, which is then topped up to the required packing height with a nonregular packing consisting of 50-mm Raschig rings in bulk. Halfway up the tower packing a section with 15-mm rings is laid for tower acid redistribution. In a typical 200,000 t/a sulphuric acid plant, the absorption tower will have a total height of 15,400, a shell ring diameter of 5,800 mm, and a packing height of 5,400 mm, giving a net weight of 293 tons. When loading the packing into the tower, it is important to avoid damage to the rings as much as possible, as broken rings can be reduced to a sludge under the action of the recycled liquid phase. With time, this sludge builds up in the recycled acid causing clogging of the packing and acid distribution system. The gas velocity in Iprochim absorption towers varies between 2 and 2.5 m/s, while the irrigation density is 36 |m.sup.3~/|m.sup.2~s. Under these conditions, a total mass transfer coefficient of about 1.095 | 10.sup.-3~ kmol S|O.sub.3~/|m.sup.2~/s/atm is provided and the column is operating at about 14-15% of the flooding speed. Chemetics has developed a metallic packing shape from its SARAMET| R~ material, which it claims provides an especially useful packing where low pressure drops are required. New tower packing Since most sulphuric acid plants have been designed with built-in expansion capability, not many new plants have been built in the last

ten years. In fact, most US acid plants were built before 1950. Consequently, many large sulphuric acid drying and absorption towers may now need to be repaired and repacked due to age, structural failure, or the need for increased capacity and production. Traditionally this has meant that the tower must either be repaired and repacked, or replaced by a new tower. These solutions are accomplished at a considerable cost. When repacked with conventional ceramic saddles, the revamped tower can provide only average production capacities. Flexeramic|R~ The Knight Division of Koch Engineering Company Inc. of Ohio, USA, has developed a new structured ceramic tower packing for sulphuric acid plants that offers an attractive new solution to the problems of a poorly operating or restricted-capacity towers. Koch's new Flexeramic structured packing is a fully-fired, high-quality stoneware product, which is available in three configurations to optimize pressure drop, capacity and efficiency. Its ceramic material of construction provides excellent corrosion resistance and service life. Its fixed geometric structure eliminates the abrasion which is common with other ceramic random packing. Maintenance of downstream equipment, such as pumps and heat exchangers, due to fouling is greatly reduced. The geometric structure of the packing also greatly reduces the channelling of both liquid and vapour. The textured ceramic material allows very uniform distribution and provides for intimate contact of sulphuric acid and sulphur trioxide gas. The result is better absorption efficiency, which translates into reduced operating costs and lower capital costs for new equipment. Lower pressure drop is another advantage of Flexeramic. The corrugated sheets of ceramic are vertically oriented in the packed tower, eliminating any horizontal surfaces which create resistance to fluid flow. TABULAR DATA OMITTED As a result, drying and absorption towers packed with Flexeramic structured packing have about half the pressure drop of towers packed with saddles. The new ceramic structured packing is especially ideal for use in the retrofit of existing drying and absorption towers. In fact, retrofitting an existing tower with Flexeramic structured packing provides 15-20% increased capacity over saddle packing. For new construction, the use of Flexeramic reduces the diameter of the brick-lined vessel for an overall reduction in capital cost. The new packing can be installed on any type of conventional internal support system. The installation cost for Flexeramic is similar to the cost of packing a tower using grid blocks, cross partition rings, and saddles.

Maintenance and service life Acid towers require virtually no maintenance, only irrigation systems and gas filters should be inspected periodically during operation through sight-windows installed above the irrigation system. During the regular downtime periods (usually 2-3 years) the interior of the gas filters should be inspected. An interior inspection of the irrigation systems in a five-year cycle is sufficient. For some metallurgical processes it may be necessary to clean dryer packing after an operating period of several years. No further maintenance measures are usually required. The developments which have been made in the fields of mechanical design, maintenance, materials, process design and construction have meant that modern acid towers now have a service life of up to 30 years. Problems common to early tower designs included cracking of packing support beams, leakage around gas and acid nozzles, and heaving of the base bricking resulting in acid leakage through the bottom of the towers. Chemetics overcame these problems using a variety of solutions. Dished tower bottoms ensure that the brick remains in compression, especially after the build up of sulphate behind the brick. Chemetics' self-supporting dome, which supports the packing, is an arch, constructed from individual self-supporting concentric rings of slotted acid brick, all constrained under compression. Conventional ceramic beam supports are subjected to bending forces from the packing which puts the material under tension causing cracking and eventual collapse of the packing. All the weight of the packing support of a Chemetics tower is transferred through the tower shell. In conventional towers, the weight of the packing and packing support is transferred to bricks in the base of the tower via pillars or arches. This method of support causes high local stresses at various points across the base of the tower, resulting in cracking and subsequent leakage. Although some contractors now incorporate dished bottoms in their towers, Chemetics is the only contractor that ensures that none of the tower weight is transferred to this dished bottom, either from internal brick structures or external supports. Another problem area that has been successfully tackled is the design of gas nozzles/ducting. Distortion of metal shells and nozzles incorporating brick linings will eventually result in cracking of the brick and/or mortar. This is especially true for towers subjected to multiple

thermal cycling i.e. on plants having many shutdowns. Chemetics recognized the importance of avoiding this distortion by ensuring that external forces from ducting, piping and support structures are minimized. FEDO reports that according to its experience, despite the use of brick linings and plastic membranes acid, leaks onto the shell of drying and absorption towers do occur due to local failure/fissure of the lining. The most vulnerable section in this respect are the tower bottom, tower pump tank interconnection and the gas inlet nozzle. The local failure of the lining can be due to any of the following factors: * Comparatively higher temperature of the incoming gas stream contributing to thermal stress/expansion, resulting in fissures in the brick lining and damage to the plastic membrane at the gas inlet nozzle. * Local overheating of the acid mass and intensive reaction at the water addition/dilution zone, resulting in erosion and damage to the brick lining. * Poor workmanship, especially in the case of leaks at the tower-pump tank interconnections. Once a leak is noticed, a thorough inspection and repair of the lining and shell will necessitate complete dismantling of the tower internals, which will not be possible in most cases because of production constraints. In such cases, the leaks are temporarily stopped wherever possible by application of acid-proof cement grout and permanent repair is carried out during a planned shutdown. Alternative arrangements for fabricating a new tower will also be undertaken simultaneously for replacement of the damaged tower in due course. In FEDO's experience, a tower will not normally be considered for a total revamp or replacement until after about 10 years of operation, which is the average life of an absorption/drying tower observed in practice in India. Process development Over the past four years, Chemetics has constructed prototype units and sponsored extensive research at local universities to study the fundamentals of liquid and gas distribution in acid towers using a variety of tower packing configurations, acid distributor designs and gas distribution systems. These research programmes, combined with on-site measurements, as well as general field experience from over thirty towers recently installed by Chemetics, now enables precise definition of the following important tower parameters: tower diameter, packing depth, packing type and size, and number of acid distribution points. Consequently,

towers specified by Chemetics have predictable absorption/drying efficiencies and most importantly accurate gas pressure drops. A detailed study of liquid distribution in a four-foot diameter tower has provided a scientific basis for designing pipe-type distributors. Comparisons of pipe versus through distributors has also confirmed that equivalent liquid distribution characteristics can be obtained from both devices. Chemetics offers both designs, although pipe distributors are preferred for economic reasons and because they are easier to install. Unlike some acid plant operators, Chemetics has not risked taking advantage of any sulphur trioxide absorption that may occur in the mist eliminator section of the tower, as a means of reducing the height and hence cost of the packed section of the towers. Chemetics has taken the approach of optimizing each section of the tower by adapting a stage-wise calculation method. Chemetics has also introduced the conical top for drying towers. The purpose of this cone compared with the traditional "dog house" designs was to ensure good distribution of gases through the full height of the tower. Tower packing support For brick-lined towers, the two most common packing support systems used today are ceramic beams which must be supported on rider walls about two metres apart, and ceramic keyed arches or domes, which require no intermediate supports. Both perform satisfactorily, so selection is largely a matter of the designer's choice based on installed costs and schedule. For alloy towers, an alloy bar grid of the same alloy is typically fabricated for the packing support. In all of these cases, one layer of placed cross-partition rings or grid blocks is typically used between the support structure and the irregularly packed tower packing. Iprochim's tower packing support consists of supporting pillars made of acid-resistant brick, as used in the tower lining, overlaid with either acid-proof cast iron or ceramic beams. The beams are overlapped and positioned is such a way as to form a grid with meshes smaller than the rings used as packing. Table III illustrates a typical composition for the cast iron used in the manufacture of grid beams. The qualities of this cast iron result from its chemical composition, its chromium content significantly increases the passivating properties of the iron. At the same time, the cast iron should have a perlitic structure, which requires its very careful casting.

The disadvantage of the cast iron grates is that in accidental cases where the sulphur acid concentration drops below 90% |H.sub.2~| SO.sub.4~, the passivating film breaks, thereby increasing corrosion and leading to destruction of the grate in a very short time. In addition, the resulting sulphuric acid is contaminated with a level of |Fe.sup.2+~ ions which exceed specifications. Ceramic beams, on the other hand, can resist acid corrosion for quite a long time provided that their surfaces are not damaged or cracked. Acid penetration under the surface protective layer leads to cracks. Enhanced by the packing force, these cracks eventually lead to the break up of beams. In China, a ceramic dome-type tower packing support (Fig. 4) has been developed which overcomes the pressure drop problems experienced with a lot of older tower designs. A paper|2~ presented at British Sulphur's Sulphur 91 international conference in New Orleans described the development of the Chinese ceramic dome packing support.
Table III Cast Iron Composition for Tower Packing Support Components Percentage C 3.2-3.5 Si 1.8-2.0 Mn 0.6-0.8 P 0.05 S 0.12 max Cr 0.5-0.7

Development of the ceramic dome The use of the dome-type construction in China has a long history. However, the dome-type packing support discussed here is different from the ordinary dome-type construction. The main feature of this new type of packing support is the degree of openings in the dome, which represent more than 50% of the structure. As there was no available formula for calculating the overall distribution of stress, the structure of the dome and the size of the elements could not be easily predetermined. An empirical modelling method for designing the dome was therefore used. Initially, a model cement concrete dome with a diameter of 500 mm was designed and constructed. The model dome was subjected to a destructive test after 30 days of concrete curing. A jack was used in the destructive test. The actual destructive load on the model dome was 13.78 tonnes. The validity of the force analysis and structure calculation was verified. Improvements to structure design were worked out after checking and observing the damaged parts of the dome. A new cement concrete dome-type packing support with a diameter of 1,700 mm was then designed. This larger dome was subjected to another destructive test, this time using a hydraulic press.

The actual destructive load on the dome was 225 tonnes and the design destructive load was 158.7 tonnes. The success of the improved design and the reliability of the calculation used was confirmed. Following these stress verification tests, an operating dome-type packing support made from granite was designed using the ad-hoc model. The diameter of the dome was 5,500 mm. After achieving the required mechanical strength and opening size, the dome was put into operation. The use of granite as the construction material, however, does have some disadvantages. Firstly, granite is a natural material and its chemical composition and crystalline structure are not homogeneous. The corrosion resistance of all parts of the dome may not be uniform and the reliability of the dome cannot be assured. Moreover, the structure of the graphite dome is more complex and the preparation and manufacture of the dome is difficult and time consuming. For these reasons, a concept to simplify the structure of the dome and improve the design was developed. A dome-type packing support wholly made of ceramic was selected. The reliability of the strength calculation and the design of the structure was confirmed by testing a model of the ceramic dome with a diameter of 1,000 mm. Figure 5 shows the structure and size of the dome. The ceramic dome has several advantages over the graphite dome. The ceramic dome structure is simpler. The acid-resistant bricks of the ceramic dome are smaller and lighter and easier to manufacture. The chemical composition and crystalline structure of the ceramic structure is homogeneous and the dome has good corrosion resistance. The packing can be loaded directly onto the dome. The dome was built with sodium silicate mortar on a special mould. After drying, the mould was removed and the dome, which was set on a steel support, was moved to the hydraulic press for destructive tests. An asbestos panel was placed on the upper surface of the dome and between the lower surface and the supporting steel structure (dome feet) to ensure an even load distribution across the dome. The behaviour of the dome bricks were observed continuously as the load on the dome was gradually increased. A small crack in a brick in the third ring was found when the load reached 109.8 tonnes. A small piece of this brick fell out when the pressure reached 125.5 tonnes. Several more bricks on the outer two rings were broken under a load of 156.9 tonnes, but the dome still retained its integrity. The destructive load is defined as the load at which the first crack is found, in this case 109.8 tonnes. Since the design destructive load of the dome was 108.7 tonnes, the ceramic model was considered to be a success.

Following the satisfactory destructive testing of this model ceramic dome, the ceramic dome-type packing support was introduced commercially. More than 100 domes of this type with diameters ranging from 1,800 mm to 5,900 mm are now in use in the sulphuric acid industry in China. Manufacture and construction The quality of the dome is assured by strict inspection of every brick. Preassembly of the dome on a mould is made by the manufacturer before delivery. A lateral pressure is applied to the wall of the tower once the dometype packing support has been installed. The wall of a newly constructed tower must be reinforced in the area where the dome is located. For reconstructed towers, a steel hoop around the tower must be installed in the corresponding place to increase the strength of the tower shell. A mould must be put in place before construction of the dome. The brick is then built up on the mould starting with the outer ring. Finally the centre part of the dome is put into place. The dome is cemented using potassium silicate mortar in strict accordance with specifications. The time required to build a dome can be reduced by using a precast mould with an umbrella shape. Normally, a ceramic dome-type packing support with a diameter of 6 metres can be constructed within one week. The ceramic dome-type packing support has several major advantages compared with the older type of support. High opening and low pressure drop A ceramic dome-type packing support with a diameter of 5,000 mm has a flow space of 55% and low fluid resistance. According to calculations based on a gas velocity of one metre/second, the pressure drop of an old arch-type packing support is 294 Pa (30 mm water column), whereas the pressure drop of a ceramic dome-type packing support is only 20-30 Pa (2-3 mm water column). Most of the older packed towers in sulphuric acid plants in China have a low gas velocity. However, when the ceramic dome-type packing support with larger packing is used, the gas velocity of the towers can be greatly increased because of the reduced fluid flow resistance. Thus, the capacity of the tower can be increased. The investment required for a new tower of a given capacity is decreased, whilst the capacity of an old tower can be increased.

Increased packing efficiency The gas flow through arch-type packing support with small openings has a high velocity. The packing near the packing support has a low efficiency because the passages for gas flow in the packing support are narrow compared to the section of the tower and the gas velocity is high. Some of the packing is therefore ineffective. The height of this ineffective packing can reach two metres. When the ceramic dome-type packing support is used, the packing is fully effective owing to the increased size of passages and lower gas velocity. This can lead to a reduction in the total height and quantity of packing fill required. The centre point of a ceramic dome-type packing support is raised relative to the periphery. For example, the height of the centre point of a five-metre dome is 450 mm higher that the outer ring of the dome. Some concern has been expressed that this can cause an increase in the height of the tower or increase the wall flow of the tower owing to the greater fluid resistance and lower gas flow at the outer ring of the dome. A detailed analysis of the design of the dome shows these concerns to be unfounded. In the case of the arch-type packing support, the arch obstructs the gas flow and a significant space is required between the lower part of the support and the top of the gas inlet port to improve the gas distribution. When the dome-type packing support is used, there is already a large space under the dome and there is nothing to obstruct the gas flow and affect gas distribution. The distance between the gas inlet and the dome can thus be decreased. The dome-type packing support also has a higher packing utilization factor, thus reducing the height of packing required. Gas flow distribution The dome-type packing support has smaller openings towards the centre and larger openings towards the outside. This can compensate for the unbalanced fluid resistance caused by a greater packing height in the outer rings of the dome. For example, in a dome-type packing support with a diameter of 5,000 mm, the core of the dome has an opening (free space) corresponding to 30%, whilst the second and third rings from the centre have an opening corresponding to 45% and 53% respectively. Other rings have an opening corresponding to more than 56%. Easier cleaning and maintenance The large free space under the dome makes cleaning and maintenance of the lower part of the tower very convenient. The working and safety

conditions for personnel entering the tower under the dome is also improved. Tower revamps When revamping old towers with the new ceramic dome-type packing support, the existing arch-type packing support must be removed. A ring of acid-resistant brick is built up along the tower wall. The top of the ring is located just under the dome and the ceramic packing support is then built on the new additional brick ring. References 1. "Converter design for S|O.sub.2~ oxidation". Sulphur (219), 26-39 (Mar-Apr 1992). 2. Zengtai, Z., Bochao, S. and Baosheng, G.: "Chinese experience in the use of the dome-type packing support in sulphuric acid plants". Sulphur '91 International Conference, New Orleans (Nov 1991). (British Sulphur). COPYRIGHT 1992 CRU Publishing Ltd. This material is published under license from the publisher through the Gale Group, Farmington Hills, Michigan. All inquiries regarding rights should be directed to the Gale Group.

Title: Do you really need a catalyst to make sulphuric acid? (Sulphuric Acid Technology) Date: 9/1/1992; Publication: Sulphur; Author: Netzer, D. Virtually all sulphuric acid production capacity is based on the contact process, which relies on a catalyst to enhance the oxidation of sulphur dioxide to sulphur trioxide. This article describes a non-catalytic system in which the lower per-pass conversion is compensated by gas recirculation. Sulphuric acid and other products such as oleum and sulphur trioxide may be formed by reacting a gas containing sulphur dioxide (S| O.sub.2~) with surplus air over a suitable oxidation catalyst to form sulphur trioxide (S|O.sub.3~) by the reversible reaction |Mathematical Expression Omitted~ and then absorbing the sulphur trioxide into highly concentrated sulphuric acid, in which it reacts with free water to form sulphuric acid.

The sulphur dioxide can be supplied as such from an external source or be formed on site by combustion of sulphur with air. That is the basic principle of the so-called "contact" process, which is used in virtually all commercial sulphuric acid production capacity. In the interests of efficiency and, later, to comply with environmental regulations, it became common practice to use first multiple contact stages and then multiple absorption stages to maximize the conversion of sulphur dioxide to sulphur trioxide. Practically all new sulphuric acid plants have two absorption stages, and many older plants in environmentally sensitive areas have been convened to work on this "double-absorption" or "DC/DA" (double-contact/double-absorption) principle. The main variations in the process depend on whether the plant is a "cold-gas" plant, receiving feed gas at around ambient temperature from outside, or a "hot-gas" plant running on feed gas generated in its own sulphur burner, since that has a profound effect on the amount and grade of reaction heat and on its management in the process. There are also differences in detail between individual developers' processes in the way process gas streams are heated and cooled between the various catalytic conversion and absorption stages. Catalytic conversion In all current double-absorption processes, sulphur trioxide formed in a first catalytic conversion stage comprising two, three or, occasionally, four separate catalyst beds with interbed cooling is abstracted from the process gas in a first (intermediate) absorption stage. The process gas then passes through another catalytic conversion stage with one or, occasionally, two catalyst beds to maximize conversion of sulphur dioxide to sulphur trioxide, next through another sulphur trioxide absorption stage, and is finally vented through a mist eliminator to the atmosphere. In a cold-gas plant, the gas passing into the first bed of each catalytic conversion stage is normally heated to its kindling temperature by heat exchange with the gases leaving the other catalyst beds. In this manner, the hot gas from each catalyst bed is cooled back to the kindling temperature for the subsequent bed, which prevents overheating of the catalyst and maximizes conversion efficiency. In a hot-gas plant, the feed gas is at a far higher temperature than is necessary or desirable in the first catalyst bed, so it is cooled in a waste heat boiler generating high-pressure steam and in reheating the gas stream leaving the intermediate absorber to the kindling temperature for the final catalytic stage. The heat generated in the catalyst beds is thus not needed for process gas heating and is utilized instead in the steam system for purposes such as superheating, steam generation or boiler feed water preheating. So whereas, in a cold-gas plant, all the high-level reaction heat is utilized in process gas heating,

eventually being rejected at low level in the product cooling water, in a hot-gas plant it and the very substantial heat of combustion of the sulphur is recovered in the form of high-pressure steam. In general, a three-stage converter with one final bed will produce an exit gas containing up to about 400 ppm by volume (ppmv) sulphur dioxide, up to about 0.1 kg of sulphuric acid mist per ton of |H.sub.2~S| O.sub.4~ produced, and up to about 100 ppmv oxides of nitrogen. In countries with severe restrictions on sulphur dioxide emissions to the atmosphere, such as Japan, it is customary to use a two-stage converter with one final converter to produce an exit gas with up to about 1,000 ppmv sulphur dioxide followed by an additional tail gas clean-up process to reduce the residual sulphur dioxide content in the exit gas to below 50 ppmv. As mentioned, a sulphur-burning sulphuric acid plant generates a substantial amount of useful heat. Heat in fact enters the system from five sources and is removed by three main systems. Heat enters as heat of compression of the main air blower, heat of combustion of sulphur to sulphur dioxide, heat of reaction (oxidation) of sulphur dioxide to sulphur trioxide, heat of reaction of water with sulphur trioxide to form sulphuric acid, and heat of dilution of the formed acid with water. Steam is generated in boilers from the high-level heat, while lower-level process heat is usually recovered by preheating boiler feed water in economizers or is rejected to the environment. The value of energy exported from a sulphuric acid plant is a significant factor in sulphuric acid plant economics. While current sulphuric acid plants can achieve overall sulphur conversion efficiencies of up to 99.7%, there is continuing pressure from the authorities for sulphuric acid plants with even higher efficiencies. Hitherto, however, the only development proposals have been for "more of the same", firmly based on contact catalytic converters. For more complete removal of sulphur dioxide from the process gas, they rely on altering the equilibrium conversion, either by removing more of the sulphur trioxide at intermediate stages or by raising the oxygen partial pressure, which can be done by using oxygen-enriched air or, in theory, by increasing the system operating pressure. But the practical and economic difficulties of building and operating air-based sulphuric acid plants operating at higher pressure are such that very, very few plants of that type have been built. Non-catalytic process In what is perhaps the first radically new sulphuric acid process concept since the contact process was first introduced around 60 years ago, the Ralph M. Parsons Co., of Pasadena, California, has proposed an entirely non-catalytic process for a sulphur-burning plant. It relies on the use of oxygen, instead of air, elevated operating pressure and gas

recirculation in a loop configuration to mitigate the far less favourable equilibrium conditions of the S|O.sub.2~/S|O.sub.3~ conversion at the temperatures needed to attain a practical reaction rate in the absence of a catalyst. Besides promising high conversion efficiency and reduced emissions, the new process makes use of fewer, smaller and simpler equipment items and is therefore likely to cost less to build and no more to operate than a conventional sulphuric acid process. Key elements of the new process The new process is a non-catalytic method for the production of sulphur trioxide at elevated pressure from elemental sulphur in the presence of oxygen and a recycle sulphur dioxide-rich gas stream in a single combustion zone (sulphur burner). The sulphur trioxide formed is separated from the combustion zone effluent, preferably by absorption in sulphuric acid. Unconverted sulphur dioxide is recycled to the sulphur combustion zone to enhance sulphur trioxide formation. A minor amount of purge gas is withdrawn from the gas circulation system to prevent inert concentrations from building up. After processing to remove its sulphur dioxide content, it is the only gaseous discharge from the process. In consequence, the process is virtually non-polluting. The combustion temperature in the new process is limited to 1,000| degrees~C and the maximum pressure is 35 kg/|cm.sup.2~g. The gas passing out of the burner zone contains, in addition to sulphur dioxide and sulphur trioxide, any inerts introduced with the oxygen and a relatively small amount of unreacted oxygen. Special attention has been paid to making the conditions in the sulphur combustion zone favourable for substantially complete utilization of the oxygen. The high-temperature product gas stream passes through a heat exchanger, in which high-pressure steam is generated for use in the process or elsewhere. The gas stream then passes to the sulphur trioxide absorber, where the formed sulphur trioxide is removed from the gas stream as sulphuric acid. The effluent gas stream from the absorption zone is essentially free of sulphur trioxide and consists mainly of sulphur dioxide and inerts. To prevent the accumulation of inerts in the gas stream, a sidestream is drawn off or purged from the system. The remaining gas, rich in sulphur dioxide, is driven back to the sulphur burner by the recycle blower. The sulphuric acid formed in the absorber is withdrawn from its base and passed to the absorber cooler for recovery of the heat of absorption and the heat of reaction. Water is added to the cooled acid at a rate set to exactly balance the rate of acid formation in the absorber and a portion of the acid is then withdrawn as product. The remainder of the acid is recirculated to the absorption zone.

Practical embodiment The flow diagram given in Fig. 1 shows how the process would be realized in an industrial plant. The effluent stream from the sulphur burner typically contains about 612 vol-% of sulphur trioxide. The following operating conditions are maintained in the sulphur burner. Temperature 650-1,000|degrees~C Pressure 35 kg/|cm.sup.2~g Oxygen purity 80% by volume The most economical operating pressure of the system is determined by the purity and supply pressure of the oxygen feed to the plant. The heat recovery train downstream of the sulphur burner has been represented as a single steam-generator, but in practice it might comprise more than one heat exchanger, depending on the detailed steam system requirements of the plant. TABULAR DATA OMITTED The absorber runs on the conventional principle of a packed tower, with the cooled sulphur trioxide-containing gas stream entering at the bottom and rising in countercurrent with sulphuric acid descending from the top. In operation, the liquid sulphuric acid feed to the top of the sulphur trioxide absorber is distributed evenly by spray nozzles over a packed section, allowing intimate contact between gas and liquid to enhance mass and heat transfer. The make-up water required may be added to the absorber acid circuit at any point between the bottom and top of the sulphur trioxide absorber. Because the oxygen feed to the sulphur burner comes from the air separation unit absolutely dry, all the water requirement of the process is supplied at this point. In contrast, a conventional catalytic sulphur-burning sulphuric acid plant picks up a proportion of the process water in the drying tower, where the incoming air is dried by contact with recirculated sulphuric acid. Heat of absorption/reaction released in the process may be recovered in the acid cooler by generation of steam or is rejected into water or air used as a cooling medium. Alternatively, electric power can be generated by using the acid cooler as the boiler in a Rankinecycle.

The circulating sulphuric acid stream contains a small but appreciable amount (typically 0.5-2.5 wt%) of physically-dissolved free sulphur dioxide -- more than in a conventional catalytic plant because the sulphur dioxide content of the gas passing through the absorber is higher. In a conventional acid plant, any sulphur dioxide in the acid is flushed out in the drying tower and is thus recycled into the system in the process air. In the non-catalytic process there is no drying tower, so a proportion of the acid is withdrawn from the absorber circuit and passed through a special stripper in which it is contacted with the oxygen feed. The sulphur dioxide is thus recovered and returned to the process. The essentially sulphur dioxide-free sulphuric acid leaving the bottom of the stripper is cooled in an acid cooler and then divided into two parts. One is removed as product. The other is used to absorb sulphur dioxide from the system purge gas in a purge gas absorber, whence it is returned to the top of the sulphur trioxide absorber. The sulphur dioxide-free purge gas is removed from the process either by venting to the atmosphere or passing the purge gas to an argon recovery operation, or the like. Table I sets out expected operating conditions for the process when installed in a 1,200-t/d sulphuric acid plant. Process advantages If the new process fulfils the promise of these figures, it offers a significant improvement over conventional sulphuric acid processes. Recycling sulphur dioxide-rich gas raises the S|O.sub.2~:|O.sub.2~ mole ratio in the combined gas feeds to the reaction zone well above the stoichiometric value, and by also using high-purity oxygen and conducting the process under pressure, significant improvements in the reaction equilibrium, heat transfer, mass transfer and reaction rates will be obtained. These improvements enable the process to be operated simply and without catalytic converters but, nonetheless, with high efficiency. The process has a lower power consumption and emits substantially less sulphur oxides, sulphuric acid mist and nitrogen oxides to the environment. There is no theoretical minimum sulphur oxide and nitrogen oxide emission level of the process, as is the case with straight-through air-based processes, where the sulphur dioxide conversion capability is limited by the equilibrium. In the closed system of the process, emissions are determined by the amount of inert gases purged from the system, and that, in turn, is primarily determined by the purity of the oxygen feed to the process. In conventional sulphuric acid plants, power is required to force a large volume of air through a long process train with substantial pressure drop and power can be saved only by making equipment and piping larger. The non-catalytic process has a substantially lower power requirement because there is a lower volume of gas to drive round the system and because there is less pressure drop on account of the absence of catalyst beds and associated heat exchangers. The process

has only one sulphur trioxide absorption stage and requires substantially less heat transfer area because heat transfer rates are higher under pressure operation. Furthermore, interactions between the various control loops are minimized. On account of the combination of relatively high operating pressure and gas compositions leaving the sulphur burner, the process can readily be adapted to produce liquid sulphur trioxide instead of sulphuric acid. The US Patent Office has recently granted Parsons a patent on the new process. The company expects to build a small-scale demonstration unit shortly. COPYRIGHT 1992 CRU Publishing Ltd. This material is published under license from the publisher through the Gale Group, Farmington Hills, Michigan. All inquiries regarding rights should be directed to the Gale Group.

Title: Recent advances in sulphuric acid production processes: virgin sulphuric acid production. (Process Technology) Date: 9/1/1990; Publication: Sulphur; Recent advances in sulphuric acid production processes VIRGIN SULPHURIC ACID PRODUCTION Even by the easy-going standards of the day, the old chamber and tower sulphuric acid processes, which constituted the only industrially realistic method of making sulphuric acid from the birth of the industry in the middle of the eighteenth century until the third decade of the present century, were intolerably filthy. They released into the environment copious amounts of sulphur dioxide, sulphuric acid fog and nitrogen oxides (which were employed as a regenerable oxidizing agent to assist the conversion of sulphur dioxide to sulphur trioxide). The contact process, which was first introduced on an industrial scale in the 1920s, was a revolution. Gone, at a stroke, were the noxious and difficult-to-control nitrogen oxides, which were replaced by several beds of a solid catalyst. Product efficiency was enormously improved; the paltry 2% of the sulphur values that remained as sulphur dioxide could be released into the atmosphere without qualms, and for the first time a product with a concentration approaching 100% could be produced in bulk. So clean and efficient was the process, in comparison not only with its predecessor but also with the majority of other contemporary bulk chemical manufacturing processes, and with the untidy and inefficient techniques often used to produce the feed gas on

which it operated, that there was little motivation to change it; it remained fundamentally the same for over 30 years. Only in the 1960s, when the rest of the chemical industry started to rival sulphuric acid manufacture in efficiency and cleanliness, did attention turn to improving the efficiency of the contact process above the 98% practical upper limit dictated by the kinetic and thermodynamic limitations of the [SO.sub.2./SO.sub.3] conversion reaction. A very convincing, though certainly not new, way of doing this was to remove the bulk of the sulphur trioxide, formed in the first two or, occasionally, three beds of catalyst, in an intermediate absorption stage, so as to increase the proportion of the remaining sulphur dioxide that would be converted to sulphur trioxide in the final catalyst bed or beds. This was the so-called "double-absorption" (also, though less aptly, known as the double-contact, double-catalysis) process, and it was not long before the authorities in the principal industrial countries, waking up to the problem of sulphur dioxide in the atmosphere, began to demand it for all new sulphuric acid plants. For 20 years after the advent of double absorption, the sulphuric acid process changed very little, except in matters of detail, which were quite often site-specific. Individual processes varied (probably as much for the purpose of avoiding infringing patents as for reasons of efficiency) in such features as the number of catalyst beds the gas passed through before and after intermediate absorption (2+2, 3+1 or - occasionally - 3+2, for example), the arrangement of the interbed cooling, the type of mass transfer device used for the absorbers and cooling tower. But these did not affect the principles of the process at all. One plant was built in France which operated under about 5 bar pressure, but in general production plants remained very much the same in principle. While big improvements have been made in ancillary processes such as ore smelting - the source of sulphur dioxide for a considerable number of sulphuric acid plants - and processes for purifying or reconcentrating "spent" sulphuric acid from diverse sources, originality in the contact section has been largely confined to plants for special purposes, as in the processing of undried feed gases from the combustion of waste hydrogen sulphide. Though the fundamental process may not have changed, aspects of it have, and in particular the recovery of the vast amounts of reaction heat it produces. Some improvements were achieved through changing to suction drying towers and increasing feed sulphur dioxide concentrations, but the greatest contribution resulted from improvements in the acid circuit, made possible through big advances in materials technology. Although, in a sulphur-burning plant, about one third of all the reaction heat is removed from the acid circuit and, in a "cold-gas" (metallurgical) plant, practically all of it is, it used to be at such low grade that it was of no practical use for anything and could only be rejected into the environment. It was only when stainless steel spiral and plate heat exchangers began to replace the old cast iron

cascade coolers that it was possible to raise the maximum temperatures in the acid circuits from 65-70 [degrees] C to 90-95 [degrees] C, making it worth while to recover the waste heat for lowlevel heating duties, such as boiler feed water preheating within the plant or district heating schemes outside it. Later, the anodically protected shell-and-tube heat exchanger was able to withstand higher temperatures still (125-160 [degrees] C) and so could be used for raising low-pressure steam. As a result of this progress, the energy efficiency of sulphuric acid plants has improved dramatically over recent years, from the 1.2 kg steam/kg acid typical in the 1970s to as much as 1.8 kg steam/kg acid in the 1990s. Where there is no worthwhile on-site use for such quantities of steam, some operators have installed facilities for cogeneration of electric power, either for their own use or, helped by improvements in the tariff structure, for sale to the local utility. Even so, more than 20% of the total heat available was still being rejected in cooling water. A technological breakthrough came in 1982 with Monsanto EnviroChem's Heat Recovery System (HRS), which can recover 95% of the process heat as steam. The basis of the HRS technology was the discovery of the surprisingly low corrosion rates of commercial stainless steels at sulphuric acid concentrations above the normal operating concentration of 98% [H.sub.2.SO.sub.4]. In the HRS process, the concentration of acid leaving the absorption tower is rigorously maintained at 99-100%, at which concentration stainless steel equipment corrodes at an acceptably low rate at operating temperatures (190-200[degrees]C) which are high enough to generate medium-pressure (10-bar) steam. To date, three plants with HRS have been operating for over two years and a further three plants are currently under construction. Monsanto's latest process An active research and development programme combined with the experience gained from designing and operating the Heat Recovery System has led to another major advance which significantly improves the economics of sulphuric acid heat recovery [1]. Monsanto's new process is based on the highly synergistic combination of two well proven technologies: HRS and the wet-catalysis process. In the new process, essentially all the process heat is recovered as steam, which eliminates the need for cooling water in the acid plant, and the heat is shifted from the production of medium-pressure steam to the production of high-pressure steam. The new technology is the basis of several pending patent applications. In the future, the successful sulphuric acid plants are likely to be those that concentrate on generating the maximum amount of electric power. Power generation is now approaching the point where the acid

plant can be justified on the basis of energy alone, with sulphuric acid as the by-product. Using Monsanto's new process a 2,500-t/d plant can export at least 32 MW electricity. The wet-catalysis process, as its name implies, is a variant of the contact process developed to operate on feed gases containing water, sulphur dioxide and sulphur trioxide generated by burning gases containing hydrogen sulphide, which produce water when burned. In a normal sulphuric acid plant, the drying tower is operated on a sidestream of product sulphuric acid which is returned to the absorber circuit and is thus reconcentrated. In a sulphur-burning plant only the combustion air is dried, and normally the amount of water absorbed in the drying tower is far outweighed by the amount of sulphur dioxide subsequently absorbed; in fact, some process water is needed to maintain the acid in the absorber circuit at a steady concentration. In a metallurgical plant, the feed gas has to be cooled and scrubbed to remove ash and certain damaging soluble impurities, and it is thus saturated with water vapour. In fact, it must be further cooled to ambient temperature to condense out as much as possible of the water vapour before it enters the drying tower, otherwise there is an unfavourable water balance and the product acid concentration cannot be maintained. Once dried, it has to be reheated in an elaborate train of heat exchangers to bring it up to the reaction temperature (390420[degrees]C). But there is normally no need to clean the gas produced by burning hydrogen sulphide, and it is undesirable to cool it down to condense moisture, then dry it, then to have to heat it up again. The wetcatalysis process is designed to obviate the need, which results in substantial capital savings. Instead, the combustion gases are cooled only to the reaction temperature and are then fed directly to the converter. Conventional vanadium catalysts have proved to operate successfully under these conditions, but the conditions and materials of construction downstream of the converter have to be chosen very carefully to safeguard against condensation of sulphuric acid vapour and the severe corrosion that could result. Monsanto has reasoned that, if it is possible to process wet gases from hydrogen sulphide combustion, why go to the trouble of drying the air in a normal sulphur-burning plant? Figure 1 is a flow diagram of the new process. Although it shows a conventional air filter, the process can be adapted to use a wet scrubber. Several major differences in the equipment are apparent. No drying tower One of the most obvious differences in this flow diagram is the absence of a drying tower and and its associated equipment, which results in proportionate capital cost savings. This eliminates cross-flow of acid

from the drying tower circuit to the heat recovery tower, which is normally needed to maintain the drying tower acid strength, and with it the problem of recovering energy from the hot return acid from the heat recovery tower circuit. Concentration control is also simpler. The heat of condensation of water vapour normally removed in the drying tower cooler is shifted to the heat recovery tower, where it adds to steam generation capacity. The blower suction temperature is reduced, which increases the efficiency of the blower, and the heat of compression is recovered in the high-pressure boiler, avoiding the problems associated with suction drying towers. Combustion air preheater Compressed air is preheated by hot acid from the HRS before it enters the sulphur burner. This provides an effective means of moving heat from medium- to high-pressure steam production. Whereas the burner inlet temperature is increased by the substantial heat recovered in the preheater, the burner exit temperature is kept down by the water vapour, which increases the mass flow and specific heat. The preheater is a fin-tube heat exchanger. Alloy materials are required where the tubes contact the hot acid, but less expensive materials can be used for the fins. Steam injection Process water is added not to the acid circuit, as in a conventional plant, but (as 0.3-bar saturated steam) to the gas leaving the third catalyst stage. The purpose of this is to maintain temperatures well above the dewpoint until the gases are completely mixed. Potential sources of injection steam include the boiler blowdown flash, deaerator vent steam, steam generated from low-temperature acid, HRS steam, or low-pressure steam from sources outside the acid plant. The steam injection nozzle is constructed of ceramic material to withstand aggressive corrosion by weak acid formed as a result of localized cooling and high water concentrations. Condensing economizer The economizer designated 3B in the flow diagram allows more of the acid heat of reaction to be recovered as high-pressure steam. As the gas leaving the third pass is cooled in superheater 3A and economizer 3B, some of the sulphur trioxide reacts with water vapour to form sulphuric acid vapour. About one-fourth of this reaction heat is recovered in the superheater and the rest is recovered in economizer 3B. Some condensation heat is also recovered because the tube wall temperatures are below the dewpoint. The economizer is constructed of the same corrosion-resistant alloy materials as are used in HRS service.

Another way of utilizing acid heat to produce high- rather than medium-pressure steam is to employ a heat exchanger in parallel or in series with the HRS boiler. Although such a set-up cannot recover heat at such high temperatures as a condensing economizer, the improved heat transfer can reduce equipment cost. Heat recovery tower The reaction of sulphur trioxide with water in the gas phase produces 33% more heat than its reaction with liquid water. [SO.sub.3](g) + [H.sub.2.O](g) [H.sub.2.SO.sub.4](l) +42.2 kcal/mole [SO.sub.3](g) + [H.sub.2.O](l) [H.sub.2.SO.sub.4](l) +31.7 kcal/mole This heat of reaction can be converted to medium-pressure steam in the HRS, which acts like a chemical heat pump by upgrading the lowpressure steam used for acid dilution in the heat recovery tower. The heat recovery system overcomes the problem of high mist levels that can be encountered with a conventional absorbing tower in wet catalytic processes by operating with exit acid temperatures of 200230[degrees]C. These temperatures approach or even exceed the dewpoint of the inlet wet gas stream, thus preventing rapid cooling and minimizing mist formation. Economic benefits The benefits of Monsanto's new design can be illustrated by comparing a 2,500-t/d "conventional plant" (a typical plant built in the 1980s with a nominal 70% energy recovery) with a 2,500-t/d plant using the new process. The economics for the new design are quite impressive. The export power is increased from 21 MW to 32 MW, while the capital cost for the new design ($44 million) is only about $6 million more than the conventional plant. Based on these economics the new process is extremely attractive and would pay out in about one year. Lower capital options for the new process can also be considered at the expense of some of the energy recovery. Reverse process [SO.sub.2] oxidation The unsteady-state oxidation of sulphur dioxide for sulphuric acid production, which was developed in the USSR, has been tested under industrial conditions for several years and its high efficiency proved. The process has been employed mainly in the non-ferrous metal industry for processing gases with low and variable sulphur dioxide concentrations (1.5-7.5% [SO.sub.2]).

As mentioned above, in metallurgical sulphuric acid plants there is a potential problem with water balance, and the lower the concentration of sulphur dioxide in the feed gas the lower its moisture content must be if the concentration in the acid circuit is to be maintained. But the bottom limit on sulphur dioxide concentration is principally set by considerations of heat balance. The reaction heat produced in the catalyst beds is used to reheat the gas leaving the drying tower to the initiation temperature of the first-stage catalyst. The lower the sulphur dioxide concentration in the feed gas, the greater will be the gas volumes between which exchange must occur. Furthermore, because of the dilution of the process gas, the temperature gradient between the hot process gas and the colder feed gas is smaller. Therefore the heat exchanger area required to provide the necessary feed gas reheat increases disproportionately as the feed gas sulphur dioxide content falls, becoming uneconomic at around 3-3.5% [SO.sub.2]. The reverse process circumvents this problem by using the catalyst mass as a heat storage medium. It alternately absorbs heat from the reaction and imparts heat to the incoming gas, rendering heat exchangers largely unnecessary. The fundamental principles and commercialization of the technique have already been discussed in detail in the past [2] and will not be repeated here. In brief, the basic idea of the process is the periodic reversal of the direction of gas flow across a fixed catalyst bed. The inlet gas mixture initially takes heat from the catalyst nearest the inlet end of the bed, cooling it in the process. Only when the gas reaches the initiation temperature does the reaction begin, and this heats the downstream zone of the catalyst mass. The progressive cooling effect of the incoming gas means that the front where the reaction begins moves further and further forward into the catalyst mass until it is nearing the outlet end, at which point the gas flow is reversed and the reaction front progresses through the catalyst in the opposite direction. Although the gas flow arrangement around the converter is radically different from the conventional system, it is still possible to use the technique in a double-absorption plant. To date, there are six industrial reverse-process single-contact installations in the USSR [3]. The first industrial double-contact plant to be put into operation started up in 1989 at the Balkhash plant. It processes copper smelter gas containing 9-11% [SO.sub.2] and uses the reverse process in the second stage of conversion (see Fig. 2). In comparison with a traditional double-absorption plant, the heat exchange surface has been reduced to about half. Heat exchangers are used only to heat the gas before the first stage of conversion, which greatly increases the thermal stability of the converter. A small heat exchanger is employed to heat the mixture to 150-180[degrees]C before the second stage in order to prevent condensation of sulphuric acid on valves and in the catalyst bed of the second stage. In cases where there is a good mist elimination system, this heat exchanger can be omitted. The second-stage conversion operates stably with sulphur

dioxide concentrations in the range 0.7-1.1% to give a 95-96% conversion. The overall conversion of the plant is 99.4-99.6%. Based on the experience from theoretical and experimental investigations and industrial operations, the Institute of Catalysis, Novosibirsk, USSR, is now in a position to recommend the reverse process for a number of industrial applications. In double-absorption systems using gases containing 10-12% [SO.sub.2], the reverse process is used in the second stage of conversion, with the traditional process employed in the first stage. The catalyst in the second stage is sandwiched between two beds of inert packing. By employing the reverse process in this way, no heat exchangers are needed to heat the gas before intermediate absorption, thus reducing the weight of metal required. For double-absorption systems processing gas with a sulphur dioxide concentrations below 10%, the reverse process is recommended for both the first and second conversion stages. For metallurgical gases containing 3.5-7% [SO.sub.2], the second stage is carried out in one catalyst bed, while one or two catalyst beds under conditions of periodic flow reversal are usually used in the first stage. Typical parameters for this type of converter are given in Table I. The efficiency of the reverse process for single-absorption systems processing metallurgical gases of low sulphur content has been proved. Recently, improvements have been made to increase the conversion of gases containing 1.5-4.5% [SO.sub.2] to 97.5%, whilst reducing the catalyst load by a factor of 1.2-1.4. This was achieved by using small heat exchangers. Topsoe's WSA-2 process In the mid 1980s, Haldor Topsoe A/S introduced a novel version of its WSA (Wet gas Sulphuric Acid process) for the removal of sulphurous compounds from the off-gases of a wide range of processes. The WSA process recovers up to 99% of the sulphur values in off-gas as concentrated (93-98 wt-%) sulphuric acid. No waste products or waste water are produced and no chemicals or other raw materials are consumed. Three plants with WSA-2 technology have been started up to date [4] and a further eight are due to be put into operation over the next two years. The three operating plants were started up in April 1986, December 1987 and December 1989 in metallurgical, power plant and coking applications respectively. Roaster off-gas

The first industrial plant to use this latest version of Topsoe's WSA process recovers the sulphur dioxide content of off-gas from a molybdenum sulphide roaster. A layout of the plant is given in Fig. 3. The sulphur dioxide gas is received as a saturated gas from a scrubber plant at about 25[degrees]C. Preheating takes place initially in the WSA condenser, a multiple glass-tubed heat exchanger/acid condenser. Further heating to about 395[degrees]C is carried out in a carbon steel gas-gas heat exchanger. The recycle of hot sulphur dioxide gas ensures corrosion-free operation of the gas-gas heat exchanger. Final heating to about 420[degrees]C is provided by an electric heater. Sulphur dioxide is oxidized in an adiabatic catalytic reactor using Topsoe's 10-mm ring-shaped VK38 catalyst. The resulting sulphur trioxide gas is cooled to about 260[degrees]C in the gas-gas heat exchanger, whereby part of the sulphur trioxide is hydrated to sulphuric acid vapour. Further cooling to less than 100[degrees]C, condensing and concentrating of product acid to approximately 97 wt% take place in the WSA condenser. As the existing stack is made of GRP, the clean gas from the WSA condenser is quenched by ambient air to about 50[degrees]C before being sent to the stack. The acid is cooled in a Hastelloy plate cooler and pumped to a carbon steel storage tank. For comparison, a conventional acid plant recovers 99 kJ/mol [SO.sub.2], whereas a WSA plant recovers 269 kJ/mol [SO.sub.2], resulting in very low energy consumption. The gas flow in this case varies from about 7,000-12,000 [Nm.sup.3./h]. As the gas is practically dust free, no increase in pressure drop has been observed across the catalyst and there has been no mechanical degradation of the catalyst. The typical conversion is 95.6%. Technical grade acid ranging between 96.0 wt% and 97.5 wt% and with very low impurity content has been achieved from the start. The only special requirement as far as materials of construction are concerned is for the WSA condenser, whose tubes are specially designed to be resistant to concentrated acids and thermal shocks. Acid-resistant bricks are used in the bottom section and fluorocarbon polymers are used to protect against condensing acid. In the wet areas (from the blower, via the scrubber, to the WSA condenser), polypropylene ducts are used. All equipment after the first stage of preheating is made of ordinary steel. The most serious problem experienced in this plant has been corrosion on the shell-side at the cold end of the WSA condenser due to a malfunction of the demister in the upstream scrubber, which caused a heavy carry-over of acidic water. Some iron sulphate was also formed in the cold end of the heat exchanger because the importance of maintaining the plant above the acid dewpoint until the catalyst has cooled to the point where it stops exuding sulphur trioxide vapour was not properly appreciated. The deposit was later removed by washing with water.

Boiler off-gas The second industrial installation was a demonstration plant that removes both nitrogen oxides and sulphur dioxide from the flue gas of a 110-MW coal-fired boiler. The layout of this so-called SNOX plant is shown in Fig. 4. Boiler flue gas enters the plant at 200[degrees]C and is dedusted in a reverse air bag filter using PTFE membrane/glass fibre bags. Downstream of the blower, the gas is heated by the sulphur trioxidecontaining gas from the sulphur dioxide reactor in a heat exchanger. Nitrogen oxides are reduced by ammonia to nitrogen and water using Topsoe monolithic DNX catalyst, which permits dust to pass through unhindered. After denitrification, the gas is heated to 400420[degrees]C in a light oil burner before entering the sulphur dioxide oxidation reactor, which consists of two vertical catalyst panels. Once the dust trapped in the catalyst has caused about a three-fold increase in the normal pressure drop, half the catalyst is dedusted. This is carried out whilst the catalyst is still hot and without interrupting plant operation. Downstream of the reactor the gas is cooled in two steps, first in the gas-gas heat exchanger and thereafter in the WSA condenser. In a larger plant, such as a 1 million-[Nm.sup.3]/h SNOX plant currently under construction, this air is used as preheated combustion air (about 205[degrees]C) for the boilers. After cooling, the acid is sent to a carbon steel storage tank. During its two years of operation, it has been demonstrated that catalyst cleaning can be carried out with screening losses even lower than those achieved in the suphuric acid industry. The WSA condenser can handle normal changes in the boiler load whilst still maintaining low mist values at the condenser outlet - always below 10 ppmv [SO.sub.3] as acid mist and msotly below 5 ppmv. Even at reduced load, the acid strength is typically 95 wt%. The acid is clear and its metal content e.g. vanadium, cadmium, nickel, arsenic and lead, is below 0.4 ppm, which is satisfactory for use in the fertilizer and chemical industry. As in the firs installation, only carbon steel or low-molybdenum alloy stee is used in the plant, except for the WSA condenser and acid cooler, where ceramics, glass, PTFE and/or lead are used. High concentration off-gases The most recent WSA plant (Fig. 5) was constructed for the coke oven industry but is equally suited to refineries or chemical plants with hydrogen sulphide or sulphur dioxide off-gases containing 6-10% [SO.sub.2]. In this case, the sulphur values are recovered from a coke oven gas cleaning plant. Sulphur dioxide gas leaves a hydrogen sulphide gas incinerator at 420[degrees]C and is taken directly to the oxidation reactor. This reactor contains an adiabatic layer of Topsoe

VK48 catalyst (sulphur dioxide oxidation catalyst with typically 7-9% [V.sub.O.sub.5]), followed by a cooled tubular part containing VK38 catalyst. Cooling is achieved by circulating molten salt (a mixture of potassium nitrate, sodium nitrite and nitrate) to a steam boiler producing steam at 38 bar. The sulphur trioxide gas leaves the reactor at about 420[degrees]C and is cooled in two steps as described earlier. In the first step, most of the sulphur trioxide is hydrated to sulphuric acid vapour and the heat of hydration is released to the salt coolant, adding to the steam production. The acid gas enters the WSA condenser at about 270[degrees]C and is cooled down by air to about 100[degrees]C, whereby the acid is condensed and concentrated. Air is mixed with the off-gas before it is sent to the stack. The materials used for the plant are carbon steel and low-molybdenum alloy steel. Only the WSA condenser has special requirements, as discussed previously. The molten salt used as coolant is non-corrosive. Because of the temperature, low Mo-alloy steel is used for this part of the system. Two pumps with submerged impellers circulate the molten salt, which has a very low viscosity and surface tension and is thus easy to pump. SPENT SULPHURIC ACID REPROCESSING Although sulphuric acid is used in many industrial processes, in many cases it does not form part of the final product. Instead it ends up as diluted waste acid, often contaminted by various impurities, to an extent which depends on the type of process involved. As environmental standards become ever more stringent, it is becoming much harder, or even impossible, to dispose of these spent acids in the traditional way. Industries are being forced to start regenerating spent acids so that they can be recycled. There are three main options for regeneration and recycling, all of which require initial preconcentration of the diluted acid to 20-75% [H.sub.2.SO.sub.4]. After prconcentration, the acid may either be used directly in other processes, be thermally decomposed to sulphur dioxide for conversion to fresh sulphuric acid, or undergo further concentration and purification to 75-98% [H.sub.2.SO.sub.4]. Bertrams technology Spent sulphuric acid has been concentrated to 96-97% [H.sub.2.SO.sub.4] by the evaporation of water for many years. As far ago as in 1915 busching registered a patent for apparatus in which a cast iron boiler with direct [evaporator.sup.5]. The main disadvantages of this arrangement are the limited life of cast iron boilers when in prolonged contact with highly concentrated sulphuric acid and the

danger that, in the event of leakage, large quantities of boiling acid will end up in the combustion chamber and escape with the flue gas. This process, which is still in use today, was the basis on which Bertrams AG, of Switzerland, was invited by Europe's largest reprocessor of spent sulphuric acid - the German chemical giant, Bayer AG - to develop improved equipment which would eliminate these problems. Today Bertrams has technology for regeneration of many different spent [acids.sup.6]. These include: concentration of spent sulphuric acid, with or without oxidative purification to decompose traces of organic materials, to permit recycling to the same user process, e.g. nitration processes; concentration of spent acid for reuse in a different process, e.g. in the fertilizer industry; preconcentration of sulphuric acid before thermal decomposition to reduce the energy consumption in cracking processes; and sulphuric acid concentration plants integrated into processes, e.g. the production of secondary alcohols or the recirculation of sulphuric acid in chlorine drying systems. These processes are, however, not suitable for certain other types of spent acid. Dissolved salts, such as ammonium sulphate, are not removed from the acid, and purification by oxidation is not usually advisable for acids containing a high proportion |[is greater than] 1.5% C) of high boiling or non-volatile organics - from alkylation or oil refining processes, for example. Preconcentration The primary problem in concentrating sulphuric acid to high concentrations lies in the steep increase in the boiling temperature as the concentration rises, as shown in Fig. 6. On the credit side, however, the degradation of organic contaminants is favoured by higher temperatures. The design of the preconcentration stage depends on the through-put, concentration range and quality of the spent acid. Substantial energy savings can be achieved in many cases by using double- or triple-effect evaporations, in which the heat content of vapours from a later stage is used to heat the pre-evaporators. Depending on the quality of the spent acid, either falling-film or forced-circulation evaporators are used. Suitable materials of construction include metals such as Hastelloy C or zirconium, graphite or plastics. In a typical three-stage preconcentration system, the first two evaporators operate under vacuum with the third evaporator operating at atmospheric pressure. The third stage is preferably heated with heat transfer oil, but steam can also be used for certain concentrations. Final concentration/purification

The acid entering the final concentration section is usually already at a concentration of 70-75% or more. However, for low throughputs that do not justify a preconcentration step, dilute acid of any concentration can be fed in. By operating under a vacuum of 80-100 mbar, which can be attained at normal cooling water temperatures, this stage is capable of achieving final acid concentrations in the range 96-98% [H.sub.2.SO.sub.4]. The key to achieving such high concentrations under these conditions is the use of enamelled steel, which possesses excellent corrosionresistance. By using forced circulation and restricting evaporation to the evaporation vessel, fouling is effectively prevented on the heat transfer surfaces. Heat is supplied by a heat transfer oil. The heating system, which is integrated into the concentration plant, is designed for high combustion efficiency irrespective of the fuel used. Gas, oil or conbustible liquid wastes are all possible, and is smaller units the heat transfer medium can be heated by electricty. For every low throughputs the acid can be heated directly by immersing quartz heating elements in the sulphuric acid. High-boiling organics can be removed by injecting an oxidizing agent at this stage, in which case the enamelled steel heat exchanger also serves as a reactor, ensuring maximum removal of organics for minimum consumption of oxidizing agent. Davy know-how Davy McKee became involved in sulphuric acid technology as a result of acquiring the German engineering company Chemiebau Dr A. Zieren in 1972. Waste acid recovery was one of Chemiebau's specialities, and this aspec of sulphuric acid technology is still very prominent in Davy McKee's portfolio. The two processes described here are the regeneration of high-quality sulphuric acid or oleum by the decomposition of spent acid and the production of commercial-grade acid from the exhaust gases of viscose fibre production, by the wet-gas double-absorption process. Thermal decomposition Since 1950, Chemiebau and Davy have successfully deigned and commissioned 13 spent acid decomposition plants with subsequent sulphuric acid production. Plants are tailored to meet the client's needs, e.g. special features may be necessary to accommodate unusual raw materials, to link up with other chemical plants or to comply with particular environmental restrictions. Although the process can be adapted for use over a wide range of capacities, it is particularly suited to processing large amounts of heavily contaminated spent acid. To date, this type of process has been used to reprocess spent acid

from refinery and nitration processes, the synthetic fibre and plstics industry and the organic chemical industry. As a result of a recent agreement, Bayer AG, of Leverkusen, and Davy McKee AG, of Frankfurt, are co-operating in this area of sulphuric acid reprocessing. Davy built a decomposition furnace for Bayer's Dormagen factory in 1978, and since then a great deal of experience has been gained in the treatment of acids from different chemical processes, including those containing high levels of organic and inorganic impurities. By working in collaboration with Bayer, Davy will be able to supply decomposition plants for a wider range of spent acids and will also gain access to detailed know-how gained from many years of operational experience. When appropriate, large-scale industrial trials can be carried out. Figure 7 shows a simplified diagram of a Davy/Bayer spent sulphuric acid decomposition unit. The high temperatures and chemical load place particularly strong demands on the design of the combustion chamber. The vertical main combustion chamber and the secondary horizontal chamber are therefore housed in steel cylinders with a special refractory lining. An outer layer of insulation prevents unnecessary heat loss and ensures that the gas temperature does not fall below the acid dewpoint. Spent acid and fuel (usually fueld oil) are sprayed in, preferably at the top of the furnace. In special cases, fuel or harmful exhaust air can be fed in laterally. Decomposition efficiency depends principally on generating the smallest possible liquid particles and on intermixing the acid, fuel and combustion air as completely and efficiently as possible. Because of the rapid and intensive heat exchange and mass transfer, only small reaction spaces are necessary. Two-component or three-component burners are used, depending on the amount and type of material to be decomposed. Air and/or steam serve as atomizing agents. Combined gas/liquid burners are also available. Preheated air is fed in via special air receivers equipped with spiral blades. The decomposition furnace can also be used as an incinerator for other, non-sulphurous gaseous or liquid waste products. About 50% of the energy supplied can be recovered from the gases and vapours generated during the decomposition in the form of saturated steam or hot air. The degree of heat recovery is dependent on the impurities present in the spent sulphuric acid. Impurities which form a melt are drawn off from the bottom of the furnace continuously or periodically. The air preheater is a specially designed radiation heat exchanger. Because of the direct gas/air flow, corrosion is avoided. The air preheater in Leverkusen has been in operation for more than 8 years.

For reasons of corrosion, waste heat boilers are operated at pressures of 60-80 bar with forced circulation. The saturated steam is superheated in the boiler itself or in a separate unit. The boiler is adapted to suit th special operational conditions. The boiler can be scrubbed and its heating surfaces cleaned by soot blowers to remove harmful deposits during operation. During shutdown periods, the decomposition furnace and the boiler are separated by a cooled sliding gate. The quench/scrubbing unit after the air preheater has been specially designed and, together with the subsequent electric precipitator, guarantees a high gas cleaning efficiency. Sulphuric acid from a viscose fibre process The exhaust gases from the viscose fibre process contain [H.sub.2.S] and [CS.sub.2] of varying concentrations. Davy has developed a wetgas double-absorption process that uses gas containing about 42 vol.% [H.sub.S] and 13 vol.% [CS.sub.2] plus additional sulphur as the feedstock. The first plant was designed, engineered and erected for Lenzing AG in Austria. It has now been in operation for 4 years, producing 98.5% [H.sub.2.SO.sub.4] with a 99.8% [SO.sub.2]/ [SO.sub.3] conversion. The plant has been fully reliable since start-up. The acid produced contains extremely low levels of iron and sulphur dioxide and is practically free from nitrogen. The process has been based on more than 40 years experience with single wet-gas catalysis. To be precise, it is in fact a wet-dry catalysis process, since it comprises three wet gas catalysis beds and a fourth dry bed after the intermediate absorption stage (Fig. 8). Since acid mist is formed in the gas phase during cooling, the design of the intermediate absorption tower and subsequent mist eliminator is of fundamental importance. Special care is taken to keep all gas temperatures above the dewpoint temperature. By using a special glass fibre filter design, it has been possible to achieve sulphur trioxide contents below 50 mg/[Nm.sup.3] after intermediate absorption and less than 10 mg/[Nm.sup.3] in the stack gas. References [1] McAlister, D. R., Grendel, R. W., Schneider, D. R., Schafer, J. R., and Tucker, J.S.: "A sulphuric acid plant for the 1990s". In "Sulphur 1990": Preprints for the International Conference, Cancun, Mexico (Apr 1990), pp. 267-278.

[2] Matros, Yu. Sh. : "Unsteady-state oxidation of sulphur dioxide for sulphuric acid production". Sulphur (183), 23-29 (Mar-Apr 1986). [3] Matros, Yu. Sh., and Bunimovich, G. A.: "Reverse-process of [SO.sub.2] oxidation in sulfuric acid production". "Sulphur 1990", pp. 249-265. [4] Jensen-Holm, H., and Rud-Bendixen, O.: "Industrial experience with the Topsoe VK58 sulphuric acid catalyst and WSA-2 process". "Sulphur 1990", pp. 291-310. [5] Kuhnlein, H. L.: "Aufarbeitung von Abfallsauren". Schweizer Ingenieur und Architekt 16 (1988). [6] "Concentration and Purification of Sulphuric Acid". Bertrams AG, Basel. COPYRIGHT 1990 CRU Publishing Ltd. This material is published under license from the publisher through the Gale Group, Farmington Hills, Michigan. All inquiries regarding rights should be directed to the Gale Group.

Title: Sulphuric acid catalysts: the continuing evolution of process technology. (Technology) Date: 8/1/1990; Publication: Fertilizer International; Sulphuric acid is made by converting sulphur dioxide into sulphur trioxide and then absorbing this gas in water water - actually, a solution of water in sulphuric acid.
2SO[.sub.2] + O[.sub.2] in equilibrium with] 2SO[.sub.3] SO[.sub.3] + H[.sub.2]O -> H[.sub.2]SO[.sub.4]

The sulphur dioxide is provided by a number of diverse routes, but the most common is by burning sulphur in a furnace at around 1000 degrees C. Other sources include the roasting of pyrites, the smelting of non-ferrous metal ores and other high temperature processes, such as burning spent sulphuric acid which has been used in oil refining. Depending on the process by which SO[.sub.2] is generated, gas streams containing 8-13% SO[.sub.2] are normally fed to the converter. Lean gases containing only 4-6% SO[.sub.2] are sometimes produced in smelter operations, and they are not always economic to use, while at the other extreme, gases containing more than 13% SO[.sub.2] are rarely produced by burning in air.

Apart from SO[.sub.2] concentration, the essential difference between a sulphur-burning plant and those which derive the sulphur dioxide in most other ways is that elemental sulphur is an essentially clean feedstock, so that the sulphur dioxide produced can be passed to the contact converter without further treatment and enters at high temperature (the so-called hot-gas plant). Sulphur dioxide laden gases from most other processes, for example pyrites roasters and metal smelters, usually need cleaning from dust prior to the contact stage and therefore is cool when it reaches the converter (the so-called coldgas plant). This loss of heat represents a considerable energy value, but if the dust were not removed, it would collect in the catalyst beds of the converter, increasing pressure drop and reducing catalyst activity. This is just one way in which the needs of the catalytic process affects operating procedures. There are many others. Since the early 1970s, the cost of energy, the cost of capital equipment and the concern for the environment have had major effects on the operation of sulphuric acid plants. The double-absorption process, which enabled SO[.sub.2]/ SO[.sub.3] conversion to rise from 98% to 99.7%, had a major impact both on raw material consumption and emission levels. The rise in the cost of energy has meant, of course, that much attention has been focused on the effective use of heat within the process, but it has also meant close attention to pressure drop and power consumption needs. Furthermore, the relatively high cost of capital plant has meant that capital cost-related factors such as plant throughput, onstream performance, and downtime have increased in importance. The choice of catalyst and the performance of the catalyst over its working lifetime affect all of these issues and more besides. Catalyst activity has an effect on the temperature at which the converter operates, which directly affects energy consumption, the conversion efficiency and the emission levels of sulphur oxides, pressure drop and gas throughput, and the period of operation possible between shutdowns. Why is a catalyst necessary? In the contact process, the gas-phase oxidation of SO[.sub.2] to SO[.sub.3] is an equilibrium reaction; that is to say, the reaction can go in either direction, depending on the conditions. 2SO[.sub.2]+ O[.sub.2] [in equilibrium with] 2SO[.sub.3] Because the forward reaction gives off heat and the backward reaction absorbs heat, if heat is removed from the system by lowering the temperature, the backward reaction is discouraged, so the position of equilibrium shifts towards sulphur trioxide (Fig. 1). But the system

requires a substantial amount of heat before it will react in either direction, and at the temperature needed to make it react at a practical rate the equilibrium yield of sulphur trioxide is unsatisfactory. What the catalyst does is to increase the rate of reaction by lowering the "activation energy" requirement of the reaction, allowing the temperature to be reduced to the point where a good conversion rate is obtained. With catalysts in use today, a temperature of about 400 degrees C is needed to initiate a self-sustaining reaction; however, since the reaction is exothermic, the temperature within the catalyst mass will rise unless heat is removed. Since the higher the temperature the lower the equilibrium SO[.sub.3] yield, the temperature rise would ultimately be self-limiting, but in practice it never reaches the natural upper limit because the temperature has to be limited to around 650 degrees C to prevent damage to the catalyst. Although it would in theory be possible to limit the temperature in the catalyst bed by withdrawing heat through cooling tubes immersed in the catalyst, this is not a very practical arrangement for large-scale use: instead, the catalyst is divided up into several separate masses or "beds" in which the reaction takes place without cooling, and the gas leaving each bed is cooled before it is admitted to the next. The converter itself is simply a vessel in which the gaseous oxidation reaction takes place. The usual arrangement is for the catalyst to be distributed in the converter in four, or sometimes five, separate beds. Reaction gases are passed through the beds sequentially, and between the "passes", the gases are cooled. In the double-absorption process, which is now the industry standard, at an intermediate point - usually after the third catalyst pass - the gases are withdrawn from the converter and passed to an intermediate absorber, where the sulphur trioxide formed so far is absorbed in very slightly diluted sulphuric acid. This allows further conversion of sulphur dioxide to trioxide when the gases are reintroduced into the converter for a final reaction stage. Although platinum-based catalysts were used in the early days of the contact process, all commercial catalysts used today are based on vanadium pentoxide as the active ingredient. The vanadium pentoxide, together with promoters" usually consisting of alkali metal sulphates, is adsorbed on a porous silica support. Sometimes, the catalyst also contains "moderators", to prevent the reaction from proceeding too quickly. How catalysts work A number of theories have been put forward suggesting ways in which the catalyst works, but the mechanism most usually accepted is that the oxidation is a homogeneous reaction taking place on both internal and external surfaces of the catalyst support, in a liquid melt of active components. Sulphur trioxide reacts with the alkali metal sulphate to form pyrosulphate melt:

SO[.sub.3](g) + SO[.sub.4]= -> S[.sub.2]O[.sub.7]=(l) It is in this melt that the oxidation mechanism takes place. According to one model (Mars & Maessen), the oxidation of SO[.sub.2] to SO[.sub.3] takes place in two stages. In the first, sulphur dioxide is oxidized in the presence of vanadium, and the oxidation state of the vanadium is reduced in the process. In the second stage, the oxidation state of the vanadium is restored. SO[.sub.2] + 2V[.sup.5] + O= [in equilibrium with] + 2V[.sup.4+] + SO[.sup.3] 0.5O[.sup.2] + 2V[.sup.4+] [in equilibrium with] 2V[.sup.5+] + O= Commercial catalysts contain 4-9 wt% vanadium pentoxide and lesser amounts of the alkali metal promoter; potassium sulphate normally accounts for the bulk of the promoter present, and the K:V atomic ratio is usually 2-4. Other alkali metal sulphates may be used in minor amounts to adjust the melting point of the pyrosulphate. Catalyst formulation - a balancing act The formulation of catalysts essentially involves balancing the characteristics and properties of the various ingredients which are mutually exclusive. High activity is required with high mechanical strength; stability over a range of temperatures is also necessary. A low bite (or strike) temperature may be advantageous, but peak activity at high temperature may also be required. A long service life is important, but so is pressure drop across the catalyst bed, and the catalyst must not be poisoned. It is possible to make a catalyst which is hard but with poor activity, or a catalyst with high activity which is very soft. It is also possible to make one which is very active at low temperature, say 350 degrees C, but which has poor performance at the normal operating temperature of die converter; equally, another may have high activity at high temperature, but does not become active until 430 degrees C. The balancing of all these factors to produce the best compromise both for normal circumstances and for specific and unusual circumstances encountered in individual plant operations - is the job of the catalyst manufacturer. Vanadium catalyst is made in the form of extruded pellets, and physical form and structure affects activity, pressure drop and the durability of the catalyst. The support material is usually a natural kieselguhr, which can be variable in behaviour. The material is composed of fossilized skeletons of marine diatoms and is mined in various parts of the world. Its absorption behaviour is affected by the size of the particles and their internal- structure, which in turn depends

on the types of diatom skeletons present. Vanadium contact catalyst was originally made in the form of solid pellets, but interest in reducing pressure drop over recent years has led to the development of rings. Further, since activity depends - among other things - on surface area, various extruded ring forms have been introduced with textured or convoluted exteriors. It should be remembered, however, that if these more complicated structures should result in more catalyst break-up during operation, with attendant loss of activity and increased pressure drop, then such improvements are all for nothing. Catalyst poisoning Many catalysts used in industrial processes are susceptible to deactivation resulting from damage or chemical contamination (poisoning) by impurities. Although the earlier platinum catalysts were easily poisoned, vanadium catalyst is relatively insensitive to poisons. Arsenic will build up in the catalyst, but unless the As[.sub.2]O[.sub.3] content in the catalyst mass exceeds 15 wt%, little decrease in activity is observed. Arsenic is rarely found in recovered or mined elemental sulphur today, but it was an impurity of native sulphur produced in former times. Nowadays, the main source of arsenic in sulphuric acid plants is in the roasting of arsenical pyrites, where special roasting techniques and processing operations are used to prevent the material from reaching the contact converter. Fluorine and chlorine are both serious poisons for sulphuric acid catalysts, the latter being introduced in sulphur cargoes from time to time by the ingress of seawater during ocean transport or contamination by sea spray or mist during storage. At elevated concentrations, fluorine compounds will attack the silica support material, leading to physical breakdown in extreme cases. Chlorine and chlorine compounds attack the vanadium active ingredient itself, leading to vanadium volatilization, especially at high temperatures. Water vapour is not deleterious to the catalyst as long as the temperature is sufficiently high to prevent condensation of sulphuric acid. There are many reasons why condensation of acid mist should be avoided in sulphuric acid plant operation, including risk of corrosion, but condensed water vapour can have an effect on the catalyst itself. At low temperature - for example, during start-up and shut-down - the ingress of humid air can lead to water being absorbed by the catalyst, impairing mechanical strength. Temperature range The point at which a catalyst becomes active, the bite or strike temperature, is an important consideration in catalyst formulation. Ideally, this should be as low as possible, since the SO/ SO[.sub.3] equilibrium is more favourable at low temperature; moreover, the lower the temperature at which the reaction can be sustained the less heat will be needed to warm the incoming gas. But the

SO[.sub.2]/SO[.sub.3] reaction is strongly exothermic, and the temperature of the gas stream in the converter can rise quickly once the reaction has begun. Accordingly, high temperatures can be reached in the middle of the catalyst mass, particularly in the first bed, where the concentration of reactants in the gas is highest. Operating temperatures up to 650 degrees C are not unusual; for effective plant operation, therefore, a catalyst must be able to tolerate such high temperatures and, moreover, maintain high activity. Conventional catalysts have a working temperature range between 400-410 degrees C and 630-650 degrees C. It is possible, by adjusting the melting point of the alkali metal sulphate promoters, to produce catalyst which becomes active at lower temperatures, down to about 370 degrees C Fig. 2). Such catalysts will contain higher proportions of sodium sulphate, and possibly also sulphates of caesium and/ or rubidium. During its working life, the bite temperature of any catalyst will rise by 25-30 degrees C as it becomes dirty, so that standard catalyst may bite at 425-430 degrees C and low bite material may begin working at 395-400 degrees C. Service life The service life of a catalyst, which may average up to ten years, is affected by all the considerations mentioned above. The catalyst may need replacing because it has been poisoned, because it has lost activity in a crucial temperature range, or because it has become physically degraded by the wear and tear of normal operation. Since the first catalyst pass bears the brunt of the demands of processing, it is this catalyst bed which is usually in need of special attention. Any dust generated during the production of the SO[.sub.2] feed for the converter, either as unfiltered smelter dust or as ash present in elemental sulphur feed, will collect in the first catalyst bed. It may have a simple clogging effect, or otherwise contribute to the deactivation of the catalyst. For this reason, in former times, it was customary to install a hot gas filter before the contact converter, but in the interest of reducing operating costs, this device is now commonly omitted from the flow-sheet of plants burning high-quality elemental sulphur. Dust also arises from the physical breakdown of the catalyst itself during service, and again, it is often the first catalyst pass which is most affected. At times of maintenance, the catalyst can be removed for screening and then replaced, or otherwise it may be sufficient simply to rake it to restore activity. Nowadays, removal for screening is often done pneumatically, and the pellets themselves must be durable enough to withstand the handling operations involved. Depending on the operating circumstances of the sulphuric acid plant and the precise nature of the feed gas, converter design for easy and regular catalyst maintenance may become a very important issue. In conventional converter design, the first catalyst bed is at the top of the converter, but in the Chemetics converter design, for example, it is at the bottom,

at ground level for ease of access to and removal of the catalyst charge (Fig. 3). Catalyst use - operating practice From the foregoing, it can be seen that contact catalysts can be formulated to suit certain conditions, by adjustment of the active ingredients. "Standard" catalysts are made to suit standard conditions, encountered in most plants over their normal operating range, with high activity over the whole temperature range 420-630 degrees C, for example. In recent years, efforts have been made to extend the operating range of standard catalyst types, so that one catalyst can be suitable for a wider range of applications. At the same time, however, other catalyst types have been developed which focus on specific aspects of use, low bite for example. Changing catalyst formulation to increase activity in one range of operating conditions may cause a decrease in activity in another range of operating conditions. Important operating parameters from the standpoint of catalyst choice are operating temperature, feed SO[.sup.2]concentration to the converter, SO[.sub.2]/ O[.sup.2] ratio, pollution and SO[.sub.2] emission regulations. For the operator, the choice is almost dazzling, and he has the additional option of mixing catalyst types - using different catalysts in individual beds to suit the conditions, and also to use more than one catalyst in a single bed. Optimizing the operation of a sulphuric acid plant can often mean optimizing the deployment of catalyst. A few examples are given to demonstrate the possibilities. Buyers' choice Most catalyst manufacturers have optimized a standard catalyst, which offers satisfactory operation over a wide range of conditions. Examples include the BASF 04-110, Haldor Topsoe VK38, and equivalent types from Monsanto and others. These are typically rugged, thermally stable, and with high activity over a broad range of operating conditions. Operating temperature range is one factor which has been the subject of development, since this should be as wide as possible with a lower limit as low as possible and a higher limit as high as possible. Recent development by BASF has resulted in a catalyst with what appears to be an extremely wide operating temperature range. The 04115 is claimed to have high activity at inlet temperatures down to 370 degrees C and excellent thermal stability up to 680 degrees C. The catalyst, which is said to be based on a revised active phase and a new (unspecified) carrier, appears to offer the ultimate in versatility in a single product. The Haldor Topsoe approach has been different. Since 1987, this company, which has been producing its VK38 ring-type catalyst for

many years, has introduced the VK48 high-vanadium, high-activity catalyst and the VK58 low-bite catalyst, as additional products to cope with specific circumstances. The VK48 product is designed to be used in the last two catalyst beds in the converter, where the SO[.sub.2]concentration is relatively low. In this way, it is possible to reduce emissions of unconverted sulphur dioxide by as much as 30%. The low-bite VK58 is typically used as a partial charge in the first catalyst bed, along with VK38 (see Table). The low-bite characteristic means that plant energy consumption is reduced and higher conversion efficiencies are possible in comparison with the use of the standard VK38 alone. Low-bite catalysts of this type can be particularly useful in smelter gases where the SO[.sub.2] feed is enriched with oxygen. The company cites as an example a case study at a Canadian copper smelter. VK58 was installed in the upper half of the first catalyst pass, using VK38 in the lower half. The smelter operated on oxygen-enriched air and the feed to the contact converter contained up to 14% SO[.sup.2] and 15% O[.sup.2] both very high figures. At a normal firstpass inlet temperature of 410-420 degrees C, this very reactive gas would take the exit temperature to 660 degrees C. The use of VK58 in this way enabled the plant to operate at an inlet temperature as low as 380 degrees C, which limits the exit gas temperature to 635 degrees C. At the other extreme, the same VK58 low-bite catalyst has been successfully employed in the fourth catalyst pass, to accommodate low inlet temperatures. Examples include both copper roaster and sulphurburning plants where, for operating reasons, inlet temperatures on the final catalyst pass were below 400 degrees C. Apart from concerns about formulation itself, the mere size and shape of the catalyst can also have significant effects on plant performance. The use of rings rather than pellets has already been mentioned, as has the fact that the rings must be durable if serious disintegration problems are not to occur. Many catalysts, whether rings or pellets, are made in the 6-8 mm size range. Larger sizes result in reductions in pressure drop, which is beneficial to plant operation as long as catalyst activity is not adversely affected by reduced surface area. Nowadays, rings and pellets in the 10-14 mm range are supplied for a combination of high activity, durability and low pressure drop. We are unlikely to have seen the end of developments in sulphuric acid catalysts, even though the basic system has remained unchanged for the best part of thirty years. As in the past, improvements in formulation and better understanding of the mechanisms involved will play their part in improving sulphuric acid plant operation in the years to come. (Figures Omitted)

COPYRIGHT 1990 CRU Publishing Ltd. This material is published under license from the publisher through the Gale Group, Farmington Hills, Michigan. All inquiries regarding rights should be directed to the Gale Group.

Title: Systems for enhanced energy recovery. (Sulphuric Acid Technology).(production management techniques)(Brief Article) Date: 1/1/2002; Publication: Sulphur; Author: Connock, Lisa Since the role of a modern sulphuric acid plant as a thermal power station has become increasingly important, different methods for recovering and utilising the released heat during sulphuric acid production have been developed. Modern systems now utilise heat evolved in the absorption and drying stages of the plant. A sulphur burning sulphuric acid plant is a net exporter of energy. Approximately 65 MW of heat is evolved in a 1000 t/d sulphur burning sulphuric acid plant. All the main process steps such as sulphur burning, conversion, and absorption are exothermic. In fact, approximately 98% of the energy input comes from energy released by the chemical reactions and the remainder comes from the main blower drive as heat of compression. The energy that is produced during sulphur burning and conversion is utilised for high-pressure steam generation and/or superheating. In the classic process cycle this represents 55-65% of the total energy. In conventional plants, the energy available from acid formation and dilution represents 35-42%, a further 2-3% of the total energy is released with the tail gas via the stack and 0.5% is lost as sensible heat in the product acid. The heat evolved in the absorption and drying stages has traditionally often been rejected to the sea or air via large shell and tube heat exchangers or air coolers. This wasted heat amounts to approximately 740 MWh per 1000 tonnes sulphuric acid produced. In the late 1980s a significant step toward more highly efficient plants was taken with the introduction of heat recovery systems generating steam from the acid circuit. In these systems, part of the heat formed in the absorption circuits, which was normally dissipated with the cooling water, is transferred to a higher level and used for the production of low-pressure steam at 6-10 bar. Such heat recovery systems are normally installed in the intermediate absorpdon circuits. Monsanto's HRS system and Lurgi's HEROS system represent two different approaches to heat recovery systems of this type. Detailed

descriptions of both processes were featured in Sulphur No. 262 (1) and so only a brief description and update are provided here. HRS Monsanto Enviro-Chem introduced the Heat Recovery System (HRS) commercially in 1987. The HRS can produce steam at pressures up to 10 atm from heat normally lost in acid cooling systems. About 0.5 kg steam/kg acid can be made this way thus boosting overall steam production on sulphur burning plants to about 1.85 kg/kg acid produced. When this steam and the higher pressure steam from Monsanto's energy efficient plant is used to make power, a 1000 t/d sulphur burning plant can produce a total of 13.1 MW (10.0 MW from plant and 3.1 MW from HRS addition). For new sulphur burning plants of different capacity, these figures can be scaled proportionately. Figure 1 shows a simplified HRS flow scheme There have been a total of 20 HRS units sold to date both on new and existing installations and in both sulphur burning and metallurgical sulphuric acid plants. The largest HRS is on a 4400 t/d sulphur burning plant for Anaconda Nickel in Australia. This technology will also be very suitable for pyrites burning plants, being able to raise the production of high-pressure steam as well as make medium pressure steam. The Heat Recovery System is basically an absorber that operates at 400[degrees]F (204[degrees]C) and uses a boiler to remove the absorption heat as steam instead of acid coolers where heat is wasted. The hot gases leaving the first stage are then cooled in the second stage and the remainder of the [SO.sub.3] absorbed. Gases leaving the tower are essentially the same as gas leaving a conventional interpass tower. The Monarch process For maximum power production Monsanto offers its patented Monarch process -- a synergistic combination of the wet gas process and Monsanto's high temperature acid heat recovery system (HRS). The wet gas process sulphuric acid plant is characterised by the absence of a drying tower. In a standard wet process plant, all parts of the equipment in contact with wet gas are kept above the dew point to prevent condensation and subsequent corrosion. Therefore, some of the process gas temperatures are kept as high as 270[degrees]C. As a result, some sensible heat as well as all of the latent heat in condensation of acid mist are unavailable for recovery. During the development and implementation of HRS operating temperatures and materials of construction were identified that would

allow use of the heat transfer treatment below the acid dew point without significant corrosion. A grass roots Monarch acid plant combines a wet gas process plant and an HRS system, along with a humidifying tower, to ensure sufficient moisture in the air, and a condensing economiser. The major part of enhanced energy recovery in a Monarch plant occurs in the condensing economiser. Dilution water, added in the form of moisture in the humidifying tower, is present in the gas leaving the third pass. As the gas is cooled in the waste heat boiler and condensing economiser, some of the [SO.sub.3] reacts with the water to form sulphuric acid vapour. About 25% of this reaction heat is recovered in the boiler and the remainder in the economiser. Some acid is condensed in the economiser, which is designed with the same alloy as the HRS tower. Two major features of the Monarch technology that are a direct result of the wet gas cooling are: * Essentially all of the process heat is recovered as steam, eliminating the need for cooling water. * The heat of utilisation is shifted from production of medium pressure steam to production of high-pressure steam, resulting in higher power production. For a 3000 t/d acid plant the net power export increase is up to 48% over a conventional sulphur burning plant and up to 16% over a sulphur burning HRS plant. The individual elements of Monarch have been demonstrated such as steam injection and the condensing economiser, but a complete system has not been put into operation as of yet. The key to commercialisation of the Monarch process will be power prices in excess of US$50/MW-hour. HEROS Lurgi's Heat RecOvery System (HEROS) was developed with particular emphasis on ease of operation and safety. Key elements of the HEROS is a venturi absorber with a dedicated acid circulation system that is installed upstream of the inter-absorption tower. Heat generated in this system is transformed into low-pressure steam in a specially designed boiler. The corrosion resistance of the materials of construction does not rely on extremely close control of operating parameters. The design permits the shut down of the HEROS while the interabsorption tower remains in full operation. This system can be retrofitted in existing sulphuric acid plants provided there is sufficient space available in the absorption section. A number of additional facilities ensure simple and safe operation. Figure 2 shows a simplified flow diagram.

HEROS can produce steam at pressures up to 10 barg saturated. About 0.6 t steam/t acid can be recovered as low-pressure steam. The precise amount depends on different factors (see Fig. 3). For a Lurgi 1000 t/d sulphur burning sulphuric acid plant with a thermal capacity of approximately 63 MW, up to 70% of the total energy is utilised for the generation of high-pressure steam. Approximately 24% of the remaining waste heat is produced in the inter absorber circuit, of which, a two-stage HEROS process makes use of about 95%. The total possible power from the plant amounts to 58.5 MW with 14.4 MW (approx 23%) of the total power attributed to HEROS. Translated into electric power, the plant produces 15MW. HEROS has been installed in 5 sulphuric acid units ranging in capacity from 130 t/d to 3,500 t/d, in both new plants and retrofits. Low-level heat recovery at Fertiberia Lurgi has also built a number of other heat recovery systems since 1976. Three main areas of application have emerged involving production of hot water for: * communal and domestic heat supply systems, * phosphoric acid concentration, * industrial utilisation. At the Sulphur 2001 Conference in Marrakech in October, E. Seitz of Lurgi Metallurgie presented the results and experiences of Fertiberia at Huelva, Spain, where for the past 15 years low level heat recovery from the sulphuric acid plant (equivalent to 20 t/h of low pressure steam) has been successfully utilised for phosphoric acid preconcentration. (2) The process can be described as an intermediate absorption shell-andtube cooler linked with a shell-and-tube heat exchanger in a phosphoric acid concentration unit by means of a closed D.I. water circuit. Low-grade energy utilisation at Kemira Kemi Besides sulphuric acid, many production sites also manufacture products such as liquid sulphur dioxide, oleum, high purity acid and liquid sulphur trioxide. When these processes are cooled in order to keep the temperatures down, low value energy is often released at low temperature. In 1998, Kemira Kemi of Sweden introduced a new heat recovery system at its sulphur burning sulphuric acid plant in Helsingborg to make use of the low grade energy from processes such as the production of liquid sulphur dioxide, oleum and high purity acid. (3) Energy from these low temperature processes is released to the main

acid circulation and then recovered in the acid coolers at a higher temperature. At Kemira Kemi the total acid system is cooled by a closed loop that delivers energy from the acid system to a district heating system. The new heat recovery system has resulted in increased energy savings in the region of 2.2 MW. The cost of the new system was 220 kEUR. Calculated with an oil price of 20 EUR per MWh the system was paid off in less than one year. Acid plant background/history In 1991 Kemira Kemi shut down two pyrite roasters and converted a third into a sulphur burning sulphuric acid plant with a capacity of 17 t/h sulphur. Combustion is carried out in two steps to minimise the formation of nitrogen oxides. The first step is substoichiometric with an air/sulphur ratio normally of 0.95. After the first step the gases pass through a boiler in which 46 bar steam is produced. When the gas passes through the boiler the temperature decreases from 1800[degrees]C to 700[degrees]C. After the second combustion stage the sulphur dioxide concentration is 17.5%. After combustion the gas is cooled down in super heaters and divided into two streams. One is taken out for production of liquid sulphur dioxide; the other goes to a static mixer before converter bed No.1. The main gas flow from combustion is mixed with the exit gas from the liquefaction plant and air from the main blower. Air is added to give an [SO.sub.2] content of 250 ppm after final absorption. The gas composition before bed No.1 is typically 10.5% sulphur dioxide, 8% oxygen and nitrogen as balance. After final absorption there is a hydrogen peroxide scrubber, which decreases the [SO.sub.2] content to 35 ppm, well below the requirement of 125 ppm. The sulphuric acid concentration in the scrubber is around 10%; therefore 1.5 tonnes water is evaporated per hour. Finally the gas passes through a final drying tower. In the tower, water from the hydrogen peroxide scrubber is condensed/absorbed. Product acid of 98% from one of the two parallel air drying towers at the front end of the plant is used to maintain the acid concentration in the final drying tower between 95 and 96%. The system was rebuilt to a single acid circuit (mono acid system) in 1999. Originally there were separate pump tanks for each tower. Today they have been replaced by one brick-lined stainless steel pump tank. Since 1998 all the drip acid from tower demister filters in the single acid circuit has been collected and processed in a NOx removal plant. The production of liquid sulphur dioxide is carried out by partial condensation. The gas concentration is lowered from 17.5% to 6%, which corresponds to the vapour pressure at a temperature of54[degrees]C.

Production of oleum (65% and 25%) and high purity sulphuric acid is carried out in a separate building. Heat recovery and cooling systems background/history In the beginning the heat generated in the absorption and drying circuits in the old pyrite roasters was rejected to the sea. In the 1980s a heat recovery system was installed and the released heat (up to 60 MW) was used for district heating. The heat recovery and cooling systems that were built in the acid plant were all based on a number of closed cooling loops. Potential fouling is then reduced to the seawater coolers and they are easy to clean. Energy released as heat in the single acid circuit is cooled off by the socalled hot water loop (HW loop). From the pump tank acid is circulated through three parallel plate heat exchangers. Product acid form one of the air drying towers is also cooled by the loop. Process gas to the liquefaction plant passes a sulphur trioxide absorber on the way to the condenser. The acid that is circulated over the [SO.sub.3] absorber is also cooled by the HW loop. A minor part of the energy that the HW loop has collected in the acid system is used for preheating boiler feed water. The main part is delivered to the district heating system. In the beginning this amounted to approximately 21 MW. There are also two seawater emergency coolers on the loop to be used in case of any failure or problems with the district heating system. The warm water loop (WW loop) works on a temperature level from 30 to 45[degrees]C. It is used for cooling the acid that is circulating over the final drying tower from which it collects the heat of water condensation and acid dilution (about 1.3 MW). Originally the closed loop was cooled by seawater to the sea. The oleum and high purity acid towers are cooled by the oleum cooling loop. The temperature range in the loop is from 25[degrees]C and 40[degrees]C. The energy from cooling with seawater was 0.3 MW. In the [SO.sub.2] liquefaction plant there is a closed cooling loop on which the condenser for the circulating cooling media is placed. The lubrication oil that is circulated together with the cooling media is separated and cooled by the same loop. The power that is cooled off by the oil coolers is 0.5 MW and temperature of the oil after the coolers is 60[degrees]C. Seawater is used to cool the loop. The 98% product acid that leaves one of the drying towers was cooled in two stages, firstly by the HW loop and then by the product-cooling loop. The 95-96% product acid from the final drying tower was cooled by the same loop using seawater. The 98% product acid was cooled

from 55[degrees]C to 30[degrees]C and the 95-96% acid was cooled from 45[degrees]C to 30[degrees]C, amounting to 0.3 MW energy. In the NOx removal p1ant the acid that is circulated over the stripper/saturation tower was cooled directly with seawater. The power was approximately 0.1 MW and the temperature level on the acid side was 40[degrees]C. Development of the heat recovery system All the low-grade energy sources available for heat recovery are shown in Table 1. They have all been cooled with seawater. The first step was to connect the product acid cooling loop to the power station for preheating of demineralised water. Installation costs were 30,000 EUR and the pay-off time was less than 1.5 years. There was a margin to increase the delivery to the direct heating system. The basic idea was to make the low-grade energy available at a higher temperature so that it could be transferred to the HW loop and from there to the district heating system. Water that is added for acid formation and dilution is normally put into a pump tank, to an absorption tower directly or to the piping leaving the tower or a specific dilution tank. The idea was that part of the water, which is normally added in liquid form, could be added as vapour instead. This would be done by heater water with energy from the above-mentioned sources. The water is then fed to an evaporation tower (cooling tower) and as the combustion air passes through the tower the temperature and humidity of the air is increased and the water is cooled. The water saturated combustion air is then passed through one of the air drying towers and the water is absorbed/condensed in the circulating acid. Heat released during water vapour condensation and acid dilution can then be taken out in the acid coolers connected to the air drying tower or in Kemira Kemi's case with a single acid circuit in the main acid coolers together with the heat of acid formation from the absorption towers. The driving force for the processes is the differences in water vapour pressure between the different streams. In the evaporation tower it is the difference between water partial pressure in air and the vapour pressure above the water that is sprayed into the tower. In the drying tower it is the difference between water partial pressure in air and water vapour pressure above acid feed to the drying tower.

Since the air drying tower was designed for higher inlet temperatures with saturated gas, the extra load due to the evaporation system is still within limits. The heat recovery system today The evaporation system was installed in 1998. In the first phase the WW loop was extended with one new heat exchanger, through which water is circulated form the pump tank at the evaporation tower. The seawater cooler is now only on stand by in case of any problems or maintenance with the heat recovery system. Later on, the oleum cooling loop was connected to the new water circulation. Cooling of the NOx removal plant was included in the oleum cooling loop. The final area to be subjected to heat recovery was the oil coolers in the liquefaction plant. Due to geographical distances they were not directly put on the new water circulation, instead they were added to the WW loop. The complete system as it looks today is shown in Fig. 4. The amount of energy recovered in the evaporation tower during normal operation of the plant is 2.2 MW. This is divided between the increase in sensible heat of air and evaporation of water. The evaporation of water accounts for 1.5 MW, equal to 2.3 t/h water. Heat recovery with desalination For sulphuric plants situated close to the coast in geographical regions where fresh water is scarce, e.g. plants in the Middle East and North African countries, a new trend is the heat recovery of low enthalpy from the circulating acid in the intermediate and final absorption towers for desalination of sea and brackish water. (4) By using plate heat exchangers, 90-95% of the heat from the circulating acid can be economically recovered, even at temperatures between 80 and 100[degrees]C, and with only minor changes to the existing systems. Hence it should be attractive for both retrofits of existing plants as well as new plants. There are big advantages from both an installation and operation standpoint when using plate heat exchangers for sulphuric acid heat recovery and falling film plate evaporationrs for the thermal exchange surface in the desalination system. The high k-value of the plate system gives smaller heat transfer areas and compact installations. The investment for recovering heat from circulating acid enhances profits and reduces the independence from external distributors of high quality water. Alfa Laval has developed computer software that can estimate the precise profitability of the investment for heat recovery with desalination for specific cases.

References (1.) Connock L.: "Maximising energy savings in sulphuric acid plants", Sulphur No. 262, pp.33-41 (May-June 1999). (2.) Arechaga E., Garralda J. and Seitz E.: "Phosphoric acid preconcentration: An application for low level heat recovery in sulphuric acid technology". Sulphur 2001, Marrakech, Morocco (Oct 2001). (3.) Lanner M. and Palssson L.: "How to make use of the low-grade energy in a sulphur burning sulphuric acid plant". Sulphur 2000, San Francisco, USA (Oct/Nov 2000). (4.) Lovato, A: "Heat recovery enhances profit", Sulphur No. 267, pp. 41-46 (March-April 2000). [Figure 3 omitted]
Table 1 Low grade energy available for heat recovery Closed loop WW loop [SO.sub.2] plant Oleum coling loop Product acid cooling loop NOx removal plant Closed loop WW loop [SO.sub.2] plant Oleum coling loop Product acid cooling loop NOx removal plant Source final drying tower oil coolers oleum & high purity acid product acid stripper/saturation tower Temperature Level ([degrees]C) 30-45 45-55 25-40 25-35 40 Effect (MW) 1.3 0.5 0.3 0.3 0.1

COPYRIGHT 2002 CRU Publishing Ltd. This material is published under license from the publisher through the Gale Group, Farmington Hills, Michigan. All inquiries regarding rights should be directed to the Gale Group. Title: Wet catalysis sulphuric acid processes dispose of problem waste gases. (controlling waste gases in sulphur production) Date: 7/1/1991; Publication: Sulphur; Though by-product hydrogen sulphide is usually converted to elemental sulphur, that is not always desirable, economic or even

practical. Although the contact process used as the basis of nearly all sulphuric acid plants in the world today is inherently unsuitable for directly processing the moist feed gas resulting from the incineration of hydrogen sulphide, as long ago as the 1930s the German company Lurgi had worked out a modification of the contact process which could do this without recourse to the cumbersome and costly expedient of cooling, drying and reheating the feed gas first. Over the years, Lurgi alone has built more than 60 plants using the original Wet Catalysis process to generate 78% sulphuric acid, and a number of plants have been built using similar processes such as Haldor Topsoe's WSA process. The original concept has subsequently been modified to produce high-concentration acid Lurgi's Concat and Haldor Topsoe's WSA-2 processes). In collaboration with Sud-Chemie, Lurgi has also developed a doublecatalysis sulphur-burning process which consumes oxygen-containing waste gases as combustion air rather than as feed gas, and Monsanto Enviro-Chem has gone so far as to abolish the drying tower in the latest version of its energy efficient HRS process. Most recently, the principle has been incorporated in two integrated combustion gas purification systems suitable for fossil-fuelled power stations and other large boiler installations - Haldor Topsoe's SNOX process and the DESONOX process, which was developed jointly by Lurgi, Lentjes, Degussa and Stadtwerke Munster. This article is primarily concerned with the use of wet catalysis as a pollution control measure. Virtually all sulphuric acid manufactured in the world today is produced by a version of the contact process, first commercialized in the 1920s. A gas containing sulphur dioxide and air is passed at temperatures ranging from 390-620'C through a catalyst comprising vanadium pentoxide on a refractory solid support. After cooling, the resulting sulphur trioxide is absorbed into pure sulphuric acid containing 1.5-2% free water, with which it reacts to form further sulphuric acid. It is a prerequisite of this process that the sulphur dioxide/air feed gas mixture should be completely dry. If it is not, some of the sulphur trioxide will react prematurely with the water vapour in the process gas to form sulphuric acid vapour, and because sulphuric acid has a very high boiling point (330[deg]C), as soon as the gas temperature is reduced below this temperature it will condense as a very intractable aerosol known as "acid mist". This fog poses a serious corrosion threat to the fabric sulphuric acid plant itself and, because only a very small proportion of it is washed out in the absorption system, elaborate means are needed to prevent it from escaping in the tail gas and causing havoc in the environment. (It is for the same reason that high concentration sulphuric acid, which releases very little water vapour, is

used in the absorption section instead of plain water or more dilute sulphuric acid.) Acid mist can also cause damage to the catalyst. In a sulphuric acid plant which bums elemental sulphur, the only potential source of moisture in the feed gas is the air feed, since any moisture the sulphur might have contained to start with will have been driven off when it was melted. Me amount of moisture present in the air taken in by a sulphur-burning plant is equivalent to only a portion of the amount of water consumed in the formation of the sulphuric acid, and the air can be dried very effectively by contacting it with part of the acid from the absorption circuit. This acid is then returned to the absorption circuit, where its concentration is restored by the reaction between the absorbed moisture and sulphur trioxide from the process gas. Indeed, some additional process water must be introduced to maintain the water balance of the plant and prevent the absorber acid concentration from climbing. Thus, in a sulphur-burning plant, the sulphur is burnt with the dried air and is cooled in a waste heat boiler only to the temperature dictated by process requirements (390-420'C, depending on the design of the process and the catalyst used). As heat is produced in the catalytic oxidation of the sulphur dioxide, further heat at a fairly high temperature level is recovered in the subsequent stages of the process. A large proportion of sulphuric acid, however, is not produced from elemental sulphur but as an involuntary by-product of metal ore roasting operations. In this case, the hot sulphur dioxide-containing gases are severely contaminated, not only with dust and ash but also with gaseous impurities which are undesirable either because they can cause damage to the sulphuric acid plant or its catalyst (hydrogen chloride or hydrogen fluoride, for example) or because they are poisonous and therefore unacceptable as contaminants in the product (mercury or arsenic, for example). To remove all these contaminants it is necessary to cool the gas and, amongst other purification procedures, to wash it with water. This has the effect of completely saturating the gas with moisture, and this moisture burden can actually exceed the total process water requirement for forming sulphuric acid in the absorption system. Metallurgical waste gases, after addition of the necessary amount of air for conversion of the sulphur dioxide to sulphur trioxide, often contain less than the optimum concentration of sulphur dioxide for sulphuric acid plant feed gas (10.5-13 vol-% for a double-absorption process), and the lower the feed gas sulphur dioxide concentration the smaller the amount of moisture that can be accepted into the drying tower on account of water balance considerations. The excess therefore has to be removed, and this is usually done by further cooling the gas to condense it. The net result of all this is that the dried feed gas has to be reheated from about 50-80[deg]C up to the catalyst initiation temperature (390-

420[deg]C), and that would be the same even if there were no need to condense out surplus moisture, as neither the wet scrubber nor the drying tower can work at higher temperatures. Just sufficient reaction heat is generated in the catalytic oxidation to do this in an elaborate and expensive series of heat exchangers. Nothing is left over for raising steam, as in a sulphur burning plant, and this unfavourable energy balance is the chief disadvantage of these so-called "coldgas" sulphuric acid plants. Classical wet catalysis process There is, however, a class of sulphuric acid plant feed gas which contains water vapour but none of the objectionable impurities associated with metallurgical operations. It results from the combustion of waste gases containing hydrogen sulphide. Mostly, hydrogen sulphide containing gases are converted to elemental sulphur by the Claus sulphur recovery process or, when they contain less than the minimum of about 20% (H.sub.2)S considered necessary for satisfactory operation of the Claus process (1,2) by one of the socalled "direct oxidation" catalytic sulphur recovery processes such as Selectox or by an oxidative scrubbing process of the Stretford or Lo-Cat type. Sometimes, though, there are other constituents in the gas which interfere with the operation of these processes or, as in the case of carbonyl sulphide (COS) or carbon disulphide (CS) largely pass through unaffected and restrict the sulphur recovery efficiency of the Claus process to 87-98% (3,4);nowadays this may not be sufficient to satisfy the applicable pollution control standards. Or it may simply not be convenient or desirable to produce elemental sulphur for logistic or commercial reasons. Under these conditions, it is preferable to incinerate the gas to convert all its sulphur content into sulphur dioxide and to arrest that. Sulphuric acid is the most universally useful commercial product to convert it into. Unlike metallurgical gases, the water vapour is not introduced as a result of a scrubbing operation but is generated during the combustion. Since the gas is not contaminated, there is no need to scrub it before using it in the sulphuric acid plant; however, if it is to be dried, it still has to be cooled to around 50[deg]C and, therefore, reheated as in a metallurgical acid plant. It is clearly more desirable to cool the hot gas only as far as the catalyst initiation temperature and avoid the need for reheating altogether, but that entails introducing moist feed gas into the plant. The main technical problems implicated in processing wet feed gases are, firstly, the need to safeguard absolutely against accidental condensation of sulphuric acid in the catalyst, which will destroy its support material 5, and in corrodible parts of the plant not designed for exposure to liquid acid and, secondly, the need to maintain an acceptable product acid concentration.

In contrast to the conventional contact process based on dry gases, in which the sulphur trioxide is absorbed in concentrated sulphuric acid, in wet catalysis processes sulphuric acid must be condensed from the vapour phase. The concentration of the sulphuric acid formed is determined by the (H.sub.2)O/ SO.sub.3 ratio in the converted gas and the temperature at which condensation occurs (6). The German company Lurgi had, in fact, already worked out a practical solution to these problems as early as the 1930s. A simplified flow diagram of the original wet catalysis process is shown in Fig. 1. The dust-free gas containing hydrogen sulphide is burnt at 5001,000[deg]C (depending on the gas composition) with a sufficiently large excess of air to give a volumetric O.sub.2/ SO.sub.2 ratio of 1.11.3 in the combustion gas. The wet combustion gases are cooled to about 440[deg]C in a waste heat boiler and are then routed directly into the three-bed, quench-cooled converter. After passing through the last bed, the gas flows directly, without cooling, into a condensation tower at 420-430[deg]C, where it is cooled by irrigation with circulating, cooled sulphuric acid. A high irrigation flow and very good gas and liquid distribution are needed to ensure that the gas is cooled, and the sulphuric acid therefore condenses, instantaneously at the gas-liquid interface and not as a result of mixing with already cooled gas, which would produce mist. But, just as in a conventional sulphuric acid absorber, it is impossible to avoid mist altogether, and any that does form is removed from the tail gas in candle filters. Drainage from the candle filters is introduced into the condensation tower irrigation circuit. The gas temperature at the condensation tower outlet is limited to about 80[deg]C on account of corrosion considerations. The moisture content of the tail gas is determined by the vapour pressure of water over the acid, which in turn is a function of the acid concentration and the acid temperature. For practical reasons, the acid concentration in a conventional wet catalysis plant is not allowed to rise above 78%, as the water content of the process gas is usually too high to allow the production of acid of more than 90% concentration, and materials of construction which can reliably withstand corrosion in the 80-90% (H.sub.2)SO.sub.4 range are unwarrantedly expensive. Using a four-bed converter, the process can attain an S02 conversion rate of about 98.5%. Hitherto, the process has only been used in relatively small-scale plants, as in most cases the primary purpose of installing it has been to clean waste hydrogen sulphide containing gases rather than to manufacture sulphuric acid per se. Over the years, Lurgi has built more than 60 plants, the largest of which, with a capacity of 250 t/d (H.sub.2) (SO.sub.4)is in the United States.

A number of other contractors have also built wet catalysis sulphuric acid plants using broadly similar processes - for example, Haldor Topsoe's WSA process. Modifications of the wet catalysis process Nowadays there is relatively little demand for 78% sulphuric acid. And the conventional wet catalysis process cannot even attain this concentration if the feed gas has a low sulphur dioxide content but is saturated with moisture. The idea of using a wet catalysis sulphuric acid process to purify low-concentration waste gases is, nonetheless, attractive: unlike most of the other desulphurization processes, it produces a useful product without generating any waste products or effluents and without any need for chemicals. Waste gas streams which were formerly considered too dilute to warrant treatment and (after incineration, if they contained reduced forms of sulphur) were merely discharged through a chimney cannot now be so disposed of on account of envirornmental regulations, and it was therefore appropriate to develop the wet catalysis sulphuric acid process to accommodate them ( 2,7-10). The Lurgi Concat process In this development of the process (Fig. 2), the bulk of the acid is condensed in a venturi scrubber, which is placed in front of the irrigated packed tower(1,6,7). In the venturi circulating acid is injected in cocurrent with the gas as it passes through the narrowest part of a constriction. In the very turbulent conditions, the gas and liquid are extremely intimately mixed and the heat of formation and condensation of sulphuric acid are dissipated. The venturi operates at 180-230'C, and the majority of the sulphur trioxide and sulphuric acid content of the process gas is removed. However, on account of the higher operating temperature, much less of the surplus water vapour comes out with the acid, and provided the (H.sub.2)O/ SO.sub.2 ratio in the gas does not exceed 5, the acid can be produced at 93% concentration. At higher (H.sub.2)O/SO.sub.2 ratios (6-30), the concentration is held at 78% to prevent undue corrosion damage. Gases of this composition cannot be treated at all by conventional wet catalysis. Additional air is added to the process gas as it passes from the venturi into the packed tower, which dilutes it and therefore reduces the water vapour partial pressure. In the packed tower, it is scrubbed with relatively dilute sulphuric acid, and evaporation of water from this irrigation acid further cools the gas, so that the remainder of its sulphuric acid content condenses out into the irrigation acid. Once again, the final stage in the process is the candle filters, which arrest any mist in the gas; drainage from them returns to the irrigation acid circuit.

The hot acid in the venturi circuit is circulated through a cooler so as to hold the inlet temperature within the safe limit for the fabric of the venturi. Part is withdrawn as product and is replaced by overflow from the irrigation acid circuit. The Concat process can operate autothermally on gases containing less than 1% by volume of sulphur dioxide and water contents well exceeding the stoichiometric ratio for high-concentration acid. Tail gas sulphur dioxide contents of less than 200 ppm can be attained using a two-or, in some cases, a three-bed converter, depending on the composition of the feed gas(6). The Topsoe WSA process Topsoe's current wet catalysis process differs mainly in the manner in which the hot acid condensation is conducted. In place of Lurgi's venturipacked tower combination, a falling-film condenser with multiple glass tubes is used. Like the Concat process, WSA is capable of producing commercial-quality sulphuric acid at 93-98% concentration. (11,12). Depending on the circumstances and the composition of the gas being processed, the cooling is provided by the incoming gas, which is simultaneously preheated, or by air. The WSA process can function on feed gases containing as little as 500 ppmv of sulphur dioxide or hydrogen sulphide and, because particular attention has been given to heat economy, the process can operate autothermally at feed gas concentrations of 1-1.5% SO.sub.2 when the feed gas is received at 220[deg]C or 2-2.5% S0.sub.2 (about 1% H.sub. 2 S) when the feed gas is at 25[deg]C. This makes it attractive for processing a wide range of otherwise quite problematic waste gas streams: Claus plant tail gas, lean hydrogen sulphide streams which may be unsuitable for the Claus process, sulphuric acid plant tail gas, metallurgical roaster gases too dilute ( Figure 3 shows the disposition of a WSA plant, commissioned in 1986, which processes off-gas from the Metals & Powders Trollhattan AB molybdenum ore roaster in Sweden. Moisture-saturated gas is received from the roaster gas scrubbing plant and is heated, first in the WSA condenser and then in the carbon steel converter outlet gas cooler, to 395[deg]C. A portion of the heated gas is recirculated to maintain all parts of this heat exchanger above the dewpoint. The gas is finally heated to about 420[deg]C and passes through an adiabatic reactor containing Topsoe VK38 catalyst. In the outlet cooler its temperature is reduced to 260[deg]C, which allows part of the sulphur trioxide to combine with moisture to form sulphuric acid vapour. This condenses to sulphuric acid on further cooling in the WSA condenser; surplus moisture is carried out in the tail gas. Table I lists typical operating conditions in the plant. There is no need for mist precipitators or candle filters; the tail gas is merely cooled to about 50[deg]C by quenching with air to protect the

GRP fume stack. The acid is cooled in a Hastelloy heat exchanger before going to store. If the WSA process is used for treating more concentrated waste gases, it is necessary to cool the conversion catalyst. In an installation processing incinerated off-gas from a coke oven gas cleaning plant, the gas is received at 420[deg]C and can therefore be fed straight into the converter without further heating. In this case only the first part of the catalyst is in an adiabatic bed, the rest being cooled by immersed tubes containing a molten mixture of potassium nitrate, sodium nitrite and sodium nitrite, which circulates through a steam boiler. The gas leaves the converter at around the same temperature as it entered. The molten salt mixture, chosen because it is non-corrosive and very mobile, besides being molten in the target temperature range, is also the coolant in the converter outlet cooler, which the gas leaves at around 270[deg]C. Because the feed gas is already hot, the WSA condenser is cooled by air, which is subsequently discharged with the tail gas. Figure 4 shows the arrangement of such a plant, and Table II gives performance data from a which processes acid gas from a coke oven gas cleaning installation at Association Cooperative Zelandaise de Carbonisation, Sluiskil, Netherlands, which was commissioned just over a year ago. Lurgi wet/dry catalysis process Because all the versions of the wet catalysis process described so far correspond to the single-catalysis process - i.e. they involve only one cycle of conversion and sulphur trioxide removal - they cannot achieve a greater sulphur dioxide conversion than 98.5%. If considered primarily as a means of sulphuric acid production, as opposed to a method of cleaning up waste gas from another process, therefore, they do not conform to the rules governing the conversion efficiency of sulphuric acid plants in many parts of the world. These frequently demand an efficiency of 99.5-99.7%, implying a double catalysis type of process. In co-operation with Sud-Chemie, of Kelheim in Bavaria, Lurgi has developed a double-catalysis process in which the first stage operates under wet catalysis conditions, and where the intermediate absorber would be in a conventional dry-gas plant there is a two-stage intermediate condenser-absorber Fig. 5). The final stages are the same as they would be in a dry-gas plant; however, this dictates that the water content of the gas must not exceed the stoichiometric amount consumed in forming the acid which condenses out in the intermediate venturi/irrigated tower system. All of the water vapour content of the gas and most of its sulphur trioxide content is removed by hot condensation of sulphuric acid in the venturi stage; the second stage

operates as a conventional absorber, removing the remainder of the sulphur trioxide into cooled 98.5% acid. The wet/dry catalysis process has been in successful operation since 1980 at Kelheim, in a 120-t/d plant processing a mixture of elemental sulphur and off-gases containing a combined total of about 0. 5 vol-% of hydrogen sulphide and carbon disulpifide from a neighbouring rayon staple plant, which is used in place of air in the sulphur burner of the plant (13,14). Most recently, Monsanto Enviro-Chem has taken the idea a step further by leaving the drying tower out of its latest version of the Heat Recovery System and running the front end as a wet catalysis system(15), not for the purpose of disposing of sulphurous waste gases but as a means of improving the economics of large sulphuric acid plant operation. This process will be considered in detail in a forthcoming edition. Applications in flue gas desulphurization As mentioned, most of the processes so far used for removing sulphur dioxide from combustion gases produce waste products or liquid effluents (or both) which are themselves polluting, and many consume chemicals also. Wet catalysis sulphuric acid processes are attractive because they suffer from none of these disadvantages. In Germany and Scandinavia it is now obligatory to remove acid forming nitrogen oxides ("NO.sub.x) as well as sulphur dioxide from the flue gases of power stations and other large industrial boiler installations, and similar regulations will follow in other European countries. Both Haldor Topsoe and Lurgi - the latter in collaboration with the boiler maker Lentjes, the catalyst manufacturer Degussa, and a municipal power station operator, Stadtwerke Munster - have developed integrated processes for removing nitrogen oxides, sulphur dioxide and other objectionable acidic impurities such as hydrogen chloride and hydrogen fluoride, which incorporate the wet catalysis sulphuric acid concept. Both use SCR (selective catalytic reduction by ammonia) to reduce the nitrogen oxides to elemental nitrogen and water vapour. This process has the great advantage of operating efficiently even in the presence of oxygen, which is always present in flue gas, and it has more or less become the standard technique for flue gas denitration as a result(16-19). The Lurgi-led development, named DESONOX, is illustrated in Fig. 6. After leaving the boiler, the flue gases are dedusted in a high temperature electrostatic precipitator to a residual dust content of less than 50 mg/Nm.sup.3. The gas is preheated in indirect exchange with the converted gas and then by a natural-gas fired burner, after which the stoichiometric amount of ammonia needed to reduce the nitrogen oxides is added to the gas before it enters the catalyst chamber. Here

it passes first through a bed of selective NO reduction catalyst(20) and then - at about 450[deg]C - through the sulphuric acid catalyst. In the succeeding heat exchanger the gas is cooled to a temperature which is still above the dewpoint of sulphuric acid. It is then further cooled to condense the sulphuric acid formed in the vapour phase and further moisture. The resulting sulphuric acid has a concentration of about 70-75% (H.sub.2)SO.sub.4 The gas then passes through a two-stage scrubber, in the first of which the majority of the remaining sulphuric acid is washed out and in the second, operating on a secondary wash acid circuit, hydrogen halides are arrested. The acid from the second scrubber is circulated through a stripper which removes the hydrogen halides before being recycled to the main wash acid circuit; the hydrogen halides are neutralized. Mist is removed from the gas in a wet electrostatic precipitator. Finally, the gas passes through the other side of the acid condenser, in which it is reheated to 80[deg]C for discharge. Gases containing up to 50 mg.Nm.sup. 3 of dust can be handled without recourse to filtration or catalyst screening. In Topsoe's SNOX process Fig. 7) the SCR and sulphur dioxide oxidation steps take place in separate reactors, and the process is designed to tolerate a certain amount of dust, so a somewhat lower standard of dust removal is acceptable. Flue gas, received from the combustion air preheater at about 200[deg]C, passes through a trim cooler to ensure its temperature does not exceed 190-200[deg]C and is dedusted to a residual dust content of about 5-10 mg/Nm.sup.3 in a reverse air bag filter, using PTFE membrane/glass fibre bags. Its temperature is then raised to about 380[deg]C in a preheater, after which it is mixed with the amounts of ammonia and air needed respectively for selective catalytic reduction of the nitrogen oxides and for sulphur dioxide oxidation. It then passes through a Topsoe monolithic DNX catalyst, which is designed to allow dust to pass through. A slight excess of ammonia can be used to ensure a high NO.sub.x removal efficiency, as any surplus is decomposed in the subsequent S0.sub.2 oxidation reactor. The gas is then heated to 400-420[deg]C in a line burner or a steam heater before entering the sulphur dioxide oxidation reactor. This contains two vertical panels of VK38 catalyst, which can operate alternately, allowing the catalyst to be screened without interrupting operation. When the pressure drop rises to about three times the normal value, the gas flow is switched through the other catalyst panel and the hot catalyst from the dust-laden panel is dumped through an enclosed screen into a container, which is hoisted to the top of reactor for reloading.

The converted gas is cooled in the flue gas preheater and then in a WSA condenser before being discharged. Once again, it is not treated separately to remove mist. The air used to provide the cooling in the WSA condenser is further heated to about 200[deg]C against the flue gas upstream of the bag filter and used as combustion air in the power station furnace. In a large plant, the air and flue gas preheaters will probably be of the rotary regenerative type. The SNOX process has been in operation since December 1987 in a demonstration-scale unit in Denmark, purifying part of the flue gas from a 110-MW boiler. It has also been chosen for installations in Italy and the USA and a recently-constructed 1-million Nm.sup.3/h unit on a 300-MW power plant in Denmark. Performance figures for the WSA section of the demonstration plant are given in Table III. The catalyst screening procedure outlined above appears to have been completely satisfactory in the demonstration plant, with very little screening loss. Acid of about 95% concentration is obtained, even when operating under reduced capacity. It contains no more than 0.2-0.4 ppm of toxic metals such as vanadium, cadmium, nickel, arsenic and lead, which is acceptable for fertilizer and many industrial uses. Except for the WSA condenser, only carbon steel or low molybdenumalloy steel is used. Various materials have been tested as coatings for the tubesheets in the WSA condenser, including lead and various fluorocarbon polymers.
References 1 . "High-grade sulphuric acid from moist sulphureous gases". Sulphur (123), 36-42 (Mar-Apr 1976). 2. Schoubye, P.: Sulphuric acid production from lean H.sub.2-S containing gases". Sulphur (137), 38-42 (Jul-Aug 1978). 3. "Pollution control in Claus sulphur recovery plants". Sulphur (109), 36-39 (Nov-Dec 1973). 4. "Some factors affecting the performance of Claus sulphur recovery plants". Sulphur (115), 38-42 (Nov-Dec 1974). 5. Sander, U. H. F., Fischer, H., Rothe, U., and Kola, R.: "Sulphur, Sulphur Dioxide and Sulphuric Acid" (ed. More), p. 286. British Sulphur, London (1984). 6. Ibid., pp. 325-331. 7. "New DPG process produces 96% acid from H,S-containing gases". Sulphur (141), 41 (Mar-Apr 1979). 8. "Topsoe wet-gas process used in two plants". Sulphur (149), 38-39 (Jul-Aug 1980). 9. Chemie Ingenieur Technik 53 (5), A 273 (1981).

10. 11.

12.

13. 14. 15.

16. 17. 18. 19.

20.

Kerner, P., and Schmitz, P. Chem. Tech. (Heidelberg) 8 (2), 83-86 (1979). Bendixen, 0. R., and Schoubye, 0. R.: "Production of sulphuric acid from sulphurous off-gases by the Topsoe WSA-2 process". "Sulphur 87" International Conference, Houston, Texas (Apr 1987), pp. 329-341. (British Sulphur). Jensen-Holm, H., and Rud-Bendixen, O.:"Industrial experience with the Topsoe VK58 sulphuric acid catalyst and the WSA-2 process". "Sulphur 1990" International Conference, Cancun, Mexico (Apr 1990), pp. 299-310. British Sulphur). Peichl, R. Chem. Tech. 11, 21-24 (1982). Schmitt, M. Chemische Industrie 33 (5), 286-290 (1981). McAlister, D. R., Grendel, R. W., Schneider, D. R., Schafer, J. R., and Tucker, J. S.: "A sulfuric acid plant for the 1990s". "Sulphur 1990" International Conference, pp. 267 278. Ohlms, N., and Brand, R. VGB Handbuch, VGB-B 301, Part C 3.3.2 (1986). Ohlms, N. VDI-Beyicht (730), 157 172 (1989). "FGD as a source of sulphuric acid". Sulphur (211), 23 (Nov Dec 1990). Bendixen, 0. R., Andreasen, J., and Laursen, J. K.: The Topsoe SNOX technology for flue gas cleaning". 2nd International Conference on Desulphurization, Sheffield (Mar 1991). Brand, R., Engler, Honnen, W., Kleine Mollhoff, P., and Koberstein, E. AIChE 82nd National Meeting & Exhibition, Anaheim, California (Jun 1989).

COPYRIGHT 1991 CRU Publishing Ltd. This material is published under license from the publisher through the Gale Group, Farmington Hills, Michigan. All inquiries regarding rights should be directed to the Gale Group.

Title: Early days. (includes prehistory of sulphuric acid)(250 Years of Vitriol, part 1)

Date: 3/1/1996; Publication: Sulphur; The experiment which led to the first industrial sulphuric acid manufacturing process was conducted in 1746. This series of articles outlines the development of sulphuric acid technology over the intervening quarter of a millennium. As "oil of vitriol", sulphuric acid has been known for more than a thousand years. What is thought to be the earliest reference to it dates back to 8th Century Arabia, though a 10th Century Persian alchemist, Abu-Bekr Ahhases (d. 940 AD), is credited with its discovery as a substance in its own right.[1] Though it is evident that sulphuric acid exercised the minds of philosopher-alchemists over the succeeding centuries, it was not until chemistry became recognized as a separate science that sulphuric acid became any more than a curiosity and its usefulness began to be realized. The inset panel lists some of the known events and personalities in the early chronology of sulphuric acid. Seeds of the industry Great Britain was the seat of the so-called "Industrial Revolution", which started off with the mechanization of textile mills in hilly areas where it was possible to make easy use of water power. Given the extent to which this and succeeding new industrial activities needed sulphuric acid, it is not surprising that the earliest example of its industrial production also belongs to Great Britain, although only by a chronological whisker. The impetus came from the progressive appreciation of the vastly superior properties of sulphuric acid over all the previously used acidic agents. (It has to be remembered that the other strong mineral acids were not available either: the original methods of producing them actually required sulphuric acid as a reactant). The textile industry was itself the earliest potential mass consumer of sulphuric acid, for use in the bleaching process. This entailed treating the textile with alkaline ashes and leaving it in sunlight, followed by "souring" acid. Traditionally the acidifying agent was sour milk (lactic acid); other, stronger organic acids were either too impure (vinegar, for example) or not yet known. Once it was realized how vastly that stage of the process could be improved by using sulphuric acid, the search was on for an economical way of producing it. The reason why sulphuric acid was not more familiar in ancient times lies in a peculiarity in the chemistry of sulphur. Sulphuric acid is formed from the reaction of sulphur trioxide (S[O.sub.3]) and water: S[O.sub.3] + [H.sub.2]O [approaches] [H.sub.2]S[O.sub.4] (1)

Because sulphur can exist in a number of oxidation states, it has another oxide - sulphur dioxide (S[O.sub.2]) - and it is that that is formed when sulphur is burnt in air or oxygen: S + [O.sub.2] [approaches] S[O.sub.2] (2) Although sulphur dioxide can subsequently be oxidized to sulphur trioxide: [Mathematical Expression Omitted] only a very small proportion of it actually is. That is because reaction (3) is a kinetically-inhibited equilibrium or reversible reaction. The position of equilibrium - in other words, the point at which the rate at which sulphur trioxide forms from sulphur dioxide and oxygen exactly balances the rate at which it decomposes back to sulphur dioxide and oxygen - determines the final conversion efficiency, and it is temperature-dependent. At the high combustion temperature of sulphur, sulphur dioxide heavily predominates, since heating encourages the reverse (decomposition) reaction. At room temperature, on the other hand, the equilibrium is very close to 100% conversion to sulphur trioxide, so once formed - sulphur trioxide is quite stable; but the rate of reaction is so slow that it is imperceptible. The art of sulphuric acid making thus lies in finding an intermediary agent to facilitate the oxidation of sulphur dioxide to sulphur trioxide. The ancient alchemists had already stumbled upon one - alkali metal nitrates - which was fortunate, as it allowed industrial production to begin on the basis of empirical knowledge around three decades before Joseph Priestley (1733-1804) discovered oxygen (1774) and Antoine Lavoisier (1743-1794) identified sulphur as an element (1777), and the concept of oxidation, upon which the whole understanding of the chemical principles of sulphuric acid synthesis depends, was postulated. The use of nitre in sulphuric acid production seems to have been rediscovered many times. From 1640, when Johann Glauber appears to have been the first to use it in a glass bell apparatus, sufficient oil of vitriol was produced to satisfy the demand of apothecaries, who were its main users, in various European countries. One such installation is recorded as having gone into production at a factory in Twickenham, west of London, in the earlier part of the 18th Century, using a process patented in the name of one Joshua Ward. A mixture of sulphur and saltpetre (potassium nitrate) - later the cheaper nitre (sodium nitrate) was burnt in the presence of water in 66-gallon glass globes, which were immersed in a bed of hot sand. In 1740 the factory was moved to nearby Richmond because of complaints about the fumes:[4] perhaps the earliest recorded case of conflict between the interests of the sulphuric acid industry and those of the environment.

The man who might be regarded as the father of sulphuric acid manufacture was Dr John Roebuck - an English inventor who was born in Sheffield and studied medicine at Edinburgh and Leiden (Netherlands). He gave up medical practice in favour of research into methods of refining precious metals and producing chemicals, and it was he who, in Birmingham in 1746, first used a lead chamber to contain the combustion of sulphur and saltpetre and to provide a corrosion-resistant surface upon which product sulphuric acid could condense. His experiment provided the basis for the industrial process which was to dominate the sulphuric acid industry for the best part of the 200 succeeding years. Following his Birmingham experiment, Roebuck and a Mr Garbett established a commercial lead chamber plant at Prestonpans, in Scotland, to supply sulphuric acid for a linen bleaching operation.[5] Bleaching operations with associated lead chamber sulphuric acid plants were established in Lancashire from 1760 onwards. Demand received a further boost at the turn of the century with the introduction by a Scottish industrialist, Charles Tennant (1768-1838), of bleaching powder, but the greatest stimulus was the Europe-wide spread of the Leblanc soda ash process, in the first stage of which salt is attacked with sulphuric acid, and then of superphosphate fertilizer production (1843).
Events in the Prehistory of Sulphuric Acid 8th Century Ref. JABR IBN HAYYAN, c.721-c.815 (Arabia) Alchemist and court physician to Caliph Harun al-Rashid - Distilled nitre with green vitriol (ferrous sulphate) 10th Century ABU-BEKR AHHASES, d. 940 (Persia) - Probable discoverer of acid as a definite substance 13th Century (c.1250) VINCENT DE BEAUVAIS (Vincentius Bellovacensius), c.1190-1264 (France) Dominican encyclopaedist ALBERTUS MAGNUS, ("Doctor Universalis"), c.1200-1280 (Germany) Dominican provincial, bishop, theologian and philosopher) Alluded to substance which was probably sulphuric acid 15th Century BASILIUS VALENTINUS - Prepared sulphuric acid by burning sulphur with saltpetre 16th Century PARACELSUS (Theophrastus Bombastus von Hohenheim), 1493-1541 (Switzerland) Alchemist, physician and therapist Prepared weak sulphuric acid by distillation from green vitriol 1570 GERHARD DORNAEUS - Discussed properties 1595 ANDREAS LIBAVIUS - (LIBAU), c.1560-1616

1 1 1

2 1

1 1

17th Century 1613 1640 1666

(Germany) Alchemist, historian and poet Described various production methods ANGELUS SALA - Verified Libavius's work JOHANN GLAUBER (Germany) - Burnt brimtone and nitre in a glass bell and collected condensate NICOLAS LEMERY, 1645-1715 (France) Chemist and apothecary With NICOLAS LE FEVRE, used saltpetre in sulphuric acid production CORNELIS DREBBEL, c.1572-1633 (England) Dutch-born chemist, technologist and inventor - Improved production from sulphur and nitre JOSHUA WARD (England) - Set up glass apparatus at Twickenham from production from sulphur and nitre JOHN ROEBUCK, 1718-1794 (England) Doctor of medicine and chemical inventor - First production in a lead chamber, prototype of the first real industrial process. 1 3 1

18th Century c.1740 1746

1 1

Elsewhere in Europe, the first lead chamber plant in France was erected at Rouen in 1766. In Germany Thiele set up a sulphuric acid facility in Berlin in 1748, but it was based on glass globes. Lead chambers were subsequently tried out near Leipzig and Cassel. The earliest known sulphuric acid plant in the United States was built in Philadelphia in 1797 by a John Harrison. Development of the chamber process The act of burning nitre or saltpetre with sulphur produces sulphur dioxide and nitrogen oxides. In the presence of water, these react together to produce, ultimately, sulphuric acid and nitrogen oxides, which restore themselves to their previous oxidation status by reacting with free oxygen in the system. On account of the multitude of nitrogen oxides, the exact sequence of reactions never was established for certain over the whole life of this now virtually-extinct process. Over the years, various theories were advanced.[6] However, the following (simplified) sequence is plausible:[7] NO + 1/2[O.sub.2] [approaches] N[O.sub.2] (4) S[O.sub.2] + [H.sub.2]O [approaches] [H.sub.2]S[O.sub.3] (5) [Mathematical Expression Omitted] [Mathematical Expression Omitted] [Mathematical Expression Omitted] [Mathematical Expression Omitted]

[Mathematical Expression Omitted] [Mathematical Expression Omitted] Overall: S[O.sub.2] + 1/2[O.sub.2] + [H.sub.2]O = [H.sub.2]S[O.sub.4] (12) Clearly the sulphuric acid resulting from Dr Roebuck's original lead chamber experiment, in which all the stages of the process were taking place in the same space, would have been heavily contaminated with nitrogen oxides (in the form of nitrosylsulphuric acid), It was also quite dilute. And every time the chamber was opened to introduce another charge, a mass of noxious nitrogen oxides would have been released into the atmosphere and lost from the process. The prime objectives of further development, therefore, were the following: * to operate continuously instead of batchwise; * to retain nitrogen oxides for re-use; * to produce more concentrated acid. Continuous production of S[O.sub.2] At an early stage it was realized that the efficiency of conversion in the lead chambers could be increased by introducing the water into the open space as a spray or as steam and by drawing a current of air through to provide the oxygen needed to regenerate the nitrogen oxides. These improvements also predicated continuous rather than batch operation. Continuous operation became possible with the development of continuous sources of sulphur dioxide. Elemental sulphur being the ideal raw material, sulphur burners were the first devices to be developed. First was the so-called pan burner, in which sulphur charged by hand shovelling was burnt in a shallow cast iron, earthenware, tile or firebrick pan in a firebrick-lined combustion chamber. Out of this was developed the multiple-hearth burner, in which the pans were stacked vertically in and sulphur charged at the top could overflow from one hearth to the next. The picturesquelynamed "Vesuvius" burner [ILLUSTRATION FOR FIGURE 1 OMITTED] was a multiple-hearth design with its own integral sulphur melter, but on account of the variability in the viscosity of molten sulphur it could not be relied upon to operate continuously and required constant supervision. Another early design was based on a horizontal rotating drum discharging into a combustion chamber. Until the establishment of the Frasch sulphur industry in the United States in 1903, virtually the sole source was the volcanic deposits of Sicily. The United States industry therefore grew up through the 19th

Century largely on the basis of the alternative material iron pyrites, of which it possessed substantial indigenous resources. From 1833 onwards the European industry, too, began to make greater use of pyrites on account of the excessive contemporary price charged for elemental sulphur by the Sicilian monopoly. The earliest form of pyrites roaster was the so-called "lump burner", designed for coarse ore. It comprised a battery of ovens which were individually stoked in sequence. It was very labour-intensive, gas volumes and sulphur dioxide concentrations were highly variable, and the pyrites was not always completely burnt. Rotary kilns of the type used in the cement industry were used occasionally, but until the advent of flash and fluidized-bed roasters the most commonly used pyrites roaster was the multiple-hearth or shelf type such as the Nichols-Herreshoff and Bethlehem Wedge furnaces. It comprised a series of vertically-stacked circular grates in an upright cylindrical shell. Each grate was traversed by bladed rakes ("rabble arms") radiating from a slowly rotating hollow, air-cooled shaft on the vertical axis of the furnace. These turned over the ore and ensured that it eventually dropped through openings onto the hearth beneath. The development of town gas production in the 19th Century generated its own demand for sulphuric acid, which was needed to scrub ammonia out of the crude gas. The by-product ammonium sulphate was of great value as a fertilizer in those days, before there was any industrial method of fixing atmospheric nitrogen, and sulphuric acid plants were established at some gas works using "spent oxide" from the iron oxide desulphurization system as the raw material. Any surplus acid was readily disposed of to superphosphate makers. In certain cases sulphuric acid plants were also fed by non-ferrous metal roaster off-gases but, until the modern concern about the environment demanded an end to it, it was more common for these gases to be discharged straight into the atmosphere. NOx recovery: the Gay-Lussac tower The use of an external device for generating sulphur dioxide necessitated a separate means of generating nitrogen oxides. At first this was done in a "nitre pot" by reaction of the sodium nitrate with a sidestream of sulphuric acid, which was returned to the chamber plant. But once synthetic ammonia became plentiful it became commoner to generate them by catalytic ammonia oxidation over a platinum catalyst. The original process did not incorporate any specific means of recovering nitrogen oxides, which were lost partly in the product acid but mainly into the atmosphere. In 1827 the famous French chemist Joseph Gay-Lussac (1778-1850) proposed recovering nitrogen oxides from the exhaust gases from the lead chambers as nitrosylsulphuric acid by contacting them in countercurrent with product acid in a packed tower. However, the first such tower was not erected until 15

years later, and it was another 25 years before it came into general use. That was because up to then the only known way of recovering the nitrogen oxides from the "nitrous vitriol" was to hydrolyse its nitrosylsulphuric acid content by dilution with water. Thereafter, it became a feature of every chamber process plant, and commonly two such towers were used in series. Acid concentration and denitration: the Glover tower The last piece of the puzzle was provided in 1859 by John Glover at the Washington Chemical Works near Durham, UK. This was another packed tower in which acid from a Gay-Lussac tower, after dilution to decompose the nitrosylsulphuric acid, was stripped by the hot incoming sulphur dioxide stream. That removed not only the nitrogen oxides but also the dilution water, allowing the product acid concentration to be at least maintained and reducing the amount of water required in the subsequent chambers. It was also found that a large proportion perhaps as much as 50% - of the sulphuric acid was generated in the Glover tower, which reduced the duty on the lead chambers. Figure 2 is a basic flow diagram for a sulphur-burning lead chamber plant with an ammonia-burning NOx generator and incorporating GayLussac and Glover towers. Improvements in the chamber train The original lead chamber was a very unsophisticated piece of equipment: it was just an empty square-cornered box, and temperature control relied on natural air cooling of the walls, which meant that it had to be very large in relation to the amount of acid produced. Over the years a number of modifications were proposed using other shapes and sizes of box with various arrangements for improving the cooling, introducing and withdrawing the gas and for dispensing the liquid which were designed to improve efficiency and reduce space requirements. Probably the most successful variation was the MillsPackard system, introduced in 1913 and improved in 1926 by R. T. Maudsley,[9] in which the chambers were frusto-conical and cooling water was run down the inclined outer surface. This has the additional benefit of prolonging the life of the fabric of the chamber. All-tower processes However, the development that did most to prolong the life of the nitrogen oxide process as a serious alternative to the contact process was the replacement of the lead chambers by a system of packed towers. This was always a possibility in brimstone-based plants but necessitated improvements in gas cleaning systems in plants which obtained their sulphur dioxide from pyrites, sulphide ore or spent acid roasting. As materials technology improved, towers were increasingly

made of other materials than lead, which made them lighter and/or simpler to construct. Three systems in particular are worthy of note. Carl Opl, an Austrian, patented a tower system in 1908, and by 1915 it had been incorporated in about 30 European sulphuric acid plants. It comprised six towers through which the process gas flowed sequentially. The first three acted as acid generators and the last three as nitrogen oxide absorbers. Acid flowed through them in three circuits: towers 1 and 6, towers 2 and 5, and towers 3 and 4. The acid entering the last three towers was cooled, and all the acid eventually passed through tower 1, from the outlet of which the product was withdrawn. The reaction space was said to be about one tenth of that of air-cooled lead chambers.[2] From about 1905 onwards, Hugo Petersen, of Germany, installed an intermediate tower upstream of the first Gay-Lussac tower in a lead chamber plant in Upper Silesia. It was fed with intermediate-strength nitrous vitriol (54-58 [degrees] Be; 68-74% [H.sub.2]S[O.sub.4]) which could either give up nitrogen oxides to oxidize any sulphur dioxide remaining in the process gas or could absorb nitrogen oxides if they were present in the process gas. A second tower was then installed between the Glover tower and the lead chambers. It was irrigated with a sidestream of acid from the first Gay-Lussac tower. In 1923 the first all-tower Petersen acid plant was built in Hungary. It had seven towers (one Glover, two production and four Gay-Lussac). Later plants were built with five towers, in which form it was very successful.[10] One such installation - a 19,000-t/a plant burning 60% S filter cake built in Turkey in 1944 - was still in operation in 1985. It had five acid bricklined lead/wood towers - Glover, Petersen Reaction, Cooling (NOx regeneration) and 2 x Gay-Lussac). Tower packings were firebrick or Raschig tings, according to the purpose of the tower. The product went mainly to a local gasworks and a superphosphate operation, though some was concentrated to 66 [degrees] Be (93% [H.sub.2]S[O.sub.4]) for sale.[11] A later tower system was devised by Pierre Kachkaroff, a stateless Russian living in Paris, in 1930.[5] A scant handful of plants were built in France,[12] Italy and the UK,[13] but although the process embodied some interesting and useful features, by the time the necessary experience in its design and operation had been amassed the nitrogen oxide sulphuric acid processes had all but had their day. It differs from earlier processes in running with a much higher than normal [N.sub.2] [O.sub.3] [NO + N[O.sub.2]] concentration in the system; the nitrous vitriol contained the equivalent of 10% [N.sub.2][O.sub.3]. As shown in Fig. 3,[12] it comprised a lead-lined concentration tower, a "denitration" (Glover) tower which was divided vertically into two unequal parts, four reaction towers and a "filtration" (Gay-Lussac) tower. The hot sulphur dioxide gas was fed directly into the concentration tower, from which 60 [degrees] Be (78%

[H.sub.2]S[O.sub.4]) acid was obtained. It was then divided into two streams which were passed in parallel through the two sections of the denitration tower, through which the acid was passed in cascade. About 20% of the [H.sub.2]S[O.sub.4] formation occurred in the denitration tower and 90% of the remainder in the first reaction tower. The towers were constructed of acid-resistant brick and cement, but the tops of all but the concentration tower were made of PVC. The towers themselves stood up to the conditions very well, but in the UK installation two glass-tubed acid coolers were troublesome and were eventually replaced with cast iron. The Kachkaroff process marks the effective end of the development of nitrogen oxides-based process as a commercial method of making sulphuric acid, although it has been utilized in a specially optimized version as a method of arresting sulphur dioxide from waste gas streams too dilute to support a contact sulphuric acid plant.[14,15] Dawn of the contact process The contact process, in which sulphur dioxide is oxidized to sulphur trioxide by passing it with air over a catalyst, was described in a patent awarded to Peregrine Phillips, a Bristol vinegar maker, in 1831, but in spite of the primitive state and expensive nitre consumption of the chamber process before the introduction of the Glover tower, it was to be more than 40 years before any significant progress towards commercialization was made. The main incentive was the growing demand for oleum ("fuming sulphuric acid"), which previously could only be made in the concentration and the purity required from ferric sulphate, for the expanding dyestuffs industry. In fact, the first contact acid was made in 1875 by Emil Jacob at Kreuznach, in Germany, by decomposing chamber acid, condensing out the water vapour, and passing the remaining gases over a catalyst. Six years later contact acid was made at Thann, in Alsace, by burning Sicilian sulphur, absorbing the sulphur dioxide in water under pressure, releasing the sulphur dioxide and mixing it with air and passing it over hot platinized asbestos. However, it was not until the present century that the reaction fundamentals of the sulphur dioxide oxidation reaction became sufficiently well understood for the process to be used commercially. From then on, it accounted for a steadily greater proportion of industrial production, overtaking chamber processes around 1940. Its advantages in terms of the compactness of the plant, efficiency, energy-economy and product purity can undoubtedly be credited for this. But what hastened its ascent and effectively sealed the fate of the chamber process was the decline of superphosphate in favour of highanalysis phosphate fertilizers based on phosphoric acid, to produce which requires sulphuric acid of a higher concentration than it is possible to obtain from a chamber acid plant without elaborate additional concentration.

References 1. Duecker, W. W.; West, J. R.: "History of the manufacture of sulfuric acid". In Duecker, W.W., and West, J. R. (eds): "The Manufacture of Sulfuric Acid". ACS Monograph Series, Reinhold Publishing Corporation, New York (1959). 2. Fairlie, A. M.: "Sulfuric Acid Manufacture". ACS Monograph Series, Reinhold Publishing Corporation, New York (1936). 3. Muir, D. R.; Terry, J. W.: "The evolution of sulphur". Proceedings of "Sulphur '82": British Sulphur Corp. International Conference, London (Nov 1982), Vol 2, pp. 593-600. 4. "Sulphuric Acid Manufacture and Uses". Imperial Chemical Industries Ltd., London (1955). 5. Fleck, A.: "The British sulphuric acid industry - A retrospect and a research project". Chemistry and Industry (1952), 1184-1193. 6. Ridler, E. S.: "Chamber process for the manufacture of sulfuric acid". In Duecker & West (eds), op. cit., pp. 103-132. 7. Riegel, E. R.: "Industrial Chemistry", 5th Edition, p. 12. Reinhold Publishing Corp., New York (1949). [Quoting Berl, E.: "Studies of the lead chamber process". Transactions of the American Institute of Chemical Engineers, 31, 193 (1935)]. 8. Eddy, E. W.; Frank, R.: "Review of the sulfuric acid industry". In Duecker & West, op. cit., pp. 1-8. 9. Schofield, M.: "Fifty years of Mills-Packard vitriol chambers". Industrial Chemist (Mar 1964), 149-151. 10. Montecatini SpA: "New trends in the manufacture of sulphuric acid". ISMA Technical Conference, Milan (1949). 11. Ucanok, M. E.: Private communication (1985). 12. Deghelt, R.: "Notes on the running and stability of a sulphuric acid plant - Kachkaroff system". ISMA Technical Conference, Paris (1951). 13. Snelling, F. C.: "A Kachkaroff sulphuric acid plant - Constructional and operational details". Chemistry and Industry (15 Mar 1958), 300306. 14. Fattinger, V.: "Production of sulphuric (and nitric) acid by a modified nitrogen-oxide sulphuric acid process". In "Fertilizer Acids" Proceedings of the British Sulphur Corporation's Third International Conference on Fertilizers, London (Nov 1979).

15. Fattinger, V.: "The nitrogen oxide sulphuric acid process 17461986" (Jun 1986). COPYRIGHT 1996 CRU Publishing Ltd. This material is published under license from the publisher through the Gale Group, Farmington Hills, Michigan. All inquiries regarding rights should be directed to the Gale Group.

Title: Advances in sulphuric acid equipment. Date: 11/1/1998; Publication: Sulphur; Author: Connock, Lisa Despite being a mature process, there is always scope to make improvements to the equipment used in sulphuric acid plants to improve the reliable operation of the plant, reduce energy consumption and lower emissions. Lisa Connock reports. Over the past decade, the changes in sulphuric acid technology have focused on subtle refinements to the equipment used in sulphuric acid plants rather than broad changes to the process. Environmental regulations and market forces have shown a need for lower emissions, higher energy recovery and increased reliability. Plate gas/gas exchangers Gas to gas heat exchangers are key components in modern sulphuric acid plants. They provide the effective heat transfer needed to maintain catalyst bed temperatures essential for good conversion efficiency. Monsanto Enviro-Chem has introduced a new alternative for gas/gas exchanger applications which provides greater material and capacity flexibility for sulphuric acid plants. Monplex[TM] gas/gas exchangers are constructed using plate technology and are designed in modular blocks. A single unit consists of one or more modular blocks of plate packs, configured in a crossflow, counterflow or other configuration. The blocks are combined in various series and/or parallel configurations to meet specific process needs. The gas flow passages are formed by directional ribs sandwiched between fiat plates. These fiat plates allow for efficient heat transfer and reduce pressure drop compared to equivalent traditional shell-and-tube heat exchanger units. With the Monplex[TM] unit the heat exchanger designer has the opportunity to customize material selection for the service, by specifying the appropriate metallurgy for each block. For example, the

cold block with stainless steel plates, the intermediate block with carbon steel plates, and the hot block with stainless steel plates. Also, if pressure and flow requirements change due to modification in the existing plant, the Monplex[TM] exchanger can easily be modified by adding additional units in parallel to meet the new process needs. The first commercial installation of a Monplex[TM] cold interpass exchanger started up in 1997 in the USA. The Monplex[TM] unit was designed with three passes on the cold side and one pass on the hot side. A 3 series x 3 parallel configuration was used with each unit with a crossflow configuration. The three cold pass blocks were constructed of 316 stainless steel, while the intermediate and hot passes were constructed of carbon steel. The exchanger was designed so that each pass could: be removed: independently of the other two, either for maintenance or replacement. The exchanger has been performing as expected. New generation alloy trough distributors Acid distribution systems are the key component to good S[O.sub.3] absorption in sulphuric acid plants. The new generation alloy trough distributor by Monsanto Enviro-Chem maintains the alloy trough and downcomer design of the previous design, but eliminates the overhead pipe system. Instead, the trough sections are connected together by a series of ducts. A set of gate valves in each trough then regulates the flow to each segment of the trough. By removing header piping from the design the new generation style distributors are more cost efficient. The new generation distributor can accommodate varying flow rates by just raising or lowering the adjustable gates in each trough. This makes the system easy to retrofit for higher capacity. Wider and deeper troughs result in very low acid velocities inside the troughs, resulting in very smooth acid flow and equal distribution of all areas of the tower. Optional flow straighteners downstream of the adjustable gates can reduce trough acid velocities further. Without the need for header piping in a trough there is now more room for downcomers in a single trough. This reduces the number of troughs required to cover a tower diameter. Systems where 6 or 7 troughs were previously needed now require only 4 or 5 troughs. New generation distributors can be made from a choice of alloy materials. Lighter materials and fewer troughs have made the system easier to install. New impaction candles for dry towers A new impaction fibre bed for dry towers, the CK, is now available from Monsanto Enviro-Chem to enable longer operating times before

washings and to extend time between maintenance shutdowns. Monsanto's standard in this service has been the CS-IP fibre bed. In sulphur burning drying tower service, CS elements usually need to be washed every 6 to 18 months depending upon tower design and the level and nature of plugging agents. Although CK elements look the same as CS elements from the outside, the internal co-knit collection layer is significantly different from standard CS collecting glass fibre media. CK beds are identical in size and capacity to standard CS beds operating at the same gas volume and pressure drop. Like the CS design, CK elements also include an alloy mesh entrainment control layer. CK elements use a metal mesh for the collecting layer but this metal mesh structure has small diameter acid-resistant glass fibres knitted together into the metal wires to increase the collection targets and thus small particle collection efficiency. The co-knit metal mesh collecting layer is considerably thicker and has a higher void fraction than the glass collecting layer used in standard CS elements. Because of this open structure, in severe plugging situations, CK elements operate much longer between cleaning than regular CS elements. Figure 1 illustrates actual field performance of standard CS-IP elements compared to new CK-IP elements in severe plugging installations where towers were highly sulphated and no upstream air filters were used. The new CK elements ran significantly longer in dry tower service before needing to be washed or repacked. For sulphur burning plants, service life is typically two years or longer. Anodic protection and remote monitoring equipment Anodic protection is an electrochemical corrosion protection technique which can be applied to a variety of process vessels, including carbon steel tanks storing concentrated sulphuric acid. A significant benefit of anodic protection is the preservation of sulphuric acid purity stored in the tank. The normal acid concentration range of protection is 93-98%. At this concentration, the acid is not very corrosive to steel the main concern is usually contamination by corrosion products resulting in an inferior grade of acid and hydrogen grooving of internal tank walls. For large tanks, anodic protection provides the most cost effective solution to combat iron contamination of strong sulphuric acid. To ensure continuous effective operation of the anodic production system after energization, Corrosion Service Co. of Ontario, Canada include a remote monitoring unit (RMU) as part of the installation. The RMU was developed to monitor the anodic protection system without being intrusive and to avoid adding extra burden to the plant operators and personnel. The RMU is a microprocessor-based computer complete with a modem and can monitor the operating parameters of the anodic

protection systems via a voice grade telephone line. The unit has builtin memory to store an average of 10 day's operating data. Sulphuric acid coolers and piping are generally made of austenitic stainless steel such as 316. The concentration is normally 93-98%, acid and oleum. In this application, anodic protection provides the benefit of preventing through wall pitting that results in equipment failure, personnel hazard and environmental impact due to the spillage. In the case of acid piping, the spacing of cathodes is critical and anodic protection is not normally cost effective for piping under 6 inch in diameter. Digital anodic protection systems with GUI Monsanto Enviro-Chem's acid cooler anodic protection systems have now graduated from analog to digital with the introduction of Filmgard 4TM, and in doing so, have greatly simplified the system. The unit Filmgard 4TM offers a touch screen graphical user interface (GUI) for the input and monitoring of data, an integrated control system using state of the art equipment, increased Power Pac output and the ability to remotely troubleshoot acid cooler problems. Filmgard 4TM utilizes a proprietary integrated digital controller, which provides a more reliable and less expensive alternative to circuit boards. The new controller has resulted in an approximately 10% reduction in the controller cost. Saramet[R] trough distributor Kvaerner Chemetics has successfully used Saramet[R] distributors in strong acid service since the early 1980s, greatly reducing the maintenance requirements of traditional cast iron units. The latest distributor development by Kvaerner Chemetics is its modern Saramet[R] trough distributor, which is based on the use of an "open box" orifice design rather than the older "weir" type arrangements [ILLUSTRATION FOR FIGURE 2 OMITTED]. The orifice design has several important advantages: * Due to the higher depth of the fluid over the orifices, minor level differences in the trough will not have as large an impact on the flow rates as in a "weir" arrangement. * The "open box" design allows easy observation and cleaning of any debris which may accumulate in the unit. * The downcomers are completely welded to bolted tubesheets in easy to manage sections, making installation quicker.

Stainless steel converter with dual heat exchangers In the 1980s, the introduction of the stainless steel converter with internal heat exchanger was a major new innovation from Kvaerner Chemetics. This design offered the advantages of superior high temperature strength and corrosion resistance of stainless steel, eliminating the need for cast iron grids and metallizing or brick lining. Kvaerner Chemetics' patented internal gas heat exchanger eliminated the problematic high temperature ducting leaving the first bed and allowed a more compact design. Building on the success of the converter, Kvaerner Chemetics has taken the design one step further with the introduction of the dual internal heat exchanger converter [ILLUSTRATION FOR FIGURE 3 OMITTED]. This design offers all the benefits of the previous converter, plus the further simplification of the ducting arrangement surrounding the converter. The dual internal exchanger design eliminates the separate vessel foundation and insulation required by external designs, and allows a far more compact layout of the contact section of the plant. Tower packings The Hiflow ring, which forms part of Rauschert's range of proprietary high performance tower packings, is experiencing increasing use in gas cooling tower equipment in sulphuric acid plants worldwide. The Hiflow rings have been supplied as 2 in. (50 mm) or 3fi in. (90 mm) rings in polypropylene or heat-stabilized polypropylene material. The characteristic grid structure of Hiflow rings provides a very high void fraction. Their low weight in combination with their high mechanical stability allows for high packed bed heights without the need for intermediate support grids. Some of the inherent features of Hiflow rings are their high load capacity for liquid and gas streams accompanied by an extremely low pressure drop. In addition, they minimize the phenomenon of liquid flow towards and down the column walls, they are economical, easy to install and remove, and insensitive to fouling. When used to replace conventional tower packings in an existing column, Hiflow rings can either increase the throughput or reduce the energy costs. Optimized range of turbo-blowers Kuhnle, Kopp & Kausch (KKK) of Frankenthal, Germany now offers a new series (SFO) of optimized single-stage turbo-blowers for sulphuric acid plants. The SFO series heavy duty machines can operate with adiabatic efficiencies of more than 90% and very high partial efficiencies, resulting in lower operating costs. All components are easily accessible for low maintenance costs and reduced down time.

The new extended range of frame sizes covers capacities of 15,000350,000 N[m.sup.3]/h. For SRU applications, KKK's integrally geared series SFOG offers the same advantages. Alfa Laval PHE in Hastelloy D205 There are basically two types of coolers that are used in sulphuric acid plants: alloy plate heat exchangers and shell and tube heat exchangers; both are alloy and anodically protected. Cooler technology changed significantly in the 1990s when the nickel alloy Hastelloy D205 was introduced as a plate material for plate heat exchangers (PHE). Hastelloy D205 opened up a whole new world of opportunities for the sulphuric acid industry. Previously the highest temperature of concentrated ([greater than] 90%) sulphuric acid a PHE could handle was 90 [degrees] C. Even this could only be attained with some sort of recirculation to the pump tank to cool the acid temperature to below 90 [degrees] C. Hastelloy D205 was an appreciated compliment to Hastelloy C276 which was, at the time, the best alloy for high concentrated sulphuric acid. Hastelloy C276 has approximately a 0.1 mm/year (4mpy) corrosion rate at 90 [degrees] C whereas Hastelloy D205 has a corrosion rate of a 0.1 mm/year (4mpy) at about 150 [degrees] C. Semi-welded plates with a single laser point weld are state of the art in the sulphuric acid industry today. The one point weld minimizes the heat affected zone, keeping higher integrity on the plate. The laser weld melts the metal, thus electrodes are not used and the risk of a less resistant weld is minimized. The key advantage of a semi-weld plate is it uses 90% less gasket material in contact with the acid than traditional gasketed plates. Plate heat exchangers have an overall heat transfer coefficient that is about 2-3 times higher than a shell and tube exchanger in sulphuric acid and can economically deal with crossing temperatures. Crossing temperatures allow engineers to cool down acid to a much lower outlet temperature than the outlet temperature of the cooling fluid. The economy of any sulphuric acid plant is highly dependent upon how you take care of the exothermic heat from your acid dilution/production and if you have a use for it. The following examples show some of the ways in which exothermic heat is currently being utilized. * Outokumpu Oy in Harjavalta, Finland, uses semi-welded PHEs in its recently built nickel refinery/acid plant to recover 40 MW of heat from the acid plant. This is made possible with PHEs in Hastelloy D205 in the intermediate absorption tower (IAT) and final absorption tower (FAT)

coolers and in Hastelloy C276 in the dryer tower and product coolers. The IAT cooler cools acid from 116 [degrees] C by heating boiler feed water to 105 [degrees] C. About half of the recovered heat is used in the nickel plant and the other half is sent to the Harjavalta district heating system and to a neighbouring copper plant. * In many countries, companies have fresh water problems. Another use is to use the exothermic heat from the acid plant as a heat source in fresh water production e.g. in desalination plants. As long as the water source has [less than] 70,000 ppm total dissolved solids (TDS), potable water of less than 5 ppm TDS can be produced. With [less than] 10,000 ppm TDS, the potable water produced is reduced to [less than]1 ppm TDS. This has been made possible by recently developed falling film PHE evaporators. * The heavy rains of "El Nino" have created a new usage opportunity in Florida, USA, where phosphate fertilizer plants have found success in using the exothermic heat from the acid plant to increase pond water evaporation and to prevent overflowing ponds. Several companies in Florida have engineered costly systems to provide safe draining of their pond water. PHEs provide two economical alternatives to this costly expenditure: Use of cooling tower water Transfer heat from the cooling tower water into the pond water to reduce the load on the cooling tower and avoid scaling problems. Flows of about 3-4000 [m.sup.3]/h (12-18000 gpm) can be circulated through PHEs. Use of a closed loop system Transfer the heat with PHEs in Hastelloy D205 into a closed loop of good quality water using the alternative pond water loop. The flow ratio loop water/pond water should be 1/5 to 1/10 to reduce costs for the closed loop control scaling caused by pond water. The acid/loop water PHE should be designed for the same heat load as the existing cooler. In this example users benefit from a spare acid cooler that can be put into operation whenever required, if El Nino hits again. Latest developments of reverse-flow reactor technology Reverse-flow reactors (RFRs) for oxidation of sulphur dioxide to sulphur trioxide have been used commercially since 1982 in sulphuric acid systems treating gases from non-ferrous metals production. RFR technology by Matros Technologies, USA is based on the periodical reversal of gas flow through catalyst beds and inert packing to make better use of the heat of reaction and to achieve optimized temperature profiles in the catalyst.

During the 1990s, extensive studies were completed that have clarified how radial temperature and flow distributions and dynamics of the catalyst state affect the process performance. Advanced unit configurations have been developed that overcome the limitations of early reactor designs and achieve higher S[O.sub.2] reactor efficiencies. Figure 4 shows an advanced double contact system using the Matros reactor. The reverse flow reactor is particular suited for the treatment of gas flows with relatively low inlet temperature and low adiabatic temperature rise. In sulphuric acid production, three main potential areas of application have been identified: * treatment of low-S[O.sub.2] gases, e.g. from non-ferrous metal smelters; * using the reactor as a second stage in DC-DA systems, in particular for retrofitting existing SC systems to DC-DA technology; * oxidation of S[O.sub.2] generated during spent sulphuric acid recovery. The technology also has the potential to be used in the design of DCDA systems that treat gases containing low to medium concentrations (3.5-6%) and thus achieve high S[O.sub.2] conversion with small or no heat exchangers. Treatment of cold gases with relatively high (up to approx. 12%) and stable S[O.sub.2] concentrations, is also a possibility often worth considering. COPYRIGHT 1998 CRU Publishing Ltd. This material is published under license from the publisher through the Gale Group, Farmington Hills, Michigan. All inquiries regarding rights should be directed to the Gale Group.

Title: Recovering used sulphuric acid. Date: 10/1/1993; Publication: Fertilizer International; Environment leads over economics There are now so few alternative permissible ways to dispose of spent sulphuric acid that increasing amounts are being purified and

reconcentrated or completely regenerated, irrespective of the market price for "virgin" acid. Sulphuric acid is peculiar among basic chemicals in that very little of it ends up incorporated in a final product; most of it is discarded at the end of the process as a waste. Although in its largest single use -- the production of phosphoric acid from phosphate rock -- sulphuric acid is transformed into dirty calcium sulphate on a gigantic scale, posing a massive and costly disposal problem for the fertilizer industry, in most of its other main uses the sulphuric acid remains as sulphuric acid, nearly always diluted to a greater or lesser degree and usually contaminated with process residues which vary widely in both character and concentration. Formerly this so-called "spent acid" was largely disposed of into the environment -- either out at sea or, after neutralization with lime, on a solid waste dump or into rivers. Some spent acid which was not too heavily diluted and contaminated was formerly consumed in single superphosphate manufacture, but this fertilizer has progressively declined in importance in favour of more concentrated varieties, and today this outlet for waste acid is strictly limited. In recent years environmental disposal has been progressively outlawed in most industrially-developed countries, even for very dilute acids, and users have been faced with the simple choice of recovering their waste acid for reuse in their process, finding another direct use for it, or ceasing operations. Since there are very few potential uses, recovery is effectively the only alternative to shutting down. Thus, although market prices for both "virgin" (freshly-made) sulphuric acid and elemental sulphur have latterly been, in real terms, at their all-time low on account of slack demand during world recession and the increasing production of "pollution" acid from metal smelters, chemical manufacturers have to consider and invest in spent acid recovery options which, if studied from a purely economic point of view, would be dismissed out of hand: production economics in such cases means no more than limitation of the net cost. Origins of spent acid Spent acid results from a variety of processes in the chemical, petrochemical, plastics, pigments and metals industries. Some processes make use of its properties as a simple mineral acid, which are often more effective when it is only moderately concentrated, to leach unwanted constituents out of a raw material, as in the titanium dioxide industry, where it is used to remove iron from ilmenite. Spent acid from titanium dioxide processing is therefore substantially diluted and is also heavily contaminated with iron sulphates and, to a lesser extent, with sulphates of other metallic impurities from the ore.

In organic chemical, petroleum and petrochemical applications sulphuric acid is often used at full strength to provide a catalytic and/or dehydrating environment for an otherwise unrelated reaction, as in the nitration of aromatic hydrocarbons for the manufacture of explosives and other derivatives or in the alkylation of petroleum cuts to produce high-octane gasoline constituents. Spent acid from such processes may still be fairly concentrated and not contain any significant burden of inorganic impurities, but it will contain varying amounts of organic contaminants ranging from simple, volatile substances to heavy, complex tars and gums, along with residues from other ingredients of the process such as (in the case of nitration processes) nitrogen oxides. Acid wastes from the plastics and fibres industries often contain ammonium sulphate in addition to organic impurities. Treatment options Any spent acid which has been substantially diluted will normally be preconcentrated as the first stage. There are then two main options for further processing. The acid may either be subjected to purification and final reconcentration or be thermally decomposed to sulphur dioxide, from which fresh sulphuric acid is subsequently produced. Which is appropriate depends on the nature and burden of the impurities. In the simplest cases, the spent or waste acid may need no more treatment than reconcentration and removal of solids by decanting or filtration. However, reconcentration is complicated by the fact that, in the 80-90% concentration range, sulphuric acid is so extremely corrosive that very special materials of construction are needed. The earliest reconcentration apparatus, introduced in about 1915 and used for many decades for recovering moderately contaminated acid, was a thick-walled cast iron boiler known as the Pauling pot. These were, however, sacrificial and had to be discarded and replaced at intervals of a few months as they gradually corroded away. Where the acid is lightly contaminated with impurities which are volatile or are readily oxidized to gaseous decomposition products, they may be driven off during reconcentration or be decomposed by the intrinsic oxidizing power of the concentrated acid without any special treatment. For example, sulphonation in the detergent industry commonly produces a waste acid containing 75-80% |H.sub.2~S| O.sub.4~ which is only lightly contaminated with hydrocarbons, and these are released by evaporation during the concentration step. Sometimes a relatively inexpensive thermal pretreatment preceding reconcentration may be needed. A different approach is needed where the impurities are predominantly inorganic salts, as where the acid has been used in titanium dioxide processing or metal treatment. Here it is necessary to design the plant to crystallize the salts as efficiently as possible so that the reconcentrated acid can at least be returned to the user process. In

certain cases it may be possible to recover byproducts. Acid recovered from that kind of spent acid is seldom of high enough purity to be acceptable in other markets. There are certain categories of spent acid which are so heavily contaminated with organic chemical compounds, such as the acid wastes produced during alkylation and other petrochemical processes, that there is simply no alternative to the most elaborate and energyintensive expedient of all: total decomposition of the acid and reconstitution of the acid. Thermal decomposition of spent sulphuric acid produces sulphur dioxide, which can then be converted again into sulphuric acid by the contact process in the same kind of plant as is used for "virgin" sulphuric acid manufacture. Preconcentration In the 25-75% |H.sub.2~S|O.sub.4~ range, the most important item in the running costs is the energy required for concentration. To keep this as low as possible, double- or triple-effect vacuum evaporation is commonly used, in which the vapours given off in one stage are utilized as the heating medium for another stage operating at a lower temperature and pressure. The detailed design for the evaporators is chosen according to the throughput, concentration and solids content of the acid. The fallingfilm type, in which liquid trickles down the inside walls of a series of vertical heated tubes aspirated by a countercurrent of disengaged vapours, is one of the most popular. Materials of construction include graphite, plastics and rubber-lined steel for concentrations up to about 50% |H.sub.2~S|O.sub.4~. More exotic materials, such as Hastelloy C, tantalum or zirconium, are needed to resist the greater corrosive strength of the acid when it exceeds 50% concentration. Where the non-volatile solids content of the acid is substantial enough to warrant it, evaporator-crystallizers of the forced-circulation or draft tube baffle type, such as those available from Swenson Process Equipment Inc. or its UK licensee Wellman Process Engineering, may be incorporated in the preconcentration train. Further concentration Above 70-75% concentration, energy costs are less important: the most important problem is to reach the final concentration safely. Materials choice is even more exacting at these concentrations, and glass or enamel linings or other highly corrosion-resistant materials are necessary, especially with spent acid containing both sulphuric and nitric acids. A number of companies offer technology and experience in this area.

Rauma Ecoplanning, of Finland, which has more than 20 years' experience in the field, claims an annual capacity in systems of its design of more than 2.5 million tonnes of spent sulphuric acid. The company offers systems for concentration up to 90% |H.sub.2~S| O.sub.4~, including the crystallization and separation of salts either before or during the concentration process. Valuable metal salts obtained from processing liquors from titanium dioxide or other metallurgical operations can be recovered for recycle too. Applications include treatment of titanium dioxide waste, typically containing 20-25% |H.sub.2~S|O.sub.4~ and 10-15% metal salts, and spent pickle liquor from steel production, which may also contain hydrofluoric and nitric acids, as well as dissolved metals such as iron, nickel, chromium, molybdenum and copper. In this case the nitric and hydrofluoric acids are separated by evaporation and the metals are crystallized as sulphates. Bertrams AG, of Switzerland, offers technology to concentrate spent acids to strengths up to 98% |H.sub.2~S|O.sub.4~, with or without oxidative purification to decompose traces of organic materials, to allow the recycled acid to be used again in the same process. The company has installed equipment to improve spent acid recovery for Bayer AG, Germany, Europe's largest spent sulphuric acid reprocessor. The primary problem in evaporating sulphuric acid solutions to high concentrations lies in the steep increase in the boiling temperature as the concentration rises. This can be reduced substantially by decreasing operating pressure (e.g. to around 60 Torr, which can be achieved relatively easily) but, on the other hand, degradation of organic contaminants is favoured by higher temperatures. The plant must be capable of removing non-volatile organic contaminants from the acid, and it is absolutely essential that heating surfaces remain free of fouling by solids or the products of thermal cracking. Since forced circulation prevents fouling, this is usually preferred for the final concentration step. Bertrams favours the use of enamelled steel for contact with hot sulphuric acid, and purification is integral with the final concentration stage. Small concentrations of high-boiling organics can be removed by injecting an oxidizing agent during the final concentration stage, in which case the enamelled evaporator serves as a reactor, too; however, this is not recommended where the concentration of organics exceeds 1.5 wt-% carbon equivalent. This type of system also does not remove dissolved salts such as ammonium sulphate. Although the traditional Pauling atmospheric-pressure, liquid-phase concentration process has the advantage of operating above 300 | degrees~ C, at which temperature, with the addition of a suitable oxidizing agent, most organic contaminants are destroyed, the process requires silicon iron equipment. This causes heat transfer limitations,

corrosion problems, high maintenance cost and the possibility of catastrophic failure. Chemetics International Co. Ltd, of Canada, advocates the use of its Saramet specialty austenitic steel alloy for such vacuum concentration duties. Anodically-protected Saramet has avowedly excellent resistance to sulphuric acid at concentrations greater than 90% and has far better heat transfer properties than traditional construction materials such as silicon iron. Chemetics's spent acid technology was originally developed to deal with diluted sulphuric acid contaminated with nitric acid, remaining after nitric acid concentration or organic nitration processes. This typically involved spent acid denitration and concentration from about 70% |H.sub.2~S|O.sub.4~ up to 96% |H.sub.2~S|O.sub.4~. More recently, the company has installed multi-stage vacuum evaporation systems to concentrate spent acid from as low as 8% |H.sub.2~S| O.sub.4~ up to 50%. Chemetics has also developed its own process for recovering sulphuric acid from titanium dioxide plant waste. It allows complete evaporation of the feed acid under conditions that minimize any breakdown to sulphur dioxide. In this way, metal sulphates can be removed in the vapour phase and a concentrated acid product is obtained by partial condensation of the vapours. The first industrial embodiment was a 100 t/d demonstration plant built in 1987 at Sorel, Quebec for a consortium comprising Tioxide Canada Inc, Kronos Canada Inc and QIT Fer & Titane Inc. In the process, preheated weak acid is preconcentrated and then passed into a spray drier, where it is atomized into a stream of very hot gases at over 100 |degrees~ C. Under these conditions, both water and sulphuric acid are vaporized, while solid metal sulphates are separated from the vapours on a sintered metal filter. The gases leaving the sintered metal filter are essentially solid-free and can be passed to a single-bed catalytic converter - containing conventional vanadium pentoxide sulphuric acid catalyst - to convert any sulphur dioxide formed in the spray drier (by oxidation of ferrous sulphate) into sulphur trioxide. From the converter, the gas stream is split into two, part going to a concentration tower and the remainder going to a recycle tower, where it is condensed to form 60% sulphuric acid. This is passed into the concentration tower, where it absorbs more sulphur trioxide and acid vapours to reach 96% strength. Since the development of this process, Chemetics has applied the same vapour-phase technology to other spent acid recovery duties, including regeneration of the sometimes very weak acid produced as "blowdown effluent" at metallurgical smelters, which are increasingly being required to adopt zero-discharge operation. Blowdown effluent arises from the need to periodically clean the gas cleaning equipment in sulphuric acid plants installed at non-ferrous metal smelters, and may contain less than 10% |H.sub.2~S|O.sub.4~, together with

variable concentrations of a wide range of metals in the form of sulphates. In some cases it is possible to increase the strength of blowdown acid to 20% by modifying operating conditions, but otherwise the acid must be preconcentrated to this strength. Pilot plant tests have confirmed that fluorides and chlorides present in the blowdown acid - which would subsequently cause damage to brickwork and to the sulphuric acid conversion catalyst - can be removed in the acid pre-concentration stage. Experience from titanium dioxide waste acid treatment indicates that more than 99.99% of all metal sulphate particles are removed at the sintered metal filter, and the pilot tests further indicated that potentially volatile components in blowdown acid - chiefly cadmium, arsenic and bismuth - reported to the solids at the sintered metal filter rather than the acid condensation system. Chemetics has also developed vapour-phase technology for treatment of acids contaminated with organic components, since it believes that in many cases vapour-phase technology is a more economical means of treating such acids than decomposition and regeneration. For acids contaminated with organics, vapour-phase technology can be used provided it can be established that the organic contaminants can be successfully oxidized under conditions which do not cause significant decomposition of the acid. In Germany, Sachtleben Chemie GmbH has been producing pigments since 1877, and in 1987 participated in a major collaborative venture to recycle waste acid, chiefly from titanium dioxide waste acid, with the construction of a purpose-built 800,000 t/a waste acid recycling plant at Duisburg. The plant, which was built by Lurgi AG at a total cost of DM 200 million, was designed to take all the waste acid from Sachtleben's own operations together with that from Kronos Titans' operations at Leverkusen as well as filter salts from Kronos' Nordenham site, both elsewhere on the Rhine. Barges bring 23% |H.sub.2~S| O.sub.4~ waste acid from Leverkusen, while reprocessed 70% | H.sub.2~S|O.sub.4~ is returned in rubber-lined trucks. In the plant, which is based on Bayer's technology, a progression of treatments is applied in sequence. The waste acids from Sachtleben and Kronos are mixed in the ratio 70:30 and the mixture is then fed to the first of a total of six processing stages. Initial vacuum evaporation takes the acid from 22% to 70%. Much of the crystallization has taken place by the time the acid concentration reaches 70%. The acid suspension from the evaporators next passes through nine cooled, agitated crystallization tanks, where it may take several hours to crystallize out all impurities prior to filtration. The crystallized salts are then removed on filter presses, and after this the filtered acid is further concentrated to 80%, using graphite heat exchangers and evaporator vessels lined with both lead and carbon bricks.

The filter salts contain significant amounts of sulphur and therefore cannot be dumped as solid waste. They are instead blended with local pyrites and coal and then subjected to thermal decomposition in a fluidized-bed roaster operating at over 1,000 |degrees~ C. Sulphur dioxide from this roaster is further cleaned and sent to the contact plant where fresh sulphuric acid is made. It is estimated that some 200,000 tonnes of sulphur-containing metal compounds are produced annually during the acid concentration steps, of which some 75,000 tonnes are insoluble (mainly iron) oxides. The residue from the roasting of the filter salts is used to a certain extent in a smelter in the Ruhr area, but the remainder is stockpiled on site, while Sachtleben investigates ways of using it in the building and construction industry. A role for membranes? In many fields, membrane separation systems are gaining attention as low-energy alternatives to relatively high-energy evaporative purification methods. Applications in spent acid processing are already being developed. These are particularly attractive where the spent acid may contain a complex mixture of other acidic and metallic impurities, since the more complex the separation challenge, the more energyintensive evaporative processes tend to become. Two companies have developed spent acid purification processes based on electrodialysis, in which the sulphate anion diffuses from the contaminated acid in one compartment of a cell through a selective anionic membrane into another compartment. The process developed by the Aquatech subsidiary of Allied-Signal Corp. has been demonstrated in commercial steel pickle liquor recovery applications since 1990 and reportedly produces recovered acid that can be returned to the original duty. Asahi Glass Co. Ltd, of Japan, has developed an electrodialysis process which reportedly recovers 90% of the sulphuric acid content of titanium dioxide spent acid containing 20-40% |H.sub.2~S|O.sub.4~ as clean acid of similar concentration. Clearly the challenge for membrane processes is to deliver regenerated acid at relatively high concentration. Thermal decomposition Most of the leading sulphuric acid plant contractors also offer sulphuric acid regeneration processes. Because the composition of spent sulphuric acid is particular to the process which produces it, the technology is often the result of joint development work with major operating companies such as Bayer AG, of Germany, and RhonePoulenc, which owns the portfolio of the former Stauffer Chemical Co.,

of the USA. Today they include the Metallurgical Division of Lurgi AG, of Germany (which owns not only its own technology but also the portfolio of the former Davy McKee AG), Monsanto Enviro-Chem, of the USA, Chemetics International Co. Ltd., of Canada, and Siry Chamon Impianti, of Italy. Total regeneration is the most practical option for processing spent acid heavily contaminated with organic impurities, especially when they are of low-volatility, and with decomposable salts such as ammonium sulphate. In all the total regeneration processes the spent acid, preconcentrated where necessary, is sprayed with a fuel (usually fuel oil) into an incineration furnace, where the organic components burn and also reduce the sulphuric acid to sulphur dioxide. Ammonium sulphate is also decomposed to sulphur dioxide and nitrogen. The gas stream, after cooling and cleaning to remove solid residues, is passed through a "cold-gas" contact sulphuric acid which regenerates clean acid. Usually the contact section of the plant is fairly standard. The key process considerations are the design and efficiency of the decomposition furnace, waste heat recovery efficiency, and the concentration of sulphur dioxide obtained. Where the spent acid contains nitrogen compounds, avoiding nitrogen oxides formation in the furnace is also an important consideration. In some cases where there are inorganic contaminants, facilities for withdrawing and handling slag from the furnace may be required. It is also important to ensure, by means of baffles, that droplets of slag cannot alight on the waste heat boiler tubesheet, where they would solidify and quickly cause plugging. Although the decomposition of both sulphuric acid and ammonium sulphate is a highly energy-intensive process, the organic content of heavily contaminated spent acids often supplies a healthy proportion or even all of the thermal energy needed, correspondingly offsetting fuel needs. Alkylation waste acid, which contains around 90% |H.sub.2~S| O.sub.4~ and only about 5% organic matter, needs supplementary fuel, but sludges from other petroleum processes such as lube oil or kerosene treatment may contain up to 50% organics and are in consequence autothermal. Where available, hydrogen sulphide or liquid sulphur can also be burnt in the furnace to increase sulphur dioxide concentrations and to reduce fuel needs. For more than 40 years Monsanto Enviro-Chem has averaged more than one spent acid regeneration plant each year. The company builds many proprietary features into its designs, including the use of Sandvik SX sulphuric acid steel as a preferred material of construction, FilmGard acid coolers and the DynaWave gas cleaning system, which obviates the need for electrostatic precipitators in cases where the generated process gas has a low to moderate solids content. The

company says that, even in cases where high solids are expected, the DynaWave system lowers capital costs because of shorter retention times. Monsanto observes that a variety of non-traditional spent acid feeds are now being considered for regeneration, including ammonium sulphate and bisulphate solutions, acids in the range 45-65% | H.sub.2~S|O.sub.4~ and feedstocks that are both cyclic in availability and variable in composition. Many of these new feedstocks contain contaminants that are undesirable in spent acid regeneration operations, but Monsanto believes that innovative designs for regeneration processes must accommodate these difficulties. The company has established itself in the design and construction of sulphuric acid plants utilizing a variety of spent acid feedstocks, as well those based on hydrogen sulphide. In one case, weak nitration spent acid is decomposed at 815 |degrees~ C in a two-stage system designed to reduce nitric oxides as well as destroying organic components. Treatment of alkylation spent acid requires a less complicated decomposition system than does methyl methacrylate (MMA) spent acid processing. Monsanto says, however, that its latest plant for MMA spent acid feedstock contains substantially less stainless steel than the other two examples, since equipment was procured at the height of a period of nickel price escalation. Thus, SX was only used in critical areas and low-cost Mondi ductile iron was used for acid piping. Lurgi Metallurgie GmbH offers a number of designs for thermal decomposition of various types of spent acid. In 1992 the company began construction of a plant to reprocess 842 t/d of spent acid from MMA production. This acid contains only 18-20% |H.sub.2~S|O.sub.4~, along with 45-47% ammonium hydrogen sulphate, 30-32% water, 3-4% organic compounds containing oxygen, and up to 1% combustible solids. Heavy oils or refinery residue are used to decompose the spent acid at temperatures up to 1,100 |degrees~ C in a decomposition furnace with vertically and horizontally-disposed chambers, after which the process gases are cooled in a gas/air heat exchanger, to provide combustion air at 490 |degrees~ C and further hot air used to superheat steam in a steam boiler. The high energy efficiency is one of the main attributes of the process, the company says. In the decomposition section, the sulphur conversion efficiency is about 99.9%, while N|O.sub.x~ emissions are limited to 80-100 ppmv. The company is in the process of designing a new three-fuel flame evaporation burner for the decomposition furnace which can operate on oxygen-rich combustion air and at the same time reduce the levels of N|O.sub.x~. Another Lurgi development is the Grillo/Lurgi rotary kiln decomposition system, for use with spent acid that has high contents of acid tars and

organics. The waste acid is injected onto a sliding coke bed in the rotary kiln, which is of mild steel construction with a refractory lining. The coke, which is produced by the process from the high carbon content of the feed, serves as a distribution medium, and to accelerate and stabilize the exothermic and endothermic reactions taking place. In the rotary kiln, which operates at around 900 |degrees~ C, the feed materials are evaporated and partially oxidized. The combustible gas components are then fully oxidized with air in two post-combustion chambers. Lurgi says that with careful management of the feed mix and the application of some oxygen, a gas containing 20% S|O.sub.2~ can be achieved, which can subsequently be processed to high-grade liquid sulphur dioxide or converted into sulphuric acid in the conventional way. Coke was also used as a heating medium in the earliest refinery sludge decomposition plants built by the former Chemical Construction Corporation (Chemico), but gave rise to too many mechanical problems. Siry Chamon Impianti, of Italy, which acquired all rights to the Chemico technology, nowadays uses a horizontal refractory-lined furnace into which the spent acid is atomized. Fuel is also supplied, even if there is an adequate heat balance from the combustion of impurities in the acid, for the purpose of stabilizing the flame. For more dilute spent acids containing substantial proportions of ammonium sulphate or nitration residues, which generate large volumes of nitrogen resulting in too lean a feed gas for satisfactory operation of the sulphuric acid plant, the furnace air is preheated, enabling fuel and, therefore, air inputs to be reduced. Siry Chamon has built 24 spent acid recovery units with daily capacities ranging from 30 to 1,450 tonnes. Among the most recent are a refinery alkylation waste regeneration system and a commercial unit reprocessing spent acids from a number of industrial sources, both in Italy. Chemetics International Co. entered the MMA spent acid field by designing and developing acid preconcentration units for projects incorporating the Rhone-Poulenc (Stauffer) decomposition technology. Its largest project to date, which is also one of the largest spent acid regeneration facilities in the world, is the 1,120-t/d MMA spent acid regeneration plant recently installed at the ICI Chemicals & Polymers works at Billingham, in the UK. This spent acid regeneration plant includes Chemetics' two-stage steam-heated preconcentrator, thermal decomposition technology developed by Rhone-Poulenc and using oxygen burners developed and supplied by l'Air Liquide, and a contact plant essentially of Chemetics design. The basis for the thermal decomposition step is the technology originally developed in the United States by Stauffer & Co (a company

which was later acquired by Rhone-Poulenc), and later modified for MMA waste acid at ICI's partly-owned subsidiary Kaohsiung Monomer Co, Taiwan. While sludge acid and spent acid from alkylation processes typically contains around 90% |H.sub.2~S|O.sub.4~ together with up to 7% hydrocarbons and very little water, spent acid from MMA production usually contains only 30-40% |H.sub.2~S|O.sub.4~ and up to 40% water. Chemetics was involved in the construction of the Kaohsiung plant and also an earlier thermal decomposition plant for Stauffer which came on stream at Dominguez, California in 1989. MMA waste acid can only be preconcentrated up to the point at which ammonium sulphate would begin to precipitate. It was found in pilot testing that, even at this practical maximum strength, at full capacity the volume of waste acid was still too large to be processed in a single decomposition furnace operating on air, which is why oxygen/fuel burners were adopted. Air burners are, however, provided for start-up and operation up to 40% capacity. After cooling, the gases from the furnace are washed with dilute acid, demisted and passed through electrostatic precipitators before entering a Chemetics-designed contact sulphuric acid plant, featuring Chemetics' patented radial-flow gas/gas heat exchanger and all-welded stainless steel converter designs. All strong acid piping is fabricated from Saramet. The use of ring-type catalyst and Chemetics radial-flow converter gives good gas distribution at low pressure drop. Economics According to Monsanto Enviro-Chem, a 300-t/d plant for recovering alkylation acid would cost around $20 million, with operating costs in the region of $40/tonne of acid recovered. Rhone-Poulenc, a leader in the field as an operator and process developer, estimates that it costs around $150/tonne to regenerate spent alkylation acid by the thermal decomposition route. Economies of scale are clearly important, especially with the more capital-intensive methods. Again RhonePoulenc suggests that companies processing less than 200-250 tonnes a day of spent acid might find it less expensive to have the acid regenerated by a toll processor, the role played by Rhone-Poulenc itself in its 170,000-t/a sulphuric acid regeneration plant at Rieme, Belgium. On the basis of early experience from the new plant at Billingham, ICI and l'Air Liquide have published comparative costings for a thermal decomposition plant based on air and oxygen. The basis for the costings is a hypothetical 800-t/d plant fed with a mixture of spent acids - 25 t/h MMA waste acid, 5 t/h acrylonitrile waste and 20 t/h alkylation waste. Total operating costs are estimated 11% lower for the oxygen based plant. Assuming an annual on-stream factor as low as 300 days/year, these costings indicate that at this scale of production the cost of

regeneration is, in round terms, in the order of $100-120/tonne of acid regenerated. This is by no means a cheap option compared to the going international price for sulphuric acid, but perhaps a price worth paying to stay in business. COPYRIGHT 1993 CRU Publishing Ltd. This material is published under license from the publisher through the Gale Group, Farmington Hills, Michigan. All inquiries regarding rights should be directed to the Gale Group. Title: Non-catalytic acid production. (Ralph M. Parsons Co.'s oxygenbased non-catalytic sulphuric acid processing technology) (Sulphuric Acid Round-up) Date: 1/1/1992; Publication: Fertilizer International; Today, virtually all sulphuric acid production is based on the contact process, in which sulphur dioxide (obtained by burning sulphur of some other sulphur compound in air) is converted by catalytic oxidation to sulphur trioxide, which is then absorbed in water. The introduction, by Ralph M Parsons Co, of an oxygen-based non-catalytic route therefore appears as a radical development. In principle, the process entails combustion of elemental sulphur in oxygen, so that a gas stream containing sulphur trioxide is produced directly. The gas stream - containing sulphur trioxide, sulphurdioxide, some unreacted oxygen, carbon dioxide from any carbon/hydrocarbon present in the sulphur, and various inerts from impurities in the oxygen - is then passed to an absorber device, where sulphuric acid is formed from the sulphur trioxide and the remaining gases are recycled back around the flowsheet. A "loop" process is thereby set up - with some rudimentary analogy to the synthesis loop in ammonia production with the need for a purge stream from the absorber to control the build-up of inerts in the gas flow. The new process is said by Parsons to involve lower equipment cost and emission of minimal gaseous air pollutants. Elemental sulphur and oxygen, together with recycled gas containing sulphur dioxide, are subjected to combustion at around less than 100[Degrees]C and less than 35
Table 1 Comparisons for HRS Super HRS Utility 840 1,000 Fuel Usage, 4,200 8,000 Btu/KW

atm pressure. A heat exchanger is used to generate high pressure steam from the reaction heat and the [SO.sub.3]-laden gas is then contacted with sulphuric acid solution in the absorber. Apart from the small purge stream, all the gases containing unreacted sulphur dioxide are recycled through the process. The acid stream from the absorber is cooled, with heat, recovery in the conventional way (Fig.4). Oxygen of at least 80% purity is used in the burner, and the company states that the [SO.sub.2]:[O.sub.2]mole ratio in the burner feed gas should be between 3:1 and 10:1. The burner then produces a gas stream typically containing 6-12% [SO.sub.3]. Based on a 1,200 tonne/day production unit, with a burner operating at 830[Degrees]C and 4 atm, conversion efficiency in sulphur is stated as 99.994% and that for oxygen 99.9%. The purge rate to atmosphere is 334 kg/h, equivalent to a sulphur dioxide emission rate of 1.9kg/hr or 0.083kg[SO.sub.2]/ tonne [H.sub.2] [SO.sub.4]. The purge gas stream consists mainly of argon, together with about 9% oxygen; it contains only 0. 16% [SO.sub.2], Parsons says. Elevated pressure and the use of oxygen rather than air reduce the size of equipment items dramatically, and the simplified flowsheet means that less equipment items are needed compared with a conventional contact plant. Other advantages cited include elimination of expensive catalyst, and a big reduction in the power requirement for blowers/compressors. High efficiency is achieved with only a single absorption stage, rather that the double contact layout required to achieve sulphur efficiencies of 99.7% by the contact route. Acid products of varying concentrations can be produced. COPYRIGHT 1992 CRU Publishing Ltd. This material is published under license from the publisher through the Gale Group, Farmington Hills, Michigan. All inquiries regarding rights should be directed to the Gale Group.

Title: FGD as a source of sulphuric acid. (flue gas desulphurization) Date: 11/1/1990; Publication: Sulphur; FGD as a source of sulphuric acid One aspect not covered in our feature on sulphuric acid technology in Sulphur No. 210 is the production of sulphuric acid from sulphur dioxide-containing flue gases. In Germany, where operators are obliged

by law to recover the sulphur content of flue gases in the form of a utilizable product, there has been a much stronger incentive to develop new and more efficient flue gas desulphurization process than in most other countries. Many of the largest power stations, which were the first to be equipped with flue gas desulphurization (FGD) systems, produce high-purity gypsum which is marketed to the building trade, to the chagrin of the natural gypsum industry. That market is now oversupplied and future FGD units must generate alternative products. Options include elemental sulphur, liquid sulphur dioxide and sulphuric acid, and examples of FGD systems using all of these routes have now been installed, with varying degrees of success. Lugri GmbH, of Frankfurt, has been involved in the development of such a process which is now in operation in a commercial-scale installation. In view of the company's pre-eminence in the area of sulphuric acid process design and engineering, it is not surprising that the product is sulphuric acid. As its name implies, the Desonox process includes provision for nitrogen oxide abatement in conformity with the latest regulations. Over and above the mandatory criteria ([SO.sub.2] and [NO.sub.x] removal efficiency, no waste streams, utilizable byproduct), Lurgi set one or two of its own: the process had to be simple, it had to be as inexpensive as possible to install and operate, and it had to be amenable to retrofitting into existing plants. Desonox fulfils these requirements, and it is applicable not only in power stations but in other installations such as titanium dioxide plants as well. Figure 1 is a block flow diagram of the main process steps. After passing through the power station high-temperature electrostatic precipitator, the flue gas enters a two-stage catalytic converter. The first stage is a selective catalytic reduction (SCR) system, in which nitric oxide and nitrogen dioxide are selectively reduced by ammonia to elemental nitrogen and water vapour. 6NO + [4NH.sub.3] [right arrow] [6H.sub.2.O] + 5N.sub.2] [6NO.sub.2] + [8NH.sub.3] [right arrow] [12H.sub.2] + [7N.sub.2] This is the standard procedure for flue gas nitrogen oxide abatement. Its principal advantage is that it can be performed in the presence of the appreciable concentration (around 8 vol-%) of residual oxygen which is a normal constituent of combustion gases. In the second catalytic stage, this oxygen is used to convert the sulphur dioxide to sulphur trioxide. [SO.sub.2] + [1/2O.sub.2] [right arrow] [SO.sub.3] The flue gases are then cooled and, in the presence of water vapour formed in the combustion and in the SCR system, the sulphur trioxide condenses as sulphuric acid. [SO.sub.3] + [H.sub.2.O] [right arrow] [H.sub.2.SO.sub.4]

The gas is then washed to remove any hydrogen chloride or hydrogen fluoride that it may contain. Ultra-fine sulphuric acid mist particles escaping from the scrubbing system are collected in a wet precipitator before the flue gas is sent to the stack. The final product is 70% sulphuric acid, which can be used in the manufacture of fertilizers. Once the process concept outlined above had been determined, a pilot plant with a capacity of 500 [Nm.sup.3./h] was designed and installed in 1985/86 at an existing cogeneration plant belonging to Stadtwerke Munster, Germany. Following successful tests, in 1987 the decision was made to build the first industrial-scale Desonox plant on the No. III unit of the Munster station. The boiler installation was built by Lentjes and the catalysts were supplied by Degussa. Figure 2 is a simplified process flow diagram of this plant. After leaving the boiler, the flue gas is passed through a hightemperature electrostatic precipitator, which cleans the gas to a residual dust content of less than 50 [mg/Nm.sup.3] flue gas. Sufficient ammonia to reduce the nitrogen oxides, but no more, is then added, and the combined gas stream passes through the [SCR/SO.sub.2] oxidation reactor at about 450[degrees]C. The gas cooler downstream of the reactor is a two-stage unit, the first of which preheats the combustion air for the power station boiler and the second reheats the purified flue gas to improve its dispersion from the stack. It cools the moist gas from 460[degrees]C to about 140[degrees]C. About 25% of the sulphur trioxide condenses there and then as sulphuric acid with a concentration of more than 7 wt-%. From this unit the gas passes next into a two-stage scrubber, which washes out most of the residual sulphur trioxide/sulphuric acid. In the second stage of the scrubber, which is the coolest, any hydrogen chloride and fluoride which may be present in the flue gas are scrubbed out. The dilute acid obtained also contains some sulphuric acid, which is recovered by continuously withdrawing a sidestream and passing it through a stripper before it is returned to the main system. The displaced hydrogen halides are neutralized with lime. After reheating, the clean flue gas is sent to the stack through a wet electrostatic precipitator, which arrests acid mist. In the model of the plant shown in the photograph, the larged ribbed box on the right is the housing of the catalytic reactor; next to it is the intermediate gas blower, and to the left of that are the heat exchanger and scrubber. On the extreme left is the lime silo. The power plant is located in the middle of a town and is therefore subject to very critical observation, in respect not only of sulphur dioxide and nitrogen oxides emissions but also noise. Nevertheless, the plant complies with the statutory waste gas emission limits. Table I shows performance data for the system. Where there is a notable

discrepancy between design parameters and observed figures, the two are compared. Following the successful conclusion of tests with the first plant, it is now intended that Unit II of the Munster station will also be equipped with Dexonox plant. At present the stack gas leaves this unit at 130[degrees]C. The process must therefore be modified in order to heat the flue gas to the temperature required for optimum catalyst efficiency (about 450[degrees]C. Most of the heat required will be supplied by a heat exchanger, which will raise the gas temperature to 420[degrees]C. The remaining 30[degrees]C increase will be attained by burning natural gas. This auxiliary heating system provides the system with a degree of flexibility and allows gas temperature fluctuations to be accommodated. After catalytic reaction, the hot flue gases are used to preheat the "cold" flue gas in order to recover heat within the system. The subsequent acid condensation and mist separation are as described above. The Desonox process has a range of benefits. There is no waste product, except for some filter cake and neutral waste water from the HC1/HF neutralization, the sulphuric acid produced is suitable for industrial use, there is no ammonia slip, the flue gas enters the stack virtually dust-free, and existing plants can be retrofitted with the system. COPYRIGHT 1990 CRU Publishing Ltd. This material is published under license from the publisher through the Gale Group, Farmington Hills, Michigan. All inquiries regarding rights should be directed to the Gale Group. Title: Filamentary filters in AN-NA applications: some of the range of products designed to separate particles from fluids are used to great advantage in ammonium nitrate and nitric acid plants.(Process Equipment) Date: 9/1/2004; Publication: Nitrogen & Methanol; Filters comprising knitted or woven wire or monofilaments of a range of durable materials are widely used in industrial applications for arresting particles which have become aspirated in gas streams. In general, the finer and more efficient this kind of filter is the less suitable it is for removing solids because it is more susceptible to blockage, but it is eminently well suited to arresting liquid spray droplets as long as the liquid formed by coalescence of the captured droplets can drain away freely. Liquid spray is almost bound to be formed in any gas-liquid contact device or any vessel in which gas or vapour is evolved from a boiling or frothing liquid (boilers, evaporators, desulphurisers and other

gas washing columns, strippers, and distillation columns, to name but a few). The reasons for wanting to arrest aspirated droplets depend on their nature and the location in the plant where they are formed. Acidic droplets are likely to damage metallic surfaces, while any kind of liquid can damage catalysts operating at high temperatures by thermal shock or fouling (or both). Sprays emitted into the atmosphere may be a health or environmental risk. Mesh filters provide a reasonably-priced, durable, effective method of arresting spray with no moving parts and without imposing too much in the way of a pressure drop penalty. The smaller the particles are, the less easy they are to remove. Small particles require a fine filter, and the finer the filter the greater is the pressure drop and, therefore, the more the energy that is required to drive the gas through the plant. Worst of all are so-called 'sub-micron' particles of mist and fume, which are formed not by aspiration from a body of liquid but by condensation from the gas stream, as the result of a chemical reaction between two gaseous constituents. A notorious example is sulphuric acid mist, which is formed in the absorption tower of a sulphuric acid plant when the dry gas stream containing sulphur trioxide comes into contact with the small amount of water vapour emanating from the 98.5% absorption acid. The particles are so fine that they can pass through any scrubber almost unaffected, and they are similarly not amenable to filtration. Expensive, cumbersome techniques such as electrostatic precipitators were formerly needed to deal with these tiresome mists, and unless the gas was being passed to a subsequent processing stage which might be damaged by it, the tendency was to leave it where was. In conventional contact sulphuric acid plants the absorber was the last thing before the discharge stack, and until the latter half of the last century pollution control regulations were none too arduous! The answer to this problem came with the development of the fibre bed filter. This was pioneered in the 1950s by the US Atomic Energy Commission, but it was not long before the chemical industry realised the advantages of the new type of filter and developed the concept further, taking advantage of newer materials such as glass fibre and, later, polypropylene for particularly corrosive environments. In the 1960s Monsanto, in the person of one Joe Brink, and ICI independently developed fibre filters which relied for their effect on the Brownian motion of sub-micron particles for removing mist from sulphuric acid plant tail gas. The market for these promptly increased with the introduction of the double-absorption process in the mid 1960s, since suppressing mist in the gas leaving the intermediate absorption tower of a double-absorption plant is vital to prevent damage in the subsequent process stages. ICI licensed this technology to Begg, Cousland & Co. Ltd in Scotland.

Although, as will be explained below, fibre-bed filters can only cope with appreciable loadings of submicron particles of liquid materials, it was realised before long that they would also work with sub-micron particles of highly soluble solid materials as long as sufficient moisture was available, either from the gas stream itself or from irrigation, to dissolve the arrested particles. In the 1970s, as new environmental legislation which considered not just the content but also the visibility of waste gas discharges began to come into effect, Monsanto developed a new application for its Brink[R] mist eliminators in controlling the fume from ammonium nitrate prilling towers--a problem up till then thought all but insoluble. Other suppliers were not slow to follow. Applications for filters based on the same general principles increase almost by the day. Principles The ideal gas filter is one which arrests 100% of the entrained particles without hindering the flow of the gas at all. Such a requirement is obviously unachievable, but it becomes less and less approachable the smaller the particles being carried by the gas are. It is not even possible to design an electrostatic precipitator which does not cause some degree of pressure drop, although the pressure drop is inherently lower than the equivalent filter using a filter medium. There are different mechanisms of interaction between entrained particles and a fibre bed filter medium. Which of them applies depends on the size of the particles and the gas velocity through the filter. They are represented in Fig. 1. The more massive the particles, the easier they are to collect on a bed of filaments. This is because, when the gas stream encounters a filament, the inertia of the particle carries it forward in the direction in which it was moving, whereas the gas flows round the filament. This collection mechanism is known as inertial impaction, and up to a point its efficiency is proportional to the gas velocity (as, of course, is the pressure drop). So these filters are often referred to as high-velocity or HV filters. As long as the filter bed is deep enough to ensure there are no direct paths that particles could follow through it, the filter medium for an HV filter can be made up of relatively coarse filaments, even metallic wire, relatively loosely packed to allow rapid, unimpeded gas flow. Any filamentary filter must be arranged in such a way that the arrested particles can coalesce to form a continuous liquid phase and drain away by gravity, otherwise the filter element would become flooded, increasing both pressure drop and the risk of re-entrainment. On account of their relatively open structure, mesh pads can be mounted horizontally to intercept an upward flow of gas and still drain

adequately, whereas the much more close-textured fibre-bed mist eliminators are best placed vertically with a horizontal gas path so that the drainage is transverse to the gas flow, rather than in countercurrent. Another collection mechanism is direct interception, in which the interstitial spaces in the filter medium are comparable with the diameter of the particles, so it is difficult for the particles to pass through the filter without touching and being captured by the medium. The humble sieve is an example of a direct interception filter. Neither of these collection mechanisms applies to sub-micron particles, since they are light enough to be deflected round the fibres of an inertial impaction filter, while if it were even possible to produce a fibre filter with small enough interstices to intercept the particles directly, the pressure drop would be enormous. Therefore a different mechanism is used which depends on Brownian motion. All molecules in a gas are in constant random motion, even when there is no apparent net movement of the gas. Sub-micron particles are small enough to pick up random motion by colliding with surrounding gas molecules. The smaller the particle, the greater is its random motion and the more likely it is to contact a target in the gas stream. This means that, even in a medium with interstitial spaces larger than the particle's diameter, in time it will impinge on a fibre. "In time" is the key to the success of this type of filter; the longer the gas takes to pass through the filter medium the more likely the particle is to be captured. In other words, its efficiency is inversely proportional to the gas flow velocity. This so-called high-efficiency (HE) or diffusion fibre filter is made up of fine filaments closely packed in a bed which is relatively deep in relation to the gas flow rate. The objective is to present as large as possible a surface area per unit volume. The earliest HE mist eliminators were hand-packed, which inevitably resulted in some unevenness in gas flow, especially between different filter elements in a multiple array of parallel elements. Nowadays computer control techniques have been applied to the creation of the fibre beds. For example, Monsanto's ES (energysaving) filter, introduced in the 1980s, is a wound structure. The fibre feed is roved (aligned and tensioned) during manufacture under the control of a computer linked to a pressure-monitoring system to ensure highly uniform packing. The behaviour of the liquid formed by coalescence of the captured particles depends on whether the filter filaments are wettable or not, since in the first case it forms a film on the filament surfaces, whereas in the second it remains as distinct globules. That is of relatively little import in a coarse mesh spray filter, as even a film will run away before it reaches the point of occluding the interstitial spaces. But in the closetextured HE type of filter, it can have a considerable effect on

performance, since the capillary effect on wettable filaments retains sufficient liquid to obstruct the gas flow. If, on the other hand, the liquid filaments are unwettable, the droplets roll off the filaments easily when they reach a certain size. For that reason, a variety of non-metallic materials are used in fibre-bed mist eliminators, ranging from glass fibre to polyester and other polymeric materials. The final choice is largely a matter of balancing cost with durability in the filter's operating environment. Under the influence of the gas flow, the liquid from a verticallydisposed (candle or panel) filter drains predominantly from the "downstream" face of the filter medium, from which there is some risk of possible re-entrainment into the gas stream. Monsanto's ES mist eliminators have a layer of coarse fibres on that face which assist drainage. Practical configurations of filter elements From the foregoing it is clear that different filter media and configurations are suited to different tasks. Commercial manufacturers of entrainment filters therefore make a range of products, although within each product type there will usually be scope for customisation to suit the specific requirements of major projects. Begg, Cousland & Co. Ltd., already mentioned, has a range of three filament-based filter types. Its 'Becoil' range of knitted wire mesh pad demisters are designed to intercept up to 100% of droplets with a size of 5 [micro]m or more. Operating by inertial impingement, they comprise multiple layers of fabric knitted from metal or plastic monofilaments which are crimped in one direction across their circumference. They are assembled with the crimps in each successive layer at 90 degrees to those in the previous one and thus holding the layers apart. The voidage in this type of demister is very uniform and the droplets collecting on the filaments fall off against the gas flow long before there is any threat of flooding. For particles in the 2-5 [micro]m range the company markets the 'Becone' coalescer, which is used in conjunction with Becoil elements. It is a pad of a composite fabric comprising both monofilaments and a 'shaggy' staple fibre yarn with many ends of the staple fibres along its length These fibre ends are much finer in gauge than the monofilament or the yarn into which they are spun, so they provide a larger surface and smaller void volume for particle capture. Coarse droplets formed by coalescence of the fine droplets captured in the Becone element become re-entrained in the gas and are then removed in the Becoil element. For sub-micron particles Begg Cousland offers the 'Becofil' fibre bed candle filter, which operates by a combination of impingement and Brownian diffusion to eliminate particles of 3 [micro]m and below.

Table 1 shows how the performance of these is determined by the thickness of the fibre and its material. Koch-Otto York's product range includes, for the coarser end of the particle spectrum, the Demister[R] pads, which are available in a variety of corrosion-resistant metals, stainless and high-alloy steels as well as Teflon[R] (Du Pont), Halar[R] (Ausimont) and Kynar[R] (Atofina), and the Flexifiber[R] family of mist eliminators as either flat panels or candle filters, which include both Brownian diffusion candles and impaction panels and candles. Table 2 compares their performance in sulphuric acid mist abatement service. In addition to mesh pad and conventional fibre-bed candle filters with very similar performance, CECO Filters--an erstwhile joint venture between Claremont Engineering and Begg, Cousland, which became an independent company in 1983--has developed a dual concentric candle filter assembly (known as Twin-Pak) in which gas enters the space between the inner and outer elements and filters through them simultaneously. CECO claims 60% greater capacity from a Twin-Pak in comparison with the same-sized conventional candle filter with a 60% reduction in pressure drop, lower capital cost and no loss in collection efficiency. Applications in AN fume abatement The reaction of ammonia with nitric acid to produce ammonium nitrate is an equilibrium: N[H.sub.3] + HN[O.sub.3] = N[H.sub.4]N[O.sub.3] No equilibrium reaction ever goes to full completion, and although the ammonium nitrate goes very close to it, there is always an appreciable partial pressure of ammonia and nitric acid vapour over ammonium nitrate in proportion to its temperature. So where these vapours cool, they tend to reunite to form solid ammonium nitrate, but because their concentration is so low to start with the particles are mainly in the submicron range. Sub-micron fume therefore forms not only in the effluent vapours from the neutralisation and concentration sections of the solution plant but also in the air in contact with the hot melt in the prilling tower or granulator. Prill tower exhaust The draught in a prilling tower is also sufficient to entrain coarser particles (dust caused by attrition or by malformation of prills). Prilling tower exhaust is the most difficult to cope with on account of its sheer volume. Early mist eliminator installations were based on glass fibre as the filtration medium, but that was found over time to be susceptible to

attack by moist ammonia. "Chemical-grade" glass fibre, pioneered by CECO Filters, is more durable, and a range of polymeric alternatives, including polyesters and certain fluoropolymers, can now be used, thanks to the development of suitable annealing techniques to lessen their tendency to shrink during service. Monsanto's original installation of Brink[R] HE filters on CFCA's ammonium nitrate prill tower at Lawrence, KS, resulted in a striking reduction, as demonstrated by the classic pair of photographs reproduced here, which appeared in Nitrogen and other publications nearly 30 years ago. The total volume of air passing up a prill tower is prodigious, and the installation required to process it all would, at the time, have been uneconomic and technically very challenging. Fortunately, as already explained, the majority of the sub-micron fume is evolved from the hot molten ammonium nitrate in the top and middle of the tower, nearest the prill head. Further down the tower, where the prills are cooler, the amounts of ammonia and nitric acid vapours are negligible. CFCA installed a shroud around the prill head which directed a fraction of the total air flow into the hot zone around the prill head and separated the rest so that it could be discharged directly into the atmosphere without treatment. Without such a selective filtration system, the only practical option is to collect all the exhaust at the top of the tower and route it through a large gas duct down to a mist elimination system at ground level, then to discharge the purified exhaust through a chimney stack. Such is the installation at Terra International's Severnside ammonium nitrate plant in the UK, which was installed by Monsanto for the plant's former owner, ICI. The 90-m high prill tower originally exhausted direct to the atmosphere through six exhauster fans at the top of the tower, but now a 3-m diameter stainless steel duct conveys the air to the filter installation at ground level, through which it is drawn by an induction fan. It passes through an irrigated mesh pad to remove coarser particles and "microprills" and then through a parallel array of 122 continuously-irrigated Brink[R] type HE2420 glass fibre candle filters, each 22 ft (6.7 m) in length and 2 feet (0.6 m) in diameter. Figure 2 is a schematic representation of such a filtration system. The pH of the circulating irrigation medium is automatically maintained slightly to the acidic side of neutral so as to prevent exposure to free ammonia and to minimise solid deposition on the filters, and a bleed stream is returned to the ammonium nitrate plant concentration section so as to maintain water balance in the filter section. The time between repacking (a task undertaken by changing out the affected elements and returning them to Monsanto) is 6-8 years. Begg Cousland undertook a project to reduce the ammonium nitrate and free ammonia loadings of 28,000 N[m.sup.3]/h of exhaust air from the prilling head shroud of a prill tower in a European location from, respectively, 50 mg/N[m.sup.3] (max.) and 120 mg (max.) to 5 mg/N[m.sup.3] or less in both cases for a maximum allowable pressure

drop of 300-350 mm WG. The total air flow through the tower was 235,000 N[m.sup.3]/h, the remainder being exhausted through the existing side outlets. This objective was comfortably achieved (actually 1 mg/N[m.sup.3]) by a tower-top installation comprising a Becoil mesh pad in 304L stainless steel and 17 Becofil candle filter elements measuring 10 ft (3.05 m) in length, 24 in (607 mm) OD and 20 in (508 mm) ID, packed with PP12 polypropylene fibre in 304L SS cages and flanges. The mesh pad was irrigated from above and below with 310 litres per minute of 30% ammonium nitrate solution, which served not only to absorb the requisite amount of ammonia but also to reduce the air temperature from 80[degrees]C to the safer operating temperature for the PP fibre of 70[degrees]C. Initially the candles were spray-washed with demineralised water from below the top flange to keep them free of solids, but this was rendered unnecessary after the irrigation liquor was changed to dilute nitric acid (pH 5). Subsequently the project was revised to reduce the total ammonium nitrate loss from the tower from its untreated value of 200 kg per day to 100 kg/d by routing more gas through the filter installation without increasing its size. This was achieved by changing the packing from polypropylene to Begg Cousland B12 glass fibre, which allowed the gas throughput to be increased to 120,000 N[m.sup.3]/h (slightly over 50% of the total tower air flow) while remaining within the pressure drop limit and still achieve a guaranteed ammonium nitrate level of 3 mg/N[m.sup.3] in the treated air (equivalent to a total daily emission of about 9 kg). The guaranteed removal efficiencies of 100% for particles over 3 [micro]m, 95% for particles in the 1-3 [micro]m range and 80% for particles in the 0.5-1.0 [micro]m range have also been achieved. Neutraliser and evaporator exhaust Being hot (up to 200[degrees]C), saturated with water vapour and containing free ammonia, neutraliser and evaporator exhausts are more aggressive towards ammonia-sensitive filtration media than prill tower exhaust. The main ammonium nitrate burden is in the form of liquid particles in the 3-5 [micro]m range, at loadings of up to 15,000 mg/N[m.sup.3] (around 4 kg/tonne). In this application highvelocity rather than Brownian diffusion mist eliminators are appropriate. Begg Cousland, for example, recommends standing candle filters with Teflon fibre packing and 304 SS structural elements. CECO Filters has used Chem-Resist, a highly chemical-resistant and virtually ammonia-proof polymer, as a less expensive alternative to Teflon in a number of neutraliser/evaporator exhaust projects. At El Dorado Chemical in Arkansas, for example, new ChemResist elements have run for more than 20 months with no signs of deterioration, in contrast to the polyester elements that they replaced, which needed replacing every 12-18 months. At Terra Nitrogen in Oklahoma

ChemResist elements are showing no signs of degradation after 2 years. Various media had been tried previously, none of which survived more than 18 months. Where the client prefers Teflon, as at DSM Geleen, CECO Filters has developed a proprietary pre-annealing process which hugely reduces shrinkage and consequent breakthrough of mist. Combining the two In a number of projects, neutraliser and evaporator exhaust have been combined with the prill tower exhaust. This has the beneficial effect of diluting the neutraliser/evaporator exhaust to the point where it is well below moisture saturation level, diminishing the need for special media. Monsanto installed two large Brink[R] mist eliminator installations on the No. 2 and No. 3 ammonium nitrate units at Mississippi Chemical's Yazoo City plant in 1994/5. Again, the prill tower exhaust was diverted to ground level and combined with the neutraliser/evaporator vapours. The installation was as shown in Fig. 2, with an irrigated mesh pad at the inlet and standing-style ES candle filters packed with a special polyethylene fibre. In some cases it has been desirable to add neutraliser and evaporator gases to prill tower exhaust which was already being filtered through fibre-bed mist eliminators. The main problem in such cases is that-unless enlarged, which is expensive--the existing installation is unlikely to be able to accommodate the additional gas flow (typically around 25%) without either a loss in efficiency or exceeding allowable pressure drop (or both). CECO Filters was able to accomplish this and more at Agrium Inc's Redwater plant in Alberta by the simple expedient of replacing the existing candle filters with TwinPak elements. Yet whereas there were 62 elements in the original installation, the enlarged gas flow could be handled in only 50 TwinPak elements, and the pressure drop was reduced into the bargain, from 25 in (63.5 cm) WG to (on average) 19 in (48.25 cm) WG. This meant that further gas flow increases could be accommodated in future if required. Using its proprietary polyester as the medium, CECO guarantees retention of 100% of particles greater than 3 [micro]m and 99.5% of particles 1-3 [micro]m. The new filter elements have already been in service for seven years. Their predecessors needed replacing every four years. The installation has comfortably achieved aerosol levels of 2 mg/N[m.sup.3] or less. Applications in nitric acid plants Absorption tower Although the production of nitric acid is reminiscent of sulphuric acid production insofar as it is generated by the reaction between nitrogen oxides and the water in circulating aqueous acid, there is no mechanism in nitric acid production akin to that which produces sub-

micron mist in sulphuric acid production. But the absorption tower is a gasliquid contact device with many stages, and an appreciable amount (perhaps as much as 1,300 mg/N[m.sup.3]) of relatively coarse liquid spray is usually entrained in the tail gas. This is harmful if allowed to enter downstream equipment such as an expander turbine, heat exchanger or catalytic NOx/[N.sub.2]O abatement reactor. Because the collection conditions are less arduous than for sulphuric acid mist or ammonium nitrate fume, a coarser collection medium can be used, and with its easier drainage characteristics it is not absolutely necessary for the filter to be mounted vertically, which allows panels or pads to be used, though candle filters can be used according to preference. Since in normal operation there should be no free ammonia at this point, glass fibre is satisfactory as the filter medium. Structural elements are made of 304L SS. Feed filtration The ammonia conversion efficiency of a nitric acid plant depends critically upon the condition of the platinum-rhodium gauze catalyst and even distribution of the air-ammonia mixture across the whole cross-section of the conversion reactor. Any solids alighting on the gauze will interfere physically with the flow of the reacting gases. Depending on its chemical nature, it may also damage the gauze chemically. Ambient air always contains dust and other impurities, while ammonia may contain particles of rust and scale resulting from corrosion in pipes and storage tanks or swarf from machinery. Iron is a poison for nitric acid catalysts. Because the air and ammonia feeds are dry and a high proportion of the solids are insoluble, anyway, there is no possibility of keeping the filter clear by natural drainage or by irrigation. The filter installation must therefore be sized to allow for the gradual occlusion of the filter elements as the arrested particles build up. Either panel or candle filters can be used and, because there is no drainage, the filters can be mounted horizontally. Because of the dry environment, glass fibre is typically used as the medium and 316 stainless for structural elements. Precious metals recovery Platinum and rhodium losses from the catalyst gauzes are worst in plants with high-pressure ammonia oxidation sections. For that reason, precious metal filters are most popular in high mono-pressure plants, which are mostly in North America. A fine-textured filter is needed because a high proportion of the entrained solids are forming by condensation from the process gas. Begg Cousland, for example, recommends high-efficiency Becofil elements with glass fibre medium. If the operating temperature is below 350[degrees]C, 304 SS can be used for the structure. Above that temperature, type 321 SS is specified.

Once again, allowance must be made for the gradual build up of pressure drop. To allow filters to be changed out in rotation without interrupting the operation of the plant, parallel sets of filters may be installed with the means to switch the gas flow between them.
Table 1: Performance of the Becofil range of fibre-bed candle filters Style TGW15 B14 B12 G25 & CM35 PP12 PT12 Material High-density/smallest dia. glass fibre High-density/medium dia. glass fibre Medium-density/ medium dia. glass fibre Medium-density/coarse dia. glass fibre High-density/ small dia. polypropylene High-density/ small dia. polypropylene Removal efficiency 100% 100% 98% 100% 95% 80% 100% 95% 100% 95% 80% 100% 95% 80% > 1[micro]m >3[micro]m < 3[micro]m > 3[micro]m > 1[micro]m, < 3[micro]m > 0.5 [micro]m, < 1[micro]m > 3 [micro]m > 1[micro]m, < 3[micro]m > 3[micro]m > 1[micro]m, < 3[micro]m > 0.5[micro]m, < 1[micro]m > 3[micro]m > 1[micro]m, < 3[micro]m > 0.5[micro]m, < 1[micro]m Pressure drop (mm [H.sub.2]O) 150-250 150-250 120-250 100-200 120-250 120-250

Style TGW15 B14 B12 G25 & CM35 PP12 PT12

Bed velocity range (m/s) < 1[micro]m 0.15-0.25 0.25-0.60 0.80-2.00 < 0.20 < 0.20

Table 2: Performance of Koch-Otto York Flexifiber[R] eliminators Primary collection mechanism Brownian diffusion Impaction cylinder Impaction panel Collection efficiency Particle Efficiency, % size [micro]m > 3 < 3 > 3 1-3 1-3 0.5-1 Essentially 100 Up to 99.5 Essentially 100 65-99 85-97 50-85 Element pressure drop mm WG (in WG) 50-500 (2-20) 100-250 (4-10) 125-180 (5-7) Bed velocity m/s (ft/min) 0.02-2.0 (5-40) 1.3-1.8 (250-350 2.03-2.54 (400-500)

Type BD IC IP

COPYRIGHT 2004 CRU Publishing Ltd.

This material is published under license from the publisher through the Gale Group, Farmington Hills, Michigan. All inquiries regarding rights should be directed to the Gale Group.

Title: Using polymers in sulphuric acid service: polymers have been used successfully in sulphuric acid corrosion protection systems for decades. Mahmoud Salehi and Dr Andreas Hopp of Steuler Industriewerke provide a brief overview of the corrosion protection materials used in sulphuric acid plants.(CORROSION PROTECTION) Date: 3/1/2005; Publication: Sulphur; Author: Hopp, Andreas The concrete and steel components in plants producing or handling sulphuric acid are exposed to highly aggressive corrosive stresses. Consequently, customised corrosion protection systems must be designed and implemented to achieve long service life of the components and to ensure that the plant and production facilities are suitably protected. Elevated and/or fluctuating temperatures intensify the corrosive effect of sulphuric acid. In addition, plant components are frequently exposed to mechanical stresses, e.g. pressure loads or abrasive stresses. Organic polymers have been used with great success in corrosion protection systems for these components for many years. Nowadays a very diverse range of materials is available. The most suitable and economical materials for individual components are selected according to the chemical, thermal and mechanical stresses that they are exposed to. Applications in sulphuric acid plants In the contact process, sulphur dioxide may be recovered from a roasting plant in a fluid bed roaster or produced by burning molten sulphur in an incinerator. As a result of the extremely high temperatures involved, reaching from 1000 to 1200[degrees]C, the fluid bed roasters and incinerators required for this process must be protected by means of a multiple-layer, refractory brick lining. After the greater part of the heat has been extracted in a waste heat boiler, the S[O.sub.2] gases originating from the fluid bed roasting process are dedusted in the hot electroprecipitator. Once the gases

have been treated, they are channelled into a Venturi scrubber where they are cooled down using the direct flow process. The most challenging area is the gas inlet zone. In order to shield the rubber lining applied to protect the steel from excessive temperatures, adequate protection must be provided in the form of a brick lining. Depending on the actual temperatures, an insulating layer consisting of foam glass is frequently applied as a first layer on the rubber lining. The subsequent layer structuring may be composed, for instance, of one layer of insulating refractory bricks followed by a layer exposed to the media consisting of acid-resistant ceramic bricks, bedded and jointed with potassium silicate mortar. It is important that the roof of the spray level is also lined with these temperature-lowering layers. The prevailing temperatures determine the grade of brick utilised for the interior layer that is exposed to the media, since extra-heavy thermal shock loads can occur in this zone. At temperatures in the range 300-350[degrees]C, graphite brick may be used. At higher temperatures, super-refractory grades such as vitreous silica bricks and silicon carbide bricks are employed. The use of these grades might also be advantageous in the cylindrical area above the cone. In the wet zone, at least two layers must be applied to the impact surface of the cone. The first layer should consist of acid-resistant ceramic bricks and the second layer, if required, of carbon bricks. The lower section of the cone as well as the bottom area are generally provided with a single brick lining, using either acid-resistant ceramic bricks or carbon bricks, depending on the degree and type of loads encountered. The moist S[O.sub.2] gas exiting the venturi scrubber is channelled through the wet electrostatic precipitator, dried in a drying tower using concentrated sulphuric acid and finally conveyed to the contact boiler. In principle, both the drying towers as well as the intermediate and end absorbers are quite similar as far as operating conditions are concerned. In both cases, components are exposed to concentrated sulphuric acid (drying tower 95-98%, absorber 93-98%). The temperature of the acid in the packed bed of the drying tower is roughly 40-70[degrees]C. In contrast, the temperature of the acid in the intermediate and final absorbers can generally reach 7090[degrees]C. Unalloyed steel (C-steel) is resistant to sulphuric acid concentrations over 92-93% [H.sub.2]S[O.sub.4] up to a maximum temperature of 25[degrees]C. The reason for this is the formation of a thin iron (II) sulphate layer, which then disintegrates at higher temperatures

thereby losing its protective effect. Over time, flowing sulphuric acid also strips the thin passive layer. However, if a 2-mm thick polyisobutylene sheet is bonded to the steel surface, which is in turn protected by means of a brick lining consisting of acid-resistant bricks and appropriate bedding and jointing materials, the resultant composite material has a virtually unlimited resistance to hot concentrated sulphuric acid as well as to material attack as a result of flow abrasion. The main criterion for its durability, in addition to the type of lining materials utilised, is the proper execution of the brick lining by skilled applicators. Bricks falling out of the lining as a result of inferior workmanship will allow the flowing, hot and concentrated sulphuric acid to come into direct contact with the polyisobutylene sheet. This flow will lead to a continuous disintegration of the surface layer, which is initially high in carbon, until such time as the acid reaches the steel substrate. The effectiveness of the protective layer that forms on the sheet can only remain fully and permanently intact, if this layer is not washed away as a result of unavoidable minute contact points with the concentrated sulphuric acids via capillaries and microcracks in the brick lining. This effectiveness can only be guaranteed with a brick lining that is intact and crack-free. As a general rule, the overall brick lining is executed as follows: a threeply brick lining in the area below the self-supporting dome, a twoply lining above the grate in the packed bed zone and a single layer (65 mm) above that. In practise, the thickness of the brick lining as well as the number of brick layers can and will vary, particularly as a function of the size of the towers. In order to offer the optimal system for a specific environment, finite element analyses are carried out during the planning and design phase, in order to obtain information with regard to areas that are particularly vulnerable to attack, such as the acid ducts or gas inlet and to determine the required procedure as regards the proper corrosion protection systems. This type of lining method is standard procedure for drying towers. In contrast, only a single brick lining is normally applied to the intermediate and final absorbers. In this case, a layer of potassium water glass cement is trowel-applied to the sheet steel that has been blasted to a white metal finish and/or ceramic paper soaked in water glass is bonded to the steel substrate. This is followed by the external lining with acid-resistant ceramic bricks that are bedded and jointed in water glass cement. Since the adhesion of the water glass cement to the steel is not particularly good, a gap can form between the lining and the sheet steel, in which a thin film of concentrated sulphuric acid will inevitably

accumulate over time. In the process, a very thin film of iron (II) sulphate will initially form on the sheet steel, which has a certain passivating effect. However, this protective effect ceases to exist once the temperature rises. These layers will build up heavily in the course of time, giving rise to such severe tensions within the brick-work that a large portion of the brick lining frequently collapses if any repair work is carried out. As an alternative to the polyisobutylene sheet described above, highgrade, thin sheets made of PTFE (polytetrafluorethylene) "Teflon" are also utilised, which are bonded with a material resembling bitumen. The chemical and thermal resistance of Teflon in this case is outstanding. However, since it is not possible to weld sheets having a thickness measuring 0.25 mm or, alternatively, 2 X 0.125 together, they must be bonded in overlapping sections. In practise, the overlap area represents a weak point. Furthermore, the processing of such thin sheets is quite difficult, as it is difficult to avoid damaging the sheets while handling them. The floors, pits and channels in such plants must also be provided with protective linings. However, the corrosive attack in these areas is significantly less than in the actual plant components. Traditionally, the protective system consists of impermeable coatings based on epoxy resin and/or polyurethane for example, which are then covered by a layer of ceramic tile, bedded and jointed with phenolic or furan resin, or water glass cement. Using the thermoplastic materials described above, gutters and channels are provided with an effective and longlasting protection. Simple coating systems based on polyurethane or special epoxy resin formulations are often sufficient for areas not exposed to heavy mechanical loads. COPYRIGHT 2005 CRU Publishing Ltd. This material is published under license from the publisher through the Gale Group, Farmington Hills, Michigan. All inquiries regarding rights should be directed to the Gale Group.

Title: Sulphuric acid equipment update: sulphuric acid producers are always searching for more efficient, longer lasting and reasonably priced equipment. In this article some of the industry's key sulphuric acid equipment suppliers showcase their leading products.(Materials and Equipment Design)

Date: 5/1/2004; Publication: Sulphur; Acid towers Whether an acid plant was built 20 years ago or 20 months ago, the towers are the most important units in a sulphuric acid plant. Most sulphuric acid towers today run with design parameters established 2030 years ago, based on three-inch ceramic saddles for mass transfer and an oversized tower diameter for operational comfort. Today's construction and operating costs make tower design a more complex matter. However, thanks to innovative technology, the industry now has a better choice for tower replacement--alloy towers. Monsanto alloy towers With 20 years of installation experience, Monsanto Enviro-Chem Systems (MECS) offers a wide range of advantages over traditional tower design. Alloy towers can be replaced within a two-week shutdown, they can be placed on the same foundation, they utilise the existing platforms, gas ducting and acid piping and they are repairable. Corrosion protection The need for corrosion protection in alloy towers resulted in the standardising of MECS' ZeCor[TM] sulphuric acid stainless steel for use in strong sulphuric acid applications ranging from 93 to 99% concentrations. The corrosion rate for ZeCor[TM] sulphuric acid stainless steel is less than 1 mil per year (0.025 mm/year) in typical drying and absorbing acid circuits, depending on the acid concentration and temperature. Extensive corrosion and workability tests have been conducted with very impressive results. To date, over 50 installations of ZeCor[TM] sulphuric acid stainless steel distributors (Fig.1), piping systems, towers and other equipment have been in operation for up to three years with corrosion results matching or exceeding laboratory results. Acid plant components fabricated from ZeCor[TM] sulphuric acid stainless steel: include towers, pump tanks, piping systems, thermowells, strainers, nozzle sleeves, mesh pads, mist eliminators, vortex breakers, orifice plates and acid distributors. Tower packing When replacing towers, there are opportunities to lower pressure drop with tower packing and mist eliminator options. Mist eliminators can also be upgraded for lower acid exit mist emissions.

In MECS' high-efficiency alloy towers, the packing is supported directly by the alloy grating, eliminating the need for grid bars or partition rings that are characteristic for the conventional brick-lined towers. This further reduces the pressure drop across the packing bed. Monsanto Enviro-Chem Systems also offers the WavePak[TM] ceramic porcelain packing for sulphuric acid towers. The packing was developed in conjunction with Saint-Gobain Norpro (formerly known as Norton Chemical Process Products). WavePak[TM] delivers significant technological advantages over other types of packing available in the sulphuric acid industry today. The product offers superior internal gas distribution, higher capacities and optimum mass transfer efficiencies. WavePak[TM] also provides a significant advantage in pressure drop savings over conventional saddles. Mist eliminators Mist can be formed in manufacturing processes in three different ways: * Mechanical forces may break up or "atomise" a liquid to form a mist. * Cooling of a gas stream may result in the condensation of vapour to form a mist. * Chemical reaction of two or more gases may take place at temperatures and pressures where the reaction products are mists. MECS' Brink[R] ES (Energy Saver) Fiber Bed Mist Eliminators incorporate a special wound fibre through computer-controlled quality and a patented bi-component design. The benefits include: * Up to 20% more gas throughput capacity per element, with no loss in collection efficiency or penalty of increased pressure drop; * Collected mist in exit gas is virtually eliminated via a proprietary reentrainment layer; * Easier and less expensive repack. The heart of ES is its bi-component fibre bed design. In a conventional fibre bed, liquid draining on the downstream face of the fibre bed is sometimes re-entrained in the exiting clean gas, due to high velocities. This re-entrainment becomes worse with higher loadings of mist and/or higher flow velocities. The ES includes a patented layer of coarse fibres downstream of the finer collecting fibre. Liquid that would re-entrain from the fine fibre bed is recollected and drained in the re-entrainment layer.

The standard ES element diameter is 2 feet (61 cm), and elements are available in lengths from 6 to 24 feet (1.83-7.32 m). Customised lengths and widths can also be designed. The wound fibre may be glass or polyester. The element cage can be fabricated from any weld able metal or can be made of fibreglass reinforced plastic (FRP) or polypropylene. MECS'Cost Saver (CS) elements are packed with a glass fibre mat collecting layer and have a patented metal alloy mesh re-entrainment control layers. The cages are constructed of stainless steel. For high inlet mist loading situations, an optional baffle screen preseparator is available for the CS elements. CS-IIP has replaced the HP element. Standard flow is 9,500 actual cubic feet per minute (acfm) and standard size is 26 inches (66 cm) in diameter and 40 inches (102 cm) high. CS-IP is principally a mesh pad replacement in sulphuric acid plant drying towers. Standard flow is 13,280 acfm, and standard size is 30 inches (76 cm) in diameter and 65 inches (165 cm) high. ES and HE are available in both forward-flow and reverse-flow styles. CS and HP elements are only available in the reverse flow style due to exit velocity re-entrainment considerations. In the standard-flange, forward-flow (SFFF) configuration, the element hangs from a tubesheet. This configuration features ease of installation and maintenance. In this style, the dirty gas enters the outside of the element and the clean gas exits through the centre core. In the reverse-flow upside-down (RFUSD) configuration, the mist eliminator is placed vertically above the tubesheet. This configuration permits the use of longer elements and vessels of reduced size. In this style, the dirty gas enters the centre core of the element and the clean gas exits through the outside. Figure 2 shows the installation of Monsanto candle mist eliminators. IMC Phosphates alloy tower installations One IMC facility that recognises the benefit of alloy towers is the New Wales site in Florida. The 01 Plant's Interpass tower was installed by MECS in September 2002 (see Fig. 3). The plant currently runs at 2,900 t/d "clean." IMC's process engineer Jim Dougherty and senior project engineer Mike Roche played key roles in the project. "IMC's alloy tower selection was primarily driven by the requirement to minimise turnaround downtime. There is no way to guarantee the

integrity of the brick lining if a brick tower of this size had to be lifted into place. And, bricking a carbon steel tower in place during the turnaround would take several weeks. There was really no option," Roche said. The field-fabricated alloy tower could be lifted into place following the demolition of the existing tower in the shortest amount of time. MECS' Alloy tower technology was selected to minimise maintenance cost relative to a carbon steel brick tower and also to meet the quick turnaround schedule. "IMC has two alloy towers at its South Pierce facility that have been in service for over a decade. South Pierce Sulphuric Maintenance Superintendent Jimmy Bennett always tells me that the only expense he has is to open and close the manway doors at turnaround for inspection," Dougherty said. "Also, IMC has learned from its experience with the alloy HRS towers from an equipment-life perspective. An alloy tower can be repaired indefinitely, so once you build one, you'll never have to buy another." IMC's New Wales facility was interested in executing a turnkey project and found that Monsanto offered the best overall package of tower technology. Other IMC facilities already had experience with Monsanto's patented Uniflo[TM] alloy trough distributor system design, Brink[R] ES-Candle mist eliminators, and Sandvik SX alloy material in the two alloy towers in operation at South Pierce. The New Wales facility was also interested in continuing its test programme of Monsanto's new ZeCor[TM] alloy. New Wales first began testing ZeCor[TM] in its drying tower distribution system and piping service in 2001. To further the testing programme, ZeCor[TM] distribution troughs and piping were designed for the new IPA tower in order to assess the ZeCor[TM] material in the most severe non-HRS service locations. At 250[degrees]F/121[degrees]C, the New Wales IPA tower distribution system and outlet piping is among the most severe non-HRS process sulphuric acid process service conditions in the world. According to Roche, the tower has operated very well since installation. At the South Pierce facility, the first SX alloy final tower was installed in 1992. The second was installed in 1995-1996. The CS (cost saver) impaction candles were used in the No. 11 plant. For the No. 10 plant at South Pierce, the Energy Saver (ES) browning candles were installed. To date, no repairs have been required for either units. Bennett has been with IMC for 37 years and knew what was needed at his site. "An old tower can be torn down and a new tower can be installed on the existing foundation in a two-week period. The existing towers were 1970s vintage towers that had flat pads. We had continuous problems with carryover out of the stack. It was a constant

battle to stay within the environmental limits," Bennett said. "It was time to start looking for new technology." Monsanto came in and did a complete re-rate of the plants where the old HRS units were installed. Bennett said the facility then selected Monsanto for the new towers and chose the SX alloy material. "Our SX towers have been operating for 12 years, and I've not had to do anything to either tower but perform inspections, ultrasonic thickness (UT) measurements, vacuuming out and clean up of the distributors since their installation." The site contracted VIP to clean the candles and distributors, and also to perform inspections. Bennett said the corrosion rates have been running well below what was expected on mils per year. "The unit No. 10 tower has ES candles installed in it--the type that hang down, and the No. 11 tower has the CS impaction candles--the type that stands up. I've never changed the candles in either tower," Bennett said. "It's hard to beat 12 years on two sets of candles; that's pretty much unheard of in the sulphuric acid industry. I would recommend an alloy tower to anyone looking to replace a tower." Based on the success of its sister facilities, IMC's Uncle Sam plant in Louisiana recently awarded Monsanto Enviro-Chem Systems a turnkey contract to design and install a new absorption tower for IMC's Unit A--a 1,600 t/d sulphuric acid unit. The installation of the new tower is scheduled to take place this summer in tandem with a planned unit turnaround in July. Unit A is in one of the original units built at this site in the 1960s. In addition to Unit A, IMC Phosphates operates two other sulphuric acid units at the site. These include Unit D, a plant producing 1,600 t/d built in the 1970s and also Unit E, producing approximately 3,200 t/d built in the 1980s. "The projected time to install the tower will be about 15 days. The old tower has reached its life expectancy. It was a 1960s vintage, carbonsteel tower, which was brick-lined. It has been repaired numerous times, and 60-70% of the shell has been repaired in some manner or another," stated Dwayne Ordeneaux, a senior project engineer at IMC Phosphates' plant in Faustina, La. "We started soliciting prices to replace the tower in kind, and we found that a brick tower was as expensive as an alloy tower. Brick is expensive, and the labour to install brick is expensive. Finding the necessary crafts skills to install the brick can also be difficult these days. The team also found that repairing a brick tower is more difficult.

"If you get a leak in a brick tower, the question is, 'Where is it?' If you do find it, you've got to plug it, remove the brick and remove the liner. If it gets behind or between the brick, it really is a nuisance," Ordeneaux said. "Whereas with the alloy tower, should you have a leak, it is easily repairable. We chose the ES candle for its high efficiency; it will give us some additional reduction in pressure drop at a reasonable cost." For the packing, Ordeneaux and his team chose a product from Koch Knight LLC. The Knight-Ware[R] Flexeramic[R] Type 88 ceramic structured packing is expected to lower the pressure drop of the packed bed by 40%, compared to standard random packing saddles used in the existing tower. Koch Knight acid tower packing media To help operators determine the optimal performance available from a tower, Koch Knight LLC offers the TECON[TM] economic analysis model for sulphuric acid mass transfer media. Three variables determine optimal tower design: mass transfer efficiency, initial cost, and lifetime cost. Technically speaking, absorption needs, pressure drop limitations and other process requirements could make a particular packing the only suitable option for a particular tower. Plant and operational parameters such as plugging potential, possible production increases expected in the near future, or the space available for a new tower may form part of the tower decision matrix. The mass transfer capacity of the packing must fit the technical, operational and budgetary needs of the facility. The lowest first cost packing option may be attractive when it fits the approved budget for a tower. However, buying the lowest cost packing option available may not maximise the tower's value over the life of the plant. A more indepth analysis of the best financial options is required. Koch Knight combines excellent technical resources for mass transfer applications with a complete array of available packing products. The T-ECON[TM] model provides plant operators with a method to study the range of Knight packings, including economical imported materials, Flexisaddle[TM] standard and low pressure drop Flexisaddle[TM] LPD[TM] random tower packing (Fig.4), and high performance Flexeramic[R] ceramic structured packing (Fig.5). The T-ECON[TM] tower analysis model simulates the tower performance with various packing options to determine the net present value, that is, the true value in today's currency of the money invested by the company in the packed bed during the life of the mass transfer media. Since a sulphuric acid tower media charge should last more than ten years, the model conservatively assumes a ten year packing

life and shows the cost effects of all the available tower packing options. In a recently concluded study for an Asian metallurgical acid plant, the T-ECON[TM] model generated the graph in Fig. 6 to show a summary of the net cash flow over a life of ten years. The graph visually compares the lifetime costs of each packing option and reveals that a higher investment made today represents the most economical long term packing solution. The T-ECON[TM] model shows that in this case Flexeramic[R] Type 88 ceramic structured packing provides the highest net present value over the ten year term. Knight-Ware[R] Flexisaddle[TM] three-inch LPD (low pressure drop) packing offers a more rapid payback time due to its lower net present value. Standard Knight-Ware Flexisaddle ceramic three-inch saddles are a good initial cost value, but the lower initial investment does not represent the best long term choice for the plant. In this case, the client selected the Flexisaddle LPD packing option as the best Knight product to meet their current needs. As the plant demands more production from the equipment, the option for installation of Flexeramic packing will be available for a future repack installation. Nowadays, sulphuric acid plants must reduce costs while simultaneously improving production and operating standards. The TECON[TM] economic modelling tool can give operators a method to know that a tower is running with the most optimised mass transfer package available in the market, at the lowest life cycle cost to provide the highest long-term profit. Maximising tower performance and the useful life of the equipment provides reliability to the process as a whole. Pumps for molten sulphur When transporting sulphur in the liquid form, it is important that the properties of sulphur are taken into consideration. Due to the abnormal variation of viscosity with temperature, which only allows sulphur to be pumped satisfactorily within the range 135-155[degrees]C, most pumps used for molten sulphur applications have a heating jacket in order to keep the temperature constant in all parts of the pumps. There are several alternatives for shaft sealing. For vertical pumps, stuffing box packing would be adequate, whilst for horizontal pumps hydrodynamic shaft sealing, mechanical seal or magnetic drive arrangements are recommended. Although vertical pumps are widely used on sulphur melting plants, it is not uncommon to use various designs of horizontal pumps. Horizontal pumps for molten sulphur can either be of heavy duty design with hydrodynamic shaft sealing (e.g. for molten sulphur

containing solids), or of modern magnetic drive design (e.g. for clean sulphur). Magnetic drive pumps have the advantage of safe operation without any leakage of hazardous hydrogen sulphide. The design of vertical pumps depends not only on the purity of sulphur, but also on the size of the sulphur tank or vessel. For example, cantilever pumps are limited in their submergence depth. For clean sulphur, single or multistage pumps with foot and intermediate bearings can be used for submergence depths of up to 8 m. For applications with impure sulphur the solid size, hardness and concentration have an influence on the design. Sleeve bearings in hardened material with internal product lubrication or even with external grease lubrication or cantilever pumps offer a suitable solution for such applications. Friatec heatable magetic drive pumps A modern pumping solution for molten sulphur applications is heatable magnetic drive pumps, which have zero leakage and easy maintenance. Zero leakage is especially important for recovered sulphur which contains mostly [H.sub.2]S gas, which should not come into contact with the atmosphere. Pumps with a mechanical seal always have some sulphur leakage, which is required in order to lubricate the seal faces. Often this leakage can be seen in the mechanical seal area as solid sulphur. Friatec-Rheinhutte heatable magnetic drive pump type RMKN (Fig. 7), has been used for molten sulphur applications for ten years with very good experience. Due to the nature of sulphur, the pumps are of special design. In the magnetic coupling/isolation area a good heat exchange is required in order to dissipate the heat caused by magnetic losses. The sleeve bearing is manufactured in erosion-resistant silicon carbide and has an intensive lubrication that will also allow operation at lower capacities. However, the pump has a definite minimum allowable flow rate in order to avoid heat generation within the pump. The intensive heating area around the pump casing and around the isolation area ensures a constant temperature during operation and a safe start-up. With the jacketed volute casing drain the pump can be safely emptied without the risk of sulphur crystallisation after the pump shut off. Friatec vertical sulphur pumps For installation in sulphur tanks below ground level, horizontal pumps cannot be used and suitable vertical pumps have to be considered. Different designs of vertical pumps are available. For recovered sulphur, pumps with shaft support bearings are suitable. For submergence depths longer than 2000 mm, additional intermediate bearings are required. The vertical shaft is supported by anti-friction

bearings on the top, outside the tank and by sleeve bearings below the mounting flange. The sleeve bearings are lubricated by the sulphur. It is recommended that the maximum pump speed of sulphur pumps is limited to 1500 rpm at 50 Hz or 1800 rpm at 60 Hz, in order to reduce the risk of temperature rise in the intermediate bearing. The radial forces and the pump vibration can be limited. The special design feature of vertical molten sulphur pumps is the heating jacket on the discharge bend, shaft and discharge pipe. Friatec-Rheinhutte vertical pump type GVSN (Fig. 8) has some additional design features. The pumps can have up to three stages, which allow a high differential head at low speed. The discharge and the shaft column are built as a complete unit to give optimum stability, especially for pumps longer than 2000 mm. In addition, all pumps have a double volute casing, which reduces the radial forces to a minimum. Mondi[TM] piping systems Acid Piping Technology (APT) specialises in products for the sulphuric acid industry. These products include Mondi piping, tower distributors, gaskets, converter internals and ceramic tower packing. Mondi piping has been used in acid plants since 1983 providing excellent performance. It is used in over 700 sulphuric acid piping systems worldwide. Mondi is a proprietary metallurgy ductile iron specially developed for acid service. It has a nodular graphite matrix, which enables it to be used in a wide range of acid concentrations. It is 95% ferrite for excellent performance joining anodically protected acid coolers. In operation, a tough sulphate film is formed on the surface. The initial corrosion of Mondi is higher in forming this film. After formation, the sulphate film remains to protect the surface. The resulting overall corrosion rate is low over the operating lifetime of the plant. Because of its improved metallurgy and heavy wall thickness, Mondi piping can operate at internal velocities of 7-10 ft/sec for 12-inch to 30-inch pipe sizes. The key components of the Mondi piping system are: * Improved metallurgy; * Heavy wall thickness; * Special fitting patterns; * Flange face finish; * Step ring gaskets.

Mondi piping is used for sulphuric acid systems having 92% to 99+% concentration, 125 psig maximum operating pressure and temperatures up to 300[degrees]F (149[degrees]C). Standard piping sizes are 3 inch to 30 inch inside diameter. Applications in acid plants are recirculation systems in drying, absorbing, cross flow stripping towers, distributors in towers, transfer piping to storage or other processes. Additional applications are for seawater used in process cooling and for vessels up to 48 inches inside diameter where sulphuric acid is used for gas drying or stripping. Mondi pipe is centrifugally cast and threaded flanges are shop installed. Mondi fittings are static cast Mondi. Fittings are close grained, free from cracks and excessive shrinkage. Over the past ten years, special fitting patterns have been developed that eliminate the need for chaplets. Currently 95% of APT's Mondi fittings are made without chaplets. A chaplet looks like a two-headed nail (Fig. 9) and is used on the sides of some elbows (Fig 10) and reducers to hold the sand core in place during casting. Chaplets are seen as a raised area on the side of a fitting. Ductile iron elbows for water service typically have chaplets made of steel which will be attacked by sulphuric acid and become leak points relatively quickly. For the Mondi fittings that do require chaplets, these chaplets are made of Mondi with a special shank design. This special shank has thin fins, which will fuse into the molten metal for tight sealing of the chaplet area. Mondi performance Measured corrosion rates from many years of actual plant operation are the true measure of Mondi performance. Figure 11 shows reported corrosion rates after 2-8 years of plant operation for 93% acid drying tower and 98% acid absorbing tower piping systems at different temperatures. Measured corrosion rates for 93% acid are 3 mils/year at 120[degrees]F to 9 mils/year at 152[degrees]F. Measured corrosion rates for 98% acid are 2.5 mils/year at 170[degrees]F to 10 mils/year at 236[degrees]F. Many plants have reported that their Mondi piping systems have operated through acid concentration excursions. This is important because acid plants do not operate at ideal conditions all the time throughout their life. Concentration excursions can be weaker acid or stronger acid even with free S[O.sub.3] conditions. The plants indicated that the Mondi piping did not show significant corrosion after the excursions. Such acid concentration excursions have caused accelerated corrosion and damage to austenitic stainless steel systems.

Weaker acid excursions can occur from equipment malfunction of the dilution water system, instrumentation, valves, boiler leaks, acid cooler leaks and plant outages. Stronger acid excursions can occur from equipment malfunction of instrumentation, valves and the dilution water system. Mondi piping is very forgiving and provides reliable performance. Mondi pipe and fittings have a large corrosion allowance due to the heavy wall thickness. Table 1 shows original thickness, replacement thickness and available corrosion allowance according to pipe size. Low corrosion rate, ability to handle concentration excursions and ample corrosion allowance for Mondi piping results in a long service life, low maintenance cost and reliable performance. For example, the calculated service life for 16-inch Mondi piping at 9 mils/year corrosion rate would be more than 30 years. New electrostatic precipitator "Carola" The electrostatic separator "Carola" (Corona Aerosol Separator) was developed with the specific objective of providing a highly efficient separator for fine particles from gas flows. The new electrostatic precipitator has considerable advantages compared with conventional systems with regard to investment and operating costs. The "Carola"-separator has been patented by the Research Centre Karlsruhe. Rauschert Verfahrenstechnik GmbH, Steinwiesen, is the exclusive licensee for applications of this system in the chemical, pharmaceutical and petrochemical industry. Function mode and configuration The electrostatic separator "Carola" (Fig. 12) works with the following four main process steps: * Cooling and moistening of the exhaust gas to be treated; * Condensation of water vapour on the sub-micron particles; * Electrostatic charging of the particles in an electric field; * Separation of the particles on an earthed surface. The exhaust gas to be cleaned flows from below in an upward direction through the separator. With the use of spray nozzles, the exhaust gas is initially super-saturated by applying cold water. The super-saturation is quickly reduced on the foreign nuclei existing in the gas and, subsequently, on the particles also (heterogeneous condensation) which grow in this way.

The main component of the aerosol separator is the compact constructed ioniser stage which was specially optimised for the operation with high water vapour content of the incineration exhaust gas. Particle charging is effected in a design-related manner and very effectively in the corona-zone by spray needles (see Fig. 13) and with low voltages in the range between 10-18 kV in accordance with the apparatus design layout. The ioniser stage consists of an earthed bottom with openings and an array of high-voltage electrodes, which are centrally arranged to the bottom openings (Figs. 13 and 14). By means of corona discharges, the particles flowing closely past the electrodes are charged electrically (operation high voltage: max. 18 kV). The high voltage is supplied by way of a compact control unit. The charged particles are precipitated on a compact collector spatially separated from the ioniser. The collector consists of an earthed tube package (surface separator). The collector and ioniser are intermittently purged by way of nozzle arrangements in order to prevent a caking of the solid substances. The timing intervals between jet spraying are normally activated according to the pressure loss. A liquid receiver with a channel between the collector and the ioniser ensures that the washing liquid with the separated particle material is discharged out of the separator. Heated sealing air is continually applied to the insulators in order to ensure their unobjectionable functioning. A sealing air fan with an electric heat register supplies this air. Control is carried out in the control cubicle. Performance and consumption data A typical installation of Carola has the following consumption data: the pressure loss of the entire unit is below 5 mbar, the amount of service water ranges between 20 and 60 1/1000 [m.sup.3.sub.N] (moist exhaust gas), and the electric energy consumption for ionisation is approximately 0.2 kW/1000 [m.sup.3.sub.N] (moist exhaust gas), for sealing air below 0.5 kW/1000 [m.sup.3.sub.N] (moist exhaust gas). The figures given are approximate values only. The exact consumption figures are determined on a project-related basis. The Carola separator is suitable for gas volume flows from approximately 500 [m.sup.3]/h to approximately 50,000 [m.sup.3]/h. Special designs and/or parallel arrangement of single aggregates for higher volume flows are possible. The incoming gas must be extensively saturated with water vapour. If this is not the case, a packed tower is arranged upstream of the

separator. Depending on the gas composition, this results in operating temperatures in the area of the ambient temperature of up to 90[degrees]C. Figure 15 shows a typical arrangement of an exhaust gas scrubbing with a Carola-separator. First, the hot exhaust gas is quenched and pre-scrubbed in a packed tower before it enters the particle separator "Carola" as a final stage of the exhaust gas scrubbing process. The maximum dust and/or aerosol concentration in the raw gas to the separator is limited because of the so-called "corona quenching". If the dust concentration is too high, the electron stream emitted by the spray electrodes collapses. As a result, no adequate electric current can be generated for an ionisation. The maximum dust concentration at the inlet to the separator is in the range of 1 to 3 g/[m.sup.3]. For higher concentrations the use of a preseparator stage, such as a venturi or a jet-spray washer, is possible. The obtainable overall separation rates depend on the type, fractioning and concentration of the particles. Overall separation rates above 99% can be achieved. If necessary, a series arrangement of two Carolaseparators is possible. Operational results for various task assignments and marginal conditions are already available. Details are obtainable on request. Technical installation for the separation of S[O.sub.3] aerosols A technical installation for the separation of S[O.sub.3] aerosols from exhaust gas has recently been erected. In order to demonstrate the potential of the system, some laboratory experiments have been carried out. The experiments were performed at a Carola laboratory plant with a gas throughput of 44 [m.sup.3]/h. The gas is watersaturated air at a temperature of 50[degrees]C. The S[O.sub.3] aerosol was generated by stripping oleum with a dry nitrogen gas flow to achieve a constant raw gas mass concentration. Figure 16 shows the results of raw gas and pure gas measurements as well as the resulting determined grade efficiency for S[O.sub.3]aerosol. The particle number concentration was measured with a mobility analyser (SMPS). The modal value in the raw gas lies approximately at 120 nm and in the pure gas approximately at 100 nm, the resulting grade efficiency ranges between 80 and 95% in the relevant particle range. The mass separation efficiency is determined by additional gravimetric measurements to 98%. As already mentioned, a major technical Carola unit has recently been erected. This plant is a unit for the separation of S[O.sub.3] aerosols from an incineration exhaust gas. The unit has been installed downstream of an S[O.sub.2] scrubber. The successful start-up of this Carola unit took place in March 2004. The main data for this separator are shown in Table 2.

Table 1: Mondi pipe and fitting corrosion allowances Driginal Size (inch) 3 4 6 8 10 12 14 16 18 20 24 30 Available thickness (inch) pipe fitting 0.34 0.41 0.49 0.51 0.56 0.61 0.66 0.70 0.74 0.81 0.89 1.15 0.48 0.52 0.55 0.60 0.68 0.75 0.82 0.89 0.96 1.03 1.16 1.37 Replacement thickness (inch) 0.197 0.204 0.225 0.249 0.270 0.291 0.330 0.376 0.375 0.396 0.442 0.511 corrosion allowance (inch) (mils) 0.143 0.206 0.265 0.261 0.290 0.391 0.330 0.324 0.365 0.414 0.448 0.638 143 206 265 261 290 319 330 324 365 414 448 638

Table 2: Carola separator for the separation of S[O.sub.3] aerosols Pre-specified data: Gas volume flow Inlet temperature S[O.sub.3] concentration (raw gas) 13,000 [m.sup.3.sub.N]/h moist 67[degrees]C 1,000 mg/[m.sup.3.sub.N] dry

Guarantee values and consumption figures: S[O.sub.3] concentration

COPYRIGHT 2004 CRU Publishing Ltd. This material is published under license from the publisher through the Gale Group, Farmington Hills, Michigan. All inquiries regarding rights should be directed to the Gale Group.

Title: Smarter acid equipment. (sulphuric acid) Date: 9/1/1995; Publication: Sulphur; Proper design of acid distributors and tower packing is critical for optimum tower performance in sulphuric acid plants. This article reviews existing technology on acid distribution and reports on experiences with an improved distributor design which is gaining wide acceptance in the industry. In modern sulphuric acid plants, good drying, absorption and [SO.sub.2] stripping from product acid require efficient contact of the gas streams with sulphuric acid. For these services, most plants use bricklined towers with ceramic packing. For good tower performance, it is necessary to distribute the acid uniformly over the tower packing, whose function is to provide the maximum effective area for acid-gas contact with minimum resistance to acid and gas flow through the

tower. The design must also avoid the generation and entrainment of acid mist as it can corrode and foul downstream equipment or cause an environmental nuisance. Over the last several decades, plant capacities have increased and towers now operate at higher throughput. In modern sulphuric acid plants with capacities up to 4,000 t/d the towers can be as large as 30 ft (9.14 m) in diameter with acid flow as high as 10,000 US gal/min (2,264 [m.sup.3]/h) and gas flow as high as 150,000 std [ft.sub.3]/min (255,000 [m.sup.3]/h). The risks of poor tower performance and acid entrainment causing catalyst fouling and corrosion of expensive downstream equipment have therefore significantly increased. Maintenance and downtime costs have also escalated, increasing the need for a better distributor. REVIEW OF DISTRIBUTORS With increasing tower sizes, uniform acid distribution is more difficult to attain and many different types and shapes of distributors have been tried in sulphuric acid plants. Early small towers used pan type distributors. As plants became larger in size, troughs with downcomers or pipe type distributors became popular. Spray type distributors have also been used for some time. Cast iron was used extensively as the material of construction until speciality alloys such as Lewmet(TM) (a trademark of Chas S. Lewis & Co.), Saramet(TM) (a trademark of Chemetics International Co.) and SX(TM) (a trademark of Sandvik AB) came on the market. Stainless steels and non-metallics such as ceramics and plastics have also been used to a limited extent. Pan type distributors Before saddle type packing became standard, towers were designed for low gas velocities and distributors were often cast in the form of pans or quadrants. Some distributors had holes in the bottom of the pans with ceramic orifices and pipes to lead the acid into the packing, while other types used overflow weirs or notches to distribute the acid over the packing. In modern towers, the gas velocities are much higher and such distributors are no longer usable because of entrainment problems. Few of these distributors are still in service and foundries that supplied them have mostly closed as a result of stricter environmental regulations. Trough type distributors Trough type distributors with downcomers (see Fig.1) are widely used in the sulphuric acid industry. The troughs are spaced across the tower at 2 to 4 feet (0.6-1.22 m) intervals and are fed from a pipe header inside the tower using orifices or an external splitter box to split the flows between troughs. Each trough uses overflow weirs to feed downcomers that carry the acid into the packing where it discharges at

low velocity without mist generation. The classic design uses cast iron with life expectancy as low as five years because of severe erosion and corrosion. With the special shapes needed, the plants now depend on a limited number of foundries which still have patterns for the size in question and spare availability can pose a problem. Fig. 1: Comparison of distributors (a) Pipe type distributor * Not sensitive to labelling * Good turndown * Uneven distribution pattern * Acid delivey creates mist/spray * Tower Blockage (30-50%) * High pressure drop * Acid entertainment * Cleaning difficulty * Corrosion of cast iron units * Alloy units sensitive to acid strength (b) Trough type distributor * Uniform distribution pattern * Acid delivey without mist/spray * Sensitive to acid flow/levelling * Poor access to packing * Cleaniong difficulty * Occupies significant height * Corrosion problems with cast iron * High maintenance for cast iron units * Alloy units sensitive to acid strength

* Complex and expensive (c) Cecebe Smart distributor * Uniform distribution * Acid delivery without mist/spray * Not sensitive to levelling * Good turndown * No tower blockage * Proven materials of construction * Less sensitive to acid strength * Easy to clean and maintain * Simple construction * Cost effective More recently the high silicon austenitic stainless steels SX(TM) and Saramet(TM) as well as several other highly corrosion resistant alloys such as Lewmet(TM) have become available. Designs using alloy troughs and tubing for downcomers are also in service[1,2] (see Sulphur Sep-Oct 1991 pp. 27-39 and Sulphur Nov-Dec 1992 pp. 31-44). Initially, the designs had 4 to 6 distribution points per square foot, a very high number by sulphuric acid plant standards, but more recently this number has been cut back to between 1.5 and 2 points per square foot. By comparison, the classic cast iron designs had one point per square foot. The use of these superior materials instead of cast iron effectively eliminates the corrosion and erosion problems as long as the acid concentration is kept within their best operating range. However, the alloys are expensive and do nothing about the inherent physical shortcomings of the trough design (see Sulphur Jul-Aug 1995 pp. 41-52). Based on its success with Monsanto's Heat Recovery System (HRS(TM)), 310 stainless steel has been proposed recently for trough units in conventional tower duties. However, due to difficulty in controlling the acid strength within a very narrow operating range and the presence of high turbulence, this approach is likely to have limited success. Major problems with the trough type distributors are:

* Long troughs in large towers are difficult to install and maintain at uniform level, resulting in variation in acid distribution across the tower and poor turndown capability. Further, there is no flow equalization between troughs. * Troughs distributors can accumulate sulphate and ceramic chips which have to be removed manually. The inside of the tower is a difficult working environment. * The troughs and downcomers block access to the packing. * The trough distributor occupies significant tower height, increasing the cost for a new tower or limiting the packing height in a retrofit tower. * Special castings or shapes may require long delivery times or have few suppliers. * The cast iron units are plagued with corrosion/erosion problems and require frequent replacement of downcomers (every 3 to 4 years), troughs (every 5 to 6 years) and feed pipes (every 7 to 8 years), resulting in considerable down time and high maintenance expense. High corrosion also leads to sulphate buildup, high pressure drop and acid contamination by corrosion products. * High silicon austenitic stainless steel units have a limited corrosion range and are unsuitable for oleum. The corrosion rate also increases significantly in acid below 93%. Pipe type distributors The pipe distributor (see Fig. 1) has been used for many years with mixed results. This device has a low initial cost but performance can be a problem if the distributor is not appropriately designed. Initially, these distributors were made from cast iron. Many modern designs have used alloys such as SX(TM), Saramet(TM), or Lewmet(TM). The holes in the pipes are usually pointed downwards or close to horizontal. The earlier units were placed above packing. However, to avoid acid splashing and mist carry-over, the pipes are now usually buried in the packing (see Fig. 2)[3]. Early cast iron designs suffered from hole erosion. This problem was eliminated in later designs by using inserts of corrosion-resistant alloy such as Lewmet(TM) or glass-filled PTFE, but the general corrosion of the cast iron was still present and periodic replacement was necessary. [Figure 2 ILLUSTRATION OMITTED] The high quality materials can be used in much lighter sections and can be fully welded. They also do not need hole reinforcement. Their prime disadvantage is the high cost of material.

Major shortcomings of the pipe type distributors include: * Pipes must be buried to avoid entrainment. * Tower blockage of up to 50% cross-sectional area can occur when a pipe distributor is buried with possible flooding, acid mist carry-over, and high pressure drop. * Sulphate and ceramic chips can accumulate in the pipes and plug holes. * Splashing by high velocity acid impinging on tower packing generates excessive mist. * Uniform irrigation is impossible as the holes are only on the pipe headers and arms. * In cast iron units holes can erode, ruining the distribution. Even those units using erosion-resistant inserts suffer from general cast iron corrosion resulting in frequent replacement. * The units made from high silicon stainless steels have a limited corrosion range. They are unsuitable in oleum and experience high corrosion rates in acids below 93%. Spray type distributors Spray type distributors are a special class of pipe distributors that have been used by two major acid plant contractors. One contractor has for nearly 20 years used cast iron pipes with upward pointing nozzles or orifices made of special cast iron or stainless steel that spray acid over the packing (see Sulphur Nov-Dec 1992 pp. 31-44). This system by its very nature produces acid mist. Therefore, to avoid acid mist entrainment the gas velocity has to be kept low by making the tower diameter larger. Another contractor built many towers in the 1980s that used a very short bed of saddles and a spray type distributor located above the packing layer. The distributor consisted of an extensive cast iron pipe network with Lewmet(TM) nozzles that sprayed acid downward over the packing and generated a considerable amount of acid mist. It was claimed that by increasing the density of acid distribution points to about four points per square foot from a conventional one point per square foot, the packed height can be significantly reduced by as much as 50% i.e. from typically 12 to 15ft (3.66-4.57 m) packed height to 6 to 8ft (1.83-2.44 m). However, these towers had a troubled history and are no longer offered. Problems included poor drying/absorption efficiency with reduced packing height, high acid mist entrainment and plugging of the distributor holes, because of the absence or failure of poor acid strainers, causing uneven distribution[4].

DEVELOPMENT OF A NEW ACID DISTRIBUTOR From the review above it is clear that despite many attempts to improve distribution technology over the years, the available distributors still suffer from problems such as maldistribution, excessive corrosion/erosion, poor access for cleaning and maintenance and process bottlenecks caused by tower blockage with localized flooding, high pressure drop and excessive acid mist generation. Thus, the compelling need for developing an improved distributor is obvious. The desirable characteristics for an ideal distributor are: * Frequent and uniformly spaced distribution points. * Negligible acid spray and mist generation. * Must not create a process bottleneck. * Uniform distribution independent of liquid flow or levelling. * Insensitivity to plugging and fouling. * Must use proven corrosion-resistant materials to give long life. * Easy to assemble and repair. Low maintenance. * Easy to inspect and clean, preferably from outside the tower. * Must be compact and not add excessively to tower height. * Must be economical. The Cecebe Smart(TM) distributor, developed and patented by Cecebe Technologies Inc., was developed with these targets in mind[5-7]. It combines the best features of trough and pipe type distributors, while eliminating or minimizing their shortcomings. An improved hybrid design The best feature of the trough type distributor is the use of downcomers that deliver acid at low velocity in the packing without generating acid spray or mist. The best feature of the pipe type distributor is its insensitivity to levelling and its ability to provide an essentially constant pressure acid supply with good turndown capability. The trough type distributor required a pipe network to supply the acid. By incorporating downcomers directly on the pipe network an improved hybrid distributor was conceived. Uniformity of distribution

Good acid distribution depends on a uniform pattern of distribution points over the entire tower cross-section and the equal supply of acid to the individual distribution points. A better distribution pattern is possible with a distributor that uses downcomers rather than pipes with holes. When pipes with holes are used to feed acid to the packing, the separation between rows of holes establishes the pattern of distribution points. This separation must be large enough to let the gas pass between the pipes. Thus, uniform distribution is impossible with pipe units as distribution points are only on the pipe header. The acid distribution between points depends on the acid head over the metering orifices or weirs used to regulate the acid flow. In large towers where the distributor is difficult to level, overflow weirs are more likely to give unequal acid flows than submerged orifices. The units with submerged orifices are also less sensitive to variation in total acid flow than those with overflow weirs, thus providing greater turndown capability. Cecebe [Smart.sup.TM] distributor The Cecebe [Smart.sup.TM] distributor (see Fig. 1) is based on a highly corrosion-resistant speciality iron alloy pipe header located just above the packing to provide a constant pressure acid reservoir. Acid flows through special [Lewmet.sup.TM] alloy orifice adapters threaded into the walls of the pipe network. [Teflon.sup.TM] (a trademark of Dupont) downcomer tubes attached to the orifice adapters deliver the acid at low velocity into the packing to avoid splashing and mist generation. The orifices and the downcomers are large enough to prevent plugging. The distribution points are uniformly located on an 8 to 10 inch grid. The orifices equalize acid flow to the downcomers and are submerged by a significant acid head to minimize any effect of poor levelling and to allow for acid flow turndown. Various parts of a Cecebe [Smart.sup.TM] distributor are shown in Figure 3. Three downcomers are shown in Figure 3a. A downcomer consists of a [Teflon.sup.TM] tube heat shrunk onto a cast [Lewmet.sup.TM] orifice adapter. The orifice adapter is attached to the distributor piping using a pipe thread (see Figs. 3b and 3c). With these proven corrosion/erosion resistant materials, the downcomer is expected to have long operating life. In any case, replacement of the downcomer is a simple task and it is available from stock on very short notice. The downcomer tubes are about twice the diameter of the orifice to ensure that the acid discharges from the tubes at low velocity. [Figure 3 ILLUSTRATION OMITTED]

This versatile distributor can also accept side or top acid feed (see Figs. 4a and 4b). It can be easily supported on brick corbels or suspended using hangers. With side entry, the whole pipe network is located on one horizontal plane, reducing the tower height and the cost for a new tower. This arrangement also allows an increase in packing height for an existing tower to improve tower performance. With top feed to the distributor, a smaller header is used because it only has to handle half the acid flow. This arrangement results in a lower distributor cost but requires more tower space. [Figures 4a-4b ILLUSTRATION OMITTED] Comparison of distributors Salient features of the pipe, trough and [Smart.sup.TM] distributors are compared in Figure 1. The simplicity and superiority of the Cecebe [Smart.sup.TM] distributor is self evident. The Cecebe design can feed as many as eight rows of distribution points from a single header, minimizing cast iron pipe headers and fittings. For the 21 ft (6.4 m) diameter tower shown in Figure 1, the Cecebe design needs 4 headers while the alloy trough will likely need 6 to 8 and a buried pipe without downcomers will need 10 to 12 side headers. The alloy trough design needs even more pipe to feed the troughs than the Cecebe design. Density of distribution points The density of distribution points controls the height of packing needed to ensure the packing is fully wetted as shown in Figure 5. A higher distribution point density will decrease this packed height. Offsetting the saving in packing by using more points is the added cost of the extra points. The metering orifices also become smaller and are much more easily plugged with debris. A good compromise appears to be around 1.5 to 2 points per square foot. Such a point density gives distribution points on a 8 to 10 inch grid. For comparison, the classic cast iron trough unit uses a 12 inch grid and the buried pipe distributors have had point separations as large as 24 inches (61 cm). [Figure 5 ILLUSTRATION OMITTED] Some alloy troughs have had as many as 4 points per square foot which corresponds to a 6 inch grid. It is clear from Figure 5 that increasing the distribution point density from one to four points per square foot one can only decrease the packing height by about 6 inches (15 cm) and not by some 6 to 8 ft (1.83-2.44 m) as claimed by others.

A distribution grid of a Cecebe [Smart.sup.TM] distributor in a large tower is shown in Figure 4 and is a significant improvement on the conventional pipe or trough approach. Materials of construction Materials were selected after careful evaluation of the available materials for use in sulphuric acid. A long life, high reliability, and economy were the primary considerations. The materials selected have been successfully used in much hotter and turbulent acid environments than in the distributor and therefore will give a long maintenance free service in this duty. The distributor header pipes use thick-walled [L-14.sup.TM], a high grade speciality iron alloy developed for sulphuric acid by Chas S. Lewis & Co. The [L-14.sup.TM] material provides 60% greater corrosion resistance than the original Lewis process iron which was developed for sulphuric acid and oleum duty. It is well proven as volutes, elbows, suction heads and discharge pipes in Lewis acid pumps up to 132[degrees]C. The design uses the highest quality standard fittings which are readily available. High quality Meehanite [HS.sup.TM] (a trademark of Meehanite Metal Corporation) or [Mondi.sup.TM] (a trademark of Monsanto) is selected, with the largest available thickness. These materials have superior mechanical and corrosion properties and have been extensively used for acid and oleum lines. The orifice adapters are cast in [Lewmet.sup.TM], an outstanding corrosion/erosion resistant Ni-Cr alloy, well proven in Lewis pump impellers, valves, and orifice plates handling hot, turbulent strong sulphuric acid and oleum. The downcomer tubing, which carries the acid from the orifice to the packing, is made of [Teflon.sup.TM], which is well known for good corrosion resistance in acid service. The grade of [Teflon.sup.TM] can be varied to suit the service. With these proven materials of construction the downcomers are also expected to give long life. Typically, glass-filled PTFE gaskets and 304/316 SS supports, bolts and nuts are used, but these can be changed to accommodate plant operator's standard or preference. With these proven materials, high quality fabrication, thick walls, high corrosion resistance and colder acid, the life expectance of the distributor is over 20 years. Distributor assembly The distributor is completely pre-assembled in the fabrication shop, marked photographed and disassembled for easy transport to the site

on a single truck. Due to simple construction, the distributor can readily be assembled in the tower by maintenance personnel using preassembly pictures and drawings. The Cecebe [Smart.sup.TM] distributor is compact, much lighter in weight than the classic trough type system, occupies less space in the top of the tower and is simple to install. Distributor fouling and cleaning Distributors in sulphuric acid plants are well known to collect sulphate, brick or packing chips. The reason for this is that the classic designs provide stagnant space where material can settle and the distributor also contains the coldest acid where solubility of iron is lowest. Sulphate may or may not be present in modern acid plants depending on the level of iron in the acid. The level or iron in turn depends on corrosion of cast iron and the iron content of any streams such as water or weak acid fed to the main acid circuits. In most plants which have adopted anodically protected stainless steel or alloy acid coolers and acid piping, iron levels are quite low, running below 5 ppm compared to 20 ppm 20 years ago and sulphate now stays in solution. On the other hand, some waste acid burning plants may add dilute acid streams with significant iron as make-up to the acid circuits, in which case sulphate may appear. In such a case, the sulphate will probably appear in the distributors. In troughs or buried pipes it will settle out in the bottoms of the headers. In the Cecebe design there is no dead or stagnant space for the sulphate to settle. Ceramic chips from brick and packing are also found in acid plants, especially during startup. A prudent owner should place [Lewmet.sup.TM] or equivalent material screen in the acid line to the tower. Normally the packing chips will be collected during the first several months of operation after which fewer precautions are needed. Downstream of the tower, the first effective filter for rubbish is the acid cooler which has gaps between tubes of about 1/4 inch (64 mm). With the orifice restriction larger than these gaps, the cooler will more likely collect the chips and not the distributor. However, an inline strainer outside the tower is an expensive way of keeping chips out of both cooler and distributor. A further feature of a good distributor is the ability to inspect and clean the distributor without entering the tower. With all piping in one plane and a limited number of headers, it is quite practical to extend the headers into nozzles at one end and provide removable covers and flanges. All of the cast iron piping and fittings are then visible and accessible. this arrangement allows external cleaning of debris from the pipe header without entering the tower[7]. No problems with sulphate or packing or brick chips have been found to date with the Cecebe distributors which have been in operation since

1991. The extent of generation of chips from packing varies with the packing source and the maintenance personnel handling it and the wise owner will minimize this problem by choosing good quality packing and skilled contractors to install it. Distributor maintenance The use of corrosion-resistant materials, easy access to packing, ready availability of components, simple assembly, and ease of cleaning results in low maintenance and downtime. Therefore, the [Smart.sup.TM] acid distributor makes a compelling economic case when the continuous maintenance downtime costs are considered over the life of the plant[8]. Features and benefits of the [Smart.sup.TM] distributor A number of criteria for an ideal distributor were listed earlier. A check suggests that the Cecebe [Smart.sup.TM] distributor meets all of these criteria as summarized below: * Uniform distribution without splashing and mist generation is provided by evenly spaced downcomers discharging acid at low velocity inside the packing. * Distribution is not sensitive to poor levelling or variation in liquid flow because of a significant liquid head over the distributor orifices. * Submerged orifices provide an ability to handle larger changes in acid flow giving a greater turndown capability. * The distributor header is not buried in the packing. This provides maximum free area for gas flow and avoids the risk of localized flooding, high pressure drop and mist generation which are inherent problems of buried pipe distributors. * Well proven corrosion-resistant materials of construction provide a long trouble free life. * The distributor can tolerate a wide variation in acid strength unlike distributors made of materials such as 310 stainless steel, [Saramet.sup.TM] and [SX.sup.TM] which have difficulty handling oleum and weaker acid. * The distributor is compact, occupying minimal tower height compared to trough distributors. * It is easy to assemble, inspect, clean and maintain. * Most components are available from stock, minimizing spares requirement.

* The construction is simple and economical. EXPERIENCE REPORT The installation list for Cecebe [Smart.sup.TM] distributors is presented in Table 1. It shows that after a successful demonstration period of three years, this new technology is gaining rapid acceptance. Table 1: Cecebe [Smart.sup.TM] acid distributors
Client A B A C D E F F F D D Acid plant type smelter sulphur burning smelter smelter regeneration sulphur burning smelter smelter smelter regeneration regeneration Startup date A B A C D E F F F D D Apr 1991 Apr 1992 Aug 1993 Jun 1994 Mar 1995 May 1995 3Q/4Q 1995 3Q/4Q 1995 3Q/4Q 1995 Jan 1996 Jan 1996 Plant size (t/d) 900 250 600 300 1,100 2,100 2,900 2,900 2,900 1,100 1,100 Remarks Downcomers installed in an existing [SARAMET.sup.TM] pipe unit Replaced a buried cast iron pipe distributor Replaced a cast iron trough distributor Replaced a [SARAMET.sup.TM] pipe distributor Replaced a[SARAMET.sup.TM] pipe distributor Selected for a new interpass absorber tower Will replace a spray type cast iron distributor Will replace a spray type cast iron distributor Will replace a spray type cast iron distributor Will replace a [SARAMET.sup.TM] pipe distributor Will replace a [SARAMET.sup.TM] Tower duty final absorber final absorber final absorber [SO.sub.2] drying drying tower interpass absorber drying tower interpass absorber final absorber interpass absorber final absorber Tower diameter 18 ft (5.49 m) 9 ft (2.74 m) 16 ft (4.88 m) 10 ft (3.05 m) 17 ft (5.18 m) 21 ft (6.40 m) 28 ft (8.53 m) 23 ft (7.01 m) 25 ft (7.62 m) 18 ft (5.49 m) 17 ft (5.18 m)

pipe distributor

The first complete Cecebe distributor was installed in a 9 ft (2.74 m) diameter final absorber tower in a 250 t/d sulphuric acid plant in western Canada in April 1992. It replaced an old cast iron pipe unit that suffered from the problems described earlier with this type of distributor. There have been no problems with plugging by sulphate or chips in this unit and it has continued to provide reliable service since installation. The precursor of the Cecebe design is a unit in a 900 t/d metallurgical acid plant in Texas. This plant was originally supplied with a trough type cast iron distributor which was later replaced by a buried pipe [Saramet.sup.TM] distributor. It was not possible to operate the plant at design rate without major acid mist carry-over from this tower. Calculations showed that the distributor was blocking sufficient tower area to cause flooding. The distributor was then modified to include downcomers which carried the acid well below the alloy pipes before it entered the packing. Since the modifications were carried out in 1991, the mist and flooding problem have disappeared and the plant can now operate in excess of design rate. Following the success of the first distributor, the same client replaced a worn out cast iron trough unit with a [Smart.sup.TM] distributor in a 16 ft (4.88 m) diameter final absorber tower of a 600 t/d sister plant in August 1993. This installation has also been very successful. The problems associated with cast iron troughs were completely eliminated. Plant personnel report negligible acid carry-over as compared to the trough unit even at rates in excess of design. This unit, when crated, weighed only 6,800 pounds (3,084 kg) and constituted only a partial truckload. Another distributor was supplied to a metallurgical acid plant for a 10 ft (3.05 m) diameter tower in which relatively strong sulphur dioxide gas is dried with 93% acid. It replaced a buried pipe [Saramet.sup.TM] distributor which gave poor performance with excessive acid mist carry-over to the downstream blower. The new distributor started up in July 1994 and has been operating without any problem. The drying efficiency has improved and the mist entertainment problem has been resolved. Earlier this year a [Smart.sup.TM] distributor was commissioned in a 1,100 t/d acid plant. An alloy buried pipe distributor in a 17 ft (5.18 m) diameter drying tower was replaced just after about five years of service. This unit had no corrosion problems but, because it occupied significant cross-sectional area of the packed tower, the localized flooding around the buried distributor had resulted in mist carry-over and very high pressure drop (22.5" W.C vs 7.5" W.C. design). A pressure drop measured in the top 3 ft (0.91 m) of packing where the distributor was buried was reported to be 10 inches W.C., about ten

times the theoretical expected value. With the new Cecebe distributor the pressure drop was drastically reduced and the production bottleneck and the mist carry-over was eliminated. Based on this success, this client is replacing buried pipe distributors in the interpass and final absorber towers. These distributors are scheduled to be installed in January 1996. A large distributor has recently been installed in a new interpass absorber tower in a 2,100 t/d sulphuric acid plant operated by a major fertilizer producer in Florida. This tower is using [Flexeramic.sup.TM], a high efficiency structured packing from Koch. This is the first application of this type of packing in the sulphuric acid industry. Therefore, a thorough investigation of alternative distribution technology was carried out by the client and the packing supplier. The [Smart.sup.TM] distributor was selected as the most efficient and cost effective. This tower is scheduled for startup in September 1995. Three large distributors (23, 25 and 28 ft diameter) have recently been supplied to a 2,900 t/d smelter acid plant in Mexico. The existing spray type distributors which have been performing poorly will be replaced. These distributors have been generating excessive mist and entertainment causing downstream corrosion damage to the blower and a number of very large and expensive heat exchangers which will now need to be replaced. The poor absorption in the final tower has been causing an environmental nuisance. These [Smart.sup.TM] distributors are designed with the acid feed line at the same level as the distributor header. This arrangement will allow about 3 ft (approx. 0.9 m) of additional packing in these towers which presently have very short packing heights (6, 7 and 8 ft) and thereby improve drying and absorption efficiency. These units will be put into service shortly. References [1.] "Pumping aggressive liquid the Lewis way", Fertilizer Focus (Aug 1991). [2.] "Preventing the sulphuric acid plant from devouring itself and its surroundings", Fertilizer Informational No. 295, p. 35-41 (Mar 1991). [3.] Trickett, A.: "Acid plant design and operation - 2". Copper '91 Conference, Ottawa, Canada (1991). [4.] Friedman, L. J.: "The sulphuric acid plant advances review and analysis", SULPHUR 88, Vienna, Austria (Nov 1988). [5.] Cameron, G. M.: "A [SMART.sup.TM] distributor for sulphuric acid plant towers", AIChE Meeting, Clearwater, Florida (May 1991). [6.] Cameron, G. M.: "Distributor for packed tower", US Patent 5,014,740 (May 14, 1991).

[7.] Cameron, G. M., Bhaga, D.: "Improving sulphuric acid tower performance using the [Smart.sup.TM] acid distributor and High Performance ([HP.sup.TM]) tower packing", SULPHUR 94, Tampa, Florida, USA (Nov 1994) [8.] Cameron, G. M., Bhaga, D.: "Sulphuric acid plant maintenance and upgrading", SULPHUR 95, Abu Dhabi, UAE (Oct 1995). COPYRIGHT 1995 CRU Publishing Ltd. This material is published under license from the publisher through the Gale Group, Farmington Hills, Michigan. All inquiries regarding rights should be directed to the Gale Group.

Title: Sulphuric acid equipment update: sulphuric acid producers are always searching for more efficient, longer lasting and reasonably priced equipment. In this article some of the industry's key sulphuric acid equipment suppliers showcase their leading products.(MATERIALS AND EQUIPMENT DESIGN) Date: 5/1/2005; Publication: Sulphur; Acid towers Whether an acid plant was built 20 years ago or 20 months ago, the towers are the most important units in a sulphuric acid plant. Most sulphuric acid towers today run with design parameters established 2030 years ago, based on three-inch ceramic saddles for mass transfer and an oversized tower diameter for operational comfort. Today's construction and operating costs make tower design a more complex matter. However, thanks to innovative technology, the industry now has a better choice for tower replacement--alloy towers. Monsanto alloy towers With 20 years of installation experience, Monsanto Enviro-Chem Systems (MECS) offers a wide range of advantages over traditional tower design. Alloy rowers can be replaced within a two-week shutdown, they can be placed on the same foundation, they utilise the existing platforms, gas ducting and acid piping and they are repairable. Corrosion protection The need for corrosion protection in alloy towers resulted in the standardising of MECS' ZeCor[TM] sulphuric acid stainless steel for use

in strong sulphuric acid applications ranging from 93 to 99% concentrations. The corrosion rate for ZeCor[TM] sulphuric acid stainless steel is less than 1 mil per year (0.025 mm/year) in typical drying and absorbing acid circuits, depending on the acid concentration and temperature. Extensive corrosion and workability tests have been conducted with very impressive results. To date, over 50 installations of ZeCor[TM] sulphuric acid stainless steel distributors (Fig. 1), piping systems, towers and other equipment have been in operation for up to three years with corrosion results matching or exceeding laboratory results. Acid plant components fabricated from ZeCor[TM] sulphuric acid stainless steel: include towers, pump tanks, piping systems, thermowells, strainers, nozzle sleeves, mesh pads, mist eliminators, vortex breakers, orifice plates and acid distributors. Tower packing When replacing towers, there are opportunities to lower pressure drop with tower packing and mist eliminator options. Mist eliminators can also be upgraded for lower acid exit mist emissions. In MECS' high-efficiency alloy towers, the packing is supported directly by the alloy grating, eliminating the need for grid bars or partition rings that are characteristic for the conventional brick-lined towers. This further reduces the pressure drop across the packing bed. Monsanto Enviro-Chem Systems also offers the WavePak[TM] ceramic porcelain packing for sulphuric acid towers. The packing was developed in conjunction with Saint-Gobain Norpro (formerly known as Norton Chemical Process Products). WavePak[TM] delivers significant technological advantages over other types of packing available in the sulphuric acid industry today. The product offers superior internal gas distribution, higher capacities and optimum mass transfer efficiencies. WavePak[TM] also provides a significant advantage in pressure drop savings over conventional saddles. Mist eliminators Mist can be formed in manufacturing processes in three different ways: * Mechanical forces may break up or "atomise" a liquid to form a mist. * Cooling of a gas stream may result in the condensation of vapour to form a mist.

* Chemical reaction of two or more gases may take place at temperatures and pressures where the reaction products are mists. MECS' Brink[R] ES (Energy Saver) Fiber Bed Mist Eliminators incorporate a special wound fibre through computer-controlled quality and a patented bi-component design. The benefits include: * Up to 20% more gas throughput capacity per element, with no loss in collection efficiency or penalty of increased pressure drop; * Collected mist in exit gas is virtually eliminated via a proprietary reentrainment layer; * Easter and less expensive repack. The heart of ES is its bi-component fibre bed design. In a conventional fibre bed, liquid draining on the downstream face of the fibre bed is sometimes re-entrained in the exiting clean gas, due to high velocities. This re-entrainment becomes worse with higher loadings of mist and/or higher flow velocities. The ES includes a patented layer of coarse fibres downstream of the finer collecting fibre. Liquid that would re-entrain from the fine fibre bed is recollected and drained in the re-entrainment layer. The standard ES element diameter is 2 feet (61 cm), and elements are available in lengths from 6 to 24 feet (1.83-7.32 m). Customised lengths and widths can also be designed. The wound fibre may be glass or polyester. The element cage can be fabricated from any weld able metal or can be made of fibreglass reinforced plastic (FRP) or polypropylene. MECS' Cost Saver (CS) elements are packed with a glass fibre mat collecting layer and have a patented metal alloy mesh re-entrainment control layers. The cages are constructed of stainless steel. For high inlet mist loading situations, an optional baffle screen preseparator is available for the CS elements. CS-IIP has replaced the HP element. Standard flow is 9,500 actual cubic feet per minute (acfm) and standard size is 26 inches (66 cm) in diameter and 40 inches (102 cm) high. CS-IP is principally a mesh pad replacement in sulphuric acid plant drying towers. Standard flow is 13,280 acfm and standard size is 30 inches (76 cm) in diameter and 65 inches (165 cm) high. ES and HE are available in both forward-flow and reverse-flow styles. CS and HP elements are only available in the reverse flow style due to exit velocity re-entrainment considerations.

In the standard-flange, forward-flow (SFFF) configuration, the element hangs from a tubesheet. This configuration features ease of installation and maintenance. In this style, the dirty gas enters the outside of the element and the clean gas exits through the centre core. In the reverse-flow upside-down (RFUSD) configuration, the mist eliminator is placed vertically above the tubesheet. This configuration permits the use of longer elements and vessels of reduced size. In this style, the dirty gas enters the centre core of the element and the clean gas exits through the outside. Figure 2 shows the installation of Monsanto candle mist eliminators. IMC Phosphates alloy tower installations One IMC facility that recognises the benefit of alloy towers is the New Wales site in Florida. The 01 Plant's Interpass tower was installed by MECS in September 2002 (see Fig. 3). The plant currently runs at 2,900 t/d "clean." IMC's process engineer Jim Dougherty and senior project engineer Mike Roche played key roles in the project. "IMC's alloy tower selection was primarily driven by the requirement to minimise turnaround downtime. There is no way to guarantee the integrity of the brick lining if a brick tower of this size had to be lifted into place. And, bricking a carbon steel tower in place during the turnaround would take several weeks. There was really no option," Roche said. The field-fabricated alloy tower could be lifted into place following the demolition of the existing tower in the shortest amount of time. MECS' Alloy tower technology was selected to minimise maintenance cost relative to a carbon steel brick tower and also to meet the quick turnaround schedule. "IMC has two alloy towers at its South Pierce facility that have been in service for over a decade. South Pierce Sulphuric Maintenance Superintendent Jimmy Bennett always tells me that the only expense he has is to open and close the manway doors at turnaround for inspection," Dougherty said. "Also, IMC has learned from its experience with the alloy HRS towers from an equipment-life perspective. An alloy tower can be repaired indefinitely, so once you build one, you'll never have to buy another." IMC's New Wales facility was interested in executing a turnkey project and found that Monsanto offered the best overall package of tower technology. Other IMC facilities already had experience with Monsanto's patented Uniflo alloy trough distributor system design,

Brink[R] ES-Candle mist eliminators, and Sandvik SX alloy material in the two alloy towers in operation at South Pierce. The New Wales facility was also interested in continuing its test programme of Monsanto's new ZeCor[TM] alloy. New Wales first began testing ZeCor[TM] in its drying tower distribution system and piping service in 2001. To further the testing programme, ZeCor[TM] distribution troughs and piping were designed for the new IPA tower in order to assess the ZeCor[TM] material in the most severe non-HRS service locations. At 250[degrees]F/121[degrees]C, the New Wales IPA tower distribution system and outlet piping is among the most severe non-HRS process sulphuric acid process service conditions in the world. According to Roche, the tower has operated very well since installation. At the South Pierce facility, the first SX alloy final tower was installed in 1992. The second was installed in 1995-1996. The CS (cost saver) impaction candles were used in the No. 11 plant. For the No. 10 plant at South Pierce, the Energy Saver (ES) browning candles were installed. To date, no repairs have been required for either units. Bennett has been with IMC for 37 years and knew what was needed at his site. "An old tower can be torn down and a new tower can be installed on the existing foundation in a two-week period. The existing towers were 1970s vintage towers that had flat pads. We had continuous problems with carryover out of the stack. It was a constant battle to stay within the environmental limits," Bennett said. "It was time to start looking for new technology." Monsanto came in and did a complete re-rate of the plants where the old HRS units were installed. Bennett said the facility then selected Monsanto for the new towers and chose the SX alloy material. "Our SX towers have been operating for 12 years, and I've not had to do anything to either tower but perform inspections, ultrasonic thickness (UT) measurements, vacuuming out and clean up of the distributors since their installation." The site contracted VIP to clean the candles and distributors, and also to perform inspections. Bennett said the corrosion rates have been running well below what was expected on mils per year. "The unit No. 10 tower has ES candles installed in it--the type that hang down, and the No. 11 tower has the CS impaction candles--the type that stands up. I've never changed the candles in either tower," Bennett said. "It's hard to beat 12 years on two sets of candles; that's pretty much unheard of in the sulphuric acid industry. I would recommend an alloy tower to anyone looking to replace a tower." Based on the success of its sister facilities, IMC's Uncle Sam plant in Louisiana recently awarded Monsanto Enviro-Chem Systems a turnkey

contract to design and install a new absorption tower for IMC's Unit A--a 1,600 t/d sulphuric acid unit. The installation of the new tower is scheduled to take place this summer in tandem with a planned unit turnaround in July. Unit A is in one of the original units built at this site in the 1960s. In addition to Unit A, IMC Phosphates operates two other sulphuric acid units at the site. These include Unit D, a plant producing 1,600 t/d built in the 1970s and also Unit E, producing approximately 3,200 t/d built in the 1980s. "The projected time to install the tower will be about 15 days. The old tower has reached its life expectancy. It was a 1960s vintage, carbonsteel tower, which was brick-lined. It has been repaired numerous times, and 60-70% of the shell has been repaired in some manner or another," stated Dwayne Ordeneaux, a senior project engineer at IMC Phosphates' plant in Faustina, La. "We started soliciting prices to replace the tower in kind, and we found that a brick tower was as expensive as an alloy tower. Brick is expensive, and the labour to install brick is expensive. Finding the necessary crafts skills to install the brick can also be difficult these days. The team also found that repairing a brick tower is more difficult. "If you get a leak in a brick tower, the question is, 'Where is it?' If you do find it, you've got to plug it, remove the brick and remove the liner. If it gets behind or between the brick, it really is a nuisance," Ordeneaux said. "Whereas with the alloy tower, should you have a leak, it is easily repairable. We chose the ES candle for its high efficiency; it will give us some additional reduction in pressure drop at a reasonable cost." For the packing, Ordeneaux and his team chose a product from Koch Knight LLC. The Knight-Ware[R] Flexeramic[R] Type 88 ceramic structured packing is expected to lower the pressure drop of the packed bed by 40%, compared to standard random packing saddles used in the existing tower. Koch Knight acid tower packing media To help operators determine the optimal performance available from a tower, Koch Knight LLC offers the T-ECON[TM] economic analysis model for sulphuric acid mass transfer media. Three variables determine optimal tower design: mass transfer efficiency, initial cost, and lifetime cost. Technically speaking, absorption needs, pressure drop limitations and other process requirements could make a particular packing the only suitable option for a particular tower. Plant and operational parameters such as

plugging potential, possible production increases expected in the near future, or the space available for a new tower may form part of the tower decision matrix. The mass transfer capacity of the packing must fit the technical, operational and budgetary needs of the facility. The lowest first cost packing option may be attractive when it fits the approved budget for a tower. However, buying the lowest cost packing option available may not maximise the tower's value over the life of the plant. A more indepth analysis of the best financial options is required. Koch Knight combines excellent technical resources for mass transfer applications with a complete array of available packing products. The T-ECON[TM] model provides plant operators with a method to study the range of Knight packings, including economical imported materials, Flexisaddle[TM] standard and low pressure drop Flexisaddle[TM] LPD[TM] random tower packing (Fig. 4), and high performance Flexeramic[R] ceramic structured packing (Fig. 5). The T-ECON[TM] tower analysis model simulates the tower performance with various packing options to determine the net present value, that is, the true value in today's currency of the money invested by the company in the packed bed during the life of the mass transfer media. Since a sulphuric acid tower media charge should last more than ten years, the model conservatively assumes a ten year packing life and shows the cost effects of all the available tower packing options. In a recently concluded study for an Asian metallurgical acid plant, the T-ECON[TM] model generated the graph in Fig. 6 to show a summary of the net cash flow over a life of ten years. The graph visually compares the lifetime costs of each packing option and reveals that a higher investment made today represents the most economical long term packing solution. The T-ECON[TM] model shows that in this case Flexeramic[R] Type 88 ceramic structured packing provides the highest net present value over the ten year term. Knight-Ware[R] Flexisaddle[TM] three-inch LPD (low pressure drop) packing offers a more rapid payback time due to its lower net present value. Standard Knight-Ware Flexisaddle ceramic three-inch saddles are a good initial cost value, but the lower initial investment does not represent the best long term choice for the plant. In this case, the client selected the Flexisaddle LPD packing option as the best Knight product to meet their current needs. As the plant demands more production from the equipment, the option for installation of Flexeramic packing will be available for a future repack installation. Nowadays, sulphuric acid plants must reduce costs while simultaneously improving production and operating standards. The T-

ECON[TM] economic modelling tool can give operators a method to know that a tower is running with the most optimised mass transfer package available in the market, at the lowest life cycle cost to provide the highest long-term profit. Maximising tower performance and the useful life of the equipment provides reliability to the process as a whole. Pumps for molten sulphur When transporting sulphur in the liquid form, it is important that the properties of sulphur are taken into consideration. Due to the abnormal variation of viscosity with temperature, which only allows sulphur to be pumped satisfactorily within the range 135-155[degrees]C, most pumps used for molten sulphur applications have a heating jacket in order to keep the temperature constant in all parts of the pumps. There are several alternatives for shaft sealing. For vertical pumps, stuffing box packing would be adequate, whilst for horizontal pumps hydrodynamic shaft sealing, mechanical seal or magnetic drive arrangements are recommended. Although vertical pumps are widely used on sulphur melting plants, it is not uncommon to use various designs of horizontal pumps. Horizontal pumps for molten sulphur can either be of heavy duty design with hydrodynamic shaft sealing (e.g. for molten sulphur containing solids), or of modern magnetic drive design (e.g. for clean sulphur). Magnetic drive pumps have the advantage of safe operation without any leakage of hazardous hydrogen sulphide. The design of vertical pumps depends not only on the purity of sulphur, but also on the size of the sulphur tank or vessel. For example, cantilever pumps are limited in their submergence depth. For clean sulphur, single or multistage pumps with foot and intermediate bearings can be used for submergence depths of up to 8 m. For applications with impure sulphur the solid size, hardness and concentration have an influence on the design. Sleeve bearings in hardened material with internal product lubrication or even with external grease lubrication or cantilever pumps offer a suitable solution for such applications. Friatec heatable magetic drive pumps A modern pumping solution for molten sulphur applications is heatable magnetic drive pumps, which have zero leakage and easy maintenance. Zero leakage is especially important for recovered sulphur which contains mostly [H.sub.2]S gas, which should not come into contact with the atmosphere. Pumps with a mechanical seal always have some sulphur leakage, which is required in order to lubricate the seal faces. Often this leakage can be seen in the mechanical seal area as solid sulphur.

Friatec-Rheinhutte heatable magnetic drive pump type RMKN (Fig. 7), has been used for molten sulphur applications for ten years with very good experience. Due to the nature of sulphur, the pumps are of special design. In the magnetic coupling/isolation area a good heat exchange is required in order to dissipate the heat caused by magnetic losses. The sleeve bearing is manufactured in erosion-resistant silicon carbide and has an intensive lubrication that will also allow operation at lower capacities. However, the pump has a definite minimum allowable flow rate in order to avoid heat generation within the pump. The intensive heating area around the pump casing and around the isolation area ensures a constant temperature during operation and a safe start-up. With the jacketed volute casing drain the pump can be safely emptied without the risk of sulphur crystallisation after the pump shut off. Friatec vertical sulphur pumps For installation in sulphur tanks below ground level, horizontal pumps cannot be used and suitable vertical pumps have to be considered. Different designs of vertical pumps are available. For recovered sulphur, pumps with shaft support bearings are suitable. For submergence depths longer than 2000 mm, additional intermediate bearings are required. The vertical shaft is supported by anti-friction bearings on the top, outside the tank and by sleeve bearings below the mounting flange. The sleeve bearings are lubricated by the sulphur. It is recommended that the maximum pump speed of sulphur pumps is limited to 1500 rpm at 50 Hz or 1800 rpm at 60 Hz, in order to reduce the risk of temperature rise in the intermediate bearing. The radial forces and the pump vibration can be limited. The special design feature of vertical molten sulphur pumps is the heating jacket on the discharge bend, shaft and discharge pipe. Friatec-Rheinhutte vertical pump type GVSN (Fig. 8) has some additional design features. The pumps can have up to three stages, which allow a high differential head at low speed. The discharge and the shaft column are built as a complete unit to give optimum stability, especially for pumps longer than 2000 mm. In addition, all pumps have a double volute casing, which reduces the radial forces to a minimum. Mondi[TM] piping systems Acid Piping Technology (APT) specialises in products for the sulphuric acid industry. These products include Mondi piping, tower distributors, gaskets, converter internals and ceramic tower packing. Mondi piping has been used in acid plants since 1983 providing excellent performance. It is used in over 700 sulphuric acid piping systems worldwide.

Mondi is a proprietary metallurgy ductile iron specially developed for acid service. It has a nodular graphite matrix, which enables it to be used in a wide range of acid concentrations. It is 95% ferrite for excellent performance joining anodically protected acid coolers. In operation, a tough sulphate film is formed on the surface. The initial corrosion of Mondi is higher in forming this film. After formation, the sulphate film remains to protect the surface. The resulting overall corrosion rate is low over the operating lifetime of the plant. Because of its improved metallurgy and heavy wall thickness, Mondi piping can operate at internal velocities of 7-10 ft/sec for 12-inch to 30-inch pipe sizes. The key components of the Mondi piping system are: * Improved metallurgy; * Heavy wall thickness; * Special fitting patterns; * Flange face finish; * Step ring gaskets. Mondi piping is used for sulphuric acid systems having 92% to 99+% concentration, 125 psig maximum operating pressure and temperatures up to 300[degrees]F (149[degrees]C). Standard piping sizes are 3 inch to 30 inch inside diameter. Applications in acid plants are recirculation systems in drying, absorbing, cross flow stripping towers, distributors in towers, transfer piping to storage or other processes. Additional applications are for seawater used in process cooling and for vessels up to 48 inches inside diameter where sulphuric acid is used for gas drying or stripping. Mondi pipe is centrifugally cast and threaded flanges are shop installed. Mondi fittings are static cast Mondi. Fittings are close grained, free from cracks and excessive shrinkage. Over the past ten years, special fitting patterns have been developed that eliminate the need for chaplets. Currently 95% of APT's Mondi fittings are made without chaplets. A chaplet looks like a two-headed nail (Fig. 9) and is used on the sides of some elbows (Fig 10) and reducers to hold the sand core in place during casting. Chaplets are seen as a raised area on the side of a fitting. Ductile iron elbows for water service typically have chaplets made of steel which will be attacked by sulphuric acid and become leak points relatively quickly. For the Mondi fittings that do require chaplets, these chaplets are made of Mondi with a special shank design. This special shank has thin

fins, which will fuse into the molten metal for tight sealing of the chaplet area. Mondi performance Measured corrosion rates from many years of actual plant operation are the true measure of Mondi performance. Figure 11 shows reported corrosion rates after 2-8 years of plant operation for 93% acid drying tower and 98% acid absorbing tower piping systems at different temperatures. Measured corrosion rates for 93% acid are 3 mils/year at 120[degrees]F to 9 mils/year at 152[degrees]F. Measured corrosion rates for 98% acid are 2.5 mils/year at 170[degrees]F to 10 mils/year at 236[degrees]F. Many plants have reported that their Mondi piping systems have operated through acid concentration excursions. This is important because acid plants do not operate at ideal conditions all the time throughout their life. Concentration excursions can be weaker acid or stronger acid even with free S[O.sub.3] conditions. The plants indicated that the Mondi piping did not show significant corrosion after the excursions. Such acid concentration excursions have caused accelerated corrosion and damage to austenitic stainless steel systems. Weaker acid excursions can occur from equipment malfunction of the dilution water system, instrumentation, valves, boiler leaks, acid cooler leaks and plant outages. Stronger acid excursions can occur from equipment malfunction of instrumentation, valves and the dilution water system. Mondi piping is very forgiving and provides reliable performance. Mondi pipe and fittings have a large corrosion allowance due to the heavy wall thickness. Table 1 shows original thickness, replacement thickness and available corrosion allowance according to pipe size. Low corrosion rate, ability to handle concentration excursions and ample corrosion allowance for Mondi piping results in a long service life, low maintenance cost and reliable performance. For example, the calculated service life for 16-inch Mondi piping at 9 mils/year corrosion rate would be more than 30 years. New electrostatic precipitator "Carola" The electrostatic separator "Carola" (Corona Aerosol Separator) was developed with the specific objective of providing a highly efficient separator for fine particles from gas flows. The new electrostatic precipitator has considerable advantages compared with conventional systems with regard to investment and operating costs.

The "Carola"-separator has been patented by the Research Centre Karlsruhe. Rauschert Verfahrenstechnik GmbH, Steinwiesen, is the exclusive licensee for applications of this system in the chemical, pharmaceutical and petrochemical industry. Function mode and configuration The electrostatic separator "Carola" (Fig. 12) works with the following four main process steps: * Cooling and moistening of the exhaust gas to be treated; * Condensation of water vapour on the sub-micron particles; * Electrostatic charging of the particles in an electric field; * Separation of the particles on an earthed surface. The exhaust gas to be cleaned flows from below in an upward direction through the separator. With the use of spray nozzles, the exhaust gas is initially super-saturated by applying cold water. The super-saturation is quickly reduced on the foreign nuclei existing in the gas and, subsequently, on the particles also (heterogeneous condensation) which grow in this way. The main component of the aerosol separator is the compact constructed ioniser stage which was specially optimised for the operation with high water vapour content of the incineration exhaust gas. Particle charging is effected in a design-related manner and very effectively in the corona-zone by spray needles (see Fig. 13) and with low voltages in the range between 10-18 kV in accordance with the apparatus design layout. The ioniser stage consists of an earthed bottom with openings and an array of high-voltage electrodes, which are centrally arranged to the bottom openings (Figs. 13 and 14). By means of corona discharges, the particles flowing closely past the electrodes are charged electrically (operation high voltage: max. 18 kV). The high voltage is supplied by way of a compact control unit. The charged particles are precipitated on a compact collector spatially separated from the ioniser. The collector consists of an earthed tube package (surface separator). The collector and ioniser are intermittently purged by way of nozzle arrangements in order to prevent a caking of the solid substances. The timing intervals between jet spraying are normally activated according to the pressure loss. A liquid receiver with a channel between the collector and the ioniser ensures that the washing liquid with the separated particle material is discharged out of the separator.

Heated sealing air is continually applied to the insulators in order to ensure their unobjectionable functioning. A sealing air fan with an electric heat register supplies this air. Control is carried out in the control cubicle. Performance and consumption data A typical installation of Carola has the following consumption data: the pressure loss of the entire unit is below 5 mbar, the amount of service water ranges between 20 and 60 1/1000 [m.sub.N.sup.3] (moist exhaust gas), and the electric energy consumption for ionisation is approximately 0.2 kW/1000 [m.sub.N.sup.3] (moist exhaust gas), for sealing air below 0.5 kW/1000 [m.sub.N.sup.3] (moist exhaust gas). The figures given are approximate values only. The exact consumption figures are determined on a project-related basis. The Carola separator is suitable for gas volume flows from approximately 500 [m.sup.3]/h to approximately 50,000 [m.sup.3]/h. Special designs and/or parallel arrangement of single aggregates for higher volume flows are possible. The incoming gas must be extensively saturated with water vapour. If this is not the case, a packed tower is arranged upstream of the separator. Depending on the gas composition, this results in operating temperatures in the area of the ambient temperature of up to 90 [degrees]C. Figure 15 shows a typical arrangement of an exhaust gas scrubbing with a Carola-separator. First, the hot exhaust gas is quenched and pre-scrubbed in a packed tower before it enters the particle separator "Carola" as a final stage of the exhaust gas scrubbing process. The maximum dust and/or aerosol concentration in the raw gas to the separator is limited because of the so-called "corona quenching". If the dust concentration is too high, the electron stream emitted by the spray electrodes collapses. As a result, no adequate electric current can be generated for an ionisation. The maximum dust concentration at the inlet to the separator is in the range of 1 to 3 g/[m.sup.3]. For higher concentrations the use of a preseparator stage, such as a venturi or a jet-spray washer, is possible. The obtainable overall separation rates depend on the type, fractioning and concentration of the particles. Overall separation rates above 99% can be achieved. If necessary, a series arrangement of two Carolaseparators is possible. Operational results for various task assignments and marginal conditions are already available. Details are obtainable on request. Technical installation for the separation of S[O.sub.3] aerosols

A technical installation for the separation of S[O.sub.3] aerosols from exhaust gas has recently been erected. In order to demonstrate the potential of the system, some laboratory experiments have been carried out. The experiments were performed at a Carola laboratory plant with a gas throughput of 44 [m.sup.3]/h. The gas is watersaturated air at a temperature of 50[degrees]C. The S[O.sub.3] aerosol was generated by stripping oleum with a dry nitrogen gas flow to achieve a constant raw gas mass concentration. Figure 16 shows the results of raw gas and pure gas measurements as well as the resulting determined grade efficiency for S[O.sub.3]aerosol. The particle number concentration was measured with a mobility analyser (SMPS). The modal value in the raw gas lies approximately at 120 nm and in the pure gas approximately at 100 nm, the resulting grade efficiency ranges between 80 and 95% in the relevant particle range. The mass separation efficiency is determined by additional gravimetric measurements to 98%. As already mentioned, a major technical Carola unit has recently been erected. This plant is a unit for the separation of S[O.sub.3] aerosols from an incineration exhaust gas. The unit has been installed downstream of an S[O.sub.2] scrubber. The successful startup of this Carola unit took place in March 2004. The main data for this separator are shown in Table 2.
Table 1: Mondi pipe and fitting corrosion allowances Original Size (inch) 3 4 6 8 10 12 14 16 18 20 24 30 Available thickness (inch) pipe fitting 0.34 0.41 0.49 0.51 0.56 0.61 0.66 0.70 0.74 0.81 0.89 1.15 0.48 0.52 0.55 0.60 0.68 0.75 0.82 0.89 0.96 1.03 1.16 1.37 Replacement thickness (inch) 0.197 0.204 0.225 0.249 0.270 0.291 0.330 0.376 0.375 0.396 0.442 0.511 corrosion allowance (inch) (mils) 0.143 0.206 0.265 0.261 0.290 0.391 0.330 0.324 0.365 0.414 0.448 0.638 143 206 265 261 290 319 330 324 365 414 448 638

Table 2: Carola separator for the separation of S[O.sub.3] aerosols Pre-specified data: Gas volume flow Inlet temperature S[O.sub.3] concentration (raw gas) Guarantee values and consumption figures: S[O.sub.3] concentration 13,000 [m.sub.N.sup.3]/h moist 67[degrees]C 1,000 mg/[m.sub.N.sup.3] dry

< 35 mg/[m.sub.N.sup.3] dry

(pure gas) Discharge volume water Electric connecting power Pressure loss Dimensions: Diameter Construction height Materials: Casing Internals

< 1 [m.sup.3]/h 4 kW < 5 mbar DN 2,000 mm 5,500 mm GFK with chemical protection coating titanium (ioniser); PP (collector)

COPYRIGHT 2005 CRU Publishing Ltd. This material is published under license from the publisher through the Gale Group, Farmington Hills, Michigan. All inquiries regarding rights should be directed to the Gale Group.

Title: Sulphuric acids storage and transport. Date: 11/1/2000; Publication: Sulphur; Author: Salzbrenner, Mark A guide to regulations and design criteria affecting non-fuming and fuming sulphuric acids. DuPont Chemicals manufactures, stores and transports both nonfuming and fuming sulphuric acid products. In the United States some regulations apply differently to non-fuming and fuming acids; also, the design criteria for storing and transporting these acids are different. Mark Salzbrenner, Technical Service Consultant for DuPont Chemicals -Sulphur Products, gives an outline review of the regulations and salient design criteria. Sulphuric acid and fuming sulphur-based acids, such as oleums, sulphur trioxide ([SO.sub.3]) and chlorosulphonic acid (CSA), are essential chemicals in today's society. They are important chemicals in the manufacture of pharmaceuticals, shampoos, detergents, surfactants, fluorochemicals, agricultural chemicals, fertilizers, lubricants, ion exchange resins, rubbers, plastics and steel. In fact, you can measure the standard of living of a society by how much sulphuric acid products are used per capita -- the more acids used, the higher the standard of living. Sulphuric acids, both non-fuming and fuming, must be handled and transported properly to avoid potential problems. DuPont expends a lot of effort to ensure that it does not cause injuries or hurt the environment with these sulphuric acid products. It meets or exceeds all regulations involved with the storage and handling of these products, and follows all Responsible Care guidelines suggested by the American

Chemical Council (formerly known as the Chemical Manufacturers Association, CMA). This article reviews some of the DuPont design criteria for the transport and storage of these acids, and also gives an overview of some of the Unites Stated regulations that apply to non-fuming and fuming sulphuric acids, including the chemicals considered "Poison Inhalation Hazard" (PIH) by the United States Department of Transportation (DOT). Fuming sulphuric acids reviewed in this article that are considered PIHs by DOT include oleums greater than 30%, sulphur trioxide ([SO.sub.3]) and chlorosulphonic acid (CSA). Noranda DuPont LLC, a joint venture of Noranda of Canada and DuPont, follows the same requirements as DuPont for storage and transportation of the non-fuming sulfuric acid products. Transport There are a number of important differences in the design of vessels for the carriage of fuming acids compared to those for non-fuming acids, which are primarily based on the physical characteristics of the respective products. Non-fuming sulphuric acid (51-100%) Sulphuric acid between 51 and 100% is considered a "Hazardous Material" by the United States Department of Transportation. It requires a "Corrosive" label (hazard class 8) and falls under Packing Group II. Sulphuric acids in this strength range can be transported by land or sea, but air transport is prohibited. This review is confined to transport by rail car and tank truck, as these are the transport modes most likely to be seen by the public. The rail car most commonly used by DuPont to transport non-fuming sulphuric acid is a car that meets DOT 11lA100W requirements. Depending on the grade of sulphuric acid, the rail car may or may not be insulated and have heating coils. The common 93% sulphuric acid (66[degrees] Baume) is usually shipped in an uninsulated rail car due to the low freezing point. By contrast, the 98% and 99% acids are usually shipped in insulated rail cars in the winter, with heating coils on most. The rail cars are constructed of carbon steel, with a baked phenolic lining. For the most part, these cars are not equipped with rollover protection for the top fittings on the car. The standard sulphuric acid cars are top-unloading with no bottom connections. The tank truck (cargo tank) most commonly used for transporting nonfuming sulphuric acids meets DOT MC-312 or DOT-412 specifications. These cargo tanks, in general, are constructed of 316 stainless steel shells. The cargo tanks may be top or bottom unloaders. DuPont prefers top unloaders, because they minimize any possibility of

the cargo tank leaking acid en route. DOT MC-307 cargo tanks are authorized by DOT for the transportation of sulphuric acid, but DuPont does not use this style of cargo tank. The tank walls are thinner than on an MC-3 12 or DOT-412, and the tank capacity (6000 gallons) is too large for the actual volume loaded in the cargo tank (approximately 3000 gallons) due to road weight restrictions. These can cause excessive liquid movement inside the cargo tank and destabilize the cargo tank during travel down the road. Fuming acids -- oleums, sulphur trioxide ([SO.sub.3]) and chlorosulphonic acid (CSA) The fuming sulphur-based acids (oleums [greater than]30%, [SO.sub.3] and CSA) are considered highly hazardous by the DOT. In addition to the "Corrosive" placard (hazard class 8), they must also display the "Poison Inhalation Hazard" warning (hazard class 6.1). Oleum less than 30% requires just the "Corrosive" placard. Oleums, [SO.sub.3] and CSA are all classified as Packing Group I. DuPont has long been recognized as a leader in the safe manufacture and transportation of these fuming sulphuric acids, and was "ahead of the curve" in the design and acquisition of transportation equipment suitable to handle these fuming acids. The transition to the "State-ofthe art" equipment began in 1988, well before the DOT came out with its ruling HM-181. This DOT ruling mandated improved transportation equipment for the "Poison Inhalation Hazard" (PIH) chemicals, which include oleums greater than 30%, sulphur trioxide ([SO.sub.3]) and chlorosulphonic acid (CSA). Some of the additional requirements mandated by HM-181 include heavier walled tanks (both rail car and cargo tanks), rollover protection and the installation of pressure relief valves (not just rupture disks). Each fuming acid has transportation equipment specifically designed for the chemical. DuPont has elected to treat all oleums as PIH's and uses the appropriate equipment for transportation. Oleum and [SO.sub.3] rail cars are constructed to meet DOT 105S300W or 105J500W specifications. The rail cars are constructed of ASTM A516-70 carbon steel and are insulated, with external heating coils. The rail cars also have full head shields. The [SO.sub.3] rail cars are also equipped with an electric heater in the eductor pipe and loading/unloading valves are insulated and electrically traced. A fourpoint thermocouple can be inserted at the customer location to allow continuous monitoring of the temperature of the rail car contents during heating. The CSA rail cars are uninsulated and constructed of stainless steel 316L. All fuming acid rail cars are top-unloading. The oleum cargo tanks meet DOT specification DOT MG-312, rated to 100 pounds per square inch (psi) Maximum Allowable Working Pressure (MAWP). The oleum cargo tanks are made of stainless steel 316L shells (sidewalls and heads) 3/8 in. thick and are insulated. The cargo tanks

are equipped with rollover protection, which meets federal regulations 49 CFR 178.340-8 requirements, and have pressure relief valves in addition to rupture disks. The CSA cargo tanks are similarly constructed, except with no insulation. The [SO.sub.3] cargo tanks have the same safety requirements, plus have an installed submerged pump to unload the contents. The pump is an additional safety factor, allowing the driver/operator to quickly stop the unloading process if a leak in the unloading system should occur. If dry air or nitrogen is used to pressure unload the cargo tank, the pressure must be bled off to a scrubber to prevent a leak in the unloading system, which takes time. The [SO.sub.3] cargo tank is also equipped with external heating coils and connections, which allow the circulation of the tractor engine's heating/cooling glycol system around the cargo tank to keep the [SO.sub.3] warm during transit. All fuming acid cargo tanks are topunloading. Storage Non-fuming and fuming sulphuric acids have many similarities, but they also have some important differences in their behaviour. These differences must be taken into consideration when designing and maintaining storage systems for these acids. The main differences involve the relative vapour pressures, and reaction with atmospheric moisture of non-fuming versus fuming acids. The materials of construction used for storage tanks are similar. Non-fuming sulphuric acid: (70-100%) Non-fuming sulphuric acid storage tanks are usually constructed of carbon (mild) steel (ASTM 516). For design standards DuPont follows API 510, 620, 650 or 653 codes. A very important consideration is to select an experienced and qualified tank designer that is familiar with sulphuric acid tanks. Equally important is to use a qualified tank erector. In general, vertical tanks are preferred over horizontal tanks. Care must be taken to design the tank to minimise hydrogen grooving, a common corrosion effect usually seen in submerged tank nozzles. If iron contamination is a problem, the carbon steel tank can be coated with a baked phenolic lining or can be constructed of stainless steel. The tanks normally vent to the atmosphere and are not pressure vessels. The common 93% acid tanks are not insulated, and the higher strength (96-100%) storage tanks usually are heated externally and insulated, depended on the local weather conditions. Fuming acids -- oleums, [SO.sub.3] and CSA For oleums and [SO.sub.3], the material of construction of choice is carbon steel. CSA can also be stored in carbon steel, but usually for

quality (iron contamination) purposes, stainless steel 316L is used. For oleums [less than]30%, the storage tanks are usually designed as atmospheric tanks. The [less than]30% oleum tanks vent to a demister to eliminate visible vapours. The oleum tanks are usually externally heated and insulated, again depending on local weather conditions. The CSA storage tanks are usually pressure vessels designed to 50-psia rating as a minimum. The recommended material of construction is stainless steel 316L. The tank is also usually vented through a scrubber/demister. CSA has a very low vapour pressure and does not usually emit vapours, but if any should be released from the storage tank they will combine with atmospheric moisture to instantly create hydrochloric and sulphuric acid mists. The CSA tanks are not insulated. Oleums [greater than]30% and [SO.sub.3] are typically stored in pressure rated tanks designed to meet 50-psia MAWP minimum. The tanks are usually carbon steel and vent to a sulphuric acid scrubber/demister to eliminate any [SO.sub.3] vapours emanating from the tank vents. State-of-the art design for an oleum or [SO.sub.3] tank is to place the uninsulated tank inside a "hot-room". The hot-room temperature is controlled at 34-41[degrees]C (95-105[degrees]F). This keeps both the liquid oleum and [SO.sub.3], and the [SO.sub.3] vapours in the storage tanks, from freezing ([SO.sub.3] vapours can freeze at 32[degrees]C). This is preferred over externally heating and insulating the tank, as the entire tank external surface can be seen and inspected at all times. More oleum and [SO.sub.3] tanks have failed from external corrosion than internal corrosion, and so it is important to be able to inspect the external tank shell easily. This aspect is considered part of a good Mechanical Integrity programme. Other regulatory requirements (OSHA, EPA) Oleums [greater than]65% and [SO.sub.3] are covered by the US Occupational Safety and Health Agency's Process (OSHA) Safety Management (PSM) regulations (29 CFR 1910.119). Non-fuming sulphuric acid, oleums less than 65% and CSA are not covered. This regulation, "Process Safety Management of Highly Hazardous Chemicals", mandates that facilities that handle, use or store the covered chemicals above a threshold level of 1000 pounds must have in place a "Prevention Programme" and an "Emergency Response Programme" specifically designed to prevent or minimise the consequences of catastrophic releases of these chemicals. The "Prevention Programme" involves developing and implementing written procedures addressing the following items: * Process Safety Information * Process Hazard Analysis

* Operating Procedures * Training * Mechanical Integrity * Management of Change * Pre-startup Reviews * Compliance Audits * Incident Investigation * Employee Participation * Hot Work Permits * Contractors The "Emergency Response Programme" requires a written plan to deal with on-site emergencies. The US Environmental Protection Agency (EPA) mandates a similar Risk Management Program under the Clean Air Act (CAA) Section (112 (r) (7)). This regulation affects all oleums (threshold level 10,000 pounds) and [SO.sub.3]. It does not affect non-fuming sulphuric acid and CSA. In addition to the requirements of the OSHA PSM programme, the EPA regulations mandate that facilities perform a Hazard Assessment of the off-site consequences of a catastrophic release. The Hazard Assessment includes the development of a "worst-case analysis", an "alternative release scenario" and the documentation of the 5-year accident history of the facility. These documents must be reviewed and updated every three years. Even though CSA is not covered by either of these regulations, DuPont has voluntarily undertaken the task of meeting the OSHA PSM and EPA CAA regulations for CSA handling, use and storage, in order to be consistent in its treatment of hazardous chemicals. It strives to prevent all accidental releases of these chemicals. In summary In dealing with sulphuric acid products, one must be aware of the similarities and differences in transportation, storage and regulation requirements affecting the various grades of nonfuming and fuming sulphuric acids. What is valid for one grade may not be for others. This is especially true with the various grade/strengths of oleum. There are different "cut-off" strengths affecting DOT, OSHA and EPA regulations.

One must be familiar with the numerous regulations to be able to handle, use, store and transport these chemicals properly.
Requirements Oleum Cargo tank specification 312/412 Rail car specification 105S300W [*] Transportation criteria Non-fuming MC-312/412 111A100W [less than]30% MC-

105J500 W [*] Cargo tank unloading Top [*]/bottom Top Rail car unloading Top Top Dome rollover protection No No [*] Rupture disk Yes [**] Yes Pressure relief valve (PRV) No [**] No [*] Pump unloading No [*] No [*] Poison inhalation hazard (PIH) No No [greater than]30% Requirements Oleum [SO.sub.3] Cargo tank specification MC-312/412 MC-312/412 Rail car specification 105S300W 105S300W 105J500W 105J500W Cargo tank unloading Top Top Rail car unloading Top Top Dome rollover protection Yes Yes Rupture disk Yes Yes Pressure relief valve (PRV) Yes Yes Pump unloading No [*] Cargo tank-yes Rail car - no Poison inhalation hazard (PIH) Yes Yes Requirements CSA Cargo tank specification MC-312/412 Rail car specification 105S300W 105J500W Cargo tank unloading Top Rail car unloading Top Dome rollover protection Yes Rupture disk Yes Pressure relief valve (PRV) Yes Pump unloading No [*] Poison inhalation hazard (PIH) Yes (*.)Recommended but not required (**.)DOT-412 Cargo Tanks require self-closing relief devices, not rupture disk assemblies

COPYRIGHT 2000 CRU Publishing Ltd. This material is published under license from the publisher through the Gale Group, Farmington Hills, Michigan. All inquiries regarding rights should be directed to the Gale Group.

Title: Zirconium passes the acid test.(SULPHURIC ACID PICKLING) Date: 5/1/2005; Publication: Sulphur; Author: Sparkowich, Steve Zirconium has proven its outstanding corrosion resistance performance in a wide variety of sulphuric acid steel pickling conditions. Steve Sparkowich, Corrosion Laboratory Manager at ATI Wah Chang, discusses the advantages of zirconium over other metals and reports on the successful use of zirconium heat exchangers in acid recovery systems. ********** Pickling is an economical method of using acid to remove impurities and scale from metals for etching surfaces in preparation for galvanising, painting, etc. (see Fig. 1). Wide variations are possible in the type, strength, and temperature of the acid solutions used. Sulphuric acid in the 5 to 40% concentration range is a common pickling acid for iron and steel. Sulphuric acid pickling tanks are typically heated to a temperature between 60[degrees]C (140[degrees]F) and 93[degrees]C (200[degrees]F) using steam or hot water circulating through a heat exchanger. Compared with non-metallic alternatives, metal heat exchangers, sometimes referred to as steam coils, are generally preferred for heating sulphuric acid pickling solutions because they are: * more compact: For the equivalent heat transfer capability, a metallic immersion heat exchanger will typically be 3-4 times smaller than a thermoplastic (e.g. PTFE) heat exchanger. The smaller size results in more room in the tank for pickling and helps to minimise the potential for damage due to mishandled work. Due to their high efficiency, metallic heat exchangers are usually small enough to be placed on the narrow end of the pickling tank where they will not interfere with the work. * easier to clean: Metal heat exchangers are much more rigid than flouropolymer or graphite units and are more easily cleaned when ferrous sulphate salts build up. * more durable: Metallic heat exchangers have inherently higher strength and toughness than non-metallic materials, such as graphite and thermoplastics, and are less prone to damage during handling and in the harsh conditions of a pickling tank. * easier to work with: Metallic heat exchangers are generally easier to fabricate or repair than alternative materials such as graphite or

thermoplastics. Good ductility and workability allow for standard methods and equipment to be used in fabrication and repair. * compatible with pressurised steam: Metallic heat exchangers are the most practical choice for use with pressured steam. Thermoplastic heat exchangers are generally not rated for higher than 35 psi (2.4 bar) steam pressure. It should be noted that at a steam pressure of 100 psi (6.9 bar), the surface temperature on the heat exchanger can be nearly 170[degrees]C (338[degrees]F). A common error is to select heat exchanger materials based on the solution temperature, which can be as much as 93[degrees]C (200[degrees]F) lower than the skin temperature on the heat exchanger. We recommend that material selection decisions for heat exchangers be based on the maximum temperature of the heating medium. Advantages of zirconium The conditions in sulphuric acid pickling tanks can be very corrosive to most available metallic heat exchanger materials. Stainless steels and other heat exchanger metals generally do not have adequate corrosion resistance in the sulphuric acid ranges used in steel pickling (see Table 1). Zirconium, however, shows superior corrosion resistance in these concentrations and temperatures. The presence of oxidising ferric ion in the pickling solution does not significantly diminish the corrosion resistance of zirconium when the sulphuric acid concentration is less than 50%. For example, when zirconium was tested in 20% [H.sub.2]S[O.sub.4] contaminated with 8% ferric ion ([Fe.sup.3+]) ferric ion at 80[degrees]C, the results showed nil corrosion of the zirconium samples. Zirconium 702 exhibits excellent corrosion resistance in 5 to 65% sulphuric acid up to boiling temperature and beyond as shown on the iso-corrosion curve in Fig. 2. Zirconium heat transfer coils, similar to the one in Fig. 3, have become widely accepted among metal finishers for over 30 years because they provide an efficient and economical means to heat sulphuric acid. Zirconium heat exchangers can be fabricated in virtually any size or configuration, depending upon space limitations and the amount of heat transfer required. Zirconium heat exchangers in acid recovery systems While zirconium does exhibit superior corrosion resistance in most sulphuric acid steel pickling environments, there are a few factors that can limit its effectiveness. The use of sulphuric acid recovery systems (ARS), also known as crystallisers, in metal finishing processes (Fig. 4) has required some precautions be taken when using zirconium heat exchangers. When using an acid recovery system, spent pickle acid is

recycled rather than being discharged, which can cause a build-up of chloride, fluoride, and other solution contaminants. The presence of chlorides may have a detrimental effect on the corrosion resistance of zirconium, particularly when ferric ions are also present. The effect of chlorides on zirconium corrosion in sulphuric acid is seen in Fig. 5. For example, in 15 wt% acid, chlorides should be maintained below 4500 ppm with Figure 6 shows how the presence of small amounts of fluoride ion can dramatically increase the corrosion rate of zirconium. For this reason, it is recommended that the fluoride concentration level be maintained below 10 ppm when using zirconium with levels below 5 ppm being preferred. High chloride and fluoride levels are known to cause corrosion, not only to zirconium, but also to metallic components in contact with the pickle solution, especially the sulphuric acid recovery systems centrifuge parts (e.g. screens, scrolls, baskets, clamping rings, etc.). Elevated chloride levels can cause localised pitting. Elevated fluoride levels cause general surface corrosion, which may cause a gradual thinning of tube diameters. In extreme cases, elevated fluoride levels may cause both general corrosion and pitting. Keeping chloride and fluoride concentrations low is important to avoid costly replacements. Sources for chlorides and fluorides There are several major sources for chlorides and fluorides: * caustic: The most commonly used caustic, diaphragm cell grade, can have up to 10,500 ppm chloride. These chlorides are dragged into the pickle tank with caustic residues. * containment pit water: The choice to pump containment pit water into the acid tank causes high-chloride spillage from the flux and caustic tanks to be put into the acid tanks. The pit must be divided so that the caustic and the caustic rinse will drain into one section, acids and acid rinses into another section, and flux into yet another section. Thus, drainage from these tanks is pumped directly back into the tanks from which it came. * chemicals added to the pickling bath: Inhibitors, accelerators, or fume-control agents may be a source of fluorides and chlorides as well as corrosive bromides and iodides. Some batches of raw sulphuric acid have been found to contain elevated levels of chlorides and fluorides. * chlorinated and/or fluorinated tap water: Evaporation of water from the heated pickle bath causes chlorides and fluorides to concentrate over time.

* 'freshening up': When work from the flux tank is placed in the pickle tank to be 'freshened up', large amounts of chloride are dragged in to the sulphuric acid. In some shops, this has proven to be the major source of chlorides in the pickling tank. Ten tips for success To reduce the potential for corrosion on zirconium heat exchangers or on other metallic components when using an acid recovery system, the following ten preventative measures should be considered: 1. Use a low chloride grade of caustic: The low cost chloride or low salt membrane grade may be about 10 cents/pound higher than diaphragm grade caustic but should have chloride levels that are ~175 times lower (i.e. 60 ppm vs. 10,500 ppm typical chloride levels). 2. Maintain low chloride and fluoride levels in the sulphuric acid pickling bath: Because sulphuric acid recovery systems allow for reuse of sulphuric acid, chlorides and fluorides have been found to accumulate in the pickling solution. Chlorides and fluorides are known to corrode zirconium and most other metals. Elevated chlorides can cause a localised pitting and elevated fluorides can result in general surface corrosion. Refer to Figure 5 for maximum recommended chloride levels for sulphuric acid pickling solutions. Fluoride concentration should be maintained below 10 ppm with levels below 5 ppm being preferred (Fig. 6). This data is based on laboratory analysis using reagent grade chemicals. It should be noted that zirconium heat exchangers in pickling solutions with elevated chloride levels do not always exhibit pitting corrosion. Some organics and other contaminants that build up in pickling solutions over time may have an inhibiting effect on corrosion and reduce the corrosion rate or reduce the potential for the onset of localised pitting corrosion. The limits in Fig. 5, however, are considered to be a conservative approach. For existing zirconium heat exchanger installations where chloride levels are high and no corrosion is evident, chloride levels should at least be stabilised. Preferably, they should be reduced to levels below the limits in Fig. 5. If chloride levels are allowed to rise, localised pitting corrosion may eventually occur. 3. Check chloride and fluoride levels in the acid tanks, rinse tanks, and caustic tank on a routine basis: Representative acid samples may be properly packaged and sent to a laboratory for analysis. The ATI Wah Chang Analytical Laboratory provides chloride, fluoride, and other inorganic chemical analysis services. If the chloride and fluoride levels are known, corrective measures can be instituted before corrosion problems occur. 4. Understand chloride and fluoride levels of all additives prior to use in pickling baths: This includes sulphuric acid, inhibitors, accelerators, fume control agents, caustic, and even water. Softened water can have high levels of chlorides. Municipal water may have chlorides and/or

fluorides. If any additives are found to have high chloride or fluoride, reasonable alternatives should be considered. 5. Consider chemical cleaning of zirconium heat exchangers: As a precaution, consider chemical cleaning of newly fabricated zirconium heat exchangers in a mixture of nitric acid-hydrofluoric acid. Chemical cleaning will remove embedded particles or surface contaminants rendering the zirconium more resistant to corrosion. Chemical cleaning also improves the surface finish, which may reduce the crystallisation of ferrous sulphate monohydrate salts. Chemical cleaning of zirconium should be performed in at least a 10:1 ratio of nitric acid to hydrofluoric acid to minimise the potential for hydrogen absorption. Because of the hazardous nature of hydrofluoric acid, a properly equipped facility should be used to perform the chemical cleaning. 6. The heat exchangers must include a second concentric zirconium tube of larger diameter at the acid/air interface of the riser pipes: This outer tube section is known as a solution level protector, air cover, or air baffle as shown on the inlet and outlet pipes of Fig. 3C. Solution level protectors are especially important when high-pressure steam (e.g. 100 psi) is used as the heating medium. Acid residues on the pipe just above the solution level will concentrate to very corrosive levels due to evaporation of water. Solution level protectors provide an extra layer of protection to this vulnerable area of the heat exchanger as well as give a visual indication of corrosion as shown in Fig. 7. Solution level protectors should be as long as possible, perhaps 20-30 cm or more, to account for the evaporative cycle of the tank. Solution level protectors should be inspected periodically to prevent heat exchanger leakage. 7. Mount heat exchangers so that the coils are always immersed: Evaporation of the pickling solution during off-shift and other downtimes may cause the solution to drop to a level that exposes the heating coils to air. Acid residues on the exposed coils will then concentrate to very corrosive levels as they dry, similar to the phenomenon described in Tip 6. 8. Insulate heat exchangers from stray currents: Stray electrical currents can reach a heat exchanger via piping, tanks walls, hangers, or other metal objects. Because corrosion is an electrochemical process, metallic heat exchangers need to be electrically isolated from contact with other metals. To eliminate the potential of stray currents, a piece of pressure hose or a dielectric union should be placed between the heat exchanger fittings and the water/steam line. Consider using a PTFE insulator as shown in Fig. 8. Also, insulate metal hangers that support the heat exchanger from contact with other metal objects. 9. Avoid grey coloured "monohydrate" crystal build-up on the coils: Build-up of ferrous sulphate monohydrate crystals is usually lower when using hot water heating versus high pressure steam heating.

Techniques that have been used to minimise crystal build-up on the heat exchanger include: a) Maintaining a smooth surface on the heat exchanger, b) Bubbling or sparging of air beneath the heat exchanger c) Keeping the bath at a temperature where ferrous sulphate monohydrate is most soluble (i.e. 140-150[degrees]F) If crystal build-up occurs, do not damage the surface of the zirconium by scraping, scratching, or marring when trying to remove the salts. These actions may embed iron particles or other contaminants that reduce the corrosion resistance of zirconium. Non-contact techniques such as soaking in hot water, pressure washing, or steam cleaning may be employed. Do not sandblast zirconium heat exchangers to remove crystal build-up or for any other reason. Sandblasting media may embed foreign particles in the surface that increase the potential for corrosion. 10. Protect the heat exchanger from damage using a barrier or shield: The heat exchanger should be protected to prevent it from being damaged. Consider having zirconium angle welded to the side of the unit as a shield. Other possible shielding materials include plastisolcoated steel, some grades of fibreglass, thermally stable plastics, or even hardwood. These ten tips will greatly increase the likelihood of success in using zirconium heat exchangers, especially when using an acid recovery system.
Table 1: Corrosion rate (mils/yr) of zirconium vs other alloys in sulphuric acid solutions Concentration 10% 55% Concentration 10% 30% 40% 55% Temp 216[degrees]F/102[degrees]C 270[degrees]F/132[degrees]C 316L SS 574 >500 >10,000 Alloy B-2 20 2 1.89 Zr702 310LSS

28,000 0.1 >100,000

Alloy C276 55 295

Reference Sparkowich, S.: "Tips for success: Zirconium heat exchangers in sulphuric acid pickling processes", OUTLOOK (A Wah Chang/ATI publication), Vol. 25, No. 2, Second Quarter 2004.

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