Fertilizer Technology

Ammonia 1. Non Catalytic Partial Oxidation : Refer Outline of Chemical Technology- Dryden
Chapter : Fuel and Industrial Gases.

2. Steam hydrocarbon reforming : Refer Outline of Chemical Technology- Dryden

Chapter : Fuel and Industrial Gases.

3. Catalytic Partial Oxidation for manufacturing synthesis gas :

Air and steam are used to produce a synthesis gas from natural gas by a combination of partial oxidation and steam reforming. The catalytic air-blown partial oxidation (CAPO) reactor is a single pressure vessel containing two reaction stages. Shift conversion is used to convert the CO content of the synthesis gas to CO2 which is then captured in an amine -based scrubbing system. Syngas reactor A wide range of technologies are in common use for the production of synthesis gases. Syngas can be produced in a steam-methane reformer, this is the method by which most hydrogen is made commercially; air/oxygen is not required. The other main process option is partial oxidation in which oxygen is one of the reactants. There are many hybrids of these two basic reaction routes such as for example, autothermal reforming, one variant of which is used as the reference process in this study. It is generally agreed that steam-methane reforming of natural gas is cheaper than oxygenblown partial oxidation. Partial oxidation using oxygen is preferred for production of synthesis gases if the feedstock is heavier than natural gas, or if a high CO:H2 ratio is required. If partial oxidation with air can be used, it appears to be less expensive than steam-methane reforming. The use of advanced synthesis gas technology, i.e. a two-stage reactor system involving a gasheated reformer (GHR), is assessed in some detail. A gas-heated reformer gives a significant gain in the efficiency of synthesis gas generation. The reactor consists of a refractory-lined vessel having an inlet conical combustion zone, in which combustionlpartial oxidation reactions take place, and a lower cylindrical volume containing a nickel-based reforming catalyst, in which the reforming reaction mainly occurs and the reactants reach equilibrium.

Air vs. Oxygen The use of oxygen (i.e. absence of nitrogen) limits the sensible heat carried out of the reactor by the syngas product. However, steam has to be added to an oxygen-blown partial oxidation unit to moderate the temperature. In an air-blown CAPO unit the nitrogen acts as a Chemical Engineering Department 1

Fertilizer Technology temperature moderator. At lower temperatures, less sensible heat is contained in the syngas and it is more likely that an air-blown configuration will show advantages. Shift conversion The shift conversion reaction is exothermic. A two-stage shift system, as in the reference design, enables a high conversion to be achieved and most of the heat to be recovered at a high temperature. The efficiency of the plant is increased if this heat is used to pre-heat the fuel gas before it enters the gas turbine. A detailed design is needed to optimise capital expenditure on heat recovery against the reduced cost of power obtained through the increased efficiency. There are various proprietary versions of this technology the development of which is largely based on ammonia plant technology introduced by ICI in the late 1980s. It usually involves the hot synthesis gas produced in one reactor being used to provide heat for reforming reactions in another reactor(UHDE have developed a version of this process where both stages take place in a single vessel). CO2 capture CO2 capture using a physical solvent is not likely to be cost-effective unless the operating pressure is increased significantly. This is because the presence of N2 in the syngas reduces the partial pressure of CO2. Available solvent would be based on methyl di-ethanolamine (MDEA) which is generally described as a physio-chemical solvent(physical and chemical absorption take place). M/s Lurgi and M/s Ammonia Casale Catalytic Partial Oxidation process : Both have jointly designed large scale Ammonia Plant with the production capacities 1.4 million metric tons of ammonia/year. The process comprises of five principal units: 1. Air Separation Unit (ASU) 2. Catalytic Partial Oxidation Unit (CPox) 3. CO-Shift Unit 4. Gas Purification Unit 5. Ammonia Synthesis Unit

M/s Lurgi and M/s Ammonia Casale Catalytic Partial Oxidation process In an ASU the pure Oxygen produced (95% oxygen) is used in the Auto thermal Reformer and a stream of 99.99% pure nitrogen for use in the Gas Purification Unit.

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Fertilizer Technology In the Catalytic Partial Oxidation Unit, feedstock natural gas is preheated and desulphrised in the conventional manner over a cobalt molybdenum catalyst followed by zinc oxide. The desulphrised gas is then saturated using condensate recycled from the CO-Shift Unit, preheated in a fired heater and pre-reformed over a nickel oxide catalyst so as to convert all higher hydrocarbons to hydrogen and methane. Steam is added to the pre-reformed gas to adjust the steam to carbon ration. The gas is further preheated in the fired heater, and then reformed to CO, H2 and CO2 in the CPox reactor by partial oxidation with oxygen. The absence of a pressure limiting steam reformer makes it feasible to raise the pressure of the CPox Reactor to 60 bars. Within the CO-shift unit, the reformed gas is passed over two beds in series of conventional HT catalyst to convert the remaining CO to H 2 and CO2. Gas purification is accomplished in two wash columns, the first removing CO2 and the 2nd removing the remaining impurities i.e. CO, CH4 and Argon. CO2 is removed by absorption in cold methanol, CO, CH4 and Ar are removed by washing the Gas with liquid nitrogen. Pure synthesis gas comprising H2 and N2 is passed to the Ammonia synthesis unit which is of conventional design. The extremely high purity of the ammonia synthesis gas results in higher conversion of gas per pass, lower circulator duty and lower refrigeration duty. This technology has got following major features: It will reduce the capital cost by approx 18-20% which will offset the perceived risk of investing in a new technology. The operating cost with this technology is expected to be lower by around 12-15% over the most advanced conventional technologies available. It has the potential for greater environmental friendliness than the conventional ammonia process. The CO2 emission is expected to reduce by around 30% with this technology as compared to other conventional technologies.

4. Ammonia manufacturing processes : Soon after the first world war development started
also in other countries, partly on basis of BASFs pioneering work. Lurgi Casale built 1920 the first plant in Italy, and based on developments by M. G. Claude the first French plant started to produce in 1922. Both the Casale and the Claude process operated under extreme high pressure. In contrast to this Uhde constructed a plant based on coke oven gas, operating under extreme low pressure(Mont Cenis process). Futher developments were by G. Fauser who worked together with Montecatini. During the 1920s several plants were built in the USA, some based on European some on American Technology. The successful US company was Nitrogen Engineering Corporation(NEC), the predecessor of Chemico. The principal manufacturing process that are used for synthetic ammonia production are steam water gas process, the steam hydrocarbon process, the coke oven gas process & electrolysis of water. Much research work is still diverted to find cheaper manufacturing methods. Many new plants use ethanol amine to remove carbon dioxide from gas streams instead of high pressure water. Nitrogen required for synthesis gas is obtained usual from an air liquefaction plant. In water gas and natural gas process, nitrogen is obtained in same manufacturing process as hydrogen. Air is added in secondary reformer of natural gas process and reacts with carbon monoxide to furnish carbon dioxide and nitrogen. Cost is greatly influenced by the pressure, temperature, catalysts and raw material used. Raw material selection depends upon the availability and cost of raw material. If the plant is near some refinery then raw material can be naphtha, natural gas or LPG, but in case it is near a coal mine, one should depend on coal as raw material for hydrogen. There may be some other cases where electricity is readily available to meet the requirements for electrolysis then hydrogen can be obtained by electrolysis of water Comparsion of processes : Many variation of the original Haber process for the synthesis of ammonia are now used in commercial practice, some varying to such an extent that they are identified by a name, often that of group of men developing them. Important among these are modified Haber Chemical Engineering Department 3

Fertilizer Technology Bosch, Claude, Casale, Fauser, and Mont Cenis processes. All of them are fundamentally the same in that nitrogen is fixed with hydrogen as ammonia in the presence of a catalyst , but have variation in arrangement and construction of equipment , composition of catalyst, temperature and pressure used. Table C gives a condensed comparison of different processes. Claude process gives 40% conversion of the gas upon passes through a single converter and 85% conversion after passes through a series of converter.

Modified Haber- Bosch Process : The ammonia concentration in the circulation gas leaving the catalyst is 10-11 mole %. In the condenser the ammonia concentration is reduced by condensation to equilibrium at the exit temperature of the condenser. The condensed ammonia is separated from the circulating gas, and the gas is boosted in pressure by a circulating compressor to overcome the pressure drop in the synthesis loop. The Claude Process : This process depart from the Haber process more than any of the other ammonia syntheses process, the residual gas is wasted to the atmosphere or utilized for its heat content. The large amount of heat evolved in operating at space velocities of 100,000 with as much as 40 % of the hydrogen nitrogen mixture converted to ammonia in one pass, called for a special converter design. In his original process, Claude used the liquefaction of air. Among advantages claimed for the Claude process are the following: 1. Greater compactness, simplicity, and ease of construction of the converter, since under the high pressure used the gases have smaller volume. 2. Elimination of the expensive heat exchangers required in processes operated at lower pressure. 3. Removal of ammonia with water cooling alone, rather than by ammonia refrigerators or scrubbing processes. Cited against these advantages are the shorter life of converters, high apparatus upkeep in the highpressure operation, and the efficiency loss in wasting approximately 20% of the makeup gas, which is unconverted. Modifications of the Claude process include recycling of the gas through the synthesis converters. Chemical Engineering Department 4

Fertilizer Technology The Casale Process : Pressure of 500-900 atm are used in this process which is otherwise distinguished by the method used for controlling catalyst temperature in the specially designed converter. A method involving recirculating gas around a synthesis loop, similar to the Haber process, is used. As in the Claude process, the higher pressures allow liquefaction of the ammonia at temperatures that can be attained by water cooling. The basis for heat control of the catalyst is to leave 2 or 3% ammonia in the gas to the converter, thereby slowing down the rate of formation of ammonia and eliminating excessive heating of the catalyst. The Fauser Process : This pressure incorporates some features not previously mentioned. Electrolytic hydrogen from Fauser cells and nitrogen from liquid air unit or from a purification unit utilizing tail gases from absorption towers in the ammonia oxidation plant are used. The mixture of hydrogen and nitrogen is compressed to 200-300 atm and, after passing through an oil separator goes to an oxygen burner. In the oxygen burner any oxygen contained in the gas mixture combines with hydrogen in the presence of a copper catalyst the water formed is condensed out in a cooler and removed in a water separator. The Mont Cenis Process : This process was originally developed to use hydrogen separated from coke oven gas by a liquefaction process, and nitrogen was obtained by the liquefaction of the air. The essential characteristics of the Mont Cenis process are its operating pressure of 100 atm or less. Mixed hydrogen and nitrogen, after being compressed to 100 atm and heated to about 3000C in interchangers, passes through a carbon monoxide purifier. In the purifier, while in contact with a nickel catalyst, carbon monoxide and oxygen contained in small quantities in the gas react with hydrogen to form methane and water. Ammonia processes of engineering contractors. Process Claude Casale Fauser NEC Uhde-Mont Cenis Start of Pilot research plant 1917 1916 1920 1915 1916 1920 1920 1921 X 1926 Industrial Licensing company Country plant 1921 1921 1923 1926 1928 Grande Paroisse Ammonia Casale Montecatini ASED Hydro Nitro Gasverarbeitungsgesellschaft (GAVEG) France Switzerland Italy Belgium Switzerland Germany Established 1919 1921 1925* 1926 1928 ca. 1926

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Fertilizer Technology Block diagram of ammonia production

Naphtha obtained from the distillation of petroleum crude is used as the source of hydrogen which acts as reactant for the production of ammonia. One mole of Ammonia requires one mole of nitrogen and three mole of hydrogen as per stoichiometry equation. Natural gas is the better option for hydrogen source and advantages over the naphtha process as most of the unit operations are reduced getting down the installation and production cost. Process description: The ammonia synthesis process is shown by the simple block diagram in series of steps as follows 1. Naphtha gas supply: Naphtha is used as feed stock and fuel for Ammonia plant and is supplied at offsite Gas Metering station at a pressure of 44kg/cm2g. After metering at offsite, the naphtha gas for process feed is directly received at Ammonia plant battery limit at 40kg/cm 2g and 40oC. Fuel gas is used for burners of feedstock preheater, primary Reformer, Auxiliary super heater and start up heater in Ammonia plant-Feed gas goes to the Desulphurization unit for sulphur removal, if any and subsequently processed to produce synthesis gas for Ammonia production. 2. Desulphurization: Raw naphtha contains high sulphur which harms the catalyst in the reforming reactor and even consumes hydrogen by undesired side reactions. A packed bed reactor is utilized for the removal of sulphur. Zinc oxide based bed absorbs the sulphur. 3. Primary reformer: Naphtha contains carbon and hydrogen compounds to separate hydrogen all the carbon is converted to carbon dioxide and hydrogen by means of steam at high temperature with the presences of nickel based catalyst. 4. Secondary reformer : Nitrogen required for the synthesis reaction is obtained from air so, the carbon dioxide and hydrogen stream is mixed with the air. 5. Shift conversion: carbon monoxide which is formed in the previous process is converted to carbon dioxide by using steam which results shift reaction producing hydrogen. High and low shift reactors are arranged for this conversion process 6. CO2 removal: All the carbon dioxide produced is removed by the absorption process. Absorption and stripping towers recover the most of the gas which is used in the urea production. 7. Methanation: The traces of carbon dioxide and carbon monoxide are converted to methane by means of hydrogen on the catalyst like nickel in methanation reactor. Heat is produced due to exothermic reaction. 8. Ammonia synthesis reactor : Iron acts as the catalyst at temperature 400oC and pressure 142 kg/cm2g the reaction proceeds for the formation of ammonia. Chemical Engineering Department 6

Fertilizer Technology 9. Chilling system: A compression absorption refrigeration system is used for liquefaction of ammonia. At 1 atm the boiling point of ammonia is -33oC. Process Design Modifications in Ammonia Production : Ever evolving technologies are been adopted by the modern industries to improve the conversion rate with efficiency and less energy consumption for complete process, some of the competitive designed techniques are give and much more are to be introduced. Process Pressure atm Temperature 0C Conversion % Mont Cenis 120 400 8-20 Stami Carbon 310 500 10-30 Fauster-Montecatini 220-230 500 10-30 Casale 500-700 500 15-25 Claude 330-630 540-590 15-25 Haber Bosch 330 500-550 10-30 Nitrogen Eng.Corp 200-300 500-550 10-30 Lummus 270-330 500-510 10-25 Kellogg 300-350 --10-30 Du Pont 900-1000 500-600 40-80 5. Ammonia : Claude process : We can compile the process description from the pages 3 to 7 and from the description of Claude converter on page 11. Claude process gives 40% conversion of the gas upon passes through a single converter and 85% conversion after passes through a series of converter. 6. Foster-dhala Casale process : No clue about this process after extensive search on I-net and available books. 7. M. W. Kellog Process : Refer Chemical Process Industries Shreve Chapter : Nitrogen Industries

8. Fauser Montecatini process :

Two other important ammonia synthesis processes were developed in the 1920s. Giacomo Fauser, an Italian consulting engineer, built a small pilot unit in 1921. He interested Montecatini in his process, an Italian firm established in 1888 to exploit a copper mine but that had entered the chemical industry in the 1910s and that pursued further expansion. Montecatini built the first Fauser ammonia plant and started it in 1923. Montecatini built several more in Italy in the 1920s but in 1925 also decided to license the Fauser process. The company licensed directly, and established the SA Ammoniaque Synthtique et Drivs (ASED) in Brussels in 1926. Evence Coppe, a large engineering contractor in the field of coke oven plants and related installations, was the second major shareholder of ASED. Montecatini and Coppe intended ASED to manufacture nitrogen fertilisers in Belgium, and to engineer and construct Fauser ammonia plants. In 1920 there was no chemical industry in Italy with the exception of Societ Generale per lIndustria Mineraria ed Agricola Montecatini, where Giacomo Fauser, a genial engineer and partner in the company, successfully started a small 4-kg/h ammonia production pilot plant in Novara. The Montecatini activity greatly contributed to the growth of the agriculture industry in Italy, providing fertilizers produced by its Italian factories. Only after the second world war was Montecatini ammonia technology licensed abroad.

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Fertilizer Technology

Fauser Montecatini Process 9. Ammonia Converters : All Ammonia converters are described in the book Chemical Technology- By Shukla and Pande

Udhe converter :
The demand for energy-efficient ammonia production dictates the following criteria for the design of the ammonia synthesis unit: High conversion rates and therefore large catalyst volume. Maximum utilisation of reaction heat for the generation of high-pressure steam. Low pressure drop in the loop. Such criteria, in turn, call for the: Use of small grain-size catalyst. Application of the radial-flow principle. High-pressure steam generation wherever feasible. The Uhde ammonia synthesis design therefore incorporates three radial-type catalyst beds arranged in either one or two ammonia converters. Features of the single-converter design : Heat exchanger between catalyst beds for indirect cooling of synthesis gas; consequently, highlyefficient temperature control. Radial flow from outside to inside through all catalyst beds. Design adaptable to full-bore or drawn-in top closure of converter, depending on project constraints. Heat exchangers extractable without removal of cartridge. An externally-arranged BFW preheater/HP steam boiler downstream of the third bed.

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Fertilizer Technology

Three-bed ammonia converter, radial flow Features of the two-converter design: Location of the first two catalyst beds in the first converter vessel and of the third bed in the second converter vessel. Radial flow from outside to inside through all catalyst beds. Simple U-tube heat exchanger between first and second catalyst beds for indirect cooling of the synthesis gas. For maximum reliability and cost-effectiveness Uhde therefore uses only well-proven magnetitebased catalysts in all three beds. The first of the three beds will typically be filled with prereduced catalyst to accelerate the initial start-up. Depending on the site-specific and project-specific conditions, the three catalyst beds are arranged in either one or two ammonia reactors. Chemical Engineering Department 9

Fertilizer Technology Uhde has always advocated three-bed reactors with high ammonia conversion rates per pass. Therefore, the Uhde ammonia synthesis unit is based on a three-bed reactor system, each bed with a radial flow. A high-conversion synthesis loop offers considerable advantages since the recycle gas quantity is considerably reduced and, consequently, power requirements for the circulator are lower and heat exchanger surfaces smaller. Refrigeration requirements also decrease over proportionately because most of the ammonia produced is condensed upstream of the loop chiller. Studies on innovative high-activity precious-metalbased catalysts have revealed that no economic advantage can be gained through their use in view of the uncertainty of future prices for the precious metals required. Furthermore, due to the different physical properties operational problems can be expected. Designs with one ammonia reactor and one waste heat boiler cannot optimally exploit the reaction heat for the generation of high-pressure steam. However, optimum heat recovery can be achieved if an additional waste heat boiler is introduced between the second and third bed. H2/N2 ratio, at methanation exit 2.95 Synthesis Loop pressure bar 140 - 210 NH3 reactor inlet vol./o 3-5 NH3 reactor outlet vol./o 20 -25 HP steam generation Per mol NH3 1.1 - 1.5 Number of reactors 1 or 2

TVA converter : Tubular converters have cooling tubes within the catalyst bed through which the
cooling medium, usually cooler feed gas, flows co-currently or counter-currently to the gas flow in the catalyst bed. Alternatively the catalyst can be placed within tubes with the cooling medium flowing on the outside. The tube cooled converters dominated until the early fifties, but are largely outdated today. Well known examples were the TVA converter(counter-current) and the NEC/Chemico design (co-current, with best approximation to the maximum rate curve)

TVA converter

Ammonia Converters-General Introduction : In the multi-bed converters the catalyst volume is divided into several beds in which the reaction proceeds adiabatically. Between the individual catalyst layers heat is removed either by injection of colder synthesis gas (quench converters) or by indirect cooling with synthesis gas or via boiler feed water heating or steam raising (indirectly cooled multi-bed converter). In the quench converters only a fraction of the recycle gas enters the first catalyst layer at about 400 C. The catalyst volume of the bed is chosen so that the gas will leave it at around 500 C. Before entering the next catalyst bed, the gas temperature is quenched by injection of cooler (125 200 C)
Chemical Engineering Department 10

Fertilizer Technology recycle gas. The same thing is done at subsequent beds. In this way the reaction profile describes a zig-zag path around the maximum reaction rate line. A schematic drawing of a quench converter together with its temperature/location and temperature/ammonia concentration profile is presented in figure. The catalyst beds may be separated by grids designed as mixing devices for main gas flow and quench gas(cold shot). A disadvantage is that not all of the recycle gas will pass over the whole catalyst volume with the consequence that a considerable amount of the ammonia formation occurs at higher ammonia concentration and therefore at reduced reaction rate. This means that a larger catalyst volume will be needed compared to an indirect cooled multi-bed converter. On the other hand, no extra space is required for inter-bed heat exchangers, so that the total volume will remain about the same as for the indirect cooled variant. As the quench concept was well suited for large capacity converters it had a triumphant success in the early generation of large single stream ammonia plants constructed in the 1960s and 1970s. Mechanical simplicity and very good temperature control contributed to the widespread acceptance. Multibed converters with indirect cooling In converters of this category the cooling between the individual beds is effected by indirect heat exchange with a cooling medium, which may be cooler synthesis gas and/or boiler feed water warming and steam raising. The heat exchanger may be installed together with the catalyst beds inside one single pressure shell but an attractive alternative, too, preferentially for large capacities, is to accommodate the individual catalyst beds in separate vessels and have separate heat exchangers. This approach is especially chosen when using the reaction heat for raising high pressure steam. The indirect cooling principle is applied today in almost all large new ammonia plants, and also in revamps an increasing number of quench converters are modified to the indirect cooling mode. Claude converter : Figure below shows an ammonia reactor that is 1.2 m in diameter and 7 m high, and operates at 1000 atm pressure, hence the gases are not ideal. An ammonia plant is comprised of a sequence of reactors. Each reactor product discharges into a cooling and condensing process from which liquid ammonia is removed. Some of the unreacted gas is fed back to the start of the reactor, and the rest is passed on to the next reactor in sequence. Entering gas contains some inert components, mainly argon and methane, that do not react, and at the end of the process have to be purged from the system. Every effort is made in the design of the overall plant to keep the ratio of the hydrogen to the nitrogen at 3 to 1 at the entrance of the reactor. Various types of catalyst have been developed to enhance the fraction conversion of the H2/N2 to NH3 on flow through the reactor.

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Fertilizer Technology

Modern converter : Today each new world-size ammonia plant employs the indirect

cooling concept raising high pressure steam up to 125 bar. Generally after the first bed an inlet - outlet heatexchanger is placed and after the second or further beds the reaction heat is used to raise high pressure steam. Brown and Root (formerly C. F. Braun) or Uhde accommodate the catalyst in several vessels. Actually the concept of separate vessels for the catalyst beds, with heat exchange after the first and waste heat boiler after second(nowadays they use also a third one followed by a boiler, too) was already introduced by C. F. Braun at time when most plants still used quench converters. The Ammonia Casale ACAR Converter has a mixed flow pattern. In each catalyst layer the gas flows through the top zone predominantly axially but traverses the lower part in radial direction. This simplifies the design by avoiding special sealing of the top end of the bed to prevent by-passing. 10. Storage and transfer equipment : Liquefied ammonia from production plants is either used directly in downstream plants or transferred to storage tanks. From these the ammonia can be transferred to road tankers, rail tank cars or ships. Ammonia is usually stored by using one or other of three methods:Fully refrigerated storage in large tanks with a typical capacity of 10,000 to 30,000 tonnes (up to 50,000) Pressurised storage spheres or cylinders up to about 1,700 tonnes Semi-refrigerated tanks Chemical Engineering Department 12

Fertilizer Technology Emissions during normal operation are negligible. Major leaks of ammonia from storage tanks are almost unknown with most of the leaks which do occur being during transport or transfer. A well designed, constructed, operated and maintained installation has a very low probability of an ammonia leak of hazardous proportions. However, even though the residual risk is small, the effects of a major leak on areas of high population density could be very serious. It is therefore good practice to build ammonia storage and handling installations at a sufficient distance from domestic housing, schools, hospitals or any area where substantial numbers of people may assemble. In some countries there are planning procedures or regulations which control the siting of ammonia storage installations and similar establishments. Where there are no formal controls, the siting of ammonia storage facilities should be given serious consideration at the design stage.It is undesirable for ammonia storage tanks to be sited close to installations where there is a risk of fire or explosion, since these could increase the possibility of a release of ammonia. Storage Tanks Anhydrous ammonia is stored in three types of tank as outlined above: Fully refrigerated at a temperature of about 33C, these tanks are provided with refrigeration equipment Non-refrigerated tanks in which the ammonia is stored at ambient temperature Semi-refrigerated spheres Refrigerated storage is preferred for storage of large quantities of liquid ammonia. The initial release of ammonia in the case of a line or tank failure is much slower than with pressurised ammonia. There are several construction types for the storage of refrigerated liquid products. The most important types are :Single containment : a single-wall insulated tank, normally with a containment bund around it Double containment : this type of storage tank has two vertical walls, both of which are designed to contain the stored amount of liquid and withstand the hydrostatic pressure of the liquid. The roof rests on the inner wall. Full containment: the two walls of this closed storage tank are also designed to contain the stored amount of liquid, but in this case the roof rests on the outer wall. The tank must be constructed in conformity with an agreed code for the construction of pressure vessels or storage tanks and taking account of its pressure and operating temperature. The design and materials of construction of the tank should be checked by consulting an appropriate national, or recognised international, standard. These could make demands on the blast resistance of storage tanks in some cases. The storage tank must be safeguarded against high pressure and in the case of refrigerated liquid ammonia also against a pressure below the minimum design pressure. The ingress of warm ammonia into cold ammonia must be avoided to eliminate risk of excessive evaporation and the "roll-over" phenomenon. All storage tanks should be equipped with two independent level indicators, each having a high level alarm. An automatic cut-off valve, operated by a very high level alarm instrument, should be installed on the feeding line. In cases of refrigerated liquid ammonia, storage tanks must be equipped with a recompression installation to liquefy the boil-off. There should be at least two refrigeration units to allow proper maintenance and to prevent the emission of ammonia via the relief valves. Furthermore, an installed alternative power supply may be necessary. An automatic discharge system to a flare may be provided in case of failure of the refrigeration equipment. The flare must be located at a suitable distance from the tanks. Relief valves should be provided, appropriate for the duty using an adequate margin between operating and relief pressure. Transfer Equipment Liquid or gas pipelines should be fitted with isolation valves. The main isolation valves should be backed up by remotely operated valves. The remote systems should be of such a type that closure is automatic in case of a power failure. Liquid ammonia has a high thermal coefficient of expansion and, therefore, some means of safe venting should be provided on pipelines in which any significant quantity can be trapped between valves, etc. Chemical Engineering Department 13

Fertilizer Technology Liquid ammonia pipelines should be fitted with remotely operated valves at suitable intervals to minimise the loss in the event of a line failure. Ammonia is transported in road tankers, rail tank cars (both pressurised) and ships (pressurised or refrigerated). Railroad and road loading Loading and unloading of rail tank cars and road tankers is usually done by loading arms. During (un)loading both the liquid supply and vapour return lines must be connected to the transport medium. The ammonia vapours can be transferred during (un)loading to a storage tank, an ammonia vapour network of the site or to a scrubber/absorber, to prevent emissions to the atmosphere. Before disconnection of equipment after (un)loading the liquid ammonia in these parts must be removed to one of the reservoirs. Preferably, this should be done by using a pressurised inert gas such as nitrogen or ammonia vapour. If inert gas is used, attention should be paid to avoid getting inert gas into tankers and storage tanks. There should be a scrubbing system or a flare in the event of venting inert gas. A weigh check must be carried out after the loading, to ensure that the maximum allowable content has not been exceeded. Modern road and rail car loading stations are equipped with a safeguard against overfilling. Ships Loading and unloading of ships is only permitted at sites which are authorised for this purpose. During (un)loading a minimum safety distance to other ships must always be maintained around the ship (eg. 30m). Both liquid and vapour return lines should be present for import and export terminals. A vapour return line is not necessary when the ship has sufficient refrigeration capacity or for the import of ammonia only. Both liquid and vapour connections must be equipped with isolation valves as near to the ship as possible. It must be possible to close these valves quickly under all conditions and the connection between tank and liquid line must be equipped with an isolation valve. The ends of loading and unloading arms should be equipped with dry break couplings. The isolation valves must be closed automatically, when these couplings are disconnected or when the (un)loading arms are too far out of position. After each loading-unloading operation, liquid ammonia contained within loading arms must be collected in a suitable evaporation tank connected to the storage tank through the vapour line. Loading arms are then purged by inert gas or ammonia vapour. If inert gas is used, attention should be paid to avoid getting the inert gas into tankers and storage tanks. There should be a scrubbing system or flare in case the inert gas has to be vented.

Nitric Acid 11. Nitric Acid : Atmospheric pressure ammonia oxidation : From the description below 12. Nitric Acid : Pressure ammonia oxidation or High pressure process : Refer Chemical
Process Industries Shreve Chapter : Nitrogen Industries 13. Nitric Acid : Intermediate pressure ammonia oxidation : Refer Outline of Chemical Technology- Dryden Chapter : Nitrogen Industries Montcatini Intermidiate pressure process To understand and describe above processes go through following writeup : All plants for the production of nitric acid are currently based on the same basic chemical operations: Oxidation of ammonia with air to give nitric oxide - Oxidation of the nitric oxide to nitrogen dioxide and absorption in water to give a solution of nitric acid. The efficiency of the first step is favoured by low pressure whereas that of the second is favoured by high pressure. These considerations, combined with economic reasons give rise to two types of nitric acid plant, single pressure plants and dual pressure plants. In the single pressure plant, the oxidation and absorption steps take place at essentially the same pressure. In dual pressure plants absorption takes place at a higher pressure than the oxidation stage. The oxidation and absorption steps can be classified as: Low pressure process/Atmospheric pressure process (pressure below 1.7bar) Chemical Engineering Department 14

Fertilizer Technology Medium pressure or Intermediate pressure process (pressure between 1.7 and 6.5bar) High pressure process (pressure between 6.5 and 13bar) Except for some very old plants, single pressure plants operate at medium or high pressure and dual pressure plants operate at medium pressure for the oxidation stage and high pressure for the absorption. The main unit operations involved in the nitric acid process are the same for all types of plant and in sequential order these are: Air filtration Air compression Air/ammonia mixing Air/ammonia oxidation over catalytic gauzes Energy recovery by steam generation and/or gas re-heating Gas cooling Gas compression, energy recovery and cooling (dual pressure plants only) Absorption, with the production of nitric acid Waste gas (tail gas) heating Energy recovery by expansion of the waste gas to atmosphere, in a gas turbine The typical plants described will be limited to the single pressure plant and to the dual pressure, medium pressure/high pressure plant, as the absorption is always based on medium or high pressures. The fertilizer industry uses weak nitric acid in the range of 50 to 65% strength and thus the high concentration (above 70% weight) nitric acid production process is not included. Processes used by the Fertilizer Industry Dual pressure processes: Low pressure/Medium pressure (oldest plant) Medium pressure/High pressure (newest plant) Single pressure processes: Medium pressure/Medium pressure High pressure/High pressure The typical capacity of the newest plants is 1,000td-1. Process Basis Ammonia is reacted with air on platinum/rhodium alloy catalysts in the oxidation section of nitric acid plants. Nitric oxide and water are formed in this process according to the main equation:4NH3 + 5O2 4NO + 6H2O (1) Simultaneously nitrous oxide, nitrogen and water are formed as well, in accordance with the following equations:4NH3 + 3O2 2N2 + 6H2O (2) 4NH3 + 4O2 2N2O + 6H2O (3) The yield of nitric oxide depends on pressure and temperature as indicated in the table. Pressure (bar) Temperature (C) NO yield (%) below 1.7 810 - 850 97 1.7 to 6.5 850 900 96 above 6.5 900 - 940 95 The catalyst typically consists of several woven or knitted gauzes formed from wire containing about 90% platinum alloyed with rhodium for greater strength and sometimes containing palladium. Air pollution and contamination from the ammonia can poison the catalyst. This effect, as well as poor ammonia-air mixing and poor gas distribution across the catalyst, may reduce the yield by 10%. Some of the platinum and rhodium vaporises during the reaction process and in most cases a platinum recovery system is installed below the catalyst. In this system a palladium alloy, known as a getter or catchment, allows a 60 to 80% recovery of the total catalyst losses. The enthalpy of the hot reaction gases is used to produce steam and/or to preheat the waste gas (tail gas). The heated waste gas is discharged to the atmosphere through a gas turbine for energy recovery. The combustion gas after this Chemical Engineering Department 15

Fertilizer Technology heat transfer for energy recovery, has a temperature of 100 to 200C, depending on the process and it is then further cooled with water. The water produced in reactions (1) to (3) is then condensed in a cooler-condenser and transferred to the absorption column. Nitric oxide is oxidised to nitrogen dioxide as the combustion gases are cooled, according to the equation:2NO + O2 2NO2 (4) For this purpose, secondary air is added to the gas mixture obtained from the ammonia oxidation to increase the oxygen content to such a level that the waste gas leaving the plant has a normal oxygen content of between 2 and 4% by volume. The absorber is operated with a counter-current flow of water. The absorption of the nitrogen dioxide and its reaction to nitric acid and nitric oxide take place simultaneously in the gaseous and liquid phases according to equations (4) and (5). These reactions depend on pressure and temperature to a large extent and are favoured by higher pressure and lower temperature. 3NO2 + H2O 2HNO3 + NO (5) Reaction (5) is exothermic and continuous cooling is therefore required within the absorber. As the conversion of NO to NO2 is favoured by low temperature, this reaction will take place significantly until the gases leave the absorption column. The nitric acid produced in the absorber contains dissolved nitrogen oxides and is then bleached by the secondary air. Medium Pressure(Intermediate), Single Pressure Plants A typical plant is represented in the block diagram and includes:Ammonia evaporation section Liquid ammonia from storage is evaporated using water or condensates and superheated to prevent any liquid carry-over. Ammonia filtration section Gaseous ammonia is filtered to remove any rust from carbon steel equipment. Some plants also use a magnetic filter on the liquid ammonia. Air filtration section High purity air is obtained by using two or three stage filtration. In some plants there is additional filtration of the air/ammonia mixture. Air compression section An air compressor is driven by a tail gas expander and by a steam condensing turbine. Mixing section Modern plants use static mixers to give the high quality mixture which is essential to maintain good catalyst operation. Catalytic reactor section The catalytic reactor is designed to give a uniform distribution of the air/ammonia mixture over the catalyst gauzes. Maintenance of the catalyst operating temperature is very important for the NO yield. This is achieved by adjusting the air/ammonia ratio and ensuring that the lower explosive limit for ammonia in air is not exceeded. Heat recovery sections The catalytic reactor is typically mounted as the upper part of a vessel which contains the first heat recovery section (steam superheater and steam generator). A set of gas/gas heat exchangers transfers the energy from the gas leaving the boiler set, to the tail gas. Cooling section A cooler condenser ensures final cooling down to 50C after the final heat recovery. Weak acid solution is formed and is separated and pumped to the absorption tower.

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Nitric Acid Production Single Pressure Plant Absorption section The modern absorber design uses counter-current flow circulation with high efficiency trays which are usually sieve trays or bubble cap trays. The tray spacing increases progressively from the bottom to the top of the absorber. Many of the trays are fitted with internal cooling coils to remove the heat of reaction. The absorption section consists of one or more columns in series. Demineralised water or steam condensate is added at the top of the tower as make-up. Process condensate from the manufacture of ammonium nitrate may be used after acidification. The acid solution leaving the absorption section is rich in dissolved nitrogen oxides and is passed to a bleaching tower where it is contacted with a counter-current flow of secondary air. The secondary air and the nitrogen oxides which have been stripped out are mixed with the gases leaving the cooling section and are recycled to the absorption section. The gas leaving the absorption section is commonly known as tail gas. Expander section The tail gas from the absorber is passed through the heat recovery and the expander sections for energy recovery and is then passed to the stack. Chemical Engineering Department 17

Fertilizer Technology Steam turbine section The expander generates insufficient energy to drive the air compressor. A steam turbine using part of the superheated steam generated in the plant makes up the deficiency. The steam turbine is also used for plant start-up. In some plants the energy make-up comes from an electric motor and the generated steam is exported. Dual Pressure Plants A typical plant is represented in the block diagram in Figure . It is similar to the single pressure plant as far as the cooling section. After the cooling section the plant layout is as follows:NOx compression section In dual pressure plants the gases leaving the cooling section are mixed with the air and nitrogen oxides from the bleaching of the acid solution and compressed to a higher pressure for the absorption stage. The heat of compression is removed from the compressed gases by heat recovery into the tail gas or the boiler feed water. Cooling section A second cooler condenser reduces the temperature of the gases to about 50C and the acid solution formed is mixed with the product acid. Absorption section The acid solution from the absorption section is passed to a column working at the pressure of the air compressor discharge, where it is stripped of the nitrogen oxides by a flow of air from the air compressor. The air and the stripped nitrogen oxides return to the NOx gas compressor. High Pressure, Single Pressure Plants A typical high pressure, single pressure plant is similar in layout to the medium pressure single pressure plant. The process parameters differ because of the higher operating pressure. The main differences are: A higher operating catalyst temperature and pressure with a lower NO yield and a greater loss of catalyst A higher inlet pressure to the gas expander allowing a higher inlet temperature and thus more energy recovered in the expander and a smaller steam turbine A higher operating pressure in the absorber with a lower tail gas NOx content

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Nitric Acid Production Dual Pressure Plant

Urea 14. The once through process : Process Operating Variables

Reactions: 2NH3+ CO2 H2NCOONH4 H2NCOONH4 H2NCONH2 + H2O Rate of Carbamate decomposition reaction increases with temperature. It is slow at < 150oC (NH3:CO2 stoichiometric) and quite rapid at 210oC. 180-210 oC in 0.3 to 1.0 hr is optimum for most process. Chemical Engineering Department 19

Fertilizer Technology At high temperature, corrosion rate is high. Pressure: Preferred pressure is 140 250 atm. Mole ratio of NH3: CO2. Excess ammonia above the stoichiometric ratio favors the rate of reaction. (3:1 = NH3: CO2) Other factors: The presence of water decreases conversion. The presence of small amount of O2, decreases corrosion. Maximize the production of urea per unit time with due regard to cost of recycling unreacted NH3 and CO2, the cost increase of reactor size, corrosion difficulties. Typical Operating Conditions: T: 180 210oC NH3:CO2 mole ratio = 3.1 - 4.1 P: 140 250 atm Retention time: 20-30 min

The once through process

15. Urea : Ammonia Partial recycle process :

Part of the off gas is recycled back to the reactor. The amount of ammonia is reduced to 15% to that of once through that must be used in other processes. Investment cost is somewhat lower than the total recycle process, this advantage apparently does not compensate the inflexibility arising from the necessity to operate a co-product plant with mutual interdependency problems.

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Partial Recycle process( Mitsui Toatsu ) Urea : Solution recycle process : Refer Outline of Chemical Technology- Dryden Chapter : Nitrogen Industries Montcatini solution recycle process :

16. Total recycle process :

Total Recycle Processes: All unconverted NH3 and CO2 is recycled back to the reactor (99% conversion). No nitrogen co-product is necessary. Most flexible urea process as it depends only on NH3 and CO2 supply. Most expensive in investment and operating cost. Classification of Total recycle Processes: Reactor outlet contains UREA, NH3, CO2, H2O, and CARBAMATE which must be decomposed before recycle. (1) Carbamate Decomposition Processes

Hot gas mixture recycle Separated gas recycle Slurry recycle Carbamate - solution recycle Stripping

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Block Diagram : Carbamate Decomposition Process The general design objectives of Carbamate Decomposition Process are: Maximize the heat recovery Minimize the amount of carbamate solution recycled (smaller pumps and less power) and amount of water returned to the reactor (better conversion). Minimize power requirement Maximize ammonia recovery (lowering operating cost and less pollution) Other important requirement is of-course minimizing investment. The problem is finding the best balance between the utility consumption and maintenance on one hand and investment on the other hand. Three major design considerations: To separate the urea from other constituents, To recover excess NH3 and Decompose the carbamate for recycle. (2) Stripping Process In 1966 Stamicarbon of Netherland introduced CO2 stripping Snamprogetti built a plant using NH3 as stripping process (requires high NH3:CO2 ratio) later switched to thermal stripping Toyo Engineering Corporation (TEC) Japan utilized CO2 stripping. Three licensors have different approaches and have improved their technology throughout the years. Closely stoichiometric amount of raw material consumption Reduced steam consumption to an apparently economic level Chemical Engineering Department 22

Fertilizer Technology Avenues available for improvements in reduction of capital cost, improved reliability and efficiency of mechanical improvements and advances in metallurgical advances. Modern stripping Processes: Snamprogetti, Stamicarbon, ACES

Total Recycle Urea process TVA plant ( Mitsui Toatsu )

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Stamicarbon CO2 Stripping process Snamprogetti process Six section Synthesis and high pressure (HP) recovery (160 bar) Medium pressure (MP) purification and recovery (17 bar) Low pressure (LP) purification and recovery (3.5 bar) Vacuum concentration (2 steps: 0.3 and 0.03 bar abs) Process condensate treatment Finishing: prilling and granulation

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Snamprogetti thermal stripping Urea Process ACES plant (UFFL) ACES is operating Five section Synthesis sections Purification section Concentration and prilling section Recovery section Process condensate treatment section

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The ACES Process

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Urea processes Operating Conditions

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17. Nitrogenous fertilizers :

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