Gasoline components Motor fuel alkylation

Alkylate was found to have excellent aviation gasoline properties. It was the highest octane fuel component then known, with high motor octane and excellent lead response. All of the properties derive from the highly-branched paraffins that form its composition. Humble Oil built the first commercial H2SO4 alkylation unit in 1938 at Baytown, Texas.3 Alkylation for aviation gasoline grew rapidly with the Allies war effort. In 1939, six petroleum companies formed a consortium to pool their alkylation technology and develop both sulfuric acid and HF acid processes for 100 octane aviation fuel. The first commercial HF alkylation unit started up in 1942. During the war 60 alkylation units were built for the Allies war effort. Half were built with sulfuric acid as the catalyst and half with HF. Licensors of motor fuelHFAlkylation processes areUOPLLC and Phillips. Licensors of H2SO4 alkylation processes are Exxon Mobil and Stratco Engineering.

Process chemistry The reactions taking place in the alkylation reactor are many and relatively complex. First the olefin reacts with the acid to form an ester; then the ester is alkylated by a t-butyl carbenium ion chain mechanism.4 The principal overall reactions are described below. Primary alkylation reactions Most of the alkylate product is made by primary alkylation reactions. In these reactions one mole of olefin reacts with one mole of isobutane to form an isoparaffin exactly 4 carbon numbers heavier. Example primary alkylation reactions, showing only the carbon framework and one or two of the principal product isomers, are shown for each of the principal feed olefins in equations (1.1)(1.5). ALKYLATION cis-Butene-2 + Isobutane 2,2,4-Trimethylpentane (1.1) (100 RON) Butene-1 + Isobutane 2,3-Dimethylhexane (1.2) (71 .3 RON) Butene-1 + Isobutane2,3,4-Trimethylpentane (1.3) (102 .7 RON) Isobutylene + Isobutane 2,2,4-Trimethylpentane (1.4) (100 RON) Propylene + Isobutane2,3-Dimethylpentane (1.5) (91 .1 RON) 2-methylbutene-2 + Isobutane 2,2,4-Trimethylhexane (1.6) (92 RON)

Feed pretreatment In the UOP HF alkylation process olefin-rich feeds from the FCC gas plant are typically deethanized, Merox treated to remove H2S and mercaptans and dried. Some refiners have also added MTBE or Selective Hydrogenation (SHP) plants upstream the alkyl. Reaction After pretreatment, the olefin feeds are combined with a large excess of recycle isobutane to provide an 614 isobutane:olefin molar ratio and injected into the circulating HF acid catalyst at the shell side inlet to the water-cooled reactor. Cooling water flows through the reactor tubes to remove the highly exothermic heat of reaction and to maintain reaction conditions at 80100F. The alkylation reaction is very fast with 100% olefin conversion. The excess isobutane, alkylate product, non-reactive hydrocarbons (propane, n-butane) in the feeds and the acid catalyst pass on to the settler vessel. The dense acid phase separates from the hydrocarbons rapidly by gravity and is then pumped back to the reactor. The hydrocarbons containing dissolved HF flow off the top of the settler to the isostripper.

Fractionation It consists of an isostripper, a depropanizer, and an HF Stripper. The isostripper is a large tower with two sidedraws with the primary function recycling isobutane to support the high isobutane:olefin molar ratio of the reactor. The tower typically has two reboilers; the upper reboiler typically maximizes the use of relatively lowcost low or medium pressure steam and the lower reboiler uses a heating medium that can give 400450F process temperatures. Alkylate is drawn off the bottom of the tower, cooled in exchangers, and sent to product storage. The next product draw up the tower is the n-butane sidedrawand above that is the isobutane recycle draw.On mostUOPunits the isobutane draw is located below the feed tray tominimize HF in the isobutane recycle The isostripper overhead vapor is a propane-enriched isobutane stream and HF which is condensed and separated into settling drum. The HF phase is pumped back to the reactor section. The HF saturated hydrocarbon phase is charged to the depropanizer.

The depropanizer and its associated HF stripper remove propane from the isobutane recycle. The depropanizer bottoms is returned to the reactors as part of the recycle isobutane. The depropanizer overhead containing the propane product and HF are condensed and separated in the overhead receiver. The acid phase is returned to the reactor section and the acid-saturated propane is stripped free of acid in the HF Stripper column. The HF stripper bottoms is an acid-free propane product which is treated with hot alumina to remove organic fluorides, cooled and treated with KOH pellets to remove traces of HF and water.

Acid regeneration A key advantage of HF alkylation over sulfuric is the ability to recover the acid from the byproduct polymer, water, and other contaminants. In the UOP HF Alkylation Process, a small stream of circulating acid is stripped with superheated isobutane in a small monel tower called the Acid Regenerator. The regenerator overhead is HF and isobutane that are recycled to the reactor; the regenerator bottoms is polymer and the HFwater azeotrope which are neutralized with aqueous KOH. The neutralized polymer has good fuel value. The amount of polymer produced is generally only 1 to 2 barrels per 1,000 barrels of alkylate product. KOH regeneration The UOP process minimizes chemical costs by regenerating the KOH used to treat products and allwaste and stormwater. ThisKOHregeneration is accomplished using lime. As the lime is mixed into the KOH, regeneration of the KOH takes place by the following reaction: 2KF + Ca(OH)2 2KOH + CaF2 The calcium fluoride forms a precipitate and can be easily separated from the regenerated KOH.

Process variables in HF alkylation Key variables are reactor temperature, isobutane to olefin molar ratio, acid strength, and acid to hydrocarbon volume ratio. Reaction temperature is one of the more important process variables as it has a significant influence on the octane number of the product. Almost all HF alkylation reactors are operated below 100F. At higher temperatures a decrease in alkylate octane number will occur. Above 120F polymerization and cracking side reactions become excessive reducing alkylate quality. In many cases, acid regeneration capacity of the HF alkylation unit would not be able to maintain proper control of the acid strength at temperatures above 110F. Extremely lowreaction temperatures may cause incomplete alkylation. Thus reaction temperatures below 80F are typically not used.

Acid strength is usually kept between 85 and 95 mass% HF. Maintenance of this strength level results from a balance between the performance of the unit feed treating systems for sulfur and water removal and acid regeneration operation. In some cases oxygenate removal systems or diene removal systems are also used on the feed where there are known to be high oxygenates (such as downstream of an MTBE unit, or high diolefins (from severe FCC conditions). The action of the acid on reactions is a complex phenomenon and is dependent on the type as well as the amount of diluents. The fresh acid is supplied by acid manufacturers at 99.0+ wt% HF. This purity is too high for optimum performance of the HF alkylation process. As the water content of the circulating acid increases, carbon steel that is not attacked by anhydrous HF, becomes less resistant to acid attack. The acid to hydrocarbon volume ratio used in the reactor of the UOP process is generally around 1:1. At some point below 0.81, excess polymerization occurs. In the most extreme cases, alkylate production could stop.

HF feed contaminants As with many refining processes, the control of contaminants coming into the unit with the normal feedstocks is critical to the long and dependable operation of the HF alkylation unit. Above the recommended maximum levels of feed stock contaminants, acid consumption, acid regeneration requirements, and in some cases unit corrosion and product quality are all measurably affected. Generally all contaminants are kept as low as possible within the capabilities of the feed treating systems. The major feed contaminants normally found in alkylation feeds are water or oxygenates, sulfur compounds, nitrogen compounds, non-condensibles, and diolefin.

HF alkylation maintenance Because HF is highly corrosive to most materials, careful control and maintenance of equipment metallurgy and condition is required. Carbon steel is the primary material used for vessels and piping and it can be used only because of a corrosion barrier layer of iron fluoride that forms on any carbon steel surface exposed to HF. The iron fluoride layer is tenacious and serves as a barrier against further carbon steel corrosion as long as the deposit remains undisturbed. Under certain conditions, such as when wet acid is in the unit, this iron fluoride scale can soften and break off leading to fouling and corrosion issues. In severe cases this can lead to considerable unscheduled feed outages as well as clear safety issues. Most refiners aggressively monitor their equipments remaining corrosion allowance and use regularly scheduled valve and flange replacement to head off any problems. For maintenance during an FCC turnaround, the normal time most alkylation turnarounds are maintained, many refiners choose to dissolve all the iron fluoride scale by using a chemical cleaning company.

Safe handling MEA is transported by road or rail tanker in its concentrated form. It is transferred in the normal way to an onsite storage bullet, which is blanketed by an inert gas. MEA is degraded on exposure to air. The use of this, and other enthanolamines, in the refinery processes is in a dilute form. This dilution and its onsite storage is very often in a suitably constructed pit usually in the proximity of the user plant. In some cases, a cone roof tank may be used for onsite storage. In all cases, though, the product must be kept free from exposure to air by inert gas blanketing. The dilution of MEA for use in the refinery process is between 15 and 20 wt%. The water for this dilution is usually treated boiler feed water, which is essentially free of impurities.

Sulfuric acid alkylation Today there are two processes for H2SO4 alkylation the Cascade process licensed by Exxon Mobil and MW Kellogg and the Stratco effluent refrigerated process. Figure 9.1.3 shows the cascade alkylation process.

Sulfuric acid consumption and regeneration Sulfuric acid alkylation uses about 100 times as much acid as HF alkylation because H2SO4 cannot be stripped from the conjunct polymer, water, and contaminants. Sulfuric acid is typically spent at 8891 wt% H2SO4, below which it is too weak to carryout alkylation. The spent acid is not a waste. It is regenerated by burning the organics which reduces the H2SO4 to SO2 and water vapor. The SO2 is then dried and oxidized to SO3 and scrubbed with water to produce 98.599.5% H2SO4. For sulfuric alkylation, aside from the direct hazards of contacting the acid, there are transportation safety issues around the need to ship and regenerate 20 500 tons of H2SO4 daily. Several refiners have built dedicated acid plants to regenerate spent acid from the alkylation unit or pipelines to and from an acid manufacturer. Acid consumption is generally expressed as the pounds of acid diluted from 99% to 90% by conjunct polymer, water, and other contaminants per gallon or barrel of alkylate. Consumption can be as low as 16 lbs per barrel alkylate for diene-free, MTBE raffinates run at ideal process conditions. Acid consumption can exceed 40 lb/ bbl of alkylate when running high levels of isobutylene, pentenes, and propylene at high temperatures.

H2SO4 contaminants Dienes Butadiene and pentadienes are a major contaminants affecting acid consumption. Dienes and can account for 1030% of the acid consumed. Dienes can dilute 520 lbs of 99% acid down to 90% per lb of diene. Some refiners use diolefin selective hydrogenation units (such as UOP-Huls SHP) to eliminate this source of acid consumption. Water and oxygenates Water can also account for 1020% of acid consumption. Wet feeds, wet isobutane recycle, and high reactor temperatures are the main sources. Oxygenates including acetone from the FCC, methanol and dimethyl ether from MTBE and TAME units also consume acid. Water and oxygenates dilute 10 lbs of 99% acid to 90 per lb of contaminant.

Sulfur and nitrogen compounds Dilute about 20 lbs of 99% acid to 90% per lb of sulfur or nitrogen. C6+ Dilutes 2 lbs of 99% acid to 90% per lb of contaminant. This can be a significant contributor to acid consumption when alkylating pentenes. Ethylene Dilutes 20 lbs of 99% acid to 90% per lb of contaminant by forming stable sulfates that stay in the acid. Ethane and lighter While inert, light ends increase compressor discharge pressure for total condensation. These indirectly increase acid consumptionwhen limited by horsepower by increasing reactor temperature.

Recent developments Motor fuel alkylation has recently received a boost from the planned phase-out of MTBE in gasoline blending formulations. Without MTBE, the best conventional components for todays reformulated gasolines are high octane paraffinic components like alkylate. While environmental legislation has increased demand for alkylate, its catalysts H2SO4 and HF came under intense environmental scrutiny in recent years. While both acids are corrosive and toxic, HF is especially hazardous since it has the potential to form toxic aerosols, which can travel significant distances downwind of an accidental release. This scrutiny challenged the petroleum industry to enhance safety and even to seek new alkylation catalysts. UOP-Texaco and Mobil-Phillips developed cosolvents called Alkad and Revap , respectively, to reduce HF aerosoling. A consortium of refiners and HF manufacturers lead by Amoco developed HF dispersion models and water spray mitigation with extensive, large-scale testing to design of release control systems. Together, cosolvents and water spray mitigation can reduce downwind HF concentrations by over 95% should a release occur.

Through the American Petroleum Institute, the industry developed a comprehensive document for safe operation of HF alkylation units entitled Recommended Practice for Safe Operation of Hydrofluoric Acid Alkylation Units, API Recommended Practice 751, first published in June, 1992 and reissued in February, 1999. Finally the efforts to find new catalysts for alkylation have yielded solid catalyst processes such as UOPs Alkylene process that are ready for commercialization. Conclusions Motor fuel alkylation using liquid hydrofluoric or sulfuric acids is one of the oldest catalytic processes used in refining and petrochemical operations. The liquid acid processes remain important despite concerns with safety and environmental properties of the liquid acids. Solid catalyst alkylation using processes such as Alkylene (UOP LLC) are emerging technology.

Anhydrous hydrofluoric acid Because of anhydrous hydrofluoric acid s (AHFs) highly toxic and corrosive nature, this item is included to highlight its characteristics and the safe handling of the acid. Anhydrous hydrofluoric acid is a colorless, mobile liquid which boils at 67F at atmospheric pressure, and therefore requires pressure containers. The acid is also hygroscopic therefore its vapor combines with the moisture of air to form fumes. This tendency to fume provides users with a built-in detector of leaks in AHF storage and transfer equipment. On the other hand, care is needed to avoid accidental spillage of water into tanks containing AHF. AHF vapor, even at very low concentrations in air, has a sharp penetrating odor that is an effective deterrent to willful overexposure by operating personnel. Both the vapor and liquid forms of AHF cause severe and painful burns on contact with the skin, eyes, or mucous membranes.

Hydrofluoric acid is very corrosive. It attacks glass, concrete, and some metals especially cast iron and alloys which contain silica (e.g., Bessemer steels). The acid also attacks such organic materials as leather, natural rubber, and wood, but does not promote their combustion. Although AHF is non-flammable, its corrosive action on metals, particularly in the presence of moisture, can result in hydrogen forming in containers and piping to create a fire and explosion hazard. Potential sources of ignition (sparks and flames) should be excluded from areas around equipment containing hydrofluoric acid. Despite its corrosive nature, AHF can be handled with relative safety if the hazards are recognized and the necessary precautions taken. This item describes certain procedures for the safe handling of large bulk quantities of AHF.

Safe handling The safe handling of AHF requires thatwell-designed equipment be properly operated and maintained by well-trained, adequately protected, responsible personnel. Tanks and other containers of AHF should be protected from heat and the direct rays of the sun. Storage-area temperatures should preferably remain below 100F. If they reach or exceed 125F, means for cooling the containers must be applied. Acid-transfer lines between the unloading station and the storage tank should tilt toward the latter to insure free drainage. Relief valves should be installed in those sections of acid-transfer lineswhere acid may be entrapped between two closed valves in the line, because expansion of the liquid might create excessive pressure and rupture the line. Noopen fires, open lights, or matches should be allowed in or around acid containers or lines. The possibility of acid acting on metal to produce hydrogen gas is ever present. Only non-sparking tools and spark-proof electrical equipment should be used in the AHF storage and handling areas.

Personal protective equipment Personal protective equipment is not a substitute for good, safe working conditions. Its purpose is to protect the wearer in the event of an accidentmajor or minor. The extent of protection needed depends upon the degree of exposure attending the particular job at hand. Protective equipment should not be worn or carried beyond the operating area. It should be thoroughly washed with sodium bicarbonate solution immediately after each use. The minimum protection required for operating and maintenance personnel includes the following items: Coveralls with sleeves to the wrists Face shield or chemical safety goggles Hard hat Poly(vinyl chloride)or neoprene-dipped gauntlets Poly(vinyl chloride)or neoprene-soled rubber shoes When taking acid samples, opening equipment which may contain hydrofluoric acid, or performing similar hazardous duties, operators should wear the following: Poly(vinyl chloride) or neoprene overalls Poly(vinyl chloride) or neoprene boots Lightweight poly(vinyl chloride) or neoprene gloves under poly(vinyl chloride)or neoprene-dipped gauntlets

Unloading and transfer of AHF AHF is shipped in rail tank cars having capacities ranging from approximately 5,400 gallons to 25,000 gallons and in road tank trucks of approximately 5,250 gallons AHF capacity. Compressed dry gas (air, hydrocarbon, or nitrogen) is the preferred means for transferring bulk quantities of AHF, but a centrifugal, rotary or positive-pressure pump can be used if necessary. The unloading of AHF tank cars or tank trucks, with transfer of the acid to plant storage, consists of five steps: (1) Spotting the tank car or tank truck at the unloading station. (2) Connecting the plant compressed-gas (or vapor) and AHF-unloading lines to the proper valves on the carrier tank. (3) Transferring the AHF from the carrier tank to the storage tank. (4) Disconnecting the plant compressed-gas (or vapor) and AHF-unloading lines from the carrier tank valves. (5) Releasing the tank car or tank truck for return to the shipper.