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Alkylation

Alkylation involves the reaction of low molecular weight olefins (primarily butylenes and sometimes propylene) with isobutane to form a gasoline range isoparaffin. Butylene is the preferred olefin because it produces higher octane products, but the feed choice largely depends on outside factors and availability. The light olefins used for the feed typically come from an [[FCC]] or [[Delayed Coking|coker]] unit. This feed usually contains significant amounts of sulfur so a pretreating unit is necessary. The isobutane is fed from such sources as a [[Olefins Plant]], [[Hydrocracking|hydrocracker]], [[Isomerization]] unit, or [[Catalytic Reforming]] unit. The alkylate product is good for use as gasoline blendstock because it is free of both olefins and aromatics, has a low sulfur content, has a high octane number, and has low vapor pressure. Polymerization was first used to achieve similar results (reacting LPG range olefins to produce gasoline product), but very few polymerization plants still exist because alkylation generates more gasoline blendstock with higher octane. The goal of this process is to achieve a product that is within the gasoline boiling range and has a MON (Motor Octane Number) from 88 to 94 and a RON (Research Octane Number) from 94 to 99. Process Chemistry Alkylation is essentially the formation of a higher molecular weight isoparaffin, called alkylate, by the reaction of lower molecular weight olefins with isobutane. The primary alkylation reaction products, along with their corresponding MON, RON, and RVP (Reid Vapor Pressure) values are shown below. Isoheptane: C3= + iC4 iC7 Isooctane: C4= + iC4 iC8 Isononane: C5= + iC4 iC9 RON 88 96 88 MON 87 94 87 RVP (psi) 3.8 2.6 4.0

Secondary reactions also occur during alkylation. If an adequate amount of isobutane is not present, the olefins will polymerize. In the absence of olefins, isoparaffins in contact with acid will disproportionate to give a lower and a higher molecular weight isoparaffin than the original. Larger isoalkyl cations will also crack to produce smaller cations and olefins. These and other secondary reactions are given below. Polymerization: 2 C3H6 C6H12 Hydrogen Transfer: C5H10 + 2 iC4H10 C5H12 + C8H18 Disproportionation: 2 C8H18 C7H16 +C9H20 Cracking: C12H26 C7H14 + C5H12 Process Description There are three main alkylation processes, each determined by the catalyst used. The options are a sulfuric acid (H2SO4), hydrofluoric acid (HF), or solid acid catalyst, with sulfuric acid being the most popular and widely used.

There are five main sections in a hydrofluoric acid alkylation plant: Reaction Refrigeration Effluent Treating (acid separation) Fractionation Blowdown In comparison to sulfuric acid alkylate, alkylate produced from hydrofluoric alkylation tends to be of lower quality. The required operating temperature for the reaction varies with catalyst type. Sulfuric acid units require refrigeration to reach sub-ambient temperatures while HF units operate at cooling water temperatures. Methods used for effluent treating also vary for each process technology. A block flow diagram for the sulfuric acid alkylation process is shown below.

Figure 1. Sulfuric Acid Alkylation Block Flow Diagram The main sections for a hydrofluoric acid alkylation plant include: Reaction Catalyst Regeneration Additive Recovery Fractionation Alkylate Water Wash A general block flow diagram for the hydrofluoric acid alkylation process is shown in Figure 2.

Figure 2. Hydrofluoric Acid Alkylation Block Flow Diagram Reaction The olefin is fed into the reactor along with recycled and fresh isobutane. The olefin feed stream is typically pretreated to remove sulfur components that cause increases in acid consumption and corrosion of process equipment. In the HF process, the feed is also dried by removing water. Refrigeration The heat of reaction in sulfuric acid alkylation is removed in the refrigeration part of the plant. Hydrocarbon vapors from the reactor are compressed, condensed, flashed, purged of light ends (propane and lighter), and returned to the reactor. Some of the refrigerant condensate is sent to a depropanizer for the removal of propane that may have been introduced in the feed. The remaining condensate is flashed across a control valve and recycled back to the reactor. The feed to the depropanizer must be caustic and water washed to remove sulfur bearing contaminants that will cause corrosion in downstream equipment. The reaction temperature is controlled by changes in pressure in the suction trap. Typical reaction temperatures range from 45 to 65F. Lowering the suction trap pressure decreases the bubble point of the refrigerant and, therefore, lowers the reaction temperature. An economizer and partial condenser may be added to the refrigeration section to improve plant efficiency and lower costs depending on the given specifications for the plant. An economizer system typically results in about 7% in compressor horsepower savings. A partial condenser separates the refrigerant (primarily isobutane) from lighter ends upstream of the depropanizer, concentrating the propane in the depropanizer feed, so this is most cost effective when unit feeds are high in propane. Effluent Treating in Sulfuric Acid Units The effluent from the reactor contains traces of acid and both neutral and acid sulfate esters, which can cause corrosion in downstream equipment. Low olefin space velocities (olefin volumetric rate / acid volume in contractor) minimize the amount of ester formation and increase the octane number of the product. There are different routes for treating the effluent, but each follows a similar procedure. An acid separator or acid settler system separates the acid from the hydrocarbons and recycles the acid back to the reactor. The hydrocarbons then proceed to a wash to decompose or neutralize any remaining acidic components. Older systems start with a caustic wash, which is followed by a water wash to eliminate the caustic. Newer systems contain an acid wash coalescer, alkaline water wash, and water wash coalescer. Other effluent treating processes include bauxite treating with an acid wash coalescer. Fractionation A typical fractionation train for sulfuric acid alkylation consists of a deisobutanizer, debutanizer, and depentanizer (if necessary). The isobutane recovered from the fractionators is recycled back to the feed. The octane value of the final product is dependent on the recycle isobutane to olefin feed ratio. After the butane (and pentane) product is drawn off from its respective column in the sulfuric acid alkylation system, the alkylate product remains. Because it does not contain a refrigeration section equipped with a depropanizer, the fractionation section for a hydrofluoric acid alkylation system will also contain a depropanizer along with a deisobutanizer and debutanizer. In the hydrofluoric acid alkylation process, the butane and propane are sent to further treatment processes, such as a caustic wash or KOH treater, to remove any trace acid. Alkylate is cooled and routed to an additive recovery unit followed by a water wash section. Additive Recovery

Blowdown A blowdown section is typically included to process refinery wastewater and spent acid from the process. This area of the plant is typically customized based on the design criteria of the client and local regulations. See [[Wastewater Treatment]]. Acidic blowdown vapors are sent to a blowdown drum to remove any remaining liquid acid and are then scrubbed with caustic before being routed to the flare system. Spent acid is either regenerated onsite or sent to storage so that it can be shipped out and regenerated externally. Hydrocarbon blowdown is sent directly to the refinerys flare system. Regeneration In the sulfuric acid alkylation plant, the regeneration of the catalyst is typically done offsite, but regeneration for a hydrofluoric alkylation plant is instead implemented onsite. An acid slipstream from the acid separation step is sent to the regeneration section, where isobutane is superheated so that it can be used as a stripping medium. Acid soluble oils are removed and neutralized while clear HF is recycled back to the reactor. Process Variables Isobutane Concentration A higher iC4 to Olefin ratio increases the octane but also increases equipment and utility costs. A lower ratio is not ideal because it favors polymerization and increases acid consumption. Olefin space velocity (the inverse of residence time in the reactor) This is defined as the volume of olefin charges per hour divided by the average volume of acid in the contactor reactor. Low space velocities, lower operating temperatures, and higher spent acid strength all increase octane. Low space velocities also reduce ester formation. Mixing Good mixing in the reactors is important to ensure an acid continuous emulsion for sulfuric acid catalyst technologies. These process variables are discussed for each type of catalyst technology below. Sulfuric Acid Alkylation Isobutane Concentration 5:1 to 10:1 (iC4 to Olefin molar ratio) -1 Olefin Space Velocity 0.1 to 0.5 hr Temperature 40 to 50F Acid in Emulsion (to settler) 60 wt% Spent Acid Strength 90 to 92 wt% H2SO4 Hydrofluoric Acid Alkylation Isobutane Concentration 5:1 to 15:1 (iC4 to Olefin molar ratio) Reactor Contact Time 5 to 25 min Temperature 70 to 100F Acid Strength 83 to 92 wt% HF Onsite Acid Regeneration Solid Catalyst Alkylation Isobutane Concentration 8:1 to 15:1 (iC4 to Olefin molar ratio) Temperature 120 to 195F No acid soluble oils created No product treatment required Some technologies do not require feed pretreatment A key process difference between sulfuric acid and hydrofluoric acid alkylation systems is the presence of acid regeneration within hydrofluoric acid unit. The acid is regenerated outside of the unit in sulfuric acid alkylation. Another principal difference between the two technologies is the

operating temperature. Sulfuric acid alkylation requires refrigeration while hydrofluoric acid alkylation can operate at cooling water temperatures. Configuration Options Technology Options The main sulfuric acid alkylation process in commercial use is the STRATCO effluent refrigerated reactor process. ExxonMobils autorefrigerated stirred reactor process and CDTECHs (now part of Lummus Technology) autorefrigerated packed reactor process known as CDAlky are less implemented but available processes. The specifications for the STRATCO design technology is listed below. STRATCO Effluent Refrigerated Reactor Multiple reactors required 2,000 to 3,500 bpsd (barrels per stream day) alkylate per reactor High space velocity (possible acid ester formation) Pressure 45 to 60 psig Temperature 45 to 60F UOP licenses one of the main hydrofluoric acid alkylation processes in commercial use today. The reactor system and the means for removing the heat of reaction are different for each licensed technology. The UOP reactor system utilizes large volumes of cooling water to maintain reaction temperature and remove the heat of reaction, and pumps are used to circulate the acid. For solid catalyst alkylation, there are several technologies available for license, but they have yet to be commercialized. Design Considerations Sulfuric Acid Safety Sulfuric acid can destroy body tissue, cause serious burns, and cause blindness if it were to come into contact with eyes. Acid can corrode equipment, potentially releasing LPG (liquefied petroleum gas) into the atmosphere where it is a fire and explosion danger. A major benefit of using H2SO4 is that it will not form large acid clouds like hydrofluoric acid will if released. Hydrofluoric Acid Safety Hydrofluoric acid is a hazardous air pollutant and at ambient temperatures, is a toxic, volatile gas. Contact with this acid can cause chemical burns and even dissolution of the bone if it is not treated. Inhalation of hydrofluoric acid can result in pulmonary edema (fluid buildup in the lungs) or even death in severe cases. Because of the seriousness of acid leaks, all procedures and guidelines during construction of the alkylation plant must be adhered to. During piping design, a minimal number of piping flanges is ideal to reduce the possibility of leaks. Mitigation systems are typically installed in plants in order to minimize the consequences of accidental releases. Solid Catalyst The use of a true solid acid catalyst eliminates the safety and environmental hazards associated with liquid acid technologies. This leads to lower maintenance costs and lower monitoring requirements by removing the need for mitigation systems and liquid acid disposal. Processes that utilize a solid acid catalyst do not produce acid soluble oils and, therefore, do not require by-product disposal. However, no solid acid catalyst technologies have been commercialized. Metallurgy

An iron fluoride layer on the metal piping and equipment (made out of killed carbon steel) in hydrofluoric acid alkylation is necessary to prevent corrosion. High temperatures can cause the protective layer to peel. Velocities in the vapor phase are kept low because high velocities will dislodge these flakes of the iron fluoride layer. The regenerator and a portion of its feed line used in HF catalyst technology is typically monel clad. Monel is a nickel alloy that is stronger than steel and resistant to corrosion. High purity sulfuric acid is typically not aggressively corrosive so carbon steel piping and equipment can be used in that type of alkylation. However, low velocities are still required in liquid sulfuric acid line to reduce the occurrence of erosion and corrosion. Technology Providers Some of the major licensors include: Sulfuric Acid (H2SO4) DuPont (STRATCO ) ExxonMobil Research & Engineering Co. Lummus Technology (CDAlky) Refining Hydrocarbon Technologies LLC Hydrofluoric Acid (HF) UOP ConocoPhillips Solid Catalyst Albemarle Catalysts, Lummus Technology and Neste Oil (AlkyClean) Exelus (ExSact) UOP Pictures Insert pictures from projects. Include client and location information. Vendor Drawings Insert Drawings (as available in public domain or licensor provided) Technical References API 751 - Safe Operation of Hydrofluoric Acid Alkylation Units Mustangers to Talk To Expert Mustangers Further Reading and Presentations Alkylation Process Engineering Department Presentations by: Duncan McGinnis (Part 1 and Part 2) Sulfuric Acid Alkylation, Sulfur Recovery, and Sulfuric Acid Regeneration DuPont

Ragsdale, Ralph. Refining Technology. John M. Campbell and Company and Ragsdale Refining Courses, 2008-2009. (Chapter 7) Leffler, William L. Petroleum Refining For the Non-Technical Person. Pennwell Publishing Company, 1985. (Chapter 8) Hydrocarbon Processings 2011 Refining Processes Handbook (slides 37-45) STRATCO H2SO4 Alkylation Documents

External Links 1. Wikipedia Alkylation Unit 2. STRATCO Alkylation Technology 3. DuPont Intro to Sulfuric Acid Alkylation Unit Process Design 4. DuPont Intro to Alkylation Chemistry 5. Hydrofluoric Acid Alkylation 6. Gasoline Upgrading: Catalytic Reforming, Isomerization, and Alkylation 7. AlkyClean Solid Acid Catalyst Alkylation Technology Key Projects List major WGM projects with this type of unit