Propane isobutane alkylation

A, Find the optimum liquid concentration of the propane isobutane mixture in an auto lefrigerated alkylation reactor. The exothermic heat (10 Btu/h) of the alkylation reaction is removed by vaporization of the liquid in the reactor. The vapor is com pressed, condensed, and flashed back into the reactor through a pressure letdown valve. The reactor must operate at 50°F, and the compressed vapors must be condensed at 110°F. 

Typical alkylation reactions are those of propane, isobutane, and n-butane by the ferf-butyl or sw-butyl ion. These systems are somewhat interconvertible by competing hydride transfer and rearrangement of the carbenium ions. The reactions were carried out using alkyl carbenium ion hexafluoroantimonate salts prepared from the corresponding halides and antimony pentafluoride in sulfuryl chloride fluoride solution and treating them in the same solvent with alkanes. The reagents were mixed at —78°C warmed up to — 20°C and quenched with ice water before analysis. The intermolecular hydride transfer between tertiary and secondary carbenium ions and alkanes is generally much faster than the alkylation reaction. Consequently, the alkylation products are also those derived from the new alkanes and carbenium ions formed in the hydride transfer reaction. 

As shown in Fig. 18.23, dry liquid feed containing olefins and isobutane is charged to a combined reactor-settler. In this example, the reactor uses the principle of a differential gravity head to circulate through a cooler before contacting a highly dispersed hydrocarbon feed in the reactor pipe. The hydrocarbon phase, generated in the settler, is sent to a fractionator, which separates LPG-quality propane, isobutane recycle, n-butane, and alkylate products. A small amount of dissolved catalyst is also removed from the propane product by a small stripper tower. 

Propylene- -Isobutane Alkylation with Propane Added. The principal... 

Two to four distillation columns are usually required to separate the liquid hydrocarbon product stream that contains unreacted isobutane, alkylate mixture, n-butane, and propane. The major column is designated as the deisobutanizer (DIB) column. Often this column separates the isobutane as the overhead stream, the alkylate as the bottom stream, and a n-butane rich sidestream. In many plants, the feed isobutane is also fed to the DIB to remove most of the n-butane. A second column is generally needed to remove propane from the isobutane. Sometimes a third column is provided to purify further the n-butane sidestream and to recover more isobutane. In an alternate arrangement, the bottom stream of the DIB column is a mixture of alkylate and n-butane. This mixture is then separated in another column. 

Returning to Table 2.2 and focusing on C-H BDEs, a good deal of information on radical stabilities can be obtained. The clear trend in BDEs of methane > ethane > propane > isobutane leads directly to the series of radical stabilities 3° > 2° > 1° > methyl. The overall effect is substantial, with over 10 kcal/mol in stabilization for f-butyl radical relative to methyl radical. The reason for this trend is hyperconjugation, which we will explore in depth when discussing carbocations (see below). Based upon BDEs, vinyl and phenyl radicals are substantially less stable than alkyl radicals. 

Propane and light ends are rejected by touting a portion of the compressor discharge to the depropanizer column. The reactor effluent is treated prior to debutanization to remove residual esters by means of acid and alkaline water washes. The deisobutanizer is designed to provide a high purity isobutane stream for recycle to the reactor, a sidecut normal butane stream, and a low vapor pressure alkylate product. 

Propylene. Propylene alkylation produces a product that is rich in dimethylpentane and has a research octane typically in the range of 89—92. The HF catalyst tends to produce somewhat higher octane than does the H2SO4 catalyst because of the hydrogen-transfer reaction, which consumes additional isobutane and results in the production of trimethylpentane and propane. 

Reactions other than those of the nucleophilic reactivity of alkyl sulfates iavolve reactions with hydrocarbons, thermal degradation, sulfonation, halogenation of the alkyl groups, and reduction of the sulfate groups. Aromatic hydrocarbons, eg, benzene and naphthalene, react with alkyl sulfates when cataly2ed by aluminum chloride to give Fhedel-Crafts-type alkylation product mixtures (59). Isobutane is readily alkylated by a dipropyl sulfate mixture from the reaction of propylene ia propane with sulfuric acid (60). 

Cj s and C s include propane, propylene, normal butane, isobutane, and butylene. Propylene and butylene are used to make ethers and alkylate, which are blended to produce high-octane gasoline. Most gas plants also include treating facilities to remove sulfur from these products. 

Above 323 K, the surface hydride catalyzes the hydrogenolysis of neopentane, isobutane, and propane, whereas ethane does not undergo any significant hydrogenolysis. The first step of the reaction is the activation of the C—H bond, whereas the next step is the activation of the C—C bond of the alkyl groups via (l-methyl migration steps. 

Theoretically, even the direct alkylation of carbenium ions with isobutane is feasible. The reaction of isobutane with a r-butyl cation would lead to 2,2,3,3-tetramethylbutane as the primary product. With liquid superacids under controlled conditions, this has been observed (52), but under typical alkylation conditions 2,2,3,3-TMB is not produced. Kazansky et al. (26,27) proposed the direct alkylation of isopentane with propene in a two-step alkylation process. In this process, the alkene first forms the ester, which in the second step reacts with the isoalkane. Isopentane was found to add directly to the isopropyl ester via intermediate formation of (non-classical) carbonium ions. In this way, the carbenium ions are freed as the corresponding alkanes without hydride transfer (see Section II.D). This conclusion was inferred from the virtual absence of propane in the product mixture. Whether this reaction path is of significance in conventional alkylation processes is unclear at present. HF produces substantial amounts of propane in isobutane/propene alkylation. The lack of 2,2,4-TMP in the product, which is formed in almost all alkylates regardless of the feed (55), implies that the mechanism in the two-step alkylation process is different from that of conventional alkylation. 

With propene, n-butene, and n-pentene, the alkanes formed are propane, n-butane, and n-pentane (plus isopentane), respectively. The production of considerable amounts of light -alkanes is a disadvantage of this reaction route. Furthermore, the yield of the desired alkylate is reduced relative to isobutane and alkene consumption (8). For example, propene alkylation with HF can give more than 15 vol% yield of propane (21). Aluminum chloride-ether complexes also catalyze self-alkylation. However, when acidity is moderated with metal chlorides, the self-alkylation activity is drastically reduced. Intuitively, the formation of isobutylene via proton transfer from an isobutyl cation should be more pronounced at a weaker acidity, but the opposite has been found (92). Other properties besides acidity may contribute to the self-alkylation activity. Earlier publications concerned with zeolites claimed this mechanism to be a source of hydrogen for saturating cracking products or dimerization products (69,93). However, as shown in reaction (10), only the feed alkene will be saturated, and dehydrogenation does not take place. 

The general treatment of the hydrocarbon stream leaving the alkylation reactor is similar in all processes. First, the acid and hydrocarbon phases have to be separated in a settler. The hydrocarbon stream is fractionated in one or more columns to separate the alkylate from recycle isobutane as well as from propane, n-butane, and (sometimes) isopentane. Because HF processes operate at higher isobutane/alkene ratios than H2S04 processes, they require larger separation units. All hydrocarbon streams have to be treated to remove impurity acids and esters. 

Problem 4.10 Name the alkyl groups originating from (a) propane, (f>) n-butane, (c) isobutane,... 

The fractionation section of the alkylation plant consists of a deisobutanizer, a debutanizer, and a rerun tower in series, and a depropanizer. The deisobutanizer overhead, which contains about 90% isobutane, recycles to the reactor. The deisobutanizer bottoms stream passes to the debutanizer, which removes normal butane diluent as an overhead stream. The debutanizer bottoms or raw alkylate stream then goes to a rerun tower for removal of the high boiling alkylate bottoms or trimers. The rerun overhead requires no further treatment to be satisfactory as an aviation gasoline blending stock. The depropanizer removes propane diluent from a slip-stream portion of the recycle isobutane stream to prevent propane build-up in the reaction system. 

The main products formed by the catalytic alkylation of isobutane with ethylene (HC1—AICI3, 25-35°C) are 2,3-dimethylbutane and 2-methylpentane with smaller amounts of ethane and trimethylpentanes.13 Alkylation of isobutane with propylene (HC1—AICI3, — 30°C) yields 2,3- and 2,4-dimethylpentane as the main products and propane and trimethylpentanes as byproducts.14 This is in sharp contrast with product distributions of thermal alkylation that gives mainly 2,2-dimethylbutane (alkylation with ethylene)15 and 2,2-dimethylpentane (alkylation with propylene).16... 

Superacids were shown to have the ability to effect the protolytic ionization of a bonds to form carbocations even in the presence of benzene.190 The formed car-bocations then alkylate benzene to form alkylbenzenes. The alkylation reaction of benzene with Ci—C5 alkanes (methane, ethane, propane, butane, isobutane, isopentane) are accompanied by the usual acid-catalyzed side reactions (isomerization, disproportionation). Oxidative removal of hydrogen by SbF5 is the driving force of the reaction ... 

For example, adding lighter propane to heavier isobutane in a refinery alkylation unit is a common practice to increase refrigerant circulation. But this will work only when the compressor driver has spare... 

One possible arrangement for a hydrofluoric acid alkylation unit is shown schematically in Fig. 1. Feedstocks are pretreated, mainly to remove sulfur compounds. The hydrocarbons and acid are intimately contacted in the reactor to form an emulsion, within which the reaction occurs. The reaction is exothermic and temperature must be controlled by cooling water. After reaction, the emulsion is allowed to separate in a settler, the hydrocarbon phase rising to the top. The acid phase is recycled. Hydrocarbons from the settler pass to a fractionator which produces an overhead stream rich in isobutane. The isobutane is recycled to the reactor. The alkylate is the bottom product of tile fraetionater (isostripper). If the olefin teed contains propylene and propane, some of the isoshipper overhead goes to a depropanizer where propane is separated as an overhead... 

The strong competition between alkylation and hydride transfer appears in the alkylation reaction of propane by butyl cations, or butanes by the propyl cation. The amount of C7 alkylation products is rather low. This point is particularly emphasized in the reaction of propane by the terf-butyl cation, which yields only 10% of heptanes. In the interaction of isopropyl cation 31 with isobutane 2 the main reaction is hydride transfer from the isobutane to the isopropyl ion followed by alkylation of propane by the isopropyl ions (Scheme 5.20). 

Propane as a degradation product of polyethylene (a byproduct in the reaction) was ruled out because ethylene alone under the same conditions does not give any propane. Under similar conditions but under hydrogen pressure, polyethylene reacts quantitatively to form C3 to C6 alkanes, 85% of which are isobutane and isopentane. These results further substantiate the direct alkane alkylation reaction and the intermediacy of the pentacoordinate carbonium ion. Siskin also found that when ethylene was allowed to react with ethane in a flow system, n-butane was obtained as the sole product, indicating that the ethyl cation is alkylating the primary C—H bond through a five-coordinate carbonium ion [Eq. (5.66)]. 

A comparative study of nanocomposites (16% Nafion-silica and commercial SAC-13) has been performed by Hoelderich and co-workers169 in the alkylation of isobutane and Raffinate II. Raffinate II, the remaining C4 cut of a stream cracker effluent after removal of dienes, isobutane, propane, and propene, contains butane, isobutylene, and butenes as main components. High conversion with a selectivity of 62% to isooctane was found for Nafion SAC-13 (batch reactor, 80°C). Both the quality of the product and the activity of the catalysts, however, decrease rapidly due to isomerization and oligomerization. Treating under reflux, the deactivated catalysts in acetone followed by a further treatment with aqueous hydrogen peroxide (80°C, 2 h), however, restores the activity. 

Feed stock for the first sulfuric acid alkylation units consisted mainly of butylenes and isobutane obtained originally from thermal cracking and later from catalytic cracking processes. Isobutane was derived from refinery sources and from natural gasoline processing. Isomerization of normal butane to make isobutane was also quite prevalent. Later the olefinic part of the feed stock was expanded to include propylene and amylenes in some cases. When ethylene was required in large quantities for the production of ethylbenzene, propane and butanes were cracked, and later naphtha and gas oils were cracked. This was especially practiced in European countries where the cracking of propane has not been economic. 

The demand for liquefied petroleum gas (LPG consisting of propanes and butanes) is projected to increase rapidly in future years.(1) World consumption is dominated by the United States and Japan. Processing of natural gas accounts for the bulk of domestic LPG however, natural gas production has leveled off forcing the LPG industry to examine other feedstock sources. Japan must look to other countries for future LPG supplies due to environmental and space limitations. An allied problem, especially in the United States, is the continuing need for isobutane to produce valuable alkylates for the gasoline pool. 

The input-output structure of the flowsheet is presented in Figure 9.1. Butene (feed rate FA,0) and isobutane (feed rate FB-0) are the raw materials. The butene feed is impure with quite large amounts of propane (FI 0). The main product is the alkylate C8Hi8, at the rate FP. The selectivity of the process is not 100%, therefore heavy products are formed at the rate FR. The inert fed into the process must also leave the plant, the flow including light byproducts that are formed in secondary reactions. Often, significant quantities of n-butane are mixed with the isobutane fresh feed. For this case, development of the flowsheet and the design of the main units is left as an exercise for the reader. 

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