Commercial Alkylation Processes

The Cy and Cg paraffias comprise about 90% of the alkylate Cg accounts for over 60%. Over 70% of the commercial alkylation processes employ sulfuric acid as the catalyst. Among the butylenes, 2-butene is superior to 1-butene. The C —fraction from the catalytic crackers is considered to be a superior feedstock to the alkylation unit. 

Solid Acid Catalysts. There have been commercial alkylation processes in operation that apply solid acids (viz., zeolites) in the manufacture of ethylbenzene... 

It is obvious that the production of trimethylpentane involves the formation of an equimolar quantity of a low-boiling paraffin corresponding to the olefin alkylating agent. Such was found to be at least semiquantita-tively the case. It will be noted also that 2 moles of isobutane are consumed for each mole of liquid paraffin produced this excessive consumption of the isobutane is usually undesirable in commercial alkylation processes. 

Regardless of the type of linear olefin used as the feedstock, there are three different types of alkylation processes currently available to produce LAB. The differences between the alkylation processes are determined by the type of catalyst used. Until 1990, the most widely nsed alkylation process employed HF acid as the Lewis-type catalyst. In this process, liqnid HF acid is used to catalyze the alkylation of benzene with the linear olefins. A second process involves the use of an aluminum chloride (AICI3) slurry as the catalyst. The presence of water with both HF acid and AICI3 acts as a co-catalyst to transform each of these catalysts into active species. The third and newest commercial alkylation process to produce LAB uses a solid bed catalyst, which eliminates the safety, handling, and disposal issues that are otherwise inherent with the other two processes. 

The other important direct alkylation processes involve reaction of electron-rich olefinic compounds with either tin metal or stannous chloride (tin(II) chloride) in the presence of stoichiometric amounts of hydrogen chloride (22). Butyl acrylate (R = C Hg) was used commercially in this process to prepare the estertin or P-carboalkoxyethyltin chlorides as iHustrated in the foUowing. 

The catalysts used in the industrial alkylation processes are strong Hquid acids, either sulfuric acid [7664-93-9] (H2SO or hydrofluoric acid [7664-39-3] (HE). Other strong acids have been shown to be capable of alkylation in the laboratory but have not been used commercially. Aluminum chloride [7446-70-0] (AlCl ) is suitable for the alkylation of isobutane with ethylene (12). Super acids, such as trifluoromethanesulfonic acid [1493-13-6] also produce alkylate (13). SoHd strong acid catalysts, such as Y-type zeoHte or BE -promoted acidic ion-exchange resin, have also been investigated (14—16). 

HF All lation. The HF alkylation process was developed ia the late 1930s and commercialized ia the 1940s. Initially, the growth rate of capacity was lower than for H2SO4, but by the 1980s, the capacity was approximately equivalent. 

HP Alkylation Process. The most widely used technology today is based on the HE catalyst system. AH industrial units built in the free world since 1970 employ this process (78). During the mid-1960s, commercial processes were developed to selectively dehydrogenate linear paraffins to linear internal olefins (79—81). Although these linear internal olefins are of lower purity than are a olefins, they are more cost-effective because they cost less to produce. Furthermore, with improvement over the years in dehydrogenation catalysts and processes, such as selective hydrogenation of diolefins to monoolefins (82,83), the quaUty of linear internal olefins has improved. 

Catalysts. Nearly aU. of the industrially significant aromatic alkylation processes of the past have been carried out in the Hquid phase with unsupported acid catalysts. For example, AlCl HF have been used commercially for at least one of the benzene alkylation processes to produce ethylbenzene (104), cumene (105), and detergent alkylates (80). Exceptions to this historical trend have been the use of a supported boron trifluoride for the production of ethylbenzene and of a soHd phosphoric acid (SPA) catalyst for the production of cumene (59,106). 

The alkylation of pyridine [110-86-1] takes place through nucleophiUc or homolytic substitution because the TT-electron-deficient pyridine nucleus does not allow electrophiUc substitution, eg, Friedel-Crafts alkylation. NucleophiUc substitution, which occurs with alkah or alkaline metal compounds, and free-radical processes are not attractive for commercial appHcations. Commercially, catalytic alkylation processes via homolytic substitution of pyridine rings are important. The catalysts effective for this reaction include boron phosphate, alumina, siHca—alurnina, and Raney nickel (122). 

Polymer Gasoline. Refinery trends tend to favor alkylation over polymerisation. Unlike the alkylation process, polymerisation does not require isobutane. The catalyst is usually phosphoric acid impregnated on kieselghur pellets. Polymerisation of butylenes is not an attractive alternative to alkylation unless isobutane is unavailable. The motor octane number of polymer gasoline is also low, and there is considerable shrinkage ia product volume. The only commercial unit to be built ia recent years is at Sasol ia South Africa. The commercial process was developed by UOP ia the 1940s (104). 

Although benzene prices have escalated in recent years, a concurrent need for butenes for use in alkylates for motor fuel has also increased and butane prices have also escalated. As a result, a search for alternative feedstocks began and Amoco Chemical Co. commercialized a process in 1977 to produce maleic anhydride from butane. A plant in JoHet came on-stream in 1977 with a capacity of 27,000 t/yr (135,136). No new plants have been built in the United States based on butenes since the commercialization of butane to maleic anhydride technology. In Europe and particularly in Japan, however, where butane is in short supply and needs for butenes as alkylation feed are also much less, butenes may become the dominant feedstock (see Maleic anhydride). 

Alkylation. Ethylbenzene [100-41 -4] the precursor of styrene, is produced from benzene and ethylene. The ethylation of benzene is conducted either ia the Hquid phase ia the preseace of a Eriedel-Crafts catalyst (AlCl, BE, EeCl ) or ia the vapor phase with a suitable catalyst. The Moasanto/Lummus process uses an aluminum chloride catalyst that yields more than 99% ethylbenzene (13). More recently, Lummus and Union Oil commercialized a zeoHte catalyst process for Hquid-phase alkylation (14). Badger and Mobil also have a vapor-phase alkylation process usiag zeoHte catalysts (15). Almost all ethylbenzene produced is used for the manufacture of styrene [100-42-5] which is obtained by dehydrogenation ia the preseace of a suitable catalyst at 550—640°C and relatively low pressure, <0.1 MPa (<1 atm). 

Among the wide variety of organic reactions in which zeolites have been employed as catalysts, may be emphasized the transformations of aromatic hydrocarbons of importance in petrochemistry, and in the synthesis of intermediates for pharmaceutical or fragrance products.5 In particular, Friede 1-Crafts acylation and alkylation over zeolites have been widely used for the synthesis of fine chemicals.6 Insights into the mechanism of aromatic acylation over zeolites have been disclosed.7 The production of ethylbenzene from benzene and ethylene, catalyzed by HZSM-5 zeolite and developed by the Mobil-Badger Company, was the first commercialized industrial process for aromatic alkylation over zeolites.8 Other typical examples of zeolite-mediated Friedel-Crafts reactions are the regioselective formation of p-xylene by alkylation of toluene with methanol over HZSM-5,9 or the regioselective p-acylation of toluene with acetic anhydride over HBEA zeolites.10 In both transformations, the p-isomers are obtained in nearly quantitative yield. 

This is the basic reaction of the commercial Nalco process. On the other hand, reduction of alkyl halides at the cathode is often described in general terms as ... 

Detal [Detergent alkylation] A process for making detergent alkylate, i.e., alkyl aromatic hydrocarbons such as linear alkyl benzenes, as intermediates for the manufacture of detergents, by reacting C10-C13 olefins with benzene in a fixed bed of an acid catalyst. Developed by UOP and CEPSA as a replacement for their Detergent Alkylate process, which uses liquid hydrogen fluoride as the catalyst. Demonstrated in a pilot plant in 1991 and first commercialized in Canada in 1996. Offered by UOP. 

HETACAT An alkylation process using a solid acid catalyst. Not commercialized as of 1997. 

The commercial development of catalytic cracking made available additional supplies of blending stocks having the necessary requirements of volatility, stability, and antiknock value. At the same time, by-product isobutane and butylenes provided charging stocks for the newly developed alkylation processes. 

Commercial alkylation may be divided into three distinct types depending on whether the catalyst used is sulfuric acid, hydrofluoric acid, or aluminum chloride. These types of alkylation are similar in many respects but have some outstanding differences. In 1946 there were 32 plants in the United States employing the sulfuric acid process, 27 using the hydrofluoric process, and one using aluminum chloride (I, 9). Since sulfuric acid alkylation is the most widely practiced of the three, it will be discussed first. 

Temperature is an important variable in the alkylation process. When alkylating isobutane with butenes, a reaction temperature of 40° to 50° F. produces the highest quality alkylate with the lowest catalyst consumption. Commercial operation has been... 

Concentrated sulfuric acid and hydrogen fluoride are still mainly used in commercial isoalkane-alkene alkylation processes.353 Because of the difficulties associated with these liquid acid catalysts (see Section 5.1.1), considerable research efforts are still devoted to find suitable solid acid catalysts for replacement.354-356 Various large-pore zeolites, mainly X and Y, and more recently zeolite Beta were studied in this reaction. Considering the reaction scheme [(Eqs (5.3)—(5.5) and Scheme 5.1)] it is obvious that the large-pore zeolitic structure is a prerequisite, since many of the reaction steps involve bimolecular bulky intermediates. In addition, the fast and easy desorption of highly branched bulky products, such as trimethylpentanes, also requires sufficient and adequate pore size. Experiments showed that even with large-pore zeolite Y, alkylation is severely diffusion limited under liquid-phase conditions.357... 

Amberlite XAD-2 and XAD-4 resins, for example, contain significant quantities of alkyl derivatives of benzene, styrene, naphthalene, and biphenyl as received from the supplier. PUF products, on the other hand, generally contain numerous contaminants peculiar to one of the several patented commercial manufacturing processes. These include, but are not limited to, the following classes of chemical contaminants isocyanate derivatives (e.g., toluene diisocyanates), alkyl amines, aliphatic acids, and brominated aromatics (e.g., fire retardants). 

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