Alkylation using monoolefins

Sodium and potassium are the two most frequently used alkali metals in side-chain alkylation. Sodium usually requires a promoter (o-chlorotoluene, anthracene) to form an organosodium intermediate that is the true catalyst of the reaction. A temperature range of 150-250°C is usually required for alkylation with monoolefins, whereas dienes and styrenes are reactive at lower temperatures. 

Uses. Fluorosulfuric acid serves as catalyst in the alkylation (qv) of branched-chain paraffins (53—58) and aromatic compounds (59), and in the polymeriza tion of monoolefins (60) and rosin (61). Addition of strong Lewis acids, such as SbF, TaF, and NbF, to fluorosulfuric acid markedly increases... 

Amylenes. Amylenes (C monoolefins) produce alkylates with a research octane in the range of 90—93. In the past, amylenes have not been used widely as an industrial alkylation charge, although in specific instances, alkylation with amylenes has been practiced (23). In the future, alkylation with amylenes will become more important as limits are placed on the vapor pressure and light olefin content of gasolines. 

Most of the industrially important alkyl aromatics used for petrochemical intermediates are produced by alkylating benzene [71-43-2] with monoolefins. The most important monoolefins for the production of ethylbenzene, cumene, and detergent alkylate are ethylene, propylene, and olefins with 10—18 carbons, respectively. This section focuses primarily on these alkylation technologies. 

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. 

The catalytic system used in the Pacol process is either platinum or platinum/ rhenium-doped aluminum oxide which is partially poisoned with tin or sulfur and alkalinized with an alkali base. The latter modification of the catalyst system hinders the formation of large quantities of diolefins and aromatics. The activities of the UOP in the area of catalyst development led to the documentation of 29 patents between 1970 and 1987 (Table 6). Contact DeH-5, used between 1970 and 1982, already produced good results. The reaction product consisted of about 90% /z-monoolefins. On account of the not inconsiderable content of byproducts (4% diolefins and 3% aromatics) and the relatively short lifetime, the economics of the contact had to be improved. Each diolefin molecule binds in the alkylation two benzene molecules to form di-phenylalkanes or rearranges with the benzene to indane and tetralin derivatives the aromatics, formed during the dehydrogenation, also rearrange to form undesirable byproducts. 

The side-chain alkylation reaction of aromatic hydrocarbons has also been studied using unsaturated aromatic olefins, especially styrene. Pines and Wunderlich 43) found that phenylethylated aromatics resulted from the reaction of styrenes with arylalkanes at 80-125° in the presence of sodium with a promoter. The mechanism of reaction is similar to that suggested for monoolefins, but addition does not take place to yield a primary carbanion a resonance stabilized benzylic carbanion is formed [Reaction (23a, b)j. 

Simple monoolefins and cycloolefins react in the presence of base catalysts under conditions similar to those used for base-catalyzed alkylation. The... 

Monomeric alkyl lithium polymerizes isoprene through an anionic type propagating species. The transition between cis 1,4 and trans 1,4 polymerization is not clear since mono-ene polymerization also occurs in this region. Increased dielectric constant of the media, the addition of ethers, or the use of high lithium alkyl concentrations increased the character from that weakly anionic for the cis-diene polymerization to the slightly more anionic requirements for 3.4-monoolefinic polymerizations. 

Tertiary phosphine groups with long alkyl chains bound directly to phosphorus or substituted at the para position of triphenylphosphine give rise to a range of interesting and potentially useful complexes. In particular these may be used to prepare polyolefin hydrogenation catalysts based on platinum(II) and palladium(II) complexes that are both more active and more selective towards reduction to monoolefins than previous catalysts based on these systems. The platinum(II) complexes are better than the palladium(II) complexes. Additionally the new phosphines are more effective than triphenylphosphine in promoting the oxidative addition of methyl iodide to trans- [Rh(PR3)2Cl(CO)]. 

Butylenes are four-carbon monoolefins that are produced by various hydrocarbon processes, principally catalytic cracking at refineries and steam cracking at olefins plants. These processes yield isomeric mixtures of 1-butene, cis- and tra s-butene-2, and isobutylene. Derivatives of butylenes range from polygas chemicals and methyl t-butyl ether, where crude butylenes streams may be used, to polybutene-1 and LLDPE, which require high-purity 1-butene. In 1997, the estimated consumption of butylenes (in billions of pounds) was alkylation, 32.0 MTBE, 12.0 other, including polygas and fuel uses, 0.5. 

The production of LAB involves the liquid-phase alkylation of benzene with linear monoolefins or alkyl chlorides. Liquid HF is used as catalyst for linear monoolefins. And the A1C13 is used as the catalyst for alkyl chlorides. Nowadays, acidic zeolite catalyst is used for olefin alkylation which generates less waste and reduces manufacture cost. The alkylate is then sulfonated to produce linear alkylbenzene sulfonate for biodegradable detergents. The manufacture of detergents is described in detail in Chapter 27. 

Light alkylate naphtha Light alkylation naphtha Naphtha (petroleum), light alkylate Definition Complex combination of hydrocarbons produced by distillation of reaction prods, of isobutane with C3-5 monoolefinic hydrocarbons consists of predominantly C7-10 branched chain sat. hydrocarbons Properties B.p. 90-160 C Uses Solvent diluent chem. feedstock fuel Trade Name Synonyms Isopar C [ExxonMobil http //www. exxonmobilchemical. com, Exxon Canada http //www.imperialoil.com,... 

Isobutane and the gases in the monoolefin series are used less extensively than propane and butane. Isobutane and isobutylene are used in manufacturing alkylate for increasing gasoline octane ratings. Isobutylene is employed in the manufacture of syn-... 

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