Alkylbenzene production

Zeolite based catalysts for linear alkylbenzene production dehydrogenation of long chain alkanes and benzene alkylation. Catal. Today, 38, 243-247. 

Alkylbenzene Product Maleic anhydride reacted (%),5h Yield (%)... 

Prior to 1965, alkylbenzene production was synthesized from petroleum tetrapropylene reacted with an aluminium chloride or hydrogen fluoride catalyst and benzene. The resultant alkylate was a hard branched-chain compound that was considered slowly biodegradable. A straight-chain alkylate, termed LAB (linear alkylbenzene), has been produced since 1965 in the United States. Extensive research has demonstrated biodegradation effectiveness in sewage treatment plants in excess of 95 percent. ... 

Friedel-Crafts alkylations are not usually performed using alkyl halides that are prone to rearrangement because the result is a mixture of products, and thus a low 5deld of any one particular product. To obtain a single alkylbenzene product, the corresponding Friedel-Crafts acylation should be performed, followed by reduction of the carbonyl using Ha/Pd or Zn(Hg)/HCl. 

Molar ratio of alkylbenzene to benzene No. of equivs. of aromatics in solution in which nitrating agent is consumed Products Relative rate... 

Linear paraffins in the C q to range are used for the production of alcohols and plasticizers and biodegradable detergents of the linear alkylbenzene sulfonate and nonionic types (see Alcohols Plasticizers Surfactants). Here the UOP Molex process is used to extract / -paraffins from a hydrotreated kerosine (6—8). 

Other sources of by-product HCl include allyl chloride, chlorobenzenes, chlorinated paraffins, linear alkylbenzene, siHcone fluids and elastomers, magnesium, fluoropolymers, chlorotoluenes, benzyl chloride, potassium sulfate, and agricultural chemicals. 

Friedel-Crafts reaction of ahyl alcohol with benzene or alkylbenzene yields many kinds of products, in which the reaction species and the product ratio depend on the type of catalyst. Zinc chloride is the most effective catalyst for producing ahyl compounds by this reaction (32). 

Biphenyl has been produced commercially in the United States since 1926, mainly by The Dow Chemical Co., Monsanto Co., and Sun Oil Co. Currently, Dow, Monsanto, and Koch Chemical Co. are the principal biphenyl producers, with lesser amounts coming from Sybron Corp. and Chemol, Inc. With the exception of Monsanto, the above suppHers recover biphenyl from high boiler fractions that accompany the hydrodealkylation of toluene [108-88-3] to benzene (6). Hydrodealkylation of alkylbenzenes, usually toluene, C Hg, is an important source of benzene, C H, in the United States. Numerous hydrodealkylation (HDA) processes have been developed. Most have the common feature that toluene or other alkylbenzene plus hydrogen is passed under pressure through a tubular reactor at high temperature (34). Methane and benzene are the principal products formed. Dealkylation conditions are sufficiently severe to cause some dehydrocondensation of benzene and toluene molecules. 

A good deal of experimental care is often required to ensure that the product mixture at the end of a Friedel-Crafts reaction is determined by kinetic control. The strong Lewis acid catalysts can catalyze the isomerization of alkylbenzenes, and if isomerization takes place, the product composition is not informative about the position selectivity of electrophilic attack. Isomerization increases the amount of the meta isomer in the case of dialkylbenzenes, because this isomer is thermodynamically the most stable. ... 

Steric fectors clearly enter into determining the ortho para ratio. The hindered 2,4,6-trimethylbenzoyl group is introduced with a 50 1 preference for the para position. Similarly, in the benzoylation of alkylbenzenes by benzoyl chloride-aluminum chloride, the amount of ortho product decreases (10.3%, 6.0%, 3.1%, 0.6%, respectively) as the branching of the alkyl group is increased along the series methyl, ethyl, i-propyl, t-butyl. ... 

Alkylation of benzene using alpha olefins produces linear alkylbenzenes, which are further sulfonated and neutralized to linear alkylbenzene sulfonates (LABS). These compounds constitute, with alcohol ethoxy-sulfates and ethoxylates, the basic active ingredients for household detergents. Production of LABS is discussed in Chapter 10. 

Aromatic compounds such as benzene react with alkyl chlorides in Ihe presence of AlCl i catalyst to yield alkylbenzenes. The reaction occurs through a carbocation intermediate, formed by reaction of the alkyl chloride with AICI3 (R—Cl + A1CI 1 - U+ + AICl4 ). How can you explain the observaiion that reaction of benzene with 1-chloropropane yields isopropylbenzene as the major product ... 

Alkylbenzenes such as toluene (methylbenzene) react with NBS to give products in which bromine substitution has occurred at the position next to the aromatic ring (the benzyiic position). Explain, based on the bond dissociation energies in Table 5.3 on page 156. 

Side-chain bromination at the benzylic position occurs when an alkylbenzene is treated with /V-bromosuccinimide (NBS). For example, propylbenzene gives (l-bromopropyl)benzene in 97% yield on reaction tvith NBS in the presence of benzoyl peroxide, (PhC02)2f as a radical initiator. Bromination occurs exclusively in the benzylic position and does not give a mixture of products. 

The higher molecular weight unbranched C10-C18 n-olefins—not only a-olefins but also n-olefins with internal double bonds, so-called n-vj/-olefins—are important initial products for the manufacture of anionic surfactants, e.g., linear alkylbenzenes or olefinsulfonates. These linear C10-C18 olefins are manufactured technically by the following procedures ... 

Raw materials for obtaining benzene, which is needed for the production of alkylbenzenes, are pyrolysis gasoline, a byproduct of the ethylene production in the steam cracking process, and coke oven gas. Reforming gasoline contains only small amounts of benzene. Large amounts of benzene are further produced by hydrodealkylation of toluene, a surplus product in industry. 

B. Historical Development of the Industrial Production of Alkylbenzenes and Alkylbenzenesulfonates... 

Alkylbenzenes and -sulfonic acids are produced today by various processes that are described in detail, with particular respect to the olefin production process, in the following chapter. The numerous LAB manufacturing processes are illustrated in Figure 2 (see also [4]). 

Table 1 shows the carbon chain distributions for several typical commercial alkylates. The carbon chain distributions for linear alkylbenzene (LAB) samples A, C, and E are determined by the distillation cut of n-paraffins used to make the LAB. LAB samples B and D represent blended alkylates made by mixing samples such as A and E in different ratios. This provides to the customer LAB products with a wide variety of molecular weights and improves the utilization of the fl-paraffin feedstocks. 

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