WO1995016651A1 - Procede de traitement d'alkylates visant a en augmenter la teneur en isomere 2-phenyl alcane - Google Patents

Procede de traitement d'alkylates visant a en augmenter la teneur en isomere 2-phenyl alcane Download PDF

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Publication number
WO1995016651A1
WO1995016651A1 PCT/US1994/012530 US9412530W WO9516651A1 WO 1995016651 A1 WO1995016651 A1 WO 1995016651A1 US 9412530 W US9412530 W US 9412530W WO 9516651 A1 WO9516651 A1 WO 9516651A1
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WIPO (PCT)
Prior art keywords
aluminum chloride
benzene
alkylate
alkylate product
chloride catalyst
Prior art date
Application number
PCT/US1994/012530
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English (en)
Inventor
Dan P. Szura
Steve L. Baxter
Edward L. Sones
Original Assignee
Vista Chemical Company
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Filing date
Publication date
Application filed by Vista Chemical Company filed Critical Vista Chemical Company
Publication of WO1995016651A1 publication Critical patent/WO1995016651A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
    • C07C15/02—Monocyclic hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
    • C07C5/2702—Catalytic processes not covered by C07C5/2732 - C07C5/31; Catalytic processes covered by both C07C5/2732 and C07C5/277 simultaneously
    • C07C5/271—Catalytic processes not covered by C07C5/2732 - C07C5/31; Catalytic processes covered by both C07C5/2732 and C07C5/277 simultaneously with inorganic acids; with salts or anhydrides of acids
    • C07C5/2718—Acids of halogen; Salts thereof; complexes thereof with organic compounds
    • C07C5/2721—Metal halides; Complexes thereof with organic compounds

Definitions

  • the present invention relates to a process for isomerizing an alkylate obtained by alkylating benzene with an alkylating agent in the presence of hydrogen fluoride and, more particularly, to a process for enhancing the 2-phenyl alkane isomer content of such an alkylate.
  • Alkyl benzenes having from about 9 to about 15 carbon atoms in the alkyl chain are necessary intermediates in the preparation of alkyl benzene sulfonates (alkylates), which are well known and widely used in surfactants and detergents.
  • alkyl benzene sulfonates alkylates
  • alkylating agent such as an alkyl chloride
  • alkyl benzene mixtures that have a minimum amount of the isomer wherein the phenyl group is bonded to the 2-carbon atom of the alkyl group (2-phenyl isomer) possess better properties when used in such detergents.
  • alkyl benzene mixtures that have a relatively high content of the 2-phenyl isomer 28-34%) are preferable in certain applications, particularly in the formulation of certain, newer liquid detergents.
  • alkyl benzenes In the production of alkyl benzenes by reacting benzene and an alkylating agent such as an olefin in the presence of a catalyst such as hydrogen fluoride, there is typically produced an isomer distribution that has a relatively low content (13-20%) of the 2-phenyl isomer. Accordingly, alkyl benzenes produced by these methods are unacceptable for use in formulating these newer liquid detergents wherein a high content of the 2-phenyl isomer is desired. It is well known that alkyl benzenes produced via the alkylation of benzene using an aluminum chloride catalyst typically produce alkyl benzene mixtures wherein the 2-phenyl isomer content is greater than about 28% by weight.
  • a reaction zone containing a reaction medium that comprises benzene and a modified aluminum chloride catalyst composition the modified catalyst composition having a catalytic activity less than a fresh aluminum chloride catalyst composition containing an equal content of aluminum chloride.
  • an alkylate product obtained by alkylating benzene with an alkylating agent such as an olefin in the presence of a catalyst such as hydrogen fluoride the alkylate product having a 2-phenyl alkane isomer content of less than about 20% by weight.
  • the alkylate product is reacted at a temperature in a range of from about 25 °C to about 80 °C for a period of time sufficient to increase the content of the 2- phenyl alkane isomer in the alkylate product to a level of greater than 22% to produce a treated alkylate product that is then recovered.
  • alkylate is primarily comprised of straight chain alkyl benzenes having from about 9 to about 15, particularly from about 10 to about 13, carbon atoms in the alkyl chain.
  • alkylates or alkyl benzenes are comprised of a very small percentage of alkyl benzenes wherein the benzene ring is bonded to the terminal carbon atom of the alkyl side chain and greater percentages of alkyl benzenes wherein the benzene ring is bonded to the second, third, fourth, etc., carbon atom of the alkyl chain.
  • alkylating benzenes with alkylating agents such as olefins and normal alkyl chlorides are well known to those skilled in the art.
  • alkylations can be conducted using an aluminum chloride catalyst, hydrogen fluoride catalyst, sulfuric acid catalyst and certain other acid catalysts.
  • aluminum chloride catalyst Under normal alkylation conditions and employing an aluminum chloride catalyst, there are usually produced anywhere from 28-34% by weight of the 2-phenyl alkane isomer depending upon process variables and average carbon number of the alkylate.
  • the 2-phenyl alkane isomer was considered undesirable for use in the production of detergents and, accordingly, processes were developed to separate the 2-phenyl alkane isomer and use the remaining isomers for the production of the detergent.
  • the 2-phenyl alkane isomer content be in the range of 28-34 % , meaning that alkylates produced using hydrogen fluoride are generally unsuitable for such liquid detergent compositions.
  • the process of the present invention upgrades such low 2-phenyl isomer alkylates by effecting isomerization of the alkylate to enhance the 2-phenyl alkane isomer content to a range of greater than about 22% by weight of the total isomer content. Accordingly, such upgraded alkylates can be blended with higher 2-phenyl isomer content alkylates.
  • the process is capable of upgrading low 2-phenyl isomer content alkylates to high 2-phenyl isomer content alkylates containing greater than 28%, generally from 28-34% by weight of the 2- phenyl isomer.
  • the process of the present invention is based on the unexpected finding that if an alkylate of low 2-phenyl alkane isomer content, i.e., less than about 20% by weight, is treated in a reaction medium containing a modified aluminum chloride catalyst composition, the 2-phenyl alkane isomer content can be dramatically increased to above about 22% by weight, even to 28-34% by weight.
  • modified aluminum chloride catalyst composition refers to an aluminum chloride catalyst that has activity less than that of a fresh aluminum chloride catalyst composition containing essentially the same amount of aluminum chloride.
  • a suitable modified aluminum chloride catalyst composition can be obtained by "doctoring” or “poisoning” a fresh aluminum chloride catalyst composition with compounds such as alkylated aromatics (both mono- and polyalkylated), polynuclear aromatics and mixtures thereof.
  • Another suitable and convenient form of modified aluminum chloride catalyst composition in accordance with the present invention is what is commonly referred to as "red oil,” resulting from the alkylation of benzene with olefins and aluminum chloride.
  • Red oil typically contains about 45-55% by weight benzene, about 30-35% by weight aluminum chloride, about 1-3% by weight hydrogen chloride and about 12-17% by weight aromatics, the aromatics primarily comprising tetralins, C 9 -C 15 monoalkylates, polyalkylated benzenes such as tetralkyl benzenes; polynuclear aromatics such as naphthalene; alkylated polynuclears, i.e., alkylated naphthalene; etc.
  • the tetralins and the polyalkylated benzene species generally account for a majority of the aromatic content of the red oil.
  • Another source of red oil is that obtained from a dealkylation reaction mixture wherein dialkylbenzenes are dealkylated in the presence of benzene and an aluminum chloride catalyst.
  • a reaction medium in a suitable reaction zone in which the treatment of the low 2-phenyl isomer alkylate is conducted.
  • the reaction medium which uses benzene, can comprise an alkylation reaction mixture in which alkylation has been substantially completed and that results from the alkylation of benzene with ah olefin optionally dissolved in an inert hydrocarbon diluent such as a paraffin, and employing an aluminum chloride catalyst.
  • Such a reaction medium will thus comprise benzene, the paraffin diluent and the red oil formed during the alkylation reaction.
  • a second reaction medium can be formed by using benzene, fresh aluminum chloride, HCl and one or more of the modifiers mentioned above to reduce the activity of the aluminum chloride catalyst to the desired level, which is generally the activity possessed by a red oil obtained from a typical aluminum chloride catalyzed alkylation reaction.
  • the reaction medium can also comprise a dealkylation reaction mixture comprising dialkylbenzenes, benzene and aluminum chloride catalyst. Such a reaction medium will contain a modified aluminum chloride catalyst.
  • reaction medium will generally contain benzene in an amount so as to provide a weight ratio of benzene to the alkylate product being treated (the low 2-phenyl isomer alkylate) of at least 1: 1. Higher ratios of benzene to the alkylate product can be tolerated with no adverse effect.
  • the modified aluminum chloride catalyst composition be present in an amount so as to constitute at least about 1 % by weight of the total weight of the alkylate product being treated, the catalyst composition being calculated as aluminum chloride. Higher amounts of aluminum chloride can be tolerated, the only restriction being that the catalyst be modified as that term is defined above.
  • the treatment of the alkylate product i.e. , the low 2-phenyl isomer alkylate
  • FIG. 10 there is shown a schematic for conducting the process of the present invention.
  • a reactor vessel 10 that provides a reaction zone
  • benzene, aluminum chloride and HCl through line 12.
  • a C 10 -C ⁇ 3 olefin, or mixtures thereof, together with a C 10 -C 13 paraffin, or mixtures thereof, is introduced into vessel 10 via feedline 14 and multiple injection lines 16, 18 and 20.
  • the alkylate to be treated is introduced via line 22 through three-way valve 24, which permits the alkylate to be introduced directly into vessel 10 via line 26 or via line 25, into line 28 leading from vessel 10, or both simultaneously. In either or both events, the alkylate to be treated is introduced at a point in the reaction zone that is substantially free of olefins.
  • the crude reaction mixture from vessel 10 including the treated alkylate product having enhanced 2-phenyl alkane isomer content passes via line 28 into settler 30, from which crude alkylate is removed via line 32 and recycled catalyst is removed via line 34.
  • the alkylate to be treated is not introduced into the reaction zone defined by reaction vessel 10 (or reaction vessel 10 in conjunction with line 28) until the alkylation reaction has been substantially completed.
  • Alkylation was initiated by adding 1/3 of the olefin/paraffin mixture to the benzene/catalyst mixture. The resulting yellow- orange solution was allowed to stir for 3 minutes before another 1/3 of the olefin/paraffin mixture was added. After 3 more minutes, the remainder of the olefin/paraffin mixture was added. At the end of the olefin addition, the reaction temperature had risen to 65 °C. The crude alkylation mixture was stirred for 15 minutes, and then a sample of low 2-phenyl N500L 1 alkylate (60 g 1.52 mol) was 5 added. The entire mixture was stirred for 10 minutes and then allowed to settle for 2 hours (the reaction temperature dropping 10°C while settling). At the end of the 2-hour period, the organic layer was decanted from the catalyst sludge and quenched by treatment with a 5% solution of aqueous sodium hydroxide.
  • the reaction mixture was sampled before and after adding the N500L alkylate 10 to be treated and the isomer distribution for each of the samples determined. The results are shown in Table 1 below.
  • modified catalysts i.e., red oil from a typical aluminum chloride catalyzed alkylation, serves as an excellent catalyst to enhance the 2-phenyl alkane isomer content of an alkylate containing less than about 20% by weight of that isomer.
  • modified aluminum chloride catalyst significantly reduces the content of branched alkylates, tetralins and branched paraffins and gives increased alkylate linearity, both of which increase biodegradability.
  • This example demonstrates the use of a modified aluminum chloride catalyst made by treating a fresh aluminum chloride catalyst with various amounts of catalyst poisons.
  • Three separate experiments were run in which fresh aluminum chloride catalyst was pretreated with 0.25, 0.5 and 1.0 molar equivalents of 1,2,4,5- tetramethylbenzene prior to its use for the isomerization of 4-phenyldodecane. Conditions for these experiments were identical to those set forth with respect to Example 2. The results are shown in Tables 4 and 5 below.
  • an alkylate produced using a hydrogen fluoride catalyst and containing a relatively low content (generally less than 20% by weight) of the 2-phenyl alkane isomer can be treated according to the process of the present invention to provide a treated alkylate in which the content of the 2-phenyl alkane isomer is increased to greater than 22%, and in most cases, greater than 30%.
  • a modified aluminum chloride catalyst the amount of undesirable, non-biodegradable side products is dramatically reduced.

Abstract

Procédé permettant d'augmenter le niveau d'un isomère 2-phénylalcane dans un alkylate, consistant à faire réagir ledit produit avec un catalyseur à base de chlorure d'aluminium modifié moins actif qu'un catalyseur à base de chlorure d'aluminium frais. On introduit dans un réacteur (10) du benzène, du chlorure d'aluminium et du HCl (12), ainsi qu'un mélange C10-C13 oléfine:paraffine (14). On introduit l'alkylate à traiter via la conduite (22) à travers la vanne (24) soit directement dans le réacteur (10) via la conduite (26), soit via la conduite (25) débouchant dans la conduite (28) en provenance de (10), ou encore via les deux conduites en même temps. Le mélange de réaction en provenance de (10) est transféré via la conduite (28) dans le décanteur (30), à partir duquel l'alkylate brut est extrait via la conduite (32) et le catalyseur est extrait via la conduite (34). L'alkylate destiné à être traité n'est pas introduit dans le réacteur tant que la réaction d'alkylation n'est pas terminée.
PCT/US1994/012530 1993-12-13 1994-11-01 Procede de traitement d'alkylates visant a en augmenter la teneur en isomere 2-phenyl alcane WO1995016651A1 (fr)

Applications Claiming Priority (2)

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US16670593A 1993-12-13 1993-12-13
US08/166,705 1993-12-13

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WO1995016651A1 true WO1995016651A1 (fr) 1995-06-22

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3352933A (en) * 1965-12-07 1967-11-14 Atlantic Refining Co Isomerization of 2-phenyl alkanes
US3391210A (en) * 1965-02-17 1968-07-02 Continental Oil Co Process for the preparation of detergent alkylate
US4301317A (en) * 1979-11-20 1981-11-17 Mobil Oil Corporation Preparation of 2-phenylalkanes
US4301316A (en) * 1979-11-20 1981-11-17 Mobil Oil Corporation Preparing phenylalkanes

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3391210A (en) * 1965-02-17 1968-07-02 Continental Oil Co Process for the preparation of detergent alkylate
US3352933A (en) * 1965-12-07 1967-11-14 Atlantic Refining Co Isomerization of 2-phenyl alkanes
US4301317A (en) * 1979-11-20 1981-11-17 Mobil Oil Corporation Preparation of 2-phenylalkanes
US4301316A (en) * 1979-11-20 1981-11-17 Mobil Oil Corporation Preparing phenylalkanes

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
J. AMER. OIL CHEM. SOC., Vol. 48, December 1971, S.E. McGUIRE et al., "Isomerizations Accompanying Friedel-Crafts Alkylations by Detergent Range Alkylating Agents", pages 872-875. *

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