WO1999003163A1

WO1999003163A1 - Alkylation reaction using supported ionic liquid catalyst composition and catalyst composition

Info

Publication number: WO1999003163A1
Application number: PCT/US1998/014149
Authority: WO
Inventors: Fawzy G. Sherif; Lieh-Jiun Shyu
Original assignee: Akzo Nobel Inc.
Priority date: 1997-07-10
Filing date: 1998-07-10
Publication date: 1999-01-21
Also published as: AU8386898A

Abstract

Aromatic compounds can be alkylated using, as the catalyst for such a reaction, a supported ionic liquid composition that comprisies an ionic liquid, which consists essentially of an organic base and a metal halide, and a support, which may be a macroporous polymer or a metal oxide, such as silica.

Description

A KYIATION REACTION USING SUPPORTED IONIC LIQUID CATALYST COMPOSITION AND CATALYST COMPOSITION

BACKGROUND OF THE INVENTION

In its broadest embodiment, the present invention relates to a supported ionic liquid catalyst composition used in an ionic liquid-catalyzed chemical reaction in which an aromatic compound is alkylated. An ionic liquid is, in general, formed when a solid Lewis acid, such as AICI3, mixes with a solid organic base, such as trimethylamine hydrochloride , at low temperature. The organic base component can also be chosen from a halide of imidazolium, pyridinium, sulfonium, phosphonium, and guanidinium, and ammonium salts. These ionic liquids are reported to be effective catalysts for many reactions, such as the alkylation of benzene or phenol, the oligomerization or dimerization of olefins , and the alkylation of paraffins with ole ins .

This invention relates to the catalytic alkylation of an aromatic molecule with a suitable alkylating reagent (for example, a C₂ to C₂o, such as a C4 to Cn olefin or a halogenated alkane of similar chain length) using, as the catalyst, a composition which is liquid at low temperatures and which comprises a support as previously described. While supported ionic liquid catalysts are known for use in alkylation reactions , they have only been suggested for use in the alkylation of aliphatic compounds (see U.S. Patent No. 5,693,585 and European Patent Publication No. 553,009) . In general, the alkylation reactions intended to be covered herein can be conducted at temperatures ranging from about 0°C to about 80°C (preferably from about 20°C to about 75°C) using a molar ratio of aromatic compound to alkylating agent (e.g., olefin) of from about 2:1 to about 100 : 1 (preferably from about 2:1 to about 16:1) with a catalyst loading on the support of from about 1% by weight to about 200% by weight (preferably from about 10% by weight to about 50% by weight) .

The term "linear alkylbenzene formation" (which is used to define a particularly preferred alkylation reaction) , as used herein, is intended to cover the process by which higher alkyl moieties are placed on benzene compounds, with the term "alkyl" being intended to cover the conventional paraffinic alkane substituents , "higher" being intended to mean C₄ or longer, preferably C_θ or longer, and the "benzene" including both unsubstituted as well as substituted (e.g., lower alkyl- substituted) benzene compounds. As is well known in the art, this process is practiced by the catalytic reaction of an unsubstituted or lower alkyl-substituted benzene compound with a higher alkene or a halo-substituted higher alkane, such as a chloro-substituted higher alkane. In commercial practice, the alkylating agent is one or more a long chain alkene or halogenated alkane, such as dodecylchloride or dodecene. Recent patents which illustrate an alkylation reaction of this type include U.S. Patent Nos . 5,196,574 to J.A. Kocal and 5,386,072 to P. Cozzi et al. The Cozzi patent, which describes the use of aluminum trichloride as a preferred alkylation catalyst, is a particular example of a prior art alkylation process to which the present invention in an improvement. A recent publication discussing the LAB reaction, in general terms, is contained in INFORM, Vol. 8, No. 1 (Jan. 1997), pp. 19-24.

A class of ionic liquids which is of special interest to the present supported composition which is used in the alkylation reaction of this invention, as the desired ionic liquid component therein, is the class of fused salt compositions which are molten at low temperature. Such compositions are mixtures of components which are liquid at temperatures below the individual melting points of the components . The mixtures can form molten compositions simultaneously upon contacting the components together, or after heating and subsequent cooling.

Examples of conventional low temperature ionic liquids or molten fused salts, which are capable of being contained in the supported Ionic liquid product of the present invention, are the chloroalumlnate salts discussed by J. S. Wilkes, et al. , J. Inorg. Chem. , Vol. 21, 1263-1264, 1982. Alkyl imidazolium or pyridinium salts, for example, can also be formed from aluminum trichloride (A1C1₃) forming the fused chloroalumlnate salts. Also, chlorogallate salts made from gallium trichloride and methylethyl-imidazolium chloride are discussed in Wicelinski et al., "Low Temperature Chlorogallate Molten Salt Systems," J. Electrochemical Soc, Vol. 134, 262-263, 1987. The use of the fused salts of 1-alkylpyridinium chloride and aluminum trichloride as electrolytes are discussed in U.S. Pat. No. 4,122,245. Other patents which discuss the use of fused salts from aluminum trichloride and alkylimidazolium halides as electrolytes are U.S. Pat. Nos . 4,463,071 and 4,463,072 and British Patent No. 2,150,740. All of these species can be contained in the ultimate product of the present invention as the ionic liquid component therein.

U.S. Patent No. 4,764,440 to S.D. Jones describes ionic liquids which comprise a mixture of a metal halide, such as aluminum trichloride, and what is termed a "hydrocarbyl- saturated onium salt" , such as trimethylphenylammonium chloride . In such ionic liquids, the onium salt component, if based on the presence of a nitrogen atom, is fully saturated with four substituent groups . These can also be selected as the ionic liquid component for the product of the present invention.

U.S. Patent No. 5,104,840 to Y. Chauvin et al. describes ionic liquids which comprise at least one alkylaluminum dihalide and at least one quaternary ammonium halide and/or at least one quaternary ammonium phosphonium halide; and their uses as

SUBSTITUTE^HEET (RULE 26) solvents in catalytic reactions . The product of this invention can use these species as the ionic liquid component therein. PCT International Patent Publication No. WO 95/21872 describes ternary ionic liquids which can comprise a metal halide, such as aluminum trichloride, an imidazolium or pyridinium halide, and a hydrocarbyl substituted quaternary ammonium halide or a hydrocarbyl substituted phosphonium halide. See page 4, lines 18-24 for the description of the hydrocarbyl substituted quaternary ammonium halide. These might also be selected as the ionic liquid component for the supported product of the present invention.

SUMMARY OF THE INVENTION

As indicated before, the present invention relates to a process for the alkylation of an aromatic compound using, as the catalyst, a supported ionic liquid composition which comprises an ionic liquid comprising an organic base and a metal halide and a support. The support is a porous solid which may be a macroporous polymer or a metal oxide, such as silica, alumina, a zeolite, or a clay. The supported catalyst which comprises the microporous polymer, which will be described in greater detail below, is deemed to be a novel composition of matter.

DETAILED DESCRIPTION OF THE INVENTION

The low temperature molten compositions, or ionic liquids, which are used as a component in the supported product that is used in the process of this invention can be referred to as fused salt compositions, or ionic aprotic solvents. By "low temperature molten" is meant that the compositions are in liquid form below about 100°C at standard pressure. Preferably, the molten composition is in liquid form below about 60° C, and more preferably below about 30°C at standard pressure. The metal halides useful in the ionic liquid component of the supported ionic liquid catalyst used in the process of this invention (and to which the selected organic base or bases, for example, are added) are those compounds which can form anions containing polyatomic chloride bridges in the presence of the alkyl-containing amine hydrohalide salt. Preferred metal halides are covalently bonded metal halides. Suitable metals which can be selected for use herein include those from Groups VIII and IB, IIB and IIIA of the Periodic Table of the Elements. Especially preferred metals are selected from the group comprising aluminum, gallium, iron, copper, zinc, and indium, with aluminum being most preferred. The corresponding most preferred halide is chloride and therefore, the most preferred metal halide is aluminum trichloride. Other possible choices for metal halides to select include those of copper (e.g., copper monochloride) , iron (e.g., ferric trichloride), and zinc (e.g., zinc dichloride) . Aluminum trichloride is most preferred because it is readily available and can form the polynuclear ion having the formula A1₂C1₇ ^". Furthermore, the molten compositions comprising this polynuclear ion are useful as described hereinbefore . Mixtures of more than one of these metal halides can be used.

Granular aluminum trichloride (+4 -14 mesh or having a particle size between 1.41 mm and 4.76 mm) can be an especially preferred metal halide to employ. It is easy to handle in air without fuming problems and has good flow properties . Its reaction with trimethylamine hydrochloride, for example, is slower and more uniform than with aluminum trichloride powder, with a temperature exotherm to about 150°C. While the resulting ionic liquid is slightly hazy due to the presence of insoluble impurities from the aluminum trichloride, the insoluble, which settle out upon storage of the liquid, do not have an adverse effect on the catalytic performance of the ionic liquid in regard to the process of the present invention. One preferred class of organic base intended to be added to the metal halide to form the ionic liquid component that is used in the process of the present invention is an alkyl-containing amine hydrohalide salt. The terminology "alkyl-containing amine hydrohalide salt", as used herein, is intended to cover monoamines , as well as diamines , triamines , other oligoamines and cyclic amines which comprises one or more "alkyl" groups and a hydrohalide anion. The term "alkyl" is intended to cover not only conventional straight and branched alkyl groups of the formula -(CH₂)_nCH₃ where n is from 0 to about 29, preferably 0 to about 17, in particular 0 to 3 , but other structures containing heteroatoms (such as oxygen, sulfur, silicon, phosphorus, or nitrogen) . Such groups can carry substituents . Representative structures include ethylenediamine, ethylenetriamine , morpholino, and poloxyalkylamine substituents. "Alkyi" include∑ "cycloalkyl" as well.

The preferred alkyl-containing amine hydrohalide salts useful in the present invention have at least one alkyl substituent and can contain as many as three alkyl substituents. The preferred compounds that are contemplated herein have the generic formula R₃N.HX, where at least one of the "R" groups is alkyl, preferably alkyl of from one to eight carbon atoms (preferably, lower alkyl of from one to four carbon atoms) and X is halogen, preferably chloride. If each of the three R groups is designated Ri, R₂ and R₃, respectively, the following possibilities exist in certain embodiments: each of R₁-R₃ can be lower alkyl optionally interrupted with nitrogen or oxygen or substituted with aryl; Ri and R₂ can form a ring with R₃ being as previously described for Rj.; R₂ and R₃ can either be hydrogen with Ri being as previously described; or R_x, R₂ and R₃ can form a bicyclic ring. Most preferably, these groups are methyl or ethyl groups. If desired the di- and trialkyl species can be used. One or two of the R groups can be aryl, but this is not preferred. The alkyl groups, and aryl, if present, can be substituted with other groups, such as a halogen. Phenyl and benzyl are representative examples of possible aryl groups to select. However, such further substitution may undesirably increase the size of the group, and correspondingly increase the viscosity of the melt. Therefore, it is highly desirable that the alkyl groups, and aryl, if present, be comprised of carbon and hydrogen groups, exclusively. Such short chains are preferred because they form the least viscous or the most conductive melts. Mixtures of these alkyl-containing amine hydrohalide salts can be used.

The mole ratio of alkyl-containing amine hydrohalide salt which is to be combined with the metal halide can, in general, range from about 1:1 to about 1:2.5. In a highly preferred embodiment, the low temperature molten composition useful as a component in the supported product that is used in the process of this invention consists essentially of the metal halide and the alkyl-containing amine hydrohalide salt.

Specifically, the most preferred low temperature molten composition is a mixture consisting essentially of a mole ratio of trimethylamine hydrochloride to aluminum trichloride of from about 1:1.5 to about 1:2, preferably about 1:2.

Typically, the metal halide and the alkyl-containing amine hydrohalide salt are solids at low temperature , i.e., below about 100° C. at standard pressure. After mixing the two solids together, the mixture can be heated until the mixture becomes a liquid. Alternatively, the heat generated by the addition of the two solids will result in forming a liquid without the need for additional external heating. Upon cooling, the mixture remains a liquid at low temperature, i.e., below about 100°C, preferably below about 60°C, and more preferably below about 30°C.

Another type of organic base which can be used in the ionic liquid component of the supported product that is used in the process of this invention is a guanidinium salt as will be described in further detail. These guanidinium salts comprise the reaction product of a guanidine or substituted guanidine compound that has been reacted with an acid to form the corresponding guanidinium salt of the acid. In general, the unsubstituted or substituted guanidine compounds will have the formula

(R₂N) ₂C=NH where R is hydrogen in the case of the unsubstituted compounds and is independently selected from alkyl (e.g., lower alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and t-butyl) and/or aryl (e.g., phenyl). The guanidine molecule, HN=C(NH₂)₂, is a strong base, pKa = 13.65, making it the strongest organic base after the quaternary ammonium hydroxides (see P. Smith, "The Chemistry of Open-Chain Organic Nitrogen Compounds", Volume I, W.A. Benjamin, Inc. New York (1965), pp. 277-279) . Alkyl guanidines are also strongly basic and form very stable salts. In salt formation, the proton is added to the dicoordinated nitrogen, forming a trigonally symmetrical cation, in which all three nitrogen atoms are seen to be equivalent. The cation with HC1, for example, can be represented as [C- (NH₂) ₃]⁺Cl^" . The cation can be represented as an immonium ion with a double bond to any of the three nitrogens or as a carbonium ion. When such a salt, with a melting point of 181°C, is mixed with a metal halide salt, such as aluminum chloride with a melting point of 190°C, for example, in a molar ratio of 1:2, respectively, an exothermic reaction takes place, resulting in the formation of a product that is a liquid about 70°C. The chloride ion present in the guanidineHCl will react with aluminum trichloride, for example, to form the A1C1₄ ^" anion. The result is an ionic liquid.

The aforementioned ionic liquid component can be supported on a solid, porous support material, such as a metal oxides (e.g., silica), a zeolite, a mesoporous material, a clay, a microporous polymer, and the like. The use of a simple impregnation of the ionic liquid component and the chosen porous support has been found to be effective in making the desired supported product. The supported ionic liquid product has a number or advantages over conventional , non-supported ionic liquids. It is, for example, more environmentally friendly and less hazardous. It is also easier to handle compared to a conventional liquid acid catalyst.

The supported ionic liquid catalyst supported on a icroporous polymer support is deemed to be a novel composition of matter. That type of microporous support is descriv=bed in U.S. Patent No. 4,519,909 to A.J. Castro, which is incorporated herein by reference. It is available from Akzo Nobel Faser A.G. under the trademark ACCUREL and is a microporous polymer having a substantially homogeneous, three-dimensional cellular structure having cells connected by pores of smaller dimension. The cells are preferably substantially spherical with an ave age diameter of from about 0.5 micron to about 100 microns and the material is hydrophobic. The ratio of the average cell diameter to the average pore diameter is from about 2:1 to about 200:1.

The following Examples, which illustrate room temperature reactions , are given to further illustrate one embodiment of the present invention.

EXAMPLE 1

First, 1.21 g of an ionic liquid composition (mole ratio of A1C1₃ : trimethylamine hydrochloride being 2:1) was impregnated onto 3.62 g of ACCUREL microporous polymer from Akzo Nobel. Then, 17.88 g of benzene and 3.22 g of dodecene was placed in a round bottom flask equipped with a stirrer. The mole ratio of benzene to dodecene was 12:1. A sample was withdrawn and analyzed by GC to show that there was no reaction in the absence of the supported ionic liquid catalyst. However, when 1.1 g of the supported ionic liquid catalyst composition was added to the mixture of benzene and dodecene, an exothermic reaction immediately took place. A sample of the product formed by this reaction was withdrawn from the flask and was analyzed by GC.

The analysis showed that dodecene had been totally converted to a dodecylbenzene composition with an 80% selectivity to monododecylbenzene . The distribution of the monododecylbenzene isomers that were produced is given below:

2-dodecylbenzene: 41.2%

3-dodecylbenzene: 19.3%

4-dodecylbenzene: 13.3%

5 and 6-dodecylbenzene : 26.2%

EXAMPLE 2

Initially, 1.53 g of an ionic liquid composition (mole ratio of A1C1₃: trimethylamine hydrochloride being 2:1) was impregnated onto 1.70 g of silica powder (DEGUSSA 530 brand) . Then, 22.85 g of benzene and 1.43 g of the supported ionic liquid catalyst composition were placed in a round bottom flask equipped with a stirrer . Subsequently, 4.0 g of dodecene was added to the flask containing benzene and the catalyst. An exothermic reaction took place immediately. A sample of the resulting product was withdrawn and was analyzed by GC, showing that the dodecene had been totally converted to a dodecylbenzene composition with 83% selectivity to monododecylbenzene. The

10

SUBSTΓΓUTE SHEET (RULE 26) distribution of the monododecylbenzene isomers that were produced is given below:

2-dodecylbenzene: 39.8%

3-dodecylbenzene : 19.6%

4-dodecylbenzene: 13.6%

5 and 6-dodecylbenzene: 27.0%

EXAMPLE 3

First, 1.38 g of an ionic liquid composition (mole ratio of A1C1₃ : trimethylamine hydrochloride being 2:1) was impregnated onto 1.0 g of ACCUREL microporous polymer from Akzo Nobel . Then, the impregnated ionic liquid (1.29 g) was added into a flask containing the remaining liquid mixture of benzene and dodecene which was described in Comparative Example 3. An exothermic reaction took place immediately with 100% conversion of the dodecene and 82% selectivity to monododecylbenzene. The distribution of the monododecylbenzene isomers that were produced is given below:

2-dodecylbenzene: 37.3%

3-dodecylbenzene: 19.0%

4-dodecylbenzene: 14.3% 5- and 6-dodecylbenzene: 29.3%

EXAMPLE 4

Initially, 3.0 g of an ionic liquid component (mole ratio of AICI₃ : trimethylamine hydrochloride being 2:1) was impregnated onto 3.0 g of ACCUREL microporous polymer from Akzo Nobel . The impregnated ionic liquid (1.56 g) was added into a flask containing 18.32 g of benzene and 3.89 g of lauryl chloride. The liquid was stirred for fifteen minutes , and a sample was taken and analyzed by GC. It was found that the lauryl chloride had been totally converted to dodecylbenzenes . The distribution of the monododecylbenzene isomers is given below:

2-dodecylbenzene : 32.2% 3-dodecylbenzene: 21.2%

4-dodecylbenzene: 17.3%

5- and 6-dodecylbenzene : 29.3% Example 5

An ionic liquid was made by mixing 13.0 g of A1C1₃ with 5.63 g of pyridine hydrochloride. The mole ratio of the A1C1₃ to the pyridine hydrochloride was 2:1. There was a very violent reaction with heat and smoke generation. The ionic liquid that was formed (1.0 g was taken) was impregnated onto 1.0 g of ACCUREL microporous polymer. Into a flask containing 21.81 g of benzene and 3.89 g of dodecene, the impregnated ionic liquid/polymer composition (0.68 g) was then added. The liquid was stirred and a sample was taken after fifteen minutes and was analyzed by GC. It was found that dodecene had been 76% converted to dodecylbenzenes with 86% selectivity to the formation of monododecyl benzene. Another sample was taken after one hour of reaction, and the conversion was about 90% with an 87% selectivity to the formation of monododecyl benzene.

COMPARATIVE EXAMPLE 6

First, 1.39 g of an ionic liquid composition (mole ratio of A1C1₃ : trimethylamine hydrochloride being 2:1) was impregnated onto 6.01 g of undried alumina extrudate (from Akzo Chemicals Inc.) . Heat was generated from the mixing process indicating that a reaction occurred between the ionic liquid and the support, possibly as a result of water content or hydroxy groups in the support. Then, 19.36 g of benzene and 5.21 g of dodecene were placed in a round bottom flask equipped with a stirrer. When 3.1 g of the above supported ionic liquid catalyst was added, no reaction took place. The addition of an additional 4.0 g of the same catalyst still produced no reaction after two hours of observation. Therefore, it appears that the alumina used in this

Comparative Example should have been dried or calcined prior to its impregnation as shown in Example 7 , which follows . Example 7

Seventy grams of an experimental alumina extrudate product: from Akzo Nobel Chemicals Inc., was dried overnight at 120°C. The pore volume of the alumina was 0.68 cc/g, and its total pore volume was calculated as 47.6 cc. This alumina product was then mixed (at 50°C - 100°C.) with 32 g of the ionic liquid trimethylammonium heptachloroaluminate, whose density was 1.475, with the volume of the ionic liquid being about 21.7 cc. The resulting mixture was then cooled to room temperature. The solid that was formed was used to catalyze the alkylation of benzene wherein 10 g of the supported ionic liquid was added to a mixture of benzene (23 g) and dodecene (5 g) . It was found that the catalytic activity for benzene alkylation with dodecene at room temperature was about 41% .

Example 8

Initially, 50 g of zeolite Y powder from Degussa Co. was pre-dried at 450°C for two hours . The pore volume of this zeolite was 0.7 cc/g and its surface area was 700 m²/g. Then, 35 cc of the ionic liquid described in Example 1 was added to 50 g of the dried zeolite Y material by the excipient wetness method, so that the volume of the ionic liquid would substantially fill the pores of the zeolite Y. The resulting material was still a powder.

Example 9

Initially, 50 g of silica pellets from Degussa was preheated at 150°C for two hours . The pore volume of this silica was 0.75 cc/g and the total volume of pores in the silica was 37.5 cc . The silica was then mixed with 37.5 cc of the ionic liquid from Example 1 to form a solid catalyst.

13

SUBSTrrUTESHEET(RULE26) Comparative Example 10

First, 50 g of activated carbon from Calgon was mixed with 15 cc of the ionic liquid described in Example 1 evolving HC1. The material solidified overnight and was tested as a solid catalyst for the alkylation of benzene. In that test, 10 g of the supported ionic liquid was added to the mixture of benzene (25 g) and dodecene (5 g) . It was found that there was no activity for benzene alkylation with dodecene at room temperature for over one hour.

COMPARATIVE EXAMPLE 11

This illustrates a recycle aromatic alkylation experiment using a non-supported ionic liquid catalyst comprising A1C1₃ and trimethylamine hydrochloride in a 2/1 mole ratio. The reactants that were employed were benzene and dodecene in a 12.2 : 1 mole ratio. The following procedure was employed:

Benzene (14.45 gm) and 2.55 gm of dodecene were added to a round bottom flask equipped with a mechanical stirrer and a thermometer. A sample was taken and analyzed by GC. The ionic liquid catalyst (0.82gm) was added to the flask containing the benzene and dodecene . An exothermic reaction took place, and temperature increased from 25°C to 45°C. A sample was withdrawn and analyzed by GC. The organic layer was removed and the used ionic liquid was left in the flask. A mixture of benzene and dodecene solution was added to the flask containing the used ionic liquid catalyst.

The above procedure was repeated for six cycles. The conversion results are shown below:

EXAMPLE 12

This Example illustrates a recycle experiment using the novel supported ionic liquid catalyst of the present invention . It was prepared by impregnating 5.1 gm of trimethylamine hydrochloride/AlCl₃ (mole ratio 2/1) ionic liquid catalyst onto 5 gm of microporous ACCUREL brand polymer.

Then, 9.77 gm of the above supported ionic liquid catalyst was packed in a column. A solution of benzene/dodecene was then prepared by mixing 624 gm of benzene and 168 gm of dodecene (mole ratio 8/1) . Seventeen grams of the above benzene/dodecene solution was then passed through the packed catalyst and the liquid was collected at the bottom of the column. The liquid was analyzed by GC. This latter procedure was repeated the above step for thirty-one cycles . The conversion results are shown below:

The preceding Examples are presented for illustrative purposes only and, for that reason, should not be construed in a limiting sense. The scope of protection sought is set forth in the Claims which follow.

Claims

We Claim:

1. A process for the alkylation of an aromatic compound by the catalyzed reaction of an alkylating agent with the aromatic compound in the presence of an effective amount of a supported ionic liquid catalyst composition which comprises a porous support which is impregnated with a catalyst, which is an ionic liquid catalyst composition, consisting essentially of (a) an organic base and (b) a metal halide.

2. The process of Claim 1 wherein the metal halide is a covalently bonded metal halide.

3. The process of Claim 2 wherein the metal of the metal halide is selected from the group comprised of aluminum, gallium, iron, copper, zinc, and indium.

4. The process of Claim 1 wherein the metal halide is aluminum trichloride.

5. The process of Claim 2 wherein the organic base is an alkyl-containing amine hydrohalide salt containing three alkyl groups .

6. The process of Claim 5 wherein the alkyl-containing amine hydrohalide salt is of the formula R₃N.HX where at least one R group is alkyl.

7. The process of Claim 5 wherein the alkyl-containing amine hydrohalide salt is of the formula R₃N.HX where at least one R group is alkyl and the metal halide contains a metal which is selected from Group VIII, Group IB, Group IIB and Group IIIA of the Periodic Table of The Elements.

8. The process of Claim 1 wherein the support is a macroporous polymer and the metal halide is a covalently bonded metal halide.

9. The process of Claim 2 wherein the support is a macroporous polymer and the metal of the metal halide is selected from the group comprised of aluminum, gallium, iron, copper, zinc, and indium.

10. The process of Claim 1 wherein the support is a macroporous polymer and the metal halide is aluminum trichloride .

11. The process of Claim 2 wherein the support is a macroporous polymer and the organic base is an alkyl-containing amine hydrohalide salt containing three alkyl groups .

12. The process of Claim 5 wherein the support is a macroporous polymer and the alkyl-containing amine hydrohalide salt is of the formula R₃N.HX where at least one R group is alkyl .

13. The process of Claim 5 wherein the support is a macroporous polymer and the alkyl-containing amine hydrohalide salt is of the formula R₃N.HX where at least one R group is alkyl and the metal halide contains a metal which is selected from Group VIII, Group IB, Group IIB and Group IIIA of the Periodic Table of The Elements .

14. The process of Claim 1 wherein the support is a metal oxide and the metal halide is a covalently bonded metal halide.

15. The process of Claim 2 wherein the support is a metal oxide and the metal of the metal halide is selected from the group comprised of aluminum, gallium, iron, copper, zinc, and indium.

16. The process of Claim 1 wherein the support is a metal oxide and the metal halide is aluminum trichloride.

17. The process of Claim 2 wherein the support is a metal oxide and the organic base is an alkyl-containing amine hydrohalide salt containing three alkyl groups.

18. The process of Claim 5 wherein the support is a metal oxide and the alkyl-containing amine hydrohalide salt is of the formula R₃N.HX where at least one R group is alkyl.

19. The process of Claim 5 wherein the support is a metal oxide and the alkyl-containing amine hydrohalide salt is of the formula R₃N.HX where at least one R group is alkyl and the metal halide contains a metal which is selected from Group VIII, Group IB, Group IIB and Group IIIA of the Periodic Table of The Elements .

20. The process of Claim 1 wherein the organic base is selected from the group consisting of a halide of imidazolium, pyridinium, sulfonium, phosphonium, guanidinium, and ammonium.

21. A supported ionic liquid composition which comprises an ionic liquid comprising an organic base and a metal halide and a support which is a microporous polymer having a substantially homogeneous, three-dimensional cellular structure having cells connected by pores of smaller dimension.

22. The composition of Claim 21 wherein the metal halide is a covalently bonded metal halide.

23. The composition of Claim 22 wherein the metal of the metal halide is selected from the group comprised of aluminum, gallium, iron, copper, zinc, and indium.

24. The composition of Claim 21 wherein the metal halide is aluminum trichloride.

25. The composition of Claim 22 wherein the organic base is an alkyl-containing amine hydrohalide salt containing three alkyl groups .

26. The composition of Claim 25 wherein the alkyl- containing amine hydrohalide salt is of the formula R₃N.HX where at least one R group is alkyl.

27. The composition of Claim 25 wherein the alkyl- containing amine hydrohalide salt is of the formula R₃N.HX where at least one R group is alkyl and the metal halide contains a metal which is selected from Group VIII, Group IB, Group IIB and Group IIIA of the Periodic Table of The Elements .

28. The composition of Claim 22 wherein the metal of the metal halide is selected from the group comprised of aluminum, gallium, iron, copper, zinc, and indium.

29. The composition of Claim 21 wherein the alkyl- containing amine hydrohalide salt is of the formula R₃N.HX where at least one R group is alkyl and the metal halide contains a metal which is selected from Group VIII, Group IB, Group IIB and Group IIIA of the Periodic Table of The Elements .

30. The composition of Claim 21 wherein the organic base is selected from the group consisting of a halide of imidazolium, pyridinium, sulfonium, phosphonium, guanidinium, and ammonium.