WO1999003163A1 - Reaction d'alkylation employant une composition de catalyseur liquide ionique sur support, et composition de catalyseur - Google Patents

Reaction d'alkylation employant une composition de catalyseur liquide ionique sur support, et composition de catalyseur Download PDF

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Publication number
WO1999003163A1
WO1999003163A1 PCT/US1998/014149 US9814149W WO9903163A1 WO 1999003163 A1 WO1999003163 A1 WO 1999003163A1 US 9814149 W US9814149 W US 9814149W WO 9903163 A1 WO9903163 A1 WO 9903163A1
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group
alkyl
metal halide
metal
support
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PCT/US1998/014149
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English (en)
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Fawzy G. Sherif
Lieh-Jiun Shyu
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Akzo Nobel Inc.
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Priority to AU83868/98A priority Critical patent/AU8386898A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H01M10/39—Accumulators not provided for in groups H01M10/05-H01M10/34 working at high temperature
    • H01M10/399—Cells with molten salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
    • B01J31/0292—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate
    • B01J31/0294—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate by polar or ionic interaction with the substrate, e.g. glass
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
    • C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
    • C07C2/66—Catalytic processes
    • C07C2/68—Catalytic processes with halides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08—Silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/323—Hydrometalation, e.g. bor-, alumin-, silyl-, zirconation or analoguous reactions like carbometalation, hydrocarbation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
    • B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
    • B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
    • B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
    • B01J31/0287—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing atoms other than nitrogen as cationic centre
    • B01J31/0288—Phosphorus
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
    • B01J31/0287—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing atoms other than nitrogen as cationic centre
    • B01J31/0289—Sulfur
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/06—Halogens; Compounds thereof
    • C07C2527/122—Compounds comprising a halogen and copper
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/06—Halogens; Compounds thereof
    • C07C2527/125—Compounds comprising a halogen and scandium, yttrium, aluminium, gallium, indium or thallium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/06—Halogens; Compounds thereof
    • C07C2527/125—Compounds comprising a halogen and scandium, yttrium, aluminium, gallium, indium or thallium
    • C07C2527/126—Aluminium chloride
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/06—Halogens; Compounds thereof
    • C07C2527/128—Compounds comprising a halogen and an iron group metal or a platinum group metal
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/06—Halogens; Compounds thereof
    • C07C2527/138—Compounds comprising a halogen and an alkaline earth metal, magnesium, beryllium, zinc, cadmium or mercury
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • 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.
  • 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 C 2 to C 2 o, 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) .
  • 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) .
  • a molar ratio of aromatic compound to alkylating agent e.g., olefin
  • 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 C 4 or longer, preferably C ⁇ or longer, and the "benzene” including both unsubstituted as well as substituted (e.g., lower alkyl- substituted) benzene compounds.
  • 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.
  • 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.
  • 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 (A1C1 3 ) forming the fused chloroalumlnate salts.
  • 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 .
  • 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.
  • 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.
  • a metal halide such as aluminum trichloride, an imidazolium or pyridinium halide
  • 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.
  • 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.
  • 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.
  • fused salt compositions or ionic aprotic solvents.
  • low temperature molten is meant that the compositions are in liquid form below about 100°C at standard pressure.
  • 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 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.
  • metal halides 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 A1 2 C1 7 " .
  • 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.
  • alkyl-containing amine hydrohalide salt 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.
  • alkyl is intended to cover not only conventional straight and branched alkyl groups of the formula -(CH 2 ) n CH 3 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 R 3 N.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.
  • each of the three R groups is designated Ri, R 2 and R 3 , respectively, the following possibilities exist in certain embodiments: each of R 1 -R 3 can be lower alkyl optionally interrupted with nitrogen or oxygen or substituted with aryl; Ri and R 2 can form a ring with R 3 being as previously described for Rj.; R 2 and R 3 can either be hydrogen with Ri being as previously described; or R x , R 2 and R 3 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.
  • 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.
  • 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.
  • 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.
  • guanidinium salt 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.
  • 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.
  • the unsubstituted or substituted guanidine compounds will have the formula
  • 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).
  • alkyl e.g., lower alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and t-butyl
  • aryl e.g., phenyl
  • Alkyl guanidines are also strongly basic and form very stable salts.
  • 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- (NH 2 ) 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.
  • 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 A1C1 4 " 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.
  • a metal oxides e.g., silica
  • a zeolite e.g., a zeolite
  • mesoporous material e.g., silica
  • a zeolite e.g., silica
  • mesoporous material e.g., a clay
  • microporous polymer e.g., a microporous polymer, and the like.
  • 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.
  • An ionic liquid was made by mixing 13.0 g of A1C1 3 with 5.63 g of pyridine hydrochloride. The mole ratio of the A1C1 3 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.
  • 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.
  • Example 7 Comparative Example should have been dried or calcined prior to its impregnation as shown in Example 7 , which follows .
  • Example 7
  • 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% .
  • 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 m 2 /g.
  • 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.
  • silica pellets from Degussa 50 g 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.
  • 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.
  • 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/AlCl 3 (mole ratio 2/1) ionic liquid catalyst onto 5 gm of microporous ACCUREL brand polymer.

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Abstract

Des composés aromatiques peuvent être alkylés au moyen d'une composition de liquide ionique sur support, utilisée comme catalyseur de cette réaction. La composition renferme un liquide ionique, et est constituée essentiellement d'une base organique, d'un halogénure métallique et d'un support, qui peut être un polymère macroporeux ou un oxyde métallique tel que de la silice.
PCT/US1998/014149 1997-07-10 1998-07-10 Reaction d'alkylation employant une composition de catalyseur liquide ionique sur support, et composition de catalyseur WO1999003163A1 (fr)

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001032308A1 (fr) * 1999-11-05 2001-05-10 Imperial Chemical Industries Plc Liquides ioniques immobilises
EP1120159A1 (fr) * 1999-11-05 2001-08-01 Hölderich, W. F., Prof. Sels fondus supportés, méthode de préparation et leur utilisation
WO2002098560A1 (fr) * 2001-05-30 2002-12-12 Exxonmobil Research And Engineering Company Preparations liquides ioniques supportees
WO2003028882A1 (fr) * 2001-10-02 2003-04-10 The Queen's University Of Belfast Procedes utilisant des zeolites en tant que catalyseurs/precurseurs de catalyseur
US7285698B2 (en) 2002-11-12 2007-10-23 University Of Petroleum, Beijing Method for manufacturing alkylate oil with composite ionic liquid used as catalyst
DE102006019460A1 (de) * 2006-04-26 2007-10-31 Süd-Chemie AG Mit einer ionischen Flüssigkeit beschichteter poröser heterogener Katalysator
DE102009011815A1 (de) 2009-03-05 2010-09-09 Marco Haumann Hybridmaterialien zur heterogen katalysierten asymmetrischen Hydrierung im Gaskontakt und Verfahren zur ihrer Anwendung
WO2013061336A2 (fr) * 2011-08-23 2013-05-02 Reliance Industries Ltd Procédé de production d'hydrocarbures aromatiques alkylés
US8664460B2 (en) 2005-12-12 2014-03-04 The Queen's University Of Belfast Oligomerisation with indium (III) chloride
US8735315B2 (en) * 2003-09-16 2014-05-27 Uop Llc Isoparaffin-Olefin alkylation
WO2014178075A2 (fr) 2013-04-19 2014-11-06 Reliance Industries Limited Composé liquide ionique
US9327272B2 (en) 2009-10-30 2016-05-03 Clariant International Ltd. Method for producing a composite material

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US5003121A (en) * 1989-08-28 1991-03-26 Uop Production of alkyl aromatic compounds
US5034564A (en) * 1990-04-12 1991-07-23 Uop Production of alkyl aromatic compounds
US5693585A (en) * 1995-06-15 1997-12-02 Institut Francais Du Petrole Aliphatic alkylation catalyst comprising an active phase containing a cuprous compound on a support

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US5003121A (en) * 1989-08-28 1991-03-26 Uop Production of alkyl aromatic compounds
US5034564A (en) * 1990-04-12 1991-07-23 Uop Production of alkyl aromatic compounds
US5693585A (en) * 1995-06-15 1997-12-02 Institut Francais Du Petrole Aliphatic alkylation catalyst comprising an active phase containing a cuprous compound on a support

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001032308A1 (fr) * 1999-11-05 2001-05-10 Imperial Chemical Industries Plc Liquides ioniques immobilises
EP1120159A1 (fr) * 1999-11-05 2001-08-01 Hölderich, W. F., Prof. Sels fondus supportés, méthode de préparation et leur utilisation
AU774373B2 (en) * 1999-11-05 2004-06-24 Johnson Matthey Plc Immobilised ionic liquids
US6969693B2 (en) 1999-11-05 2005-11-29 Johnson Matthey Plc Immobilised ionic liquids
WO2002098560A1 (fr) * 2001-05-30 2002-12-12 Exxonmobil Research And Engineering Company Preparations liquides ioniques supportees
US6673737B2 (en) 2001-05-30 2004-01-06 Exxonmobil Research And Engineering Company Ionic liquid compositions
WO2003028882A1 (fr) * 2001-10-02 2003-04-10 The Queen's University Of Belfast Procedes utilisant des zeolites en tant que catalyseurs/precurseurs de catalyseur
US7119235B2 (en) 2001-10-02 2006-10-10 The Queen's University Of Belfast Process utilizing zeolites as catalysts/catalyst precursors
US7285698B2 (en) 2002-11-12 2007-10-23 University Of Petroleum, Beijing Method for manufacturing alkylate oil with composite ionic liquid used as catalyst
US8735315B2 (en) * 2003-09-16 2014-05-27 Uop Llc Isoparaffin-Olefin alkylation
US8664460B2 (en) 2005-12-12 2014-03-04 The Queen's University Of Belfast Oligomerisation with indium (III) chloride
DE102006019460A1 (de) * 2006-04-26 2007-10-31 Süd-Chemie AG Mit einer ionischen Flüssigkeit beschichteter poröser heterogener Katalysator
US8334232B2 (en) 2006-04-26 2012-12-18 Sud-Chemie Ag Porous heterogeneous catalyst coated with an ionic liquid
DE102009011815A1 (de) 2009-03-05 2010-09-09 Marco Haumann Hybridmaterialien zur heterogen katalysierten asymmetrischen Hydrierung im Gaskontakt und Verfahren zur ihrer Anwendung
US9327272B2 (en) 2009-10-30 2016-05-03 Clariant International Ltd. Method for producing a composite material
WO2013061336A2 (fr) * 2011-08-23 2013-05-02 Reliance Industries Ltd Procédé de production d'hydrocarbures aromatiques alkylés
WO2013061336A3 (fr) * 2011-08-23 2013-06-20 Reliance Industries Ltd Procédé de production d'hydrocarbures aromatiques alkylés
WO2014178075A2 (fr) 2013-04-19 2014-11-06 Reliance Industries Limited Composé liquide ionique
US9624248B2 (en) 2013-04-19 2017-04-18 Reliance Industries Limited Ionic liquid compound

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