WO2000041809A1 - Catalyseur a base de liquide ionique pour alkylation - Google Patents

Catalyseur a base de liquide ionique pour alkylation Download PDF

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Publication number
WO2000041809A1
WO2000041809A1 PCT/GB1999/004196 GB9904196W WO0041809A1 WO 2000041809 A1 WO2000041809 A1 WO 2000041809A1 GB 9904196 W GB9904196 W GB 9904196W WO 0041809 A1 WO0041809 A1 WO 0041809A1
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Prior art keywords
halide
ionic liquid
process according
aromatic hydrocarbon
catalyst
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PCT/GB1999/004196
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English (en)
Inventor
Brian Ellis
Fabienne Hubert
Peter Wasserscheid
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Bp Chemicals Limited
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Priority to AU16721/00A priority Critical patent/AU1672100A/en
Publication of WO2000041809A1 publication Critical patent/WO2000041809A1/fr

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    • 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
    • B01J31/0278—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
    • 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
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
    • 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
    • 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
    • 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
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides

Definitions

  • This invention relates to a process for the alkylation of aromatic hydrocarbons using an ionic liquid as a catalyst.
  • Alkylation of aromatic hydrocarbons is well known in the art and may be carried out by the reaction of an alkyl halide with an aromatic hydrocarbon in the presence of a Lewis acid catalyst such as hydrofluoric acid, boron trifluoride, concentrated sulphuric acid, zeolites and combinations thereof.
  • a Lewis acid catalyst such as hydrofluoric acid, boron trifluoride, concentrated sulphuric acid, zeolites and combinations thereof.
  • the use of these types of acids incurs one or more disadvantages. Acids which are corrosive such as hydrofluoric require extensive safety measures for both personnel and equipment. If the acid is relatively inactive, e.g. cone, sulphuric acid, relatively large volumes of the acid may need to be employed.
  • the use of zeolites requires the use of relatively high reaction temperatures.
  • EP-A-0693045 describes a method for the alkylation of aromatics using an ionic liquid as catalyst.
  • the ionic liquid catalyst is used as such or is used as a solution in an aliphatic hydrocarbon such as e.g. hexane, heptane, cyclohexane or a halohydrocarbon such as chloropentane.
  • WO 98/03454 describes a process for making linear alkylbenzenes e.g.
  • dodecyl benzene from a benzene reactant and a conventional alkylating agent such as a chloroalkane or an olefin having an average carbon atom content of more than 10 using a low temperature molten ionic liquid as a catalyst.
  • the molten ionic liquid comprises a mixture of a metal halide such as aluminium trichloride and an alkyl-containing amine hydrohalide salt such as trimethylamine hydrochloride.
  • WO 98/50153 describes a process for making linear alkylbenzenes eg dodecyl benzene from a benzene reactant and a conventional alkylating agent such as a chloroalkane or an olefin having an average carbon atom content of more than 10 using an ionic liquid as a catalyst.
  • the ionic liquid catalyst which comprises a mixture of a metal halide such as aluminium trichloride and an alkyl-containing amine hydrohalide salts such as trimethylamine hydrochloride is formed in-situ in the alkylation reactor. It has now been found that a catalyst comprising an ionic liquid which has been complexed with an aromatic hydrocarbon prior to use in an alkylation process provides a substantial improvement in catalyst activity compared to prior art alkylation catalysts.
  • the present invention provides a catalyst comprising a pre-formed complex of an ionic liquid and an aromatic hydrocarbon wherein the ionic liquid comprises
  • R is a C1-C6 alkyl group
  • M is aluminium or gallium
  • X is a halogen atom
  • n is 0, 1 or 2 and,
  • a second component selected from the group consisting of an alkyl ammonium halide, an imidazolium halide, a pyridinium halide, a hydrocarbyl substituted quaternary ammonium halide, a hydrocarbyl substituted quaternary phosphonium halide and mixtures thereof
  • R is a C1-C6 alkyl group
  • M is aluminium or gallium
  • X is a halogen atom
  • n is 0, 1 or 2 and,
  • a second component selected from the group consisting of an alkyl ammonium halide, an imidazolium halide, a pyridinium halide, a hydrocarbyl substituted quaternary ammonium halide, a hydrocarbyl substituted quaternary phosphonium halide and mixtures thereof
  • a further embodiment of the present invention provides a process for the alkylation of aromatic hydrocarbons comprising the steps :
  • R is a C1-C6 alkyl group
  • M is aluminium or gallium
  • X is a halogen atom
  • n is 0, 1 or 2
  • a second component selected from the group consisting of an alkyl ammonium halide, an imidazolium halide, a pyridinium halide, a hydrocarbyl substituted quaternary ammonium halide, a hydrocarbyl substituted quaternary phosphonium halide and mixtures thereof ; and
  • step (B) reacting an aromatic hydrocarbon with an olefin in the presence of the product of step (A).
  • pre-formed complex is meant that a complex of the ionic liquid and an aromatic hydrocarbon is formed prior to the use of the complex in an alkylation reaction.
  • ionic liquid is meant a mixture of components (a) and (b) as specified above where said mixture is a liquid at ambient temperature or is a liquid after the components have been subjected to a heating step to form a homogeneous liquid and the mixture remains in the liquid state after the source of heat has been withdrawn.
  • Ionic liquids are suitably liquids at a temperature below 100°C, preferably below 60°C and even more preferably below 40°C.
  • the component (a) is of formula R n MX3_ n wherein R is a C1-C6 alkyl group, M is aluminium or gallium, X is a halogen atom and n is 0, 1 or 2.
  • M is preferably aluminium.
  • X may be fluorine, bromine, chlorine or iodine, preferably chlorine.
  • n is 0 or 1, more preferably, n is 0.
  • R is a Cl- C6 alkyl group, such as methyl, ethyl, n-butyl, sec-butyl, and t-butyl, preferably ethyl.
  • Component (a) is suitably an aluminium halide, such as aluminium trichloride, or an alkyl aluminium halide such as an alkyl aluminium dihalide e.g. ethyl aluminium dichloride or a dialkyl aluminium halide.
  • component (a) is suitably a gallium halide such as gallium trichloride, an alkyl gallium halide such as an alkyl gallium dihalide e.g. ethyl gallium dichloride or a dialkyl gallium halide.
  • Component (a) is most preferably, aluminium trichloride.
  • the aluminium trichloride may be in granular (e.g. +4 to -14 mesh) or powder form.
  • the component (b) is selected from the group consisting of an alkyl ammonium halide, an imidazolium halide, a pyridinium halide, a hydrocarbyl substituted quaternary ammonium halide, a hydrocarbyl substituted quaternary phosphonium halide and mixtures thereof.
  • the alkyl ammonium halide may be derived from a monoamine, a diamine, a triamine or a polyamine and includes cyclic amines.
  • the alkyl ammonium halide is of the formula R 3 N.HX, wherein each R group is independently selected from hydrogen or an alkyl group with the proviso that at least one R group is an alkyl group; and X is a halide.
  • the alkyl group may have 1-30 carbon atoms, preferably 1-10 carbon atoms.
  • the alkyl group may be saturated or unsaturated, preferably saturated.
  • the alkyl group may be straight or branched chain.
  • the alkyl group may be substituted or unsubstituted e.g. by a substituent containing heteroatoms such as oxygen or nitrogen or by an aryl substituent.
  • the alkyl group is unsubstituted.
  • the alkyl groups may be the same or different.
  • the halide group, X may be fluoride, chloride, bromide or iodide but is preferably chloride.
  • the alkyl ammonium halides may be an ammonium halide of methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, butylamine, dibutylamine, tributylamine, ethylenediamine, diethylenetriamine, triethylenetetramine, morpholines and polyoxyalkylene amines.
  • the alkyl ammonium halide is triethylamine hydrochloride.
  • hydrocarbyl substituted imidazolium halide or the hydrocarbyl substituted pyridinium halide is suitably selected from l-alkyl-3 -alkyl imidazolium halides and 1 -alkyl pyridinium halides respectively.
  • these compounds include the following: l-methyl-3 -ethyl imidazolium chloride, l-ethyl-3 -butyl imidazoliium chloride, l-methyl-3 -butyl imidazolium chloride, l-methyl-3 -butyl imidazolium bromide, l-methyl-3 -propyl imidazolium chloride, l-methyl-3 -hexyl imidazolium chloride, l-methyl-3 -octyl imidazolium chloride, l-methyl-3 -decyl imidazolium chloride, l-methyl-3 -dodecyl imidazolium chloride, l-methyl-3 -hexadecyl imidazolium chloride, l-methyl-3 -octadecyl imidazolium chloride,
  • the imidazolium halides may be prepared by any of the methods known in the art, such as those described in FR-A-2626572.
  • a l-alkyl-3 -methyl imidazolium halide may be prepared by mixing dry 1-methylimidazole with a 1 -alkyl haloalkane. If a homogeneous mixture is desired the mixing may be carried out in the presence of a suitable solvent such as acetonitrile.
  • the components are then placed e.g. in a Corius tube inside a dry box.
  • the Corius tube is then closed within the dry box using a super seal and is sealed under vacuum.
  • the two components form two layers inside the Corius tube and the resulting mixture is then heated to about 100°C for about a week.
  • the resultant product is then cooled to room temperature to form a viscous product which is then transferred from the dry box to a Schlenk round bottomed flask and left under vacuum for a few hours.
  • the resultant viscous liquid is then analysed so as to characterise the l-alkyl-3 -methyl imidazolium halide. This procedure may be readily scaled-up using methods known to the man skilled in the art.
  • component (b) is a hydrocarbyl substituted quaternary ammonium halide
  • the quaternary ammonium halide may be substituted by one or more hydrocarbyl groups e.g. 1-4.
  • the hydrocarbyl group may be hydrogen, alkyl, aryl, aralkyl or alkaryl. Where there are two or more hydrocarbyl groups, each hydrocarbyl group may be the same or different with the proviso that at least one hydrocarbyl group is alkyl.
  • the hydrocarbyl group is alkyl
  • the alkyl group suitably has 1-20 carbon atoms, preferably 1- 18 and more preferably from 1-6 carbon atoms.
  • the alkyl group may be saturated or unsaturated, preferably saturated.
  • the alkyl group may be unsubstituted or substituted, preferably unsubstituted.
  • the hydrocarbyl substituted quaternary ammonium halide is a tetra-alkyl ammonium halide.
  • component (b) is a hydrocarbyl substituted phosphonium halide
  • the phosphonium halide may be substituted by one or more hydrocarbyl groups e.g. 1-4 hydrocarbyl groups.
  • the hydrocarbyl group may be hydrogen, alkyl, aryl, aralkyl or alkaryl. Where there are two or more hydrocarbyl groups, each hydrocarbyl group may be the same or different with the proviso that at least one hydrocarbyl group is alkyl.
  • the hydrocarbyl group is alkyl
  • the alkyl group suitably has 1-20 carbon atoms, preferably 1-18 and more preferably from 1-6 carbon atoms.
  • the alkyl group may be saturated or unsaturated, preferably saturated.
  • the alkyl group may be unsubstituted or substituted, preferably unsubstituted.
  • the hydrocarbyl substituted phosphonium halide is a tetra-alkyl phosphonium halide. It is well understood in the art that the mole ratio of the components in an ionic liquid which is used as catalyst should be such that the components remain in a liquid state under the reaction conditions. Typically the mole ratio of component (a) to component (b) is 1: 1 to 4: 1, preferably 1.5:1 to 2.5: 1, more preferably 2:1.
  • the ionic liquid may suitably be prepared by mixing components (a) and (b) in an atmosphere inert under conventional reaction conditions e.g. as described in EP-A-
  • the metal halide such as aluminium trichloride can be purified by repeated sublimations until a clear melt is formed at the bottom of the sublimator and the aluminium trichloride takes on a lustrous, shiny appearance
  • the hydrocarbyl substituted imidazolium or pyridinium halides can be purified by repeated recrystallisations from solutions thereof in a suitable solvent
  • the hydrocarbyl substituted quaternary ammonium or phosphonium halide can be purified by dissolving the halide in a suitable solvent such as e.g. ethanol and precipitating the halide from the ethanol solution by dilution with e.g. diethyl ether followed by filtration and drying in an inert atmosphere.
  • the ionic liquid Prior to use, the ionic liquid is complexed with an aromatic hydrocarbon.
  • the aromatic hydrocarbon may be benzene, alkyl substituted benzenes, bicyclic aromatic hydrocarbons or polycyclic aromatic hydrocarbons or mixtures thereof.
  • the alkyl substituted benzenes may be monoalkyl, dialkyl, trialkyl or tetraalkyl substituted benzenes.
  • the alkyl group preferably has 1-20 carbon atoms, more preferably, 2-6 carbon atoms, especially 2 carbon atoms.
  • the alkyl group may be saturated or unsaturated, preferably saturated.
  • the alkyl substituted benzene is toluene, ethylbenzene, the diethylbenzenes (1,2 diethylbenzene, 1,3 diethylbenzene and 1,4 diethylbenzene) and the dimethylbenzenes (1,2 dimethylbenzene, 1,3 dimethylbenzene and 1,4 dimethylbenzene).
  • the bicyclic aromatic hydrocarbons are suitably the diphenyls.
  • the polycyclic aromatic hydrocarbons are suitably the napthalenes.
  • Suitable mixtures include a mixture of benzene, ethylbenzene, diethylbenzenes, triethylbenzenes and tetraetylbenzenes.
  • the mixture of aromatic hydrocarbons may comprise the products of the alkylation reaction.
  • the aromatic hydrocarbon to be complexed with the ionic liquid is the same or substantially the same as the aromatic hydrocarbon to be alkylated in order to minimise the formation of by-products and to avoid contamination of the desired alkylation products.
  • the aromatic hydrocarbon to be complexed with the ionic liquid may comprise at least a portion of the alkylation products formed in the alkylation reaction.
  • the relative amounts of ionic liquid and the aromatic hydrocarbon should be such that at least a portion of the ionic liquid forms a complex with the non-aliphatic hydrocarbon e.g. 1:2 to 2:1 by volume, preferably 1 : 1 by volume.
  • the alkylation process of the present invention is suitable for the alkylation of aromatic hydrocarbons such as monocyclic aromatic hydrocarbons e.g. benzene and toluene, bicyclic aromatic hydrocarbons e.g. the diphenyls and polycyclic aromatic hydrocarbons such as naphthalenes.
  • aromatic hydrocarbons such as monocyclic aromatic hydrocarbons e.g. benzene and toluene, bicyclic aromatic hydrocarbons e.g. the diphenyls and polycyclic aromatic hydrocarbons such as naphthalenes.
  • the olefins that may be used in the alkylation process of the present invention are suitably C2-C10 olefins, preferably the lower olefins, e.g. the C2-C4 olefins, particularly ethylene, propylene and the butenes (butene-1, butene-2 and isobutene).
  • the mole ratio of olefin to the aromatic hydrocarbon is suitably in the range from 0.1 to 0.9, preferably from 0.2 to 0.4.
  • the alkylation reaction may suitably be carried out at a temperature in the range from 80 to 200°C, preferably from 100 to 170°C.
  • the reaction pressure of the alkylation reaction may be in the range from 0.5 to 3.0 MPa, preferably from 1.0 to 2.4 MPa.
  • the reactor pressure used is dependent upon the vapour pressure of the aromatic hydrocarbon and the desire to achieve a set olefin to aromatic hydrocarbon ratio (within the ranges described above).
  • the alkylation reaction is suitably carried out in an atmosphere inert under the reaction conditions such as e.g. nitrogen.
  • the catalyst (pre-formed complex of the ionic liquid and aromatic hydrocarbon) is suitably used in an amount from 0.01 to 1.0% w/w, preferably from 0.05 to 0.5% w/w based on the total weight of the hydrocarbon reactants in the reaction mixture.
  • the catalyst may be used with a co-catalyst such as e.g. an alkyl halide.
  • the alkyl group of the alkyl halide is suitably such that it corresponds to the olefin used for alkylation of the aromatic hydrocarbon.
  • Examples of the alkyl halides that may be suitably used include ethyl chloride and tertiary butyl chloride.
  • the co-catalyst is soluble in the non-aliphatic hydrocarbon solvent used to prepare the ionic liquid complex.
  • water may be used as the co-catalyst.
  • the amount of water used is preferably 0.01 -2% w/w, more preferably 0.1-0.3% w/w based on the total weight of the pre-formed complex catalyst.
  • the volume of the ionic liquid was found to be 109.2 ml, with a weight of 124.32 g, indicating a density of 1.14 g/ml.
  • the density of the ionic liquid is lower than that of ionic liquid layer of the Comparative Example 1 due to the presence of dissolved/complexed benzene.
  • Example 1 The catalysts prepared in Example 1 and the Comparative Example 1 were used in the alkylation of benzene with ethylene to form ethylbenzene.
  • the procedure was carried out as follows. A 1 litre stainless steel autoclave was initially charged with ethylene (0.567 mol) at a temperature of 21.6°C to give a partial pressure of 14.1 barg. Benzene ( 250 ml, 2.80 mol) was then delivered to the autoclave via a suitable high- pressure liquid pump, such that the ratio of benzene to ethylene in the autoclave was 5 : 1.
  • the reactants were then stirred at 800 rpm using a double-paddle stainless steel stirrer, and then heated by connecting the autoclave to a thermostatically-controlled oil heating bath maintained at a temperature of 150°C.
  • the autoclave was fully lagged to facilitate the heating process, such that a constant temperature of 130°C and pressure of about 20 barg was attained in the autoclave after 3 hours.
  • 10 mis of ionic liquid catalyst (as prepared in Comparative Example 1 or Example 1) was delivered to the autoclave over 2-3 seconds under 20 bar nitrogen pressure, and this point was taken as the start of reaction. All feeds to the autoclave were isolated during operation.
  • reaction progress was monitored by the decrease in reactor pressure, (due to the consumption of ethylene in the alkylation reaction) and the level of reaction exotherm as measured by the temperature increase. After 50 minutes residence time, the mixing and heating equipment were switched off, and the reactor left to cool overnight.
  • the reactants were then stirred at 800 rpm using a double-paddle stainless steel stirrer, and then heated by connecting the autoclave to a thermostatically-controlled oil heating bath maintained at a temperature of 150°C.
  • the autoclave was fully lagged to facilitate the heating process, such that a constant temperature of 130°C and pressure of about 20 barg was attained in the autoclave after 3 hours.
  • the autoclave was then charged with 37.49 g (0.28 mol) of aluminium trichloride (A1C1 3 ) slurried in 100 ml benzene (added over 2-3 seconds under 20 bar nitrogen pressure) and this point was taken as the start of the reaction. All feeds to the autoclave were isolated during operation.
  • reaction progress was monitored by the decrease in reactor pressure, (due to the consumption of ethylene in the alkylation reaction) and the level of reaction exotherm as measured by the temperature increase. After 50 minutes residence time, the mixing and heating equipment were switched off, and the reactor left to cool overnight.
  • the tabulated data shows almost a ten-fold decrease in time to 80% ethylene conversion for Example 1 when compared with the Comparative Examples due to the greater reactivity of the ionic liquid catalyst of the present invention compared to the prior art ionic liquid alkylation catalysts.

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Cette invention concerne un catalyseur qui comprend un complexe préformé d'un liquide ionique et d'un hydrocarbure aromatique. Le liquide ionique comprend les éléments suivants: (a) un premier composant correspondant à la formule RnMX3-n où R représente un groupe alkyle C1-C6, M représente aluminium ou gallium, X représente un atome halogène et n est égal à 0, 1 ou 2; et (b) un second composant choisi dans le groupe comprenant un halogénure d'ammonium d'alkyle, un halogénure d'imidazolium, un halogénure de pyridinium, un halogénure d'ammonium quaternaire substitué par hydrocarbyle, un halogénure de phosphonium quaternaire substitué par hydrocarbyle et des mélange de ces derniers. Ce catalyseur peut être utilisé lors de l'alkylation d'hydrocarbures aromatiques à l'aide d'oléfines, par exemple lors de l'alkylation de benzène à l'aide d'éthylène. L'utilisation de ce complexe catalytique préformé permet d'atteindre un taux de transformation élevé du mélange de départ.
PCT/GB1999/004196 1999-01-15 1999-12-13 Catalyseur a base de liquide ionique pour alkylation WO2000041809A1 (fr)

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AU16721/00A AU1672100A (en) 1999-01-15 1999-12-13 Ionic liquid catalyst for alkylation

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GB9900747.8 1999-01-15

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Cited By (28)

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WO2001064622A2 (fr) * 2000-03-01 2001-09-07 Akzo Nobel N.V. Procede de preparation d'une suspension seche d'halogenure d'ammonium
WO2003089389A3 (fr) * 2002-04-22 2004-03-18 Chevron Phillips Chemical Co Procede de production de catalyseurs liquides ioniques
WO2005042447A1 (fr) * 2003-10-31 2005-05-12 Chevron Phillips Chemical Company, Lp Procede et systeme pour le contact entre un catalyseur ionique liquide et de l'oxygene, permettant d'ameliorer une reaction chimique
US20070142686A1 (en) * 2005-12-21 2007-06-21 Chevron Oronite Company Llc Method of making an alkylated aromatic using acidic ionic liquid catalyst
US7259284B2 (en) 2000-05-31 2007-08-21 Chevron Phillips Chemical Company, Lp Method for manufacturing high viscosity polyalphaolefins using ionic liquid catalysts
US7285698B2 (en) 2002-11-12 2007-10-23 University Of Petroleum, Beijing Method for manufacturing alkylate oil with composite ionic liquid used as catalyst
CN100348320C (zh) * 2005-03-24 2007-11-14 北京化工大学 一种生产烷基化油的离子液体催化剂及其制备方法
US7351780B2 (en) 2002-04-22 2008-04-01 Chevron Phillips Chemical Company, Lp Method for manufacturing high viscosity polyalphaolefins using ionic liquid catalysts
MD4062C1 (ro) * 2010-01-16 2011-03-31 Институт Химии Академии Наук Молдовы Compoziţie catalitică pentru reacţia Morita-Baylis-Hillman
US7951889B2 (en) 2003-10-31 2011-05-31 Chevron Phillips Chemical Company Lp Method and system to add high shear to improve an ionic liquid catalyzed chemical reaction
DE102011007559A1 (de) 2010-04-19 2011-10-20 Basf Se Verfahren zur Herstellung von Elektrolyten für die Aluminiumabscheidung
DE102011007566A1 (de) 2010-04-19 2012-01-19 Basf Se Verfahren zur Herstellung von Zusammensetzungen, welche Aluminiumtrihalogenide enthalten
WO2012084642A1 (fr) * 2010-12-22 2012-06-28 Solvay Sa Fabrication de chlorure de vinyle par hydrochloration d'acétylène en présence d'un système catalytique constitué d'au moins un liquide ionique
WO2013061336A2 (fr) * 2011-08-23 2013-05-02 Reliance Industries Ltd Procédé de production d'hydrocarbures aromatiques alkylés
US8871954B2 (en) 2011-01-10 2014-10-28 Reliance Industries Limited Process for the preparation of alditol acetals
WO2014178075A2 (fr) 2013-04-19 2014-11-06 Reliance Industries Limited Composé liquide ionique
US8936719B2 (en) 2006-03-22 2015-01-20 Ultraclean Fuel Pty Ltd. Process for removing sulphur from liquid hydrocarbons
US8969595B2 (en) 2011-01-10 2015-03-03 Reliance Industries Limited Method of making diacetal compound in aqueous medium
US9029575B2 (en) 2011-01-10 2015-05-12 Reliance Industries Limited Process for preparation of acetals
CN105032491A (zh) * 2015-07-03 2015-11-11 浙江大学 一种用于烷基化反应含离子液体负载型催化剂的制备方法
WO2016071871A1 (fr) * 2014-11-07 2016-05-12 Reliance Industries Limited Procédé de transalkylation basé sur un composé liquide ionique
US9441169B2 (en) 2013-03-15 2016-09-13 Ultraclean Fuel Pty Ltd Process for removing sulphur compounds from hydrocarbons
CN108568317A (zh) * 2017-03-09 2018-09-25 新乡市瑞丰新材料股份有限公司 一种三氯化铝络合催化剂、其制备方法及应用
US10144685B2 (en) 2014-02-07 2018-12-04 Saudi Basic Industries Corporation Removal of aromatic impurities from an alkene stream using an acid catalyst
US10214697B2 (en) 2013-03-15 2019-02-26 Ultraclean Fuel Pty Limited Process for removing sulphur compounds from hydrocarbons
US10519080B2 (en) 2014-02-07 2019-12-31 Saudi Basic Industries Corporation Removal of aromatic impurities from an alkene stream using an acid catalyst, such as an acidic ionic liquid
CN114478390A (zh) * 2021-12-20 2022-05-13 西安近代化学研究所 一种钛基酸性离子液体、制备方法及应用
CN117384065A (zh) * 2023-12-13 2024-01-12 潍坊裕凯化工有限公司 一种2-亚甲基戊二腈制备方法

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WO2001064622A3 (fr) * 2000-03-01 2002-02-28 Akzo Nobel Nv Procede de preparation d'une suspension seche d'halogenure d'ammonium
WO2001064622A2 (fr) * 2000-03-01 2001-09-07 Akzo Nobel N.V. Procede de preparation d'une suspension seche d'halogenure d'ammonium
US7259284B2 (en) 2000-05-31 2007-08-21 Chevron Phillips Chemical Company, Lp Method for manufacturing high viscosity polyalphaolefins using ionic liquid catalysts
US7615598B2 (en) 2002-04-22 2009-11-10 Chevron Phillips Chemical Company Lp Method for manufacturing high viscosity polyalphaolefins using ionic liquid catalysts
US7351780B2 (en) 2002-04-22 2008-04-01 Chevron Phillips Chemical Company, Lp Method for manufacturing high viscosity polyalphaolefins using ionic liquid catalysts
WO2003089389A3 (fr) * 2002-04-22 2004-03-18 Chevron Phillips Chemical Co Procede de production de catalyseurs liquides ioniques
US6984605B2 (en) 2002-04-22 2006-01-10 Chevron Phillips Chemical Company, Lp Method for manufacturing ionic liquid catalysts
US7285698B2 (en) 2002-11-12 2007-10-23 University Of Petroleum, Beijing Method for manufacturing alkylate oil with composite ionic liquid used as catalyst
US7951889B2 (en) 2003-10-31 2011-05-31 Chevron Phillips Chemical Company Lp Method and system to add high shear to improve an ionic liquid catalyzed chemical reaction
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US7309805B2 (en) 2003-10-31 2007-12-18 Chevron Phillips Chemical Company Lp Method and system to contact an ionic liquid catalyst with oxygen to improve a chemical reaction
WO2005042447A1 (fr) * 2003-10-31 2005-05-12 Chevron Phillips Chemical Company, Lp Procede et systeme pour le contact entre un catalyseur ionique liquide et de l'oxygene, permettant d'ameliorer une reaction chimique
US8163856B2 (en) 2003-10-31 2012-04-24 Chevron Phillips Chemical Company Lp Method and system to add high shear to improve an ionic liquid catalyzed chemical reaction
CN100348320C (zh) * 2005-03-24 2007-11-14 北京化工大学 一种生产烷基化油的离子液体催化剂及其制备方法
AU2006327205B2 (en) * 2005-12-21 2013-04-04 Chevron Oronite Company Llc A method of making an alkylated aromatic using acidic ionic liquid catalyst
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US20070142686A1 (en) * 2005-12-21 2007-06-21 Chevron Oronite Company Llc Method of making an alkylated aromatic using acidic ionic liquid catalyst
US8936719B2 (en) 2006-03-22 2015-01-20 Ultraclean Fuel Pty Ltd. Process for removing sulphur from liquid hydrocarbons
MD4062C1 (ro) * 2010-01-16 2011-03-31 Институт Химии Академии Наук Молдовы Compoziţie catalitică pentru reacţia Morita-Baylis-Hillman
DE102011007566A1 (de) 2010-04-19 2012-01-19 Basf Se Verfahren zur Herstellung von Zusammensetzungen, welche Aluminiumtrihalogenide enthalten
DE102011007559A1 (de) 2010-04-19 2011-10-20 Basf Se Verfahren zur Herstellung von Elektrolyten für die Aluminiumabscheidung
WO2012084642A1 (fr) * 2010-12-22 2012-06-28 Solvay Sa Fabrication de chlorure de vinyle par hydrochloration d'acétylène en présence d'un système catalytique constitué d'au moins un liquide ionique
US9029575B2 (en) 2011-01-10 2015-05-12 Reliance Industries Limited Process for preparation of acetals
US8871954B2 (en) 2011-01-10 2014-10-28 Reliance Industries Limited Process for the preparation of alditol acetals
US8969595B2 (en) 2011-01-10 2015-03-03 Reliance Industries Limited Method of making diacetal compound in aqueous medium
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
US10214697B2 (en) 2013-03-15 2019-02-26 Ultraclean Fuel Pty Limited Process for removing sulphur compounds from hydrocarbons
US9441169B2 (en) 2013-03-15 2016-09-13 Ultraclean Fuel Pty Ltd Process for removing sulphur compounds from hydrocarbons
RU2654697C2 (ru) * 2013-04-19 2018-05-22 Релайанс Индастриз Лимитед Ионная жидкость
WO2014178075A2 (fr) 2013-04-19 2014-11-06 Reliance Industries Limited Composé liquide ionique
WO2014178075A3 (fr) * 2013-04-19 2014-12-24 Reliance Industries Limited Composé liquide ionique
JP2016516810A (ja) * 2013-04-19 2016-06-09 リライアンス、インダストリーズ、リミテッドＲｅｌｉａｎｃｅ Ｉｎｄｕｓｔｒｉｅｓ Ｌｉｍｉｔｅｄ イオン性液体化合物
US9624248B2 (en) 2013-04-19 2017-04-18 Reliance Industries Limited Ionic liquid compound
US10519080B2 (en) 2014-02-07 2019-12-31 Saudi Basic Industries Corporation Removal of aromatic impurities from an alkene stream using an acid catalyst, such as an acidic ionic liquid
US10144685B2 (en) 2014-02-07 2018-12-04 Saudi Basic Industries Corporation Removal of aromatic impurities from an alkene stream using an acid catalyst
WO2016071871A1 (fr) * 2014-11-07 2016-05-12 Reliance Industries Limited Procédé de transalkylation basé sur un composé liquide ionique
CN105032491A (zh) * 2015-07-03 2015-11-11 浙江大学 一种用于烷基化反应含离子液体负载型催化剂的制备方法
CN108568317A (zh) * 2017-03-09 2018-09-25 新乡市瑞丰新材料股份有限公司 一种三氯化铝络合催化剂、其制备方法及应用
CN114478390A (zh) * 2021-12-20 2022-05-13 西安近代化学研究所 一种钛基酸性离子液体、制备方法及应用
CN114478390B (zh) * 2021-12-20 2023-11-10 西安近代化学研究所 一种钛基酸性离子液体、制备方法及应用
CN117384065A (zh) * 2023-12-13 2024-01-12 潍坊裕凯化工有限公司 一种2-亚甲基戊二腈制备方法
CN117384065B (zh) * 2023-12-13 2024-02-20 潍坊裕凯化工有限公司 一种2-亚甲基戊二腈制备方法

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