FR2829132A1 - Catalytic composition, for alkylation of aromatic hydrocarbons, comprises Bronsted acid(s) dissolved in non-aqueous liquid medium with ionic nature - Google Patents

Catalytic composition, for alkylation of aromatic hydrocarbons, comprises Bronsted acid(s) dissolved in non-aqueous liquid medium with ionic nature Download PDF

Info

Publication number
FR2829132A1
FR2829132A1 FR0209920A FR0209920A FR2829132A1 FR 2829132 A1 FR2829132 A1 FR 2829132A1 FR 0209920 A FR0209920 A FR 0209920A FR 0209920 A FR0209920 A FR 0209920A FR 2829132 A1 FR2829132 A1 FR 2829132A1
Authority
FR
France
Prior art keywords
methyl
ionic liquid
catalytic composition
anion
bis
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
FR0209920A
Other languages
French (fr)
Other versions
FR2829132B1 (en
Inventor
Bourbigou Helene Olivier
Lionel Magna
Olivia Martin
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
IFP Energies Nouvelles IFPEN
Original Assignee
IFP Energies Nouvelles IFPEN
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from FR0111398A external-priority patent/FR2829039B1/en
Application filed by IFP Energies Nouvelles IFPEN filed Critical IFP Energies Nouvelles IFPEN
Priority to FR0209920A priority Critical patent/FR2829132B1/en
Priority to NL1021362A priority patent/NL1021362C2/en
Priority to GB0220196A priority patent/GB2383962B/en
Priority to JP2002256703A priority patent/JP4273256B2/en
Priority to US10/232,837 priority patent/US7256152B2/en
Publication of FR2829132A1 publication Critical patent/FR2829132A1/en
Application granted granted Critical
Publication of FR2829132B1 publication Critical patent/FR2829132B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • 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
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/26—Catalytic processes with hydrides or organic compounds
    • 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
    • B01J31/0215—Sulfur-containing compounds
    • B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding 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
    • B01J31/0278—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
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/20—Olefin oligomerisation or telomerisation
    • 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
    • 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
    • B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
    • B01J2231/52—Isomerisation reactions
    • 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
    • C07C2531/025—Sulfonic acids

Landscapes

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

Abstract

A catalytic composition comprises at least one Bronsted acid, dissolved in a non-aqueous liquid medium with an ionic nature. A catalytic composition comprises at least one Bronsted acid, dissolved in a non-aqueous liquid medium of formula (I) with an ionic nature. Q<+>A<-> Q<+> = organic cation; and A<-> = anion that is different from the Bronsted acid anion. Independent claims are included for: (1) An acid catalysis process which uses catalytic composition; (2) A method of alkylation of aromatic hydrocarbons by 2-20C olefin which involves using the catalytic composition; (3) Dimerization of isobutene which involves using catalytic composition, such that molar ratio of Bronsted acid to ionic liquid is 0.001/1-0.1/1; (4) Oligomerization of olefins which involves using catalytic composition, such that molar ratio of Bronsted acid to ionic liquid is 0.01/1-1/1; (5) Alkylation of at least one olefin with an isoparaffin to produce paraffinic hydrocarbons, by using catalytic composition, such that molar ratio of isoparaffin to olefin is 2/1-100/1. The isoparaffin is chosen from isobutane, methyl-2-butane, methyl-2-pentane or methyl-3-pentane. The olefin is ethylene, propylene, n-butene, isobutene, n-pentene or isopentene; (6) Isomerization of double bond of 4-30C olefin; and (7) Purification of olefin mixture.

Description

<Desc/Clms Page number 1> <Desc / Clms Page number 1>

La présente invention concerne l'oligomérisation des oléfines. The present invention relates to the oligomerization of olefins.

Il a été décrit et revendiqué dans la demande de brevet français déposée le 31 août 2001 sous le numéro d'enregistrement national 01/11 398 que l'addition d'au moins un acide de Bronsted, noté HB, dans un milieu liquide non-aqueux à caractère ionique (milieu de type sel fondu ) comprenant au moins un cation organique Q+ et un anion A-et dans laquelle, lorsque A et B sont identiques, le rapport molaire de l'acide de Bronsted sur le liquide ionique est inférieur à 1/1, conduit à des compositions liquides qui peuvent être utilisées comme catalyseurs et solvants pour des réactions de catalyse acide. It has been described and claimed in the French patent application filed on August 31, 2001 under the national registration number 01/11 398 that the addition of at least one Bronsted acid, noted HB, in a non-liquid medium. aqueous ionic character (medium of molten salt type) comprising at least one organic cation Q + and one anion A - and in which, when A and B are identical, the molar ratio of Bronsted acid to the ionic liquid is less than 1/1, leads to liquid compositions which can be used as catalysts and solvents for acid catalysis reactions.

Dans cette demande de brevet, il était mentionné que la composition catalytique décrite pouvait être utilisée plus particulièrement dans l'alkylation d'hydrocarbures aromatiques, mais aussi dans l'oligomérisation des oléfines, la dimérisation de l'isobutène, l'alkylation de l'isobutan par les oléfines, l'isomérisation des n-paraffines en iso-paraffines et l'isomérisation des n-oléfines en iso-oléfines. In this patent application, it was mentioned that the catalytic composition described could be used more particularly in the alkylation of aromatic hydrocarbons, but also in the oligomerization of olefins, the dimerization of isobutene, the alkylation of olefins. isobutan by olefins, isomerization of n-paraffins to iso-paraffins and isomerization of n-olefins to iso-olefins.

La présente invention a pour objet d'illustrer le procédé d'oligomérisation des oléfines utilisant une telle composition catalytique. The object of the present invention is to illustrate the process for oligomerization of olefins using such a catalytic composition.

La composition catalytique servant de catalyseur et de solvant est décrite plus particulièrement dans la demande 01/11 398 comme comprenant au moins un acide de Bronsted, noté HB, dissous dans un milieu liquide non-aqueux à caractère ionique (milieu de type sels fondus ) de formule générale Q+A-, dans laquelle Q+ représente un cation organique et A-représente un anion et pour laquelle, lorsque A et B sont identiques, le rapport molaire de l'acide de Bronsted sur le liquide ionique est inférieur à 1/1, de préférence de 0,01/1 à 0,7/1. The catalytic composition serving as catalyst and solvent is described more particularly in application 01/11 398 as comprising at least one Bronsted acid, denoted HB, dissolved in a non-aqueous liquid medium of ionic nature (medium of molten salt type) of general formula Q + A-, in which Q + represents an organic cation and A- represents an anion and for which, when A and B are identical, the molar ratio of Bronsted acid to the ionic liquid is less than 1 / 1, preferably 0.01 / 1 to 0.7 / 1.

Le milieu de type sels fondus dans lequel est dissous l'acide de Bronsted selon l'invention a pour formule générale Q+A-dans laquelle Q+ représente un ammonium quaternaire et/ou un phosphonium quaternaire et/ou un trialkylsulfonium et A-représente tout anion connu comme étant non-coordinant et susceptible de former un sel liquide à basse température, c'est-à-dire au-dessous de150 C. The medium of molten salt type in which the Bronsted acid according to the invention is dissolved has the general formula Q + A - in which Q + represents a quaternary ammonium and / or a quaternary phosphonium and / or a trialkylsulfonium and A - represents any anion known to be non-coordinating and capable of forming a liquid salt at low temperature, i.e. below 150 C.

Les anions A-utilisables dans le cadre de l'invention seront de préférence choisis parmi les anions tétrafluoroborate, tétraal kylbo rates, hexafluorophosphate, hexafluoroantimonate, alkylsulfonates (par exemple le méthylsulfonate), perfluoroalkylsulfonates (par exemple le trifluorométhylsulfonate), fluorosulfonate, The anions A-which can be used in the context of the invention will preferably be chosen from the anions of tetrafluoroborate, tetraal kylbo rates, hexafluorophosphate, hexafluoroantimonate, alkylsulfonates (for example methylsulfonate), perfluoroalkylsulfonates (for example trifluoromethylsulfonate), fluorosulfonate

<Desc/Clms Page number 2><Desc / Clms Page number 2>

sulfates, phosphates, perfluoroacétates (par exemple le trifluoroacétate), perfluoroalkylsulfonamides (par exemple l'amidure de bis-trifluorométhane- sulfonyl N (CF3SO2) 2-), fluorosulfonamides, perfluoroalkylsulfométhides (par exemple le méthylure de tris-trifluorométhanesulfonyle C (CF3SO2) 3-) et carboranes. sulfates, phosphates, perfluoroacetates (eg trifluoroacetate), perfluoroalkylsulfonamides (eg bis-trifluoromethanesulfonyl N (CF3SO2) 2-) amide, fluorosulfonamides, perfluoroalkylsulfomethides (eg tris3-trifluoromethanesulfonyl N (CF3SO2) 2-) methylide, perfluoroalkylsulfomethides (eg tris3Sulfon2fluoromethide methylide (CFes 3SO2) -) and carboranes.

Les ammonium et/ou phosphonium quaternaires utilisés selon l'invention, répondent de préférence aux formules générales NRlR2R3R4+ et PR1 R2R3R4+, ou aux formules générales R1 R2N=CR3R4+ et R1 R2p=CR3R4+ où R1, R2, R3 et R4, identiques ou différents, représentent l'hydrogène à l'exception, pour NR1 R2R3R4+, du cation NH4+, de préférence un seul substituant représentant l'atome d'hydrogène, ou des restes hydrocarbyles ayant de 1 à 12 atomes de carbone, par exemple des groupements alkyles, saturés ou non saturés, cycloalkyles ou aromatiques, aryle, alkaryl ou aralkyl, comprenant de 1 à 12 atomes de carbone. Les ammonium et/ou phosphonium peuvent également être dérivés d'hétérocycles azotés ou phosphorés comportant 1,2 ou 3 atomes d'azote et/ou de phosphore, de formules générales :

Figure img00020001

dans lesquelles les cycles sont constitués de 4 à 10 atomes, de préférence 5 à 6 atomes, RI et R2 étant définis comme précédemment. The quaternary ammonium and / or phosphonium used according to the invention preferably correspond to the general formulas NRlR2R3R4 + and PR1 R2R3R4 +, or to the general formulas R1 R2N = CR3R4 + and R1 R2p = CR3R4 + where R1, R2, R3 and R4, identical or different, represent hydrogen with the exception, for NR1 R2R3R4 +, of the NH4 + cation, preferably a single substituent representing the hydrogen atom, or hydrocarbyl residues having from 1 to 12 carbon atoms, for example alkyl groups, saturated or unsaturated, cycloalkyl or aromatic, aryl, alkaryl or aralkyl, comprising from 1 to 12 carbon atoms. Ammonium and / or phosphonium can also be derived from nitrogenous or phosphorus heterocycles comprising 1,2 or 3 nitrogen and / or phosphorus atoms, of general formulas:
Figure img00020001

in which the rings consist of 4 to 10 atoms, preferably 5 to 6 atoms, R1 and R2 being defined as above.

L'ammonium ou le phosphonium quaternaire peuvent également consister en un cation répondant à l'une des formules générales :

Figure img00020002

dans lesquelles R1, R2 et R3, identiques ou différents, sont définis comme précédemment et R5 représente un reste alkylène ou phénylène. The quaternary ammonium or phosphonium can also consist of a cation corresponding to one of the general formulas:
Figure img00020002

in which R1, R2 and R3, which are identical or different, are defined as above and R5 represents an alkylene or phenylene residue.

Parmi les groupements R1, R2, R3 et R4 on mentionnera les radicaux méthyle, éthyle, propyle, isopropyl, butyle, secondaire butyle, tertiaire butyle, amyle, méthylène, éthylidène, phényle ou benzyle ; R5 pourra être un groupement méthylène, éthylène, propylène ou phénylène. Among the groups R1, R2, R3 and R4, there will be mentioned the methyl, ethyl, propyl, isopropyl, butyl, secondary butyl, tertiary butyl, amyl, methylene, ethylidene, phenyl or benzyl radicals; R5 may be a methylene, ethylene, propylene or phenylene group.

Le cation ammonium et/ou phosphonium est choisi de préférence dans le

Figure img00020003

groupe formé par le N-butylpyridinium, le N-éthylpyridinium, le butyl-3 méthyl-1 The ammonium and / or phosphonium cation is preferably chosen from
Figure img00020003

group formed by N-butylpyridinium, N-ethylpyridinium, butyl-3 methyl-1

<Desc/Clms Page number 3> <Desc / Clms Page number 3>

Figure img00030001

imidazolium, le diéthylpyrazolium, l'éthyl-3 méthyl-1 imidazolium, le pyridinium, le triméthylphénylammonium, le tétrabutylphosphonium et le méthyléthylpyrrolidi- nium.
Figure img00030001

imidazolium, diethylpyrazolium, 3-ethyl-1-methylimidazolium, pyridinium, trimethylphenylammonium, tetrabutylphosphonium and methylethylpyrrolidinium.

Les trialkylsulfonium utilisés selon l'invention ont pour formule générale SR1 R2R3+, où R1, R2 et R3, identiques ou différents, représentent des restes hydrocarbyles ayant de 1 à 12 atomes de carbone, par exemple des groupements alkyles, saturés ou non saturés, cycloalkyles ou aromatiques, aryles, alkaryles ou aralkyles, comprenant de 1 à 12 atomes de carbone. The trialkylsulfonium used according to the invention have the general formula SR1 R2R3 +, where R1, R2 and R3, identical or different, represent hydrocarbyl residues having from 1 to 12 carbon atoms, for example alkyl groups, saturated or unsaturated, cycloalkyl or aromatic, aryl, alkaryl or aralkyl, comprising from 1 to 12 carbon atoms.

A titre d'exemples des liquides ioniques utilisables selon l'invention, on peut citer l'hexafluorophosphate de N-butylpyridinium, le tétrafluoroborate de N-éthyl pyridinium, l'hexafluoroantimonate de butyl-3 méthyl-1 imidazolium, l'hexafluorophosphate de butyl-3 méthyl-1 imidazolium, le trifluorométhylsulfonate de

Figure img00030002

butyl-3 méthyl-1 imidazolium, le fluorosulfonate de pyridinium, l'hexafluoro- phosphate de triméthylphénylammonium, le bis-trifluorométhylsulfonylamidure de butyl-3 méthyl-1 imidazolium, le bis-trifluorométhylsulfonylamidure de triéthyl- sulfonium, le bis-trifluorométhylsulfonylamidure de tributylhexylammonium, le
Figure img00030003

trifluoroacétate de butyl-3 méthyl-1 imidazolium et le bis-trifluorométhylsulfonyl- amidure de butyl-3 di-méthyl-1, 2 imidazolium. Ces sels peuvent être utilisés seuls ou en mélange. Ils ont une fonction de catalyseur et de solvant. As examples of the ionic liquids which can be used according to the invention, mention may be made of N-butylpyridinium hexafluorophosphate, N-ethyl pyridinium tetrafluoroborate, butyl-3-methyl-1 imidazolium hexafluorophosphate, butyl hexafluorophosphate. -3 methyl-1 imidazolium, trifluoromethylsulfonate
Figure img00030002

3-butyl-1-methylimidazolium, pyridinium fluorosulfonate, trimethylphenylammonium hexafluorophosphate, 3-butyl-1-methylsulfonylimidazolium bis-trifluoromethylsulfonylamidide, bis-triethyl-tri-sulfonylammonium bis-trifluoromethylsulfonyl amide the
Figure img00030003

3-butyl-1-methyl-1-imidazolium trifluoroacetate and 3-butyl-1-methyl-1,2-imidazolium bis-trifluoromethylsulfonyl-amide. These salts can be used alone or as a mixture. They have a catalyst and solvent function.

Les acides de Bronsted utilisés selon l'invention sont définis comme étant des composés organiques acides susceptibles de donner au moins un proton. Ces acides de Bronsted ont pour formule générale HB, dans laquelle B représente un anion. The Bronsted acids used according to the invention are defined as being acidic organic compounds capable of giving at least one proton. These Bronsted acids have the general formula HB, in which B represents an anion.

Les anions B sont de préférence choisis parmi les anions tétrafluoroborate, tétraalkylborates, hexafluorophosphate, hexafluoroantimonate, alkylsulfonates (par exemple le méthylsulfonate), perfluoroalkylsulfonates (par exemple le trifluor- méthylsulfonate), fluorosulfonate, sulfates, phosphates, perfluoroacétates (par exemple le trifluoroacétate), perfluoroalkylsulfonamides (par exemple l'amidure de bis-trifluorométhanesulfonyle N (CF3S02) 2-), fluorosulfonamides, perfluoroalkyl- sulfométhides (par exemple le méthylure de tris-trifluorométhanesulfonyle C (CF3SO2) 3-) et carboranes. The anions B are preferably chosen from the anions of tetrafluoroborate, tetraalkylborates, hexafluorophosphate, hexafluoroantimonate, alkylsulphonates (for example methylsulphonate), perfluoroalkylsulphonates (for example trifluoro-methylsulphonate), fluorosulphonate, sulphates, peroroachates, for example perfluoroalkylsulfonamides (eg bis-trifluoromethanesulfonyl N (CF3SO2) 2- amide), fluorosulfonamides, perfluoroalkylsulfomethides (eg tris-trifluoromethanesulfonyl methylide C (CF3SO2) 3-) and carboranes.

Les acides de Bronsted utilisés selon l'invention peuvent être utilisés seuls ou en mélange. The Bronsted acids used according to the invention can be used alone or as a mixture.

<Desc/Clms Page number 4> <Desc / Clms Page number 4>

Dans la demande de brevet français déposée le 17 juin 2002 sous le numéro d'enregistrement 02/07 454, concernant la dimérisation de l'isobutène, il a été mentionné que, lorsque A et B sont identiques, le rapport molaire de l'acide de Bronsted HB sur le liquide ionique Q+A-est inférieur à 1/1. Dans les exemples illustrant le procédé de dimérisation de l'isobutène, on a utilisé, de façon encore plus préférée une composition catalytique selon la définition de l'invention telle que le rapport molaire de l'acide de Bronsted HB sur le liquide ionique Q+A-est de 0,001/1 à 0, 1/1. In the French patent application filed on June 17, 2002 under the registration number 02/07 454, concerning the dimerization of isobutene, it was mentioned that, when A and B are identical, the molar ratio of the acid of Bronsted HB on the ionic liquid Q + A - is less than 1/1. In the examples illustrating the isobutene dimerization process, even more preferably a catalytic composition according to the definition of the invention such as the molar ratio of Bronsted HB acid to ionic liquid Q + was used. A-is 0.001 / 1 to 0.11.

De façon préférée, dans la formule des acides de Bronsted utilisés selon la présente invention, B représente un anion de même nature chimique que l'anion A- présent dans le liquide ionique. Dans ce cas, le rapport molaire de l'acide de Bronsted sur le liquide ionique est également inférieur à 1/1, mais il est de préférence de 0,1/1 à 1/1. Preferably, in the formula of the Bronsted acids used according to the present invention, B represents an anion of the same chemical nature as the anion A- present in the ionic liquid. In this case, the molar ratio of Bronsted acid to ionic liquid is also less than 1/1, but it is preferably 0.1 / 1 to 1/1.

La composition catalytique de l'invention peut comprendre en outre au moins un acide de Lewis. Les acides de Lewis considérés sont ceux qui sont solubles dans les milieux ioniques. A titre d'exemples, on peut citer le tristrifluorométhylsulfonate de scandium, tris-trifluorométhylsulfonate d'ytterbium, le tris (bis-trifluorométhanesulfonylamidure) de scandium, le trichlorure d'aluminium, le tétrachlorure de zirconium, le trichlorure de titane, le triphénylbore, le trifluorure de bore et le pentafluorure d'antimoine. The catalytic composition of the invention can also comprise at least one Lewis acid. The Lewis acids considered are those which are soluble in ionic media. Mention may be made, by way of examples, of scandium tristrifluoromethylsulfonate, ytterbium tris-trifluoromethylsulfonate, scandium tris (bis-trifluoromethanesulfonylamide), aluminum trichloride, zirconium tetrachloride, titanium trichloride, triphenylamide, scandium. boron trifluoride and antimony pentafluoride.

Si on utilise un acide de Lewis, la concentration de cet acide de Lewis dans le liquide ionique n'est pas critique. Elle est avantageusement de 1 à 500 mmoles de composé acide de Lewis par litre de liquide ionique, de préférence de 2 à 200 mmoles par litre, et de manière plus préférée de 2 à 100, voire de 2 à 50 par litre. If a Lewis acid is used, the concentration of this Lewis acid in the ionic liquid is not critical. It is advantageously from 1 to 500 mmoles of Lewis acid compound per liter of ionic liquid, preferably from 2 to 200 mmoles per liter, and more preferably from 2 to 100, or even from 2 to 50 per liter.

Les composés entrant dans la composition catalytique utilisée dans le procédé de l'invention peuvent être mélangés dans un ordre quelconque. Le mélange peut se faire par une simple mise en contact suivie d'une agitation jusqu'à formation d'un liquide homogène. Ce mélange peut être fait en dehors du réacteur utilisé pour l'application catalytique ou dans ce réacteur. The compounds entering into the catalytic composition used in the process of the invention can be mixed in any order. Mixing can be done by simple contact followed by stirring until a homogeneous liquid is formed. This mixing can be done outside the reactor used for the catalytic application or in this reactor.

Le procédé d'oligomérisation selon l'invention s'applique d'une manière générale aux oléfines de 4 à 20 atomes de carbone. The oligomerization process according to the invention is generally applicable to olefins of 4 to 20 carbon atoms.

Le rapport volumique entre les réactifs et le sel liquide peut être compris entre 0,1/1 et 1000/1, de préférence entre 1/1 et 100/1. Il sera choisi de façon à obtenir les meilleures sélectivités. The volume ratio between the reactants and the liquid salt can be between 0.1 / 1 and 1000/1, preferably between 1/1 and 100/1. It will be chosen so as to obtain the best selectivities.

<Desc/Clms Page number 5> <Desc / Clms Page number 5>

La réaction peut être conduite en système fermé, en système semi-ouvert ou en continu avec un ou plusieurs étages de réaction. A la sortie du réacteur, la phase organique contenant les produits de réaction est séparée. The reaction can be carried out in a closed system, in a semi-open system or continuously with one or more reaction stages. On leaving the reactor, the organic phase containing the reaction products is separated.

Dans le procédé d'oligomérisation de l'invention, on peut ajouter à la composition catalytique un solvant organique comme un hydrocarbure aliphatique non ou partiellement miscible avec le liquide ionique qui permet une meilleure séparation des phases. In the oligomerization process of the invention, it is possible to add to the catalytic composition an organic solvent such as an aliphatic hydrocarbon which is not or partially miscible with the ionic liquid, which allows better separation of the phases.

La température à laquelle on effectue la réaction d'oligomérisation va par exemple de-50 C à 200 OC ; elle est avantageusement inférieure à 100 C. The temperature at which the oligomerization reaction is carried out ranges for example from -50 ° C. to 200 ° C.; it is advantageously less than 100 C.

Les exemples suivants illustrent l'invention, mais ils ne doivent en aucune manière en limiter la portée. The following examples illustrate the invention, but they should in no way limit its scope.

EXEMPLE 1 : Préparation du système catalytique [BMI][ (CF3S02hN]/HTF2N (70/30 poids) :
On a mélangé à température ambiante, sous atmosphère inerte, 6,42g (15, 3 mmoles) de bis (trifluorométhylsulfonyl) amidure de butyl-1-méthyl-3- imidazolium ( [BMJj+KCFsSCsN]') contenant 10 ppm d'eau-préparé à partir de chlorure de butyl-1-méthyl-3-imidazolium et de bis (trifluorométhylsulfonyl) amidure de lithium-avec 2,74 g (9,75 mmoles) d'acide bistriflylamidure (CF3S02) 2NH. Le mélange est agité quelques minutes et conduit à une solution limpide contenant 29,91 % en poids d'acide. EXAMPLE 1 Preparation of the catalytic system [BMI] [(CF3S02hN] / HTF2N (70/30 weight):
6.42 g (15.3 mmol) of bis (trifluoromethylsulfonyl) butyl-1-methyl-3-imidazolium amide ([BMJj + KCFsSCsN] ') containing 10 ppm of water were mixed at room temperature, under an inert atmosphere. -prepared from butyl-1-methyl-3-imidazolium chloride and lithium bis (trifluoromethylsulfonyl) amide-with 2.74 g (9.75 mmol) of bistriflylamide (CF3S02) 2NH acid. The mixture is stirred for a few minutes and results in a clear solution containing 29.91% by weight of acid.

EXEMPLE 2 : Oligomérisation isobutène/butene-1 avec la composition de l'Exemple 1
Dans un tube Fisher-Porter de volume 50 mL, muni d'un barreau magnétique et préalablement séché à l'étude et tiré sous vide, on introduit, sous atmosphère d'argon, 6 mL (soit 9,16g) du mélange préparé dans l'Exemple 1. EXAMPLE 2 Isobutene / butene-1 Oligomerization with the Composition of Example 1
In a Fisher-Porter tube with a volume of 50 mL, fitted with a magnetic bar and previously dried during the study and drawn under vacuum, is introduced, under an argon atmosphere, 6 mL (i.e. 9.16 g) of the mixture prepared in Example 1.

Puis, on introduit, à température ambiante, 30 mL d'une charge liquide contenant 48,5 % d'isobutène, 48,2 % de butène-1 et 3,3 % de n-butane (standard interne). Then, 30 ml of a liquid feed containing 48.5% of isobutene, 48.2% of butene-1 and 3.3% of n-butane (internal standard) are introduced at room temperature.

L'agitation est alors mise en route (temps zéro de la réaction). Le démarrage de la réaction se traduit par une augmentation de la température du système jusqu'à 52,9 C. Après 35 minutes de réaction, l'agitation est arrêtée. La phase gazeuse est totalement récupérée et analysée par CPV (colonne PONA, isotherme 25 OC). Stirring is then started (zero reaction time). The start of the reaction results in an increase in the temperature of the system to 52.9 C. After 35 minutes of reaction, the stirring is stopped. The gas phase is completely recovered and analyzed by CPV (PONA column, 25 OC isotherm).

99,0 % de l'isobutène et 51,2 % de butène-1 de départ ont été convertis. La phase organique surnageante est séparée de la phase liquide ionique et traitée à la 99.0% of the starting isobutene and 51.2% of butene-1 was converted. The supernatant organic phase is separated from the ionic liquid phase and treated with

<Desc/Clms Page number 6><Desc / Clms Page number 6>

soude (10N) pour éliminer les éventuelles traces d'acide. Après séchage sur MgS04, la phase organique est analysée par CPV (avec l'heptane comme étalon externe). Cette phase est composée de 28,0 % de dimères, 51,3 % de trimères, 19,8 % de tétramères et 0,9 % de pentamères. soda (10N) to remove any traces of acid. After drying over MgSO4, the organic phase is analyzed by CPV (with heptane as an external standard). This phase is composed of 28.0% of dimers, 51.3% of trimers, 19.8% of tetramers and 0.9% of pentamers.

EXEMPLE 3 : Réutilisation du système de l'Exemple 2
L'ensemble de la phase organique surnageante de l'Exemple 2 est soutiré. EXAMPLE 3: Reuse of the system of Example 2
All of the supernatant organic phase of Example 2 is withdrawn.

On rajoute 30 mL d'une charge constituée de 48,5 % d'isobutène, 48,2 % de butene-1 et 3,3 % de n-butane. On opère comme dans l'Exemple 2. Après 48 minutes de réaction, la conversion de l'isobutène est de 97,8 %, celle du butene-1 de 19,7 %. Les produits de réaction sont à 32,5 % des dimères, 49,1 % des trimères, 16,0 % des tétramères et 2,4 % de pentamères.30 mL of a feed consisting of 48.5% isobutene, 48.2% 1-butene and 3.3% n-butane are added. The operation is carried out as in Example 2. After reaction for 48 minutes, the conversion of isobutene is 97.8%, that of butene-1 is 19.7%. The reaction products are 32.5% dimers, 49.1% trimers, 16.0% tetramers and 2.4% pentamers.

Claims (13)

REVENDICATIONS 1. Procédé d'oligomérisation d'oléfines caractérisé en ce qu'il met en jeu une composition catalytique comprenant au moins un acide de Brnsted, noté HB, dissous dans un milieu liquide non-aqueux à caractère ionique de formule générale Q+A-, dans laquelle Q+ représente un cation organique et A-représente un anion et pour laquelle, lorsque A et B sont identiques, le rapport molaire de l'acide de Bronsted sur le liquide ionique est inférieur à 1/1. CLAIMS 1. Process for the oligomerization of olefins, characterized in that it involves a catalytic composition comprising at least one Brnsted acid, denoted HB, dissolved in a non-aqueous liquid medium with ionic character of general formula Q + A -, in which Q + represents an organic cation and A- represents an anion and for which, when A and B are identical, the molar ratio of Bronsted acid to the ionic liquid is less than 1/1. 2. Procédé selon la revendication 1 caractérisée en ce que, dans la formule générale Q+A-, l'anion A-est choisi parmi les anions tétrafluoroborate, tétraalkyl- borates, hexafluorophosphate, hexafluoroantimonate, alkylsulfonates, perfluoralkylsulfonates, fluorosulfonate, sulfates, phosphates, perfluoroacétates, perfluor- alkylsulfonamides, fluorosulfonamides, perfluoroalkylsulfométhides et carboranes. 2. Method according to claim 1 characterized in that, in the general formula Q + A-, the anion A- is chosen from tetrafluoroborate, tetraalkyl borates, hexafluorophosphate, hexafluoroantimonate, alkylsulfonates, perfluoralkylsulfonates, fluorosulfonate, sulfates, phosphates , perfluoroacetates, perfluoroalkylsulfonamides, fluorosulfonamides, perfluoroalkylsulfomethides and carboranes. 3. Procédé selon la revendication 1 ou 2 caractérise en ce que, dans la formule générale Q+A-, Q+ représente un ammonium quaternaire et/ou un phosphonium quaternaire et/ou un trialkylsulfonium et A-représente tout anion connu comme étant non-coordinant et susceptible de former un sel liquide à basse température, c'est-à-dire au-dessous de 150 C. 3. Method according to claim 1 or 2, characterized in that, in the general formula Q + A-, Q + represents a quaternary ammonium and / or a quaternary phosphonium and / or a trialkylsulfonium and A- represents any anion known to be non-. coordinating and capable of forming a liquid salt at low temperature, i.e. below 150 C. 4. Procédé selon la revendication 3 caractérisé en ce que le cation ammonium et/ou phosphonium quaternaire est choisi parmi : - les cations ammonium et/ou phosphonium quaternaires répondant à l'une des formules générales NR1 R2R3R4+ et PR1 R2R3R4+, ou à l'une des formules générales R1 R2N=CR3R4+ et R1 R2p=CR3R4+ où R1, R2, R3 et R4, identiques ou différents, représentent l'hydrogène à l'exception, pour4. Method according to claim 3 characterized in that the ammonium cation and / or quaternary phosphonium is chosen from: - quaternary ammonium and / or phosphonium cations corresponding to one of the general formulas NR1 R2R3R4 + and PR1 R2R3R4 +, or to the one of the general formulas R1 R2N = CR3R4 + and R1 R2p = CR3R4 + where R1, R2, R3 and R4, identical or different, represent hydrogen with the exception, for NR1 R2R3R4+, du cation NH4+, un seul substituant représentant l'atome d'hydrogène, ou des restes hydrocarbyles ayant de 1 à 12 atomes de carbone, - les cations ammonium et/ou phosphonium quaternaires dérivés d'hétérocycles azotés ou phosphorés comportant 1,2 ou 3 atomes d'azote et/ou de phosphore, de formules générales : NR1 R2R3R4 +, the NH4 + cation, a single substituent representing the hydrogen atom, or hydrocarbyl residues having from 1 to 12 carbon atoms, - quaternary ammonium and / or phosphonium cations derived from nitrogenous or phosphorus heterocycles comprising 1, 2 or 3 atoms of nitrogen and / or phosphorus, of general formulas: <Desc/Clms Page number 8> <Desc / Clms Page number 8> dans lesquelles R', R-et R, identiques ou différents, sont définis comme précédemment et R5 représente un reste alkylène ou phénylène. in which R ', R - and R, identical or different, are defined as above and R5 represents an alkylene or phenylene residue.
Figure img00080002
Figure img00080002
 6 atomes, RI et R2 étant définis comme précédemment ; - les cations ammonium et/ou phosphonium quaternaires répondant à l'une des formules générales : 6 atoms, R1 and R2 being defined as above; - quaternary ammonium and / or phosphonium cations corresponding to one of the general formulas: dans lesquelles les cycles sont constitués de 4 à 10 atomes, de préférence 5 à in which the rings consist of 4 to 10 atoms, preferably 5 to
Figure img00080001
Figure img00080001
 5. Procédé selon la revendication 4 caractérisé en ce que le cation ammonium et/ou phosphonium quaternaire est choisi dans le groupe formé par le 5. Method according to claim 4 characterized in that the ammonium cation and / or quaternary phosphonium is chosen from the group formed by the
Figure img00080003
Figure img00080003
 N-butylpyridinium, le N-éthylpyridinium, le butyl-3 méthyl-1 imidazolium, le diéthylpyrazolium, l'éthyl-3 méthyl-1 imidazolium, le pyridinium, le triméthylphénylammonium, le tétrabutylphosphonium et le méthyléthylpyrrolidinium. N-butylpyridinium, N-ethylpyridinium, 3-butyl-1-methylimidazolium, diethylpyrazolium, 3-ethyl-1-methylimidazolium, pyridinium, trimethylphenylammonium, tetrabutylphosphonium and methylethylpyrrolidinium. 6. Procédé selon la revendication 3 caractérisé en ce que le cation trialkylsulfonium répond à la formule générale SR1 R2R3+, dans laquelle Rl, R2 et R3, identiques ou différents, représentent des restes hydrocarbyles ayant de 1 à 12 atomes de carbone. 6. Method according to claim 3, characterized in that the trialkylsulfonium cation corresponds to the general formula SR1 R2R3 +, in which R1, R2 and R3, which are identical or different, represent hydrocarbyl residues having from 1 to 12 carbon atoms. 7. Procédé selon l'une des revendications 1 à 6 caractérisé en ce que le liquide ionique est choisi parmi l'hexafluorophosphate de N-butylpyridinium, le tétrafluoroborate de N-éthyl pyridinium, l'hexafluoroantimonate de butyl-3 méthyl-1 imidazolium, l'hexafluorophosphate de butyl-3 méthyl-1 imidazolium, le trifluorométhylsulfonate de butyl-3 méthyl-1 imidazolium, le fluorosulfonate de 7. Method according to one of claims 1 to 6 characterized in that the ionic liquid is chosen from N-butylpyridinium hexafluorophosphate, N-ethyl pyridinium tetrafluoroborate, butyl-3-methyl-1 imidazolium hexafluoroantimonate, 3-butyl-1-methyl-imidazolium hexafluorophosphate, 3-butyl-1-methyl-imidazolium trifluoromethylsulfonate,
Figure img00080004
Figure img00080004
 pyridinium, l'hexafluorophosphate de triméthylphénylammonium, le bis-trifluorométhylsulfonylamidure de butyl-3 méthyl-1 imidazolium, le bis-trifluorométhylsulfonylamidure de triéthylsulfonium, le bis-trifluorométhylsulfonylamidure de tributylhexylammonium, le trifluoroacétate de butyl-3 méthyl-1 imidazolium et le bis-trifluorométhylsulfonylamidure de butyl-3 di-méthyl-1, 2 imidazolium. pyridinium, trimethylphenylammonium hexafluorophosphate, bis-trifluoromethylsulfonylamide-3-methyl-1imidazolium, bis-trifluoromethylsulfonylamidide, bis-trifluoromethylsulfonylamidide-trifluoromethylsulfonylamidide-3-methyl-1-methyl-imidazolium, bis-trifluoromethylsulfonylamidide, bis-trifluoromethylsulfonylamidium-trifluoromethylsulfonyl-methyl-trifluoromethyl-1-methyl-methyl-tri-methyl-1-methyl-1-methyl-methyl-1-methyl-1-methyl-1-methyl-1-methyl-tri-sulfonyl sulfonylamide of butyl-3-di-methyl-1, 2 imidazolium. 8. Procédé selon l'une des revendications 1 à 7 caractérisé en ce que l'anion B de l'acide de Bronsted est choisi parmi les anions tétrafluoroborate, tétraalkyl- 8. Method according to one of claims 1 to 7 characterized in that the anion B of Bronsted acid is chosen from tetrafluoroborate and tetraalkyl anions. <Desc/Clms Page number 9><Desc / Clms Page number 9> borates, hexafluorophosphate, hexafluoroantimonate, alkylsulfonates, perfluoralkylsulfonates, fluorosulfonate, sulfates, phosphates, perfluoroacétates, perfluor- alkylsulfonamides, fluorosulfonamides, perfluoroalkylsulfométhides et carboranes. borates, hexafluorophosphate, hexafluoroantimonate, alkylsulfonates, perfluoroalkylsulfonates, fluorosulfonate, sulfates, phosphates, perfluoroacetates, perfluoroalkylsulfonamides, fluorosulfonamides, perfluoroalkylsulfomethides and carboranes. 9. Procédé selon l'une des revendications 1 à 8 caractérisé en ce que, dans la formule de l'acide de Bronsted, B représente un anion de même nature chimique que l'anion A-présent dans le liquide ionique et le rapport molaire de l'acide de Bronsted sur le liquide ionique est de 0,1/1 à 1/1. 9. Method according to one of claims 1 to 8 characterized in that, in the formula of Bronsted acid, B represents an anion of the same chemical nature as the anion A-present in the ionic liquid and the molar ratio of Bronsted's acid on the ionic liquid is 0.1 / 1 to 1/1. 10. Procédé selon l'une des revendications 1 à 9 caractérisé en ce qu'elle comprend en outre au moins un acide de Lewis soluble dans le liquide ionique. 10. Method according to one of claims 1 to 9 characterized in that it further comprises at least one Lewis acid soluble in the ionic liquid. 11. Procédé selon la revendication 10 caractérisé en ce que ledit acide de Lewis est choisi parmi le tris-trifluorométhylsulfonate de scandium, tris-trifluoro- méthylsulfonate d'ytterbium, le tris (bis-trifluorométhanesulfonylamidure) de 11. The method of claim 10 characterized in that said Lewis acid is selected from scandium tris-trifluoromethylsulfonate, ytterbium tris-trifluoromethylsulfonate, tris (bis-trifluoromethanesulfonylamide)
Figure img00090001
Figure img00090001
 scandium, le trichlorure d'aluminium, le trétrachlorure de zirconium, le trichlorure de titane, le triphénylbore, le trifluorure de bore et le pentafluorure d'antimoine. scandium, aluminum trichloride, zirconium tretrachloride, titanium trichloride, triphenylboron, boron trifluoride and antimony pentafluoride. 12. Procédé selon l'une des revendications 10 et 11 caractérisé en ce que la concentration dudit acide de Lewis dans le liquide ionique est de 1 à 500 mmoles de composé acide de Lewis par litre de liquide ionique. 12. Method according to one of claims 10 and 11 characterized in that the concentration of said Lewis acid in the ionic liquid is from 1 to 500 mmoles of Lewis acid compound per liter of ionic liquid. 13. Procédé selon l'une des revendications 1 à 12 caractérisé en ce que l'on oligomérise au moins une oléfine de 4 à 20 atomes de carbone.13. Method according to one of claims 1 to 12, characterized in that at least one olefin of 4 to 20 carbon atoms is oligomerized.
FR0209920A 2001-08-31 2002-08-05 PROCESS FOR THE OLIGOMERIZATION OF OLEFINS Expired - Lifetime FR2829132B1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
FR0209920A FR2829132B1 (en) 2001-08-31 2002-08-05 PROCESS FOR THE OLIGOMERIZATION OF OLEFINS
NL1021362A NL1021362C2 (en) 2001-08-31 2002-08-30 Catalyst and solvent composition and catalyst processes using this composition.
GB0220196A GB2383962B (en) 2001-08-31 2002-08-30 Catalytic composition and use therefor
JP2002256703A JP4273256B2 (en) 2001-08-31 2002-09-02 Catalyst and solvent composition, and catalyst method using the composition
US10/232,837 US7256152B2 (en) 2001-08-31 2002-09-03 Composition of catalyst and solvent and catalysis processes using this composition

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0111398A FR2829039B1 (en) 2001-08-31 2001-08-31 CATALYST AND SOLVENT COMPOSITION FOR ACIDIC CATALYSIS PROCESSES
FR0209920A FR2829132B1 (en) 2001-08-31 2002-08-05 PROCESS FOR THE OLIGOMERIZATION OF OLEFINS

Publications (2)

Publication Number Publication Date
FR2829132A1 true FR2829132A1 (en) 2003-03-07
FR2829132B1 FR2829132B1 (en) 2004-06-18

Family

ID=26213168

Family Applications (1)

Application Number Title Priority Date Filing Date
FR0209920A Expired - Lifetime FR2829132B1 (en) 2001-08-31 2002-08-05 PROCESS FOR THE OLIGOMERIZATION OF OLEFINS

Country Status (1)

Country Link
FR (1) FR2829132B1 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007014613A2 (en) 2005-08-03 2007-02-08 Merck Patent Gmbh Dehydration of alcohols to form alkenes or ethers
WO2007057406A1 (en) * 2005-11-21 2007-05-24 Basf Se Method for producing highly reactive isobutylene homo- or copolymers from technical flows of c4-hydrocarbon using bronsted acid catalyst complexes
FR3130644A1 (en) * 2021-12-21 2023-06-23 IFP Energies Nouvelles Encapsulated catalyst composition
FR3130643A1 (en) * 2021-12-21 2023-06-23 IFP Energies Nouvelles Catalytic composition in the form of a Pickering emulsion

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2611700A1 (en) * 1987-03-05 1988-09-09 Inst Francais Du Petrole Process for the dimerisation or codimerisation of olefins
WO1995021872A1 (en) * 1994-02-10 1995-08-17 Bp Chemicals Limited Ionic liquids
WO1995021871A1 (en) * 1994-02-10 1995-08-17 Bp Chemicals Limited Ionic liquids
WO2000016902A1 (en) * 1998-09-24 2000-03-30 Bp Chemicals Limited Ionic liquids

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2611700A1 (en) * 1987-03-05 1988-09-09 Inst Francais Du Petrole Process for the dimerisation or codimerisation of olefins
WO1995021872A1 (en) * 1994-02-10 1995-08-17 Bp Chemicals Limited Ionic liquids
WO1995021871A1 (en) * 1994-02-10 1995-08-17 Bp Chemicals Limited Ionic liquids
WO2000016902A1 (en) * 1998-09-24 2000-03-30 Bp Chemicals Limited Ionic liquids

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007014613A2 (en) 2005-08-03 2007-02-08 Merck Patent Gmbh Dehydration of alcohols to form alkenes or ethers
WO2007014613A3 (en) * 2005-08-03 2007-03-29 Merck Patent Gmbh Dehydration of alcohols to form alkenes or ethers
WO2007057406A1 (en) * 2005-11-21 2007-05-24 Basf Se Method for producing highly reactive isobutylene homo- or copolymers from technical flows of c4-hydrocarbon using bronsted acid catalyst complexes
FR3130644A1 (en) * 2021-12-21 2023-06-23 IFP Energies Nouvelles Encapsulated catalyst composition
FR3130643A1 (en) * 2021-12-21 2023-06-23 IFP Energies Nouvelles Catalytic composition in the form of a Pickering emulsion
WO2023117553A3 (en) * 2021-12-21 2023-08-17 IFP Energies Nouvelles Catalytic composition in the form of a pickering emulsion
WO2023117554A3 (en) * 2021-12-21 2023-08-17 IFP Energies Nouvelles Catalytic composition in the form of an encapsulated pickering emulsion

Also Published As

Publication number Publication date
FR2829132B1 (en) 2004-06-18

Similar Documents

Publication Publication Date Title
EP0709356B1 (en) Catalytic composition and aliphatic hydrocarbon alkylation process
EP1138388B1 (en) Catalytic composition for dimerisation, codimerisation and oligomerisation of olefins
EP0448445B1 (en) Liquid non-aqueous composition with an ionic character and its use as a solvent
EP0135441B1 (en) Process for the synthesis of butene-1 by dimerisation of ethylene
EP0665057B1 (en) Catalytic composition and process for the disproportionation of olefins
FR2761618A1 (en) Catalytic composition used for alkylation of aliphatic hydrocarbon
FR2875235A1 (en) PROCESS FOR SEPARATING OXYGEN COMPOUNDS CONTAINED IN A HYDROCARBONATED LOAD USING AN IONIC LIQUID
EP0748653A1 (en) New catalytic composition containing transition metals complexes and insatured compounds hydrogenation process
EP0646412B1 (en) Catalyst composition and process for the dimerisation of olefins
FR2748019A1 (en) IMPROVED PROCESS FOR THE CONVERSION OF ETHYLENE TO BUTENE-1 WITH THE USE OF ADDITIVES BASED ON QUATERNARY AMMONIUM SALTS
EP1136123B1 (en) Catalytic composition and catalytic process of dimerisation, codimerisation and oligomerisation of olefins
EP1122230B1 (en) Process for the selective dimerisation of propylene principally to ramified dimers
FR2951728A1 (en) NOVEL COMPLEXES AND PROCESS FOR THE ORGANOMETALLIC SYNTHESIS OF GROUP 6 GRAFTS ON ANIONS AND THEIR USES IN A PROCESS FOR MATING OLEFINS
FR2829132A1 (en) Catalytic composition, for alkylation of aromatic hydrocarbons, comprises Bronsted acid(s) dissolved in non-aqueous liquid medium with ionic nature
FR2843110A1 (en) Isomerization of an olefin by displacement of the double bond, uses a composition comprising a Bronsted acid and ionic liquid containing an organic cation as catalyst/solvent
FR2829133A1 (en) Catalytic composition, for alkylation of aromatic hydrocarbons, comprises Bronsted acid(s) dissolved in non-aqueous liquid medium with ionic nature
EP1136124B1 (en) Catalytic composition and process of dimerisation, codimerisation and oligomerisation of olefins
EP1106595B1 (en) Improved hydroformylation process with cobalt and/or rhodium based catalysts in a biphasic medium
EP0576323B1 (en) Process for the alkylation of aliphatic hydrocarbons
FR2735467A1 (en) METHOD FOR MOVING THE DOUBLE LINK OF OLEFINS USING A CATALYTIC COMPOSITION BASED ON TRANSITIONAL METAL COMPLEXES
EP2599542A1 (en) Catalytic composition and process for the selective dimerization of isobutene
FR2829039A1 (en) Catalytic composition, for alkylation of aromatic hydrocarbons, comprises Bronsted acid(s) dissolved in non-aqueous liquid medium with ionic nature
FR2951727A1 (en) NOVEL COMPLEXES AND METHODS FOR ORGANOMETALLIC SYNTHESIS OF GROUP 6 AND THEIR USE IN A PROCESS FOR OLEFIN METATHESIS
FR2843111A1 (en) Purification of linear olefins by transformation of branched chain alpha olefins, using a catalyst/solvent composition base on a Bronsted acid and a non-aqueous ionic liquid
WO2019105844A1 (en) New catalytic composition based on nickel and a phosphonium, and use thereof for the oligomerisation of olefins

Legal Events

Date Code Title Description
CD Change of name or company name
PLFP Fee payment

Year of fee payment: 15

PLFP Fee payment

Year of fee payment: 16

PLFP Fee payment

Year of fee payment: 17

PLFP Fee payment

Year of fee payment: 18

PLFP Fee payment

Year of fee payment: 19

PLFP Fee payment

Year of fee payment: 20