• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The invention relates to a catalytic composition comprising: at least one oxidation state nickel precursor (+ II) and containing a phosphine ligand complexed with nickel, at least one Lewis base, and at least one activating agent selected from the group formed by the chlorinated or brominated hydrocarbylaluminum compounds, taken alone or in a mixture, such that the molar ratio of the Lewis base group and the nickel complexed phosphine ligand of the composition to the nickel is between 5 and 30. The invention also relates to the use of said catalytic composition.
    公开号:FR3039431A1
    申请号:FR1557248
    申请日:2015-07-29
    公开日:2017-02-03
    发明作者:Pierre-Alain Breuil；Olivia Chaumet-Martin
    申请人:IFP Energies Nouvelles IFPEN；
    IPC主号:
    专利说明:

    The present invention relates to a novel nickel-based composition and its use as a catalyst in chemical transformation reactions, and in particular in a process for oligomerizing an olefinic feedstock. The invention also relates to a process for oligomerizing an olefin feedstock comprising bringing said feedstock into contact with the nickel-based composition according to the invention, and in particular a process for dimerizing ethylene, in particular butene-1 using said nickel-based composition according to the invention.
    Prior art
    The transformation of ethylene using a homogeneous nickel catalyst has been studied since 1950. This research has led to the development and commercialization of various processes.
    The development of catalytic systems capable of dimerizing ethylene to butenes involves the choice of suitable metal and ligands. Among the existing systems, several nickel-based catalyst systems using phosphine ligands have been developed.
    Thus, US Pat. No. 5,237,118 B describes a process for the oligomerization of ethylene using a catalytic composition comprising a nickel compound of zero degree of oxidation, a phophine ligand in variable proportions relative to the nickel compound. This patent also describes the use of a fluorinated organic acid for carrying out the oligomerization process.
    No. 4,242,531 B describes a process for the dimerization of olefins and uses a catalytic system based on chlorinated nickel compounds of oxidation state +2 and a halogenated alkylaluminum type activator. This patent is for the production of butenes-2.
    Patent FR 1,547,921 describes a catalytic composition based on nickel halide and phosphine which requires a prior reduction of the composition in order to prepare the active catalyst. The yields of butenes are of the order of 63% C4 including 3% butene-1.
    Patent FR 1, 588,162 describes a process for the dimerization of olefins between C2 and C4 implementing a catalytic system comprising a nickel compound and a phosphine and in particular alkyl halides with yields of butenes of the order of 80%. This patent is for the production of butenes-2.
    There is therefore still a need to develop new catalytic compositions that are more efficient in terms of yield and selectivity for the oligomerization of olefins, in particular for the dimerization of ethylene, in particular butene-1.
    The Applicant in his research has developed a novel catalyst composition comprising at least one nickel precursor, preferably halogenated, of oxidation state (+ II) and containing a phosphine ligand complexed with nickel, at least one Lewis base, and at least one activating agent selected from the group consisting of chlorinated or brominated hydrocarbylaluminum compounds, taken alone or in admixture, such as the molar ratio of the Lewis base group and the phosphine ligand complexed to the nickel of the composition on the nickel is between 5 and 30. It has surprisingly been found that such compositions exhibit interesting catalytic properties. In particular, these compositions have a good catalytic yield / selectivity couple in the oligomerization of olefins, more specifically in the dimerization of ethylene to butene-1.
    An object of the invention is to provide a novel nickel-based composition. Another object of the invention is to provide a novel catalyst system comprising said composition for chemical transformation reactions, in particular for the oligomerization of olefins, in particular the dimerization of ethylene to butene-1.
    Detailed description of the invention
    Composition according to the invention
    The catalytic composition according to the invention comprises: at least one oxidation state nickel precursor (+ II) containing a phosphine ligand complexed with nickel, at least one Lewis base, and at least one activating agent chosen from the group formed by the chlorinated and brominated compounds of hydrocarbylaluminium, taken alone or as a mixture, such that the molar ratio of the Lewis base group and phosphine ligand provided by the nickel precursor to the nickel supplied by said precursor is between 5 and 30.
    The nickel precursor according to the invention is advantageously represented by the following formula: NiX 2 (PR 1 R 2 R 3) 2, in which the groups R 1, R 2 and R 3, which are identical to or different from one another, linked or not to each other, and chosen from aromatic groups substituted or unsubstituted and optionally containing heteroelements, and / or from cyclic or unsubstituted or substituted cyclic hydrocarbon groups and optionally containing heteroelements, and wherein X is chosen from halogens such as chlorine, bromine or bromine; iodine or substituted or unsubstituted aromatic groups containing or not containing heteroelements, and / or from cyclic or unsubstituted or substituted cyclic hydrocarbon groups and optionally containing heteroelements, preferably X is chlorine or bromine.
    The aromatic groups R 1, R 2 and R 3 of the phosphine ligand PR 1 R 2 R 3 complexed with nickel are preferably chosen from the group consisting of phenyl, o-tolyl, m-tolyl, p-tolyl, mesityl, 3,5-dimethylphenyl, 4- n-butylphenyl, 4-methoxyphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-isopropoxyphenyl, 4-methoxy-3,5-dimethylphenyl, 3,5-di-tert-butyl-4-methoxyphenyl, 4- chlorophenyl, 3,5-di (trifluoromethyl) phenyl, benzyl, naphthyl, bisnaphthyl, pyridyl, bisphenyl, furanyl, thiophenyl.
    The hydrocarbyl groups R 1, R 2 and R 3 of the phosphine ligand PR 1 R 2 R 3 complexed with nickel advantageously comprise 1 to 20 carbon atoms, preferably 2 to 15 carbon atoms, preferably 3 to 10 carbon atoms. Preferably, the hydrocarbyl groups R 1, R 2 and R 3 of the phosphine ligand PR 1 R 2 R 3 complexed with nickel are chosen from the group formed by the groups methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, pentyl, cyclopentyl, hexyl and cyclohexyl. , octyl, 2-ethylhexyl, benzyl, adamantyl.
    Preferred nickel precursors are chosen from bis (trimethylphosphine) nickel dichloride, nickel bis (triethylphosphine) dichloride, bis (triisopropylphosphine) nickel dichloride, bis (tri-n-butylphosphine) nickel dichloride, dichloride nickel bis (triisobutylphosphine), bis (tri-tert-butylphosphine) nickel dichloride, bis (tripentylphosphine) nickel dichloride, bis (tricyclopentylphosphine) nickel dichloride, bis (trihexylphosphine) nickel dichloride, nickel bis (tricyclohexylphosphine), bis (tri (2-ethylhexyl) phosphine) nickel dichloride, bis (trioctylphosphine) nickel dichloride, bis (triphenylphosphine) nickel dichloride, bis (tri (2-tolyl) dichloride phosphine), bis (tri (3-tolyl) phosphine) nickel dichloride, bis (tri (4-tolyl) phosphine) nickel dichloride, bis (tri (2-naphthyl) phosphine) nickel dichloride, Nickelbis (tribenzylphosphine) dichloride, taken alone or in mixed.
    The nickel precursors described in the invention are prepared according to techniques known to those skilled in the art such as those described in the publication Organometallics, 2014, 33, 2012-2018 or US4176086.
    The catalytic composition according to the invention further comprises a Lewis base. For the purposes of the present invention, the term "Lewis base" means any chemical entity of which one constituent has a doublet or more of free or non-binding electrons. The Lewis bases according to the invention correspond in particular to any entity comprising an oxygen, phosphorus or nitrogen atom having a doublet of free or non-binding electrons, or a π double bond capable of forming with nickel a type η2 coordination, in particular to any entity comprising an oxygen, phosphorus or nitrogen atom having a pair of free or non-binding electrons.
    The Lewis base according to the invention is preferably chosen from diethyl ether, methyl tert-butyl ether, tetrahydrofuran, 1,4-dioxane, isoxazole, pyridine, pyrazine, pyrimidine, and phosphines of formula PR'1R'2R'3 in which the groups R'1, R'2 and R'3, identical to each other, linked or not with each other, are chosen from substituted or unsubstituted aromatic groups and optionally containing heteroelements and / or or from substituted or unsubstituted aromatic groups containing or not containing heteroelements, and preferably from phosphines of formula PR'1R'2R'3, R'1, R'2 and R'3 having the above definition, pyridine 1,4-dioxane and tetrahydrofuran.
    The aromatic groups R'1, R'2 and R'3 of the phosphine PR'1R'2R'3 are preferably selected from the group consisting of phenyl, o-tolyl, m-tolyl, p-tolyl and mesityl groups. , 3,5-dimethylphenyl, 4-n-butylphenyl, 4-methoxyphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-isopropoxyphenyl, 4-methoxy-3,5-dimethylphenyl, 3,5-di-tert butyl-4-methoxyphenyl, 4-chlorophenyl, 3,5-di (trifluoromethyl) phenyl, benzyl, naphthyl, bis-naphthyl, pyridyl, bisphenyl, furanyl, thiophenyl.
    The hydrocarbyl groups R'1, R'2 and R'3 of the phosphine PR'1R'2R'3 advantageously comprise 1 to 20 carbon atoms, preferably 2 to 15 carbon atoms, preferably 3 to 10 carbon atoms. of carbon. Preferably, the hydrocarbyl groups R'1, R'2 and R'3 of the phosphine PR'1R'2R'3 are chosen from the group formed by the groups methyl, ethyl, propyl, isopropyl, n-butyl, tert- butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, 2-ethylhexyl, benzyl, adamantyl.
    According to the invention, the molar ratio of the Lewis base group and phosphine ligand provided by the nickel precursor to the nickel provided by said precursor is between 5 and 25, preferably between 5 and 20, more preferably between 5 and 15. Preferably, this molar ratio is between 6 and 30, preferably between 6 and 25, more preferably between 6 and 20, even more preferably between 6 and 15.
    For the sake of clarity, it is to be understood in the present invention by the expression of this molar ratio that the number of moles of phosphine ligands present in the nickel precursor is taken into account in the calculation of the molar ratio, thus the number of moles of phosphine ligands added to the nickel precursor is added to the number of moles of Lewis base in the composition and then to the number of moles of nickel supplied by the nickel precursor.
    Advantageously according to the invention, the molar ratio of the activating agent on the base of Lewis and phosphine provided by the nickel precursor of the composition is greater than or equal to 1, preferably greater than or equal to 1.5, of preference greater than or equal to 2.
    According to the invention, the activating agent used in the catalytic composition according to the invention is preferably chosen from the group formed by the chlorinated and brominated hydrocarbylaluminium compounds, taken alone or as a mixture.
    Advantageously, said activating agent is selected from the group consisting of methylaluminum dichloride (MeAlCl 2), ethylaluminum dichloride (EtAlCl 2), ethylaluminium sesquichloride (Et 3 Al 2 Cl 3), diethylaluminum chloride (Et 2 AlCl), chloride of diisobutylaluminum (/ Bu2AlCl), isobutylaluminum dichloride (BuAICI2), alone or in admixture.
    According to the invention, the molar ratio of the activating agent to the nickel precursor is preferably greater than or equal to 5, more preferably greater than or equal to 6, and preferably less than or equal to 30, preferably less than or equal to 30, equal to 25, more preferably less than or equal to 20.
    The molar ratios cited in the present invention in particular with respect to the nickel precursor are understood and expressed relative to the number of moles of nickel introduced into the catalytic composition.
    The compositions according to the invention may also optionally comprise a solvent. It is possible to use a solvent chosen from organic solvents and in particular from ethers, alcohols, chlorinated solvents and saturated, unsaturated, aromatic or non-aromatic hydrocarbons, cyclic or otherwise. Preferably, the solvent is chosen from hexane, cyclohexane, methylcyclohexane, heptane, butane or isobutane or any other hydrocarbon fraction having boiling points above 70 ° C., preferably between 70 ° C. This 200 ° C. and preferably between 90 ° C. and 180 ° C., the monoolefins or olefins preferably comprising 4 to 20 carbon atoms, cycloocta-1,5-diene, benzene, toluene, ortho -xylene, mesitylene, ethylbenzene, dichloromethane, chlorobenzene, methanol, ethanol, pure or in mixture, and ionic liquids. In the case where the solvent is an ionic liquid, it is advantageously chosen from the ionic liquids described in US Pat. No. 6,951,831 B2 and FR 2,895,406 B1.
    Use of the composition according to the invention
    The compositions according to the invention can be used as a catalyst in a chemical transformation reaction, such as the reaction of hydrogenation, hydroformylation, cross-coupling or oligomerization of olefins. In particular, these compositions are used in a process for oligomerizing an olefin feed advantageously having 2 to 10 carbon atoms.
    Preferably, the oligomerization process is a process for dimerizing ethylene, in particular butene-1.
    The oligomerization process according to the invention operates advantageously in the presence of a solvent.
    The solvent of the oligomerization process may be chosen from organic solvents and preferably from chlorinated solvents and saturated or unsaturated hydrocarbons, aromatic or otherwise, cyclic or otherwise. In particular, said solvent is chosen from hexane, cyclohexane, methylcyclohexane, heptane, butane or isobutane, monoolefins or diolefins preferably comprising 4 to 20 carbon atoms, benzene, toluene, toluene or toluene. ortho-xylene, mesitylene, ethylbenzene, dichloromethane, chlorobenzene, pure or in admixture, and ionic liquids. In the case where said reaction solvent is an ionic liquid, it is advantageously chosen from the ionic liquids described in US Pat. No. 6,951,831 B2 and FR 2,895,406 B1. Oligomerization is defined as the conversion of a monomer unit into a compound or mixture of compounds of the general formula CpH2p with 4 <p <80, preferably with 4 <p <50, most preferably with 4 <p <26 and more preferably with 4 <p <14.
    The olefins used in the oligomerization process are olefins having from 2 to 10 carbon atoms. Preferably, said olefins are chosen from ethylene, propylene, n-butenes and n-pentenes, alone or as a mixture, pure or diluted.
    In the case where said olefins are diluted, said olefins are diluted with one or more alkane (s) or any other petroleum fraction, such as they are found in "cuts" from petroleum refining or petrochemical processes, such as catalytic cracking or steam cracking.
    Preferably, the olefin used in the oligomerization process is ethylene.
    Said olefins can come from non-fossil resources such as biomass. For example, the olefins used in the oligomerization process according to the invention can be produced from alcohols, and in particular by dehydration of alcohols.
    The concentration of nickel in the catalytic solution is advantageously between 1 × 10 -8 and 1 mol / L, and preferably between 1 × 10 -6 and 1 × 10 -2 mol / L.
    The oligomerization process advantageously operates at a total pressure of between atmospheric pressure and 20 MPa, preferably between 0.1 and 8 MPa, and at a temperature between -40 and + 250 ° C., preferably between -20 ° C. C and 150 ° C.
    The heat generated by the reaction can be removed by any means known to those skilled in the art.
    The oligomerization process can be carried out in a closed system, in a semi-open system or continuously, with one or more reaction stages. A vigorous stirring is advantageously used to ensure good contact between the reagent (s) and the catalytic system.
    The oligomerization process may be carried out batchwise. In this case, a selected volume of the solution comprising the composition according to the invention is introduced into a reactor preferably provided with the usual stirring, heating and cooling devices.
    The oligomerization process can also be carried out continuously. In this case, the solution comprising the composition according to the invention is injected into a reactor in which the olefin reacts, preferably with a temperature control.
    The catalytic composition is destroyed by any usual means known to those skilled in the art, then the reaction products and the solvent are separated, for example by distillation. The olefin that has not been transformed can be recycled to the reactor.
    The process according to the invention can be carried out in a reactor with one or more series reaction stages, the olefinic feedstock and / or the pre-conditioned catalytic composition being introduced continuously, either in the first stage or in the first and any other floor. At the outlet of the reactor, the catalytic composition may be deactivated, for example by injection of a diluted amine or not and / or of a basic aqueous solution and / or of an acidic aqueous solution. Unconverted olefins and alkanes optionally present in the feed are then separated from the oligomers by distillation.
    The products of the present process can find application as, for example, automotive fuel components, fillers in a hydroformylation process for the synthesis of aldehydes and alcohols, as components for the chemical, petrochemical, pharmaceutical or pharmaceutical industry. perfumery and / or fillers in a metathesis process for the synthesis of propylene and / or as a feedstock for a process for the production of butadiene via oxidative dehydrogenation or via a metal catalysis step, for example.
    The following examples illustrate the invention without limiting its scope. EXAMPLES
    Implementation of the catalytic test:
    The reactor is previously dried under vacuum and placed under an ethylene atmosphere. 93 ml of n-heptane are introduced into the reactor under an ethylene atmosphere. 6 mL of a solution containing nickel nickel dichloride bis (tri-n-butylphosphine) NiCl2 (P (nBu) 3) 2 or nickel bis (tricyclohexylphosphine) NiCl2 (PCy3) 2 (5 or 10 pmol) nickel complex and optionally phosphine tri-n-butylphosphine or P (nBu) 3 or tricyclohexylphosphine or PCy3, pyridine or tetrahydrofuran (40, 80 or 130 pmol) are then introduced into the reactor. Between 1 and 2 g of ethylene are then solubilized in the reactor, stirring is started and the temperature programmed at 40 ° C. After degassing the reactor, the temperature is programmed at 45 ° C (test temperature). 1 ml of a solution of ethylaluminum dichloride (75 or 150 pmol) are then introduced. The reactor is put to the test pressure (20 bar). The consumption of ethylene is monitored until the introduction of 50 g of ethylene. The ethylene feed is then cut off. The gas phase is quantified and qualified by GC, the liquid phase is weighed, neutralized and qualified by GC.
    Catalytic tests
    Examples 1-3: Study of the nickel precursor NiCbfPfnBufa)
    nNi = 5 pmol, 15 eq. EtAlCl 2, 45 ° C, 2 MPa, 100 mL n-heptane. * Comparative example. cons = consumed. eq = molar equivalent, ** corresponding C4 yield percentage weight of the C4 cut formed in the products, *** percentage of 1-C4 in the C4 cut.
    Examples 4-10: NiCbiPCvsL nickel precursor study
    nNi = 5 pmol, 15 eq. EtAlCl 2, 45 ° C, 2 MPa, 100 mL-heptane. Comparative Example, a nNi = 10 pmol. cons = consumed. eq = molar equivalent, ** corresponding C4 yield percentage weight of the C4 cut formed in the products, *** percentage of 1-C4 in the C4 cut.
    It can be seen that the catalytic compositions according to the invention (inlets 2, 3, 5, 6, 7, 8, 9 and 10) make it possible to obtain a butene (C4) cut in a yield of at least 89% and a butene-1 (1-C4) selectivity of at least 51% compared to catalytic compositions not according to the invention (inputs 1 and 4) which have a yield of up to 92% C 4 and a selectivity to butene-1 (1-C4) of between 5 and 40%.
    权利要求:
    Claims (16)
    [1" id="c-fr-0001]
    A catalytic composition comprising: at least one oxidation state nickel precursor (+ II) containing a phosphine ligand complexed with nickel, at least one Lewis base, and at least one activating agent chosen from the group formed; by the chlorinated and brominated hydrocarbylaluminium compounds, taken alone or as a mixture, such that the molar ratio of the Lewis base group and phosphine ligand provided by the nickel precursor to the nickel provided by said precursor is between 5 and 30; .
    [2" id="c-fr-0002]
    2. The composition of claim 1 wherein the molar ratio of the activating agent on the Lewis base and phosphine ligand provided by said nickel precursor is greater than or equal to 1.
    [3" id="c-fr-0003]
    3. Composition according to claim 1 or 2 wherein the nickel precursor is represented by the formula:

    with the groups R 1, R 2 and R 3, which are identical or different from one another, whether or not they are linked to one another, and which are chosen from aromatic groups which may or may not be substituted and which contain or do not contain heteroelements, and / or from substituted or unsubstituted cyclic hydrocarbon groups; or not and containing or not hetero elements, -X selected from halogens such as chlorine, bromine or iodine or aromatic groups substituted or not and containing or not heteroelements, and / or from cyclic hydrocarbon groups or not , substituted or unsubstituted and optionally containing heteroelements.
    [4" id="c-fr-0004]
    4. Composition according to one of the preceding claims, in which the nickel precursor is chosen from bis (trimethylphosphine) nickel dichloride, bis (triethylphosphine) nickel dichloride, bis (triisopropylphosphine) nickel dichloride, bis-nickel dichloride. (tri-n-butylphosphine), bis (triisobutylphosphine) nickel dichloride, bis (tri-tert-butylphosphine) nickel dichloride, bis (tripentylphosphine) nickel dichloride, bis (tricyclopentylphosphine) nickel dichloride, dichloride nickel bis (trihexylphosphine), nickel bis (tricyclohexylphosphine) dichloride, nickel bis (tri (2-ethylhexyl) phosphine), nickel bis (trioctylphosphine) dichloride, nickel bis (triphenylphosphine) dichloride, nickel bis (tri (2-tolyl) phosphine) dichloride, bis (tri (3-tolyl) phosphine) nickel dichloride, bis (tri (4-tolyl) phosphine) nickel dichloride, bis ( tri (2-naphthyl) phosphine), dichloru re nickel bis (tribenzylphosphine), taken alone or in mixture.
    [5" id="c-fr-0005]
    5. Composition according to one of the preceding claims wherein the molar ratio of the Lewis base and phosphine provided by said nickel precursor on the nickel provided by said precursor is between 5 and 25, preferably between 5 and 20. more preferably between 5 and 15.
    [6" id="c-fr-0006]
    6. Composition according to one of the preceding claims wherein the Lewis base is selected from diethyl ether, methyl tert-butyl ether, tetrahydrofuran, 1,4-dioxane, isoxazole, pyridine, pyrazine, pyrimidine , and phosphines of formula PR'1R'2R'3in which the R'1, R'2 and R'3 groups, which are identical to each other, whether or not linked to one another, are chosen from substituted or unsubstituted aromatic groups and containing or not heteroelements and / or among substituted or unsubstituted aromatic groups and optionally containing heteroelements.
    [7" id="c-fr-0007]
    7. Composition according to Claim 6, in which the aromatic groups R'1, R'2 and R'3 of the phosphine PR'1R'2R'3 are chosen from the group formed by the phenyl, o-tolyl and n-tolyl groups. tolyl, p-tolyl, mesityl, 3,5-dimethylphenyl, 4-n-butylphenyl, 4-methoxyphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-isopropoxyphenyl, 4-methoxy-3,5-dimethylphenyl, 3,5-di-tert-butyl-4-methoxyphenyl, 4-chlorophenyl, 3,5-di (trifluoromethyl) phenyl, benzyl, naphthyl, bisnaphthyl, pyridyl, bisphenyl, furanyl, thiophenyl.
    [8" id="c-fr-0008]
    8. Composition according to claim 6 wherein the hydrocarbyl groups R'1, R'2 and R'3 of the phosphine PR'1R'2R'3 comprise 1 to 20 carbon atoms, preferably 2 to 15 carbon atoms, preferably between 3 and 10 carbon atoms.
    [9" id="c-fr-0009]
    9. Composition according to claim 8 wherein the hydrocarbyl groups R'1, R'2 and R'3 of the phosphine PR'1R'2R'3 are selected from the group consisting of methyl, ethyl, propyl, isopropyl, π-butyl, tert-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, 2-ethylhexyl, benzyl, adamantyl.
    [10" id="c-fr-0010]
    10. Composition according to one of the preceding claims wherein the activating agent is selected from the group consisting of chlorinated or brominated hydrocarbylaluminium compounds alone or in mixture.
    [11" id="c-fr-0011]
    11. The composition of claim 10 wherein the activating agent is selected from the group consisting of methylaluminum dichloride (MeAICI2), ethylaluminum dichloride (EtAICI2), ethylaluminium sesquichloride (Et3AI2Cl3), diethylaluminum chloride (Et2AICI), diisobutylaluminum chloride (/ Bu2AICI), isobutylaluminum dichloride (/ BuAICI2), alone or in admixture.
    [12" id="c-fr-0012]
    12. A process for oligomerizing an olefin feedstock comprising bringing said feedstock into contact with a composition according to one of claims 1 to 11.
    [13" id="c-fr-0013]
    The process of claim 12 wherein the feedstock comprises olefins having a carbon number of from 2 to 10.
    [14" id="c-fr-0014]
    14. The method of claim 12 or 13 conducted in closed system, semi-open system, continuously or discontinuously.
    [15" id="c-fr-0015]
    15. Method according to one of claims 12 to 14 wherein the reaction is a dimerization reaction of ethylene.
    [16" id="c-fr-0016]
    16. Use of the products of the process according to one of claims 12 to 15 as components of automotive fuels, as fillers in a hydroformylation process for the synthesis of aldehydes and alcohols, as components for the chemical industry, petrochemical, pharmaceutical or perfumery and / or as fillers in a metathesis process for the synthesis of propylene and / or as feedstock for a process for the production of butadiene via oxidative dehydrogenation or via a metal catalysis step.
    类似技术:
    公开号 | 公开日 | 专利标题
    FR3045414A1|2017-06-23|NOVEL NICKEL AND PHOSPHINE-TYPE LIGAND CATALYST COMPOSITION AND LEWIS BASE AND USE THEREOF IN OLEFIN OLIGOMERIZATION PROCESS
    EP2567752B1|2018-11-21|New nickel-based catalytic composition and method for oligomerising olefins using said composition
    WO2017072026A1|2017-05-04|Nickel-based catalytic composition in the presence of a specific activator and use thereof in a olefin oligomerisation method
    EP2939742A1|2015-11-04|Novel nickel-based catalytic composition and use thereof in a method for oligomerising olefins
    WO2017016688A1|2017-02-02|Novel catalytic composition comprising nickel and a ligand of the phosphine complexed with nickel type, and use thereof in an olefin oligomerisation method
    CA2889601A1|2015-10-28|New nickel-based cyclic compounds and their use in an olefin transformation process
    FR3039430B1|2019-07-05|NOVEL NICKEL AND PHOSPHINE LIGAND CATALYST COMPOSITION AND USE THEREOF IN OLEFIN OLIGOMERIZATION PROCESS
    EP2572782B1|2014-10-22|Method for separating butene-2 from a C4 cut containing butene-2 and butene-1 by selective oligomerisation of the butene-1
    EP3013841B1|2017-05-03|Novel nickel-based complex and use thereof in a method for the oligomerisation of olefins
    WO2019105844A1|2019-06-06|New catalytic composition based on nickel and a phosphonium, and use thereof for the oligomerisation of olefins
    TWI756197B|2022-03-01|Novel catalytic composition based on nickel and a phosphine type ligand and a lewis base, and its use in a process for the oligomerization of olefins
    WO2019105843A1|2019-06-06|New catalytic composition based on nickel, a phosphorus compound and a sulfonic acid, and use thereof for the oligomerization of olefins
    FR3051683A1|2017-12-01|CHROMIUM-BASED CATALYTIC COMPOSITION AND PHOSPHINE-BASED LIGAND AND USE THEREOF IN PROCESS OF OCTENES
    FR3051793A1|2017-12-01|NICKEL COMPLEXES AND SECONDARY PHOSPHINE OXIDE TYPE LIGANDS AND USE THEREOF IN A METHOD OF OLIGOMERIZING OLEFINS
    同族专利:
    公开号 | 公开日
    US20180221861A1|2018-08-09|
    US10300473B2|2019-05-28|
    WO2017016688A1|2017-02-02|
    TWI727962B|2021-05-21|
    FR3039431B1|2019-05-31|
    CN108136382B|2021-06-15|
    TW201709982A|2017-03-16|
    CN108136382A|2018-06-08|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    GB1211738A|1966-12-09|1970-11-11|Gelsenberg Benzin Ag|Polymerisation of olefines|
    US3485881A|1967-10-09|1969-12-23|Phillips Petroleum Co|Dimerization of olefins|
    US3485892A|1967-11-22|1969-12-23|Sun Oil Co|Catalyst system and process for polymerization of olefins|
    LU51826A1|1965-09-06|1966-10-26|
    FR1588162A|1966-04-14|1970-04-10|
    US4176086A|1977-08-25|1979-11-27|Phillips Petroleum Company|Catalyst preparation|
    US4242531A|1978-08-14|1980-12-30|Phillips Petroleum Company|Olefin dimerization|
    US5237118A|1992-08-21|1993-08-17|Phillips Petroleum Company|Ethylene oligomerization|
    EP0646413B1|1993-09-22|2000-03-01|Institut Français du Pétrole|Nickel containing catalytic composition and process for dimerization and oligomerization of olefins|
    DE10303931B4|2002-02-04|2013-04-18|Institut Français du Pétrole|Catalytic composition for dimerization, co-dimerization, oligomerization and polymerization of olefins|
    CN1204155C|2002-09-03|2005-06-01|中国石油化工股份有限公司|Ligand of catalyzer for olefinic polymerization and transition metal complex|
    US7232869B2|2005-05-17|2007-06-19|Novolen Technology Holdings, C.V.|Catalyst composition for olefin polymerization|
    FR2895406B1|2005-12-22|2010-08-13|Inst Francais Du Petrole|PROCESS FOR THE PRODUCTION OF 2,3-DIMETHYLBUT-1-ENE|
    CN103328519A|2010-12-31|2013-09-25|株式会社普利司通|Bulk polymerization of conjugated dienes using nickel-based catalyst system|FR3045414B1|2015-12-18|2019-12-27|IFP Energies Nouvelles|NOVEL CATALYTIC COMPOSITION BASED ON NICKEL AND LIGAND PHOSPHINE TYPE AND A LEWIS BASE AND ITS USE IN A PROCESS OF OLEFIN OLIGOMERIZATION|
    FR3074065B1|2017-11-30|2019-12-13|IFP Energies Nouvelles|NOVEL CATALYTIC COMPOSITION BASED ON NICKEL, A PHOSPHONIUM AND ITS USE FOR OLEFIN OLIGOMERIZATION|
    FR3082759A1|2018-06-22|2019-12-27|IFP Energies Nouvelles|CATALYTIC COMPOSITION BASED ON NICKEL AND AN ORGANIC REDUCER|
    法律状态:
    2016-07-19| PLFP| Fee payment|Year of fee payment: 2 |
    2017-02-03| PLSC| Publication of the preliminary search report|Effective date: 20170203 |
    2017-07-31| PLFP| Fee payment|Year of fee payment: 3 |
    2018-07-25| PLFP| Fee payment|Year of fee payment: 4 |
    2019-07-25| PLFP| Fee payment|Year of fee payment: 5 |
    2020-07-28| PLFP| Fee payment|Year of fee payment: 6 |
    2021-07-26| PLFP| Fee payment|Year of fee payment: 7 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1557248|2015-07-29|
    FR1557248A|FR3039431B1|2015-07-29|2015-07-29|NOVEL NICKEL-BASED CATALYTIC COMPOSITION AND NICKEL COMPLEX PHOSPHINE-LIKE LIGAND AND USE THEREOF IN OLEFIN OLIGOMERIZATION PROCESS|FR1557248A| FR3039431B1|2015-07-29|2015-07-29|NOVEL NICKEL-BASED CATALYTIC COMPOSITION AND NICKEL COMPLEX PHOSPHINE-LIKE LIGAND AND USE THEREOF IN OLEFIN OLIGOMERIZATION PROCESS|
    CN201680044321.9A| CN108136382B|2015-07-29|2016-04-20|Novel catalytic composition comprising nickel and a phosphine-type ligand complexed with nickel and use thereof in a process for oligomerizing olefins|
    US15/748,494| US10300473B2|2015-07-29|2016-04-20|Catalytic composition comprising nickel and a ligand of the phosphane complexed with nickel type, and use thereof in a olefin oligomerisation method|
    PCT/EP2016/058807| WO2017016688A1|2015-07-29|2016-04-20|Novel catalytic composition comprising nickel and a ligand of the phosphine complexed with nickel type, and use thereof in an olefin oligomerisation method|
    TW105123792A| TWI727962B|2015-07-29|2016-07-27|Novel catalytic composition based on nickel and a nickel-complexed phosphine-type ligand, and its use in a process for oligomerizing olefins|
    [返回顶部]