EP3463653A1 - Katalytische zusammensetzung mit chrom und einem liganden auf phosphinbasis und deren verwendung in einem octenherstellungsverfahren - Google Patents

Katalytische zusammensetzung mit chrom und einem liganden auf phosphinbasis und deren verwendung in einem octenherstellungsverfahren

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Publication number
EP3463653A1
EP3463653A1 EP17723148.7A EP17723148A EP3463653A1 EP 3463653 A1 EP3463653 A1 EP 3463653A1 EP 17723148 A EP17723148 A EP 17723148A EP 3463653 A1 EP3463653 A1 EP 3463653A1
Authority
EP
European Patent Office
Prior art keywords
composition
groups
chromium
chosen
compounds
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.)
Withdrawn
Application number
EP17723148.7A
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English (en)
French (fr)
Inventor
Pierre-Alain Breuil
David Proriol
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IFP Energies Nouvelles IFPEN
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IFP Energies Nouvelles IFPEN
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Publication of EP3463653A1 publication Critical patent/EP3463653A1/de
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
    • B01J31/1875—Phosphinites (R2P(OR), their isomeric phosphine oxides (R3P=O) and RO-substitution derivatives thereof)
    • B01J31/188—Amide derivatives thereof
    • 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
    • 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
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
    • B01J31/1875—Phosphinites (R2P(OR), their isomeric phosphine oxides (R3P=O) and RO-substitution derivatives thereof)
    • 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
    • C07C2/32—Catalytic processes with hydrides or organic compounds as complexes, e.g. acetyl-acetonates
    • 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
    • C07C2/36—Catalytic processes with hydrides or organic compounds as phosphines, arsines, stilbines or bismuthines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
    • B01J2531/62—Chromium
    • 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
    • C07C2531/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • C07C2531/14—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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • C07C2531/24—Phosphines

Definitions

  • the present invention describes a catalyst composition based on chromium and a particular ligand.
  • the invention also relates to the process for preparing said composition and its use in a process for producing octene from ethylene.
  • Chromium-based catalyst systems or compositions and diphosphine ligands are known to catalyze the selective conversion of ethylene to octene-1.
  • the effectiveness of such systems is a function of the reaction conditions and the choice of the ligand structure. In particular, the nature and position of all the substituents of the ligand used have a decisive influence on the performance of the catalytic system.
  • One of the defects of these catalytic compositions is the obligation of their implementation at low temperature, that is to say at a temperature of between 45 and 60 ° under penalty of significant deactivation of the catalytic system and the loss of selectivity. in octene-1.
  • the operation at high temperature is advantageous in that it makes it possible in particular to increase the viscosity and thus the management of the heavy by-products formed.
  • None of the ligands described comprises the molecule fragment corresponding to the structure N (R 6 ) with R 6 corresponding to the formula -XOP-, with X being a divalent bridging group advantageously chosen from alkylidenes.
  • the described catalytic compositions have shown a high-temperature degraded octene-1 selectivity.
  • the Applicant in his research has developed a novel catalyst composition
  • a novel catalyst composition comprising at least one chromium precursor, at least one heteroatomic ligand described by the general formula (I) (R 1 ) 2 P-O- (CH 2 ) nN [P (R 2 ) 2] 2, and at least one activator.
  • the composition according to the invention has shown particularly advantageous catalytic properties, especially in the olefin tetramerization reaction and more particularly in the tetramerization reaction of ethylene in octene-1. Surprisingly, it has been observed that the compositions according to the invention have a very good productivity in octene-1 notwithstanding the implementation of the tetramerisation process at temperatures going beyond 60 ⁇ , or even beyond 80 ⁇ .
  • compositions according to the invention can be implemented in a tetramerization reaction under higher temperature conditions than the conventional compositions of the prior art, without impairing the productivity of octene-1 of the catalytic system, nor its selectivity towards the production of octene-1.
  • alkyl means a linear or branched hydrocarbon chain having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms.
  • Preferred alkyl groups are preferably selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl and hexyl. These alkyl groups may be substituted with heteroelements or groups containing heteroelements such as a halide, an alkoxy.
  • alkoxy substituent means an alkyl-O- group in which the term alkyl has the meaning given above. Preferred examples of alkoxy substituents are methoxy or ethoxy.
  • cyclic alkyl is meant a monocyclic hydrocarbon group having a number of carbons greater than 3, preferably between 4 and 24, more preferably between 5 and 18, preferably a cyclopentyl, cyclohexyl, cyclooctyl or cyclododecyl, or polycyclic (bicyclic or tricyclic) group having a carbon number greater than 3, preferably between 5 and 18, such as, for example, adamantyl or norbornyl groups; .
  • These groups may be substituted by heteroelements or groups containing heteroelements such as a halide, an alkoxy.
  • aromatic is meant a mono- or polycyclic aromatic group substituted or not, preferably mono- or bicyclic substituted or unsubstituted, having a number of carbon atoms between 5 and 20.
  • the group is polycyclic, it is that is, it comprises more than one ring aromatic ring, the ring rings can advantageously be condensed two by two or attached in pairs by bonds ⁇ .
  • the aromatic group according to the invention may contain a heteroelement such as nitrogen, oxygen or sulfur. These groups may be substituted by heteroelements or groups containing heteroelements such as a halide, an alkoxy.
  • the present invention relates to a composition
  • a composition comprising:
  • groups R 1 and R 2 which are identical or different from each other, whether or not they are linked together, are chosen from cyclic or non-cyclic alkyl groups and aromatic groups, and n is an integer greater than or equal to 1,
  • the integer n of the fragment - (CH 2) n - of the ligand is between 1 and 15.
  • the molar ratio between the ligand and the chromium precursor is between 0.01 and 100.
  • the molar ratio between the activator and the chromium precursor is between 1 and 10,000.
  • the chromium precursor is selected from CrCl 3 , CrCl 3 (tetrahydrofuran) 3 , Cr (acetylacetonate) 3 , Cr (naphthenate) 3 , Cr (2-ethylhexanoate) 3 , Cr (acetate) 3 .
  • the groups R 1 and R 2 of the ligand which are identical or different from each other, whether or not they are linked together, are chosen from a cyclic or non-cyclic alkyl group, aromatic or otherwise, having from 1 to 15 carbon atoms.
  • the groups R 1 and R 2 which are identical to or different from each other, linked or not to each other, are chosen from methyl, trifluoromethyl, ethyl, n-propyl, i-propyl, n-butyl and i-butyl groups, and -butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, adamantyl, substituted or unsubstituted, whether or not containing heteroelements; phenyl, o-tolyl, m-tolyl, p-tolyl, mesityl, 3,5-dimethylphenyl, 4-n-butylphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-isopropoxyphenyl, 4-methoxyphenyl, 3,5-dimethylphenyl, 3,5-ditert-butyl-4-methoxyphenyl, 2-ch
  • the activating agent is chosen from tris (hydrocarbyl) aluminum compounds, chlorinated or brominated hydrocarbylaluminum compounds, aluminum halides, aluminoxanes, organoboron compounds, organic compounds capable of giving a proton, taken alone. or in mixture.
  • the invention also relates to the process for preparing the composition according to the invention, comprising contacting
  • groups R 1 and R 2 which are identical or different from each other, whether or not they are linked together, are chosen from cyclic or non-cyclic alkyl groups and aromatic groups, and n is an integer greater than or equal to 1,
  • compositions according to the invention as a catalyst.
  • the invention relates to a process for the tetramination of ethylene to octene-1.
  • compositions according to the invention are provided.
  • the present invention relates to a composition
  • a composition comprising:
  • groups R 1 and R 2 which are identical or different from each other, whether or not they are linked together, are chosen from cyclic or non-cyclic alkyl groups and aromatic groups, and n is an integer greater than or equal to 1,
  • the chromium precursor according to the invention may be chosen from chromium compounds used in olefin oligomerization processes.
  • the chromium precursor present in the composition according to the invention may comprise one or more identical or different anions chosen from the group formed by halides, carboxylates, acetylacetonates, alkoxy and aryloxy anions.
  • the chromium compound may be a chromium (II) or chromium (III) salt, but also a salt of different oxidation state that may comprise one or more identical or different anions such as, for example, halides, carboxylates, acetylacetonates, alkoxy or aryloxy anions.
  • the chromium precursors preferably used in the invention are the chromium (III) compounds because they are more accessible, but a chromium (I) or chromium (II) compound may also be suitable.
  • the chromium precursor is selected from CrCl 3 , CrCl 3 (tetrahydrofuran) 3 , Cr (acetylacetonate) 3 , Cr (naphthenate) 3 , Cr (2-ethylhexanoate) 3 , Cr (acetate) 3 .
  • the heteroatomic liqand is selected from CrCl 3 , CrCl 3 (tetrahydrofuran) 3 , Cr (acetylacetonate) 3 , Cr (naphthenate) 3 , Cr (2-ethylhexanoate) 3 , Cr (acetate) 3 .
  • the integer number n of the - (CH 2 ) n - fragment of the ligand according to the invention is preferably between 1 and 15, more preferably between 2 and 15, even more preferably between 2 and 10, and even more preferably between 3 and 6.
  • the groups R 1 and R 2 which are identical to or different from each other, whether or not linked to one another, are chosen from a cyclic or non-cyclic alkyl group having from 1 to 15 carbon atoms, preferably from 1 to 10 carbon atoms, or an aromatic group having a number of carbons greater than 3, preferably between 4 and 24, more preferably between 5 and 18.
  • the groups R 1 and R 2 identical or different.
  • the groups R 1 and R 2 which are identical to or different from each other, whether or not linked to one another are chosen from methyl, ethyl, i-propyl, n-butyl, i-butyl and t-butyl groups. , cyclopentyl, cyclohexyl.
  • the groups R 1 and R 2 which are identical to or different from each other, whether or not linked to one another are chosen from phenyl, o-tolyl, m-tolyl, p-tolyl, mesityl and 2-methoxyphenyl groups.
  • the activating agent is the activating agent
  • the composition according to the invention may include an activating agent.
  • the activating agent may be chosen from compounds known to those skilled in the art. Mixtures of activating agents may also be used.
  • the activating agents according to the invention are chosen from tris (hydrocarbyl) aluminum compounds, chlorinated or brominated compounds of hydrocarbylaluminium, aluminum halides, aluminoxanes, organoboron compounds, organic compounds capable of giving a proton , taken alone or mixed.
  • alkylaluminium halides such as dimethylaluminum chloride, diethylaluminum chloride, ethylaluminium dichloride, methylaluminum sesquichloride, ethylaluminium sesquichloride, methylaluminum dichloride, dichloride, and the like. isobutylaluminum, aluminum trichloride; and aluminoxanes, used alone or as a mixture.
  • Aluminoxanes are well known to those skilled in the art as oligomeric compounds that can be prepared by the controlled addition of water to an aluminum alkyl, for example trimethylaluminum. Such compounds can be linear, cyclic or mixtures of these compounds. They are generally represented by the formula [RAIO] a wherein R is a hydrocarbon group and a is a number from 2 to 50.
  • the aluminoxane is chosen from methylaluminoxane (MAO) and / or ethylaluminoxane (EAO) and or among modified aluminoxanes such as modified methylaluminoxane (MMAO).
  • said activating agent is preferably chosen from Lewis acids of tris (aryl) borane type such as tris (perfluorophenyl) borane, tris (3,5-bis (trifluoromethyl) phenyl) borane, tris (2,3,4,6-tetrafluorophenyl) borane, tris (perfluoronaphthyl) borane, tris (perfluobiphenyl) borane and their derivatives and (aryl) borates associated with a triphenylcarbenium cation or to a trisubstituted ammonium cation such as triphenylcarbenium tetrakis (perfluorophenyl) borate, ⁇ , ⁇ -dimethylanilinium tetrakis (perfluorophenyl) borate, ⁇ , ⁇ -diethylanilinium tetrakis (3,5-bis
  • said activating agent is chosen from organic compounds capable of giving a proton
  • said activating agent is preferably chosen from the acids of formula HY in which Y represents an anion, such as HBF 4 or F 3 CS0 3 H.
  • compositions according to the invention are preferably prepared by placing in contact with each other.
  • groups R 1 and R 2 which are identical or different from each other, whether or not they are linked together, are chosen from cyclic or non-cyclic alkyl groups and aromatic groups, and n is an integer greater than or equal to 1,
  • the molar ratio between the ligand and the chromium precursor is between 0.01 and 100, and preferably between 0.5 and 5, in particular 0.8 and 3.
  • the molar ratio between the activator and the chromium precursor is between 1 and 10,000, preferably between 100 and 5000, even more preferably between 200 and 3500.
  • compositions according to the invention may be prepared in situ in the presence or in the absence of the filler, in particular ethylene.
  • the compositions according to the invention may be in the presence or absence of a solvent.
  • a solvent advantageously chosen from solvents capable of dissolving the reagents.
  • organic solvents There may be mentioned saturated or unsaturated aliphatic hydrocarbon solvents such as pentane, hexane, cyclohexane, methylcyclohexane, or heptane, cyclohexene, cyclooctene or cyclooctadiene.
  • Aromatic solvents such as benzene, toluene or xylenes may be mentioned. There may be mentioned oxygenated solvents such as diethyl ether or tetrahydrofuran, chlorinated solvents such as dichloromethane or chlorobenzene. These solvents can be used alone or as a mixture.
  • the temperature at which the components of the composition according to the invention are mixed is advantageously between -40 and + 150 °, preferably between 0 and + 80 °, for example at a temperature close to room temperature (15 to 30 ° C.). The mixing can be carried out under an atmosphere of ethylene or inert gas.
  • Another object of the invention relates to the use of the compositions according to the invention as a catalyst.
  • compositions according to the invention can be used as a catalyst in a chemical transformation reaction, in particular in an oligomerization process comprising contacting said feedstock comprising olefins having a number of carbon atoms of between 2 and 10 with the composition according to the invention, said method is advantageously operated at a total pressure of between atmospheric pressure and 20 MPa and at a temperature between -40 and 250 ⁇ C.
  • composition according to the invention is advantageously used in an olefin tetramerization process, in particular in an ethylene tetramerisation process in octene-1.
  • the solvent of the oligomerization process may be chosen from organic solvents and preferably from ethers, alcohols, chlorinated solvents and saturated or unsaturated hydrocarbons, aromatic or otherwise, cyclic or otherwise.
  • 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.
  • reaction solvent is an ionic liquid
  • it is advantageously chosen from the ionic liquids described in US Pat. Nos. 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 C p H 2p 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.
  • said olefins are chosen from ethylene, propylene, n-butenes and n-pentenes, alone or as a mixture, pure or diluted.
  • said olefins are diluted, said olefins are diluted with one or more alkane (s), as found in "cuts" from petroleum refining processes, such as catalytic cracking or cracking at the same time. steam.
  • the olefin used in the oligomerization process and in particular in the tetramerization process according to the invention is ethylene.
  • Said olefins can come from non-fossil resources such as biomass.
  • the olefins used in the oligomerization process according to the invention and in particular in the tetramerization process according to the invention can be produced from alcohols, and in particular by dehydration of alcohols.
  • the oligomerization process in particular the tetramerization process according to the invention, advantageously operates at a total pressure of between atmospheric pressure and 20 MPa, preferably between 0.1 and 8 MPa, and at a temperature of between -40 and + 250 °, preferably between 0 and 150 °, preferably between 20 and 135 °, preferably between 45 and 100 °, preferably between 75 and 100 °, preferably between 80 and 100 °.
  • the heat generated by the reaction can be removed by any means known to those skilled in the art.
  • the oligomerization process in particular the tetramerization process according to the invention, can be carried out in a closed system, in a semi-open system or continuously, with one or more reaction stages. Vigorous agitation is advantageously used to ensure good contact between the reagent (s) and the catalytic system.
  • the products of the present process can be used, for example, as components in plastics and more particularly polyethylene, motor fuels, as fillers in a hydroformylation process for the synthesis of aldehydes and alcohols, as components for chemical, pharmaceutical or perfume industry and / or as fillers in a metathesis process for the synthesis of propylene for example.
  • the molar ratio between the ligand and the chromium is 2.
  • methylaluminoxane (MAO) is used in a MAO molar ratio on the Cr (acac) 3 precursor of 600.
  • the reaction is carried out under 4.5 MPa. ethylene.
  • the ligands are evaluated at three different temperatures or 45 ⁇ C, 80 ⁇ and 100 ⁇ C.
  • the Ref ligand below is used as a comparative and evaluated under the same conditions and L3.
  • a 100 ml reactor is pressurized with ethylene.
  • the reaction solvent is introduced into the reactor as well as the MAO (10% by weight in toluene).
  • the reactor is then placed under 0.5 MPa of ethylene and stirred for 5 minutes.
  • the solution formed by the chromium precursor Cr (acac) 3 and the ligand is then introduced into the reactor.
  • the reactor is then placed under 2 MPa of ethylene pressure and heated to the test temperature. The pressure is completed at 4.5 MPa and agitation at 1000 rpm is started.
  • the system is under pressure control.
  • the ethylene feed is cut off and the reactor cooled.
  • the liquid phase and the optionally formed polymer are recovered and weighed.
  • the polymer is weighed after drying at 100 ° for one night.
  • the liquid phase is then neutralized with a sulfuric acid solution at 10% by weight.
  • the analysis of the liquid phase is carried out by gas phase chromatography with an HP 685 GC equipped with a PONA brand column.
  • the results of the experiments are shown in the table below.
  • the ethylene consumption described in the table corresponds to the amount (in grams) of ethylene converted during the catalytic test into reaction products.
  • the activity described in g / (g Cr. H) in the table corresponds to the amount of ethylene (in grams) converted by one gram of chromium from the catalytic composition reported over one hour of reaction.
  • Figure 1 shows the evolution of the C8 productivity as a function of the reaction temperature.
  • the productivity C8 described in FIG. 1 corresponds to the amount of octenes (in gram) transformed by one gram of chromium resulting from the catalytic composition reported over one hour of reaction. It is calculated by multiplying the activity by the percentage of C8 which is the weight percentage of C8 compared to the products formed.
  • a % percentage weight compared to the products formed.
  • b % 1 -C 6 percentage of hexene-1 in the C 6 section .
  • c % 1 -C 8 percentage of octene-1 in the C 8 section .
  • compositions according to the invention make it possible to significantly increase the proportion of C8 (% C8) relative to the other products formed when the temperature is brought from 45 ⁇ to 80 ⁇ .
  • productivity 08 observed with the compositions (with L1, L2 and L3) according to the invention is thus much greater than that observed with the composition used as a comparative example (Ref).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
EP17723148.7A 2016-05-31 2017-05-17 Katalytische zusammensetzung mit chrom und einem liganden auf phosphinbasis und deren verwendung in einem octenherstellungsverfahren Withdrawn EP3463653A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1654932A FR3051683B1 (fr) 2016-05-31 2016-05-31 Composition catalytique a base de chrome et d'un ligand a base de phosphine et son utilisation dans un procede de procuction d'octenes
PCT/EP2017/061884 WO2017207280A1 (fr) 2016-05-31 2017-05-17 Composition catalytique a base de chrome et d'un ligand a base de phosphine et son utilisation dans un procede de procuction d'octenes

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EP3463653A1 true EP3463653A1 (de) 2019-04-10

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EP17723148.7A Withdrawn EP3463653A1 (de) 2016-05-31 2017-05-17 Katalytische zusammensetzung mit chrom und einem liganden auf phosphinbasis und deren verwendung in einem octenherstellungsverfahren

Country Status (5)

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US (1) US10646858B2 (de)
EP (1) EP3463653A1 (de)
CN (1) CN109195703B (de)
FR (1) FR3051683B1 (de)
WO (1) WO2017207280A1 (de)

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Publication number Priority date Publication date Assignee Title
DE10303931B4 (de) 2002-02-04 2013-04-18 Institut Français du Pétrole Katalytische Zusammensetzung zur Dimerisierung, Co-Dimerisierung, Oligomerisierung und Polymerisation der Olefine
CA2510190C (en) * 2002-12-20 2011-10-11 Sasol Technology (Pty) Limited Trimerisation of olefins
FR2895406B1 (fr) 2005-12-22 2010-08-13 Inst Francais Du Petrole Procede pour la fabrication de 2,3-dimethylbut-1-ene
CN100443178C (zh) * 2006-03-10 2008-12-17 中国石油天然气股份有限公司 一种乙烯低聚的催化剂组合物及其应用
KR101074202B1 (ko) * 2007-01-18 2011-10-14 에스케이종합화학 주식회사 에틸렌 사량체화 촉매계 및 이를 이용한 1-옥텐의 제조방법
CN103044181A (zh) * 2011-10-17 2013-04-17 中国石油天然气股份有限公司 一种乙烯四聚反应制备辛烯-1的方法
ES2750659T3 (es) * 2012-05-09 2020-03-26 Sasol Tech Pty Ltd Tetramerización de etileno
ES2656088T3 (es) * 2012-05-09 2018-02-23 Sasol Technology (Proprietary) Limited Tetramerización de etileno
CN104511311B (zh) * 2013-09-30 2017-07-07 华东理工大学 一种高选择性的乙烯三聚、四聚催化剂体系及其使用方法

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US20190168202A1 (en) 2019-06-06
CN109195703A (zh) 2019-01-11
US10646858B2 (en) 2020-05-12
FR3051683B1 (fr) 2020-10-09
FR3051683A1 (fr) 2017-12-01
WO2017207280A1 (fr) 2017-12-07

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