CN112570026A - Catalyst system for ethylene oligomerization and oligomerization method - Google Patents
Catalyst system for ethylene oligomerization and oligomerization method Download PDFInfo
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- CN112570026A CN112570026A CN201910930700.3A CN201910930700A CN112570026A CN 112570026 A CN112570026 A CN 112570026A CN 201910930700 A CN201910930700 A CN 201910930700A CN 112570026 A CN112570026 A CN 112570026A
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000005977 Ethylene Substances 0.000 title claims abstract description 62
- 239000003054 catalyst Substances 0.000 title claims abstract description 48
- 238000006384 oligomerization reaction Methods 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 11
- 239000000460 chlorine Substances 0.000 claims abstract description 11
- 239000003446 ligand Substances 0.000 claims abstract description 10
- 239000011651 chromium Substances 0.000 claims abstract description 9
- -1 alkyl compound Chemical class 0.000 claims abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 7
- 239000004711 α-olefin Substances 0.000 claims abstract description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 6
- 229910000077 silane Inorganic materials 0.000 claims abstract description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 5
- 150000002736 metal compounds Chemical class 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 11
- MJSNUBOCVAKFIJ-LNTINUHCSA-N chromium;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Cr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MJSNUBOCVAKFIJ-LNTINUHCSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 230000001502 supplementing effect Effects 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- VURFVHCLMJOLKN-UHFFFAOYSA-N Diphosphine Natural products PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- WCFQIFDACWBNJT-UHFFFAOYSA-N $l^{1}-alumanyloxy(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]O[Al] WCFQIFDACWBNJT-UHFFFAOYSA-N 0.000 claims description 2
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 claims description 2
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 claims description 2
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 2
- 239000011636 chromium(III) chloride Substances 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 abstract description 16
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 abstract description 10
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 4
- 150000001412 amines Chemical class 0.000 abstract description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 20
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 8
- CJYMDPCRSWLYSQ-UHFFFAOYSA-N n,n-bis(diphenylphosphanyl)propan-2-amine Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)N(C(C)C)P(C=1C=CC=CC=1)C1=CC=CC=C1 CJYMDPCRSWLYSQ-UHFFFAOYSA-N 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 150000003623 transition metal compounds Chemical class 0.000 description 3
- 238000005829 trimerization reaction Methods 0.000 description 3
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000005046 Chlorosilane Substances 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- AJGJROVYVKUHID-UHFFFAOYSA-N OPNP Chemical compound OPNP AJGJROVYVKUHID-UHFFFAOYSA-N 0.000 description 1
- SCHRRICRQNJJKN-UHFFFAOYSA-N P.[O] Chemical class P.[O] SCHRRICRQNJJKN-UHFFFAOYSA-N 0.000 description 1
- 229910007161 Si(CH3)3 Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000006353 environmental stress Effects 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920013639 polyalphaolefin Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- PPDADIYYMSXQJK-UHFFFAOYSA-N trichlorosilicon Chemical compound Cl[Si](Cl)Cl PPDADIYYMSXQJK-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- 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
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0255—Phosphorus containing compounds
- B01J31/0264—Phosphorus acid amides
-
- 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
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0274—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 containing silicon
-
- 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
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0275—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 also containing elements or functional groups covered by B01J31/0201 - B01J31/0269
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—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
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2234—Beta-dicarbonyl ligands, e.g. acetylacetonates
-
- 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
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/20—Olefin oligomerisation or telomerisation
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C2531/22—Organic complexes
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention relates to a catalyst system for preparing linear alpha-olefin by ethylene oligomerization, which is characterized in that chlorine-containing bridged silane is added into a ternary system of a chromium-containing metal compound, a diphosphonic amine ligand and an aluminum-containing alkyl compound as an accelerant, so that the ethylene oligomerization activity and the content of 1-hexene and 1-octene in an oligomerization product can be effectively improved. The invention also provides a method for catalyzing ethylene oligomerization reaction by using the catalyst system.
Description
Technical Field
The invention belongs to the field of ethylene oligomerization catalysis, and relates to a catalyst system for preparing linear alpha-olefin by ethylene oligomerization and a method for catalyzing ethylene oligomerization by using the catalyst system.
Background
The low-carbon linear alpha-olefin (C6-C10) is an important chemical product, wherein 1-hexene and 1-octene can be used as comonomers of Linear Low Density Polyethylene (LLDPE) to improve the tensile property, impact resistance, environmental stress crack resistance, heat resistance, flexibility, transparency and the like of the LLDPE, and the 1-decene can be used for synthesizing polyalphaolefin synthetic oil.
At present, alpha-olefin of C6-C10 is mainly prepared by an ethylene oligomerization method, and the alpha-olefin with wide distribution is obtained by the ethylene oligomerization method, and needs to be purified by methods such as rectification and the like, and has the advantages of low-value low-carbon olefin generation and high cost. Therefore, the preparation of 1-hexene and 1-octene by ethylene high-selectivity trimerization and tetramerization has very important economic significance, wherein the preparation of 1-hexene by ethylene trimerization is industrialized, and the preparation of 1-octene by ethylene tetramerization is already completed in a pilot plant.
Preparation of 1-octene by tetramerization of ethylene with Cr (III)/PNP (PNP ═ Ph)2P-N(R)-PPh2Diphosphine ligand) as main catalyst and Methyl Aluminoxane (MAO) as cocatalyst. Patent CN104511311 discloses a high-selectivity ethylene trimerization and tetramerization catalyst system and a use method thereof, wherein a diphosphine amine ligand structure is improved, and the selectivity of 1-hexene and 1-octene is improved. CN105562090, CN107282124, CN105562100, CN107282122 and the like disclose a series of monophosphine oxygen and diphosphine oxygen ligand compounds for ethylene tetramerization, which can catalyze ethylene oligomerization reaction in the presence of a transition metal compound, water and a cocatalyst. Patents CN107282133, CN107282131, etc. disclose that a PCCP type bisphosphine ligand can catalyze ethylene tetramerization reaction in the presence of a transition metal compound, an aluminum-containing cocatalyst and tert-butyl hydroperoxide. CN107282127 discloses an OPNP type ligand for ethylene tetramerization, which can catalyze ethylene tetramerization reaction in the presence of a transition metal compound, an aluminum-containing cocatalyst and tert-butyl hydroperoxide.
Disclosure of Invention
The invention aims to provide a catalyst system for preparing a linear alpha-olefin (mainly C8 olefin) mixture by catalyzing ethylene oligomerization and an oligomerization method, wherein a chlorine-containing bridged silane promoter is added into a Cr (III)/PNP/aluminoxane system, so that the catalytic activity can be effectively improved, and the content of 1-octene in an oligomerization product is higher.
The catalyst system for ethylene oligomerization consists of A, B, C, D four parts, wherein: the catalyst component A is a chromium-containing compound; the catalyst component B is a diphosphine amine ligand; the catalyst component C is an aluminum-containing alkyl compound; catalyst component D is a chlorine-containing bridged silane.
In the catalyst component A, the chromium-containing compound is CrCl3(THF)3、Cr(acac)3、Cr(CH3COO)3Is preferably one of Cr (acac)3。
In the catalyst component B, the diphosphonic amine ligand is Ph2PN(R1)PPh2Wherein R1 is methyl, isopropyl, tert-butyl, cyclopentyl, cyclohexyl, phenyl, preferably isopropyl.
In the catalyst component C, the aluminum-containing alkyl compound is one or a mixture of methylaluminoxane, ethylaluminoxane and isobutylaluminoxane, and methylaluminoxane is preferred.
In the catalyst component D, chlorosilane is R2mCl3-mSiR3SiCl3-nR4nM is 0, 1, 2, 3, n is 0, 1, 2, 3; r2 is-CH3、-CH2CH3Is preferably-CH3(ii) a R3 is-O-, -CH2-、-CH2CH2-、-CH2CH2CH2-、-C(Cl2) -, preferably-CH2-; r4 is-CH3、-CH2CH3Is preferably-CH3。
In the catalyst system, the molar ratio of the component A to the component B is 1: 0.8-1: 1.2, and preferably 1: 1.
In the catalyst system, the molar ratio of the component A to the component C is 1: 10-1: 1000, and preferably 1: 300.
In the catalyst system, the molar ratio of the component A to the component D is 1: 0.1-1: 50, and preferably 1: 10.
In the catalyst system, the component A, B, C, D can be added to the reaction system in a physical manner by premixing or directly added to the reaction system in batches.
The invention also provides the application of the catalyst system in the aspect of ethylene oligomerization, which comprises the following steps: heating the reaction kettle to 120 ℃ before reaction, keeping the temperature for 1h at constant temperature, vacuumizing and supplementing N2Three times, then reducing the temperature to the preset temperature, vacuumizing and filling ethylene twice and maintaining the ethylene environment. Adding a solvent, starting a stirrer, adding the catalyst component C, the catalyst component D, the catalyst component B and the catalyst component A in sequence after the temperature is constant, or adding the catalyst component A, B, C, D in one step after premixing, and carrying out ethylene oligomerization under a certain ethylene pressure. Stopping introducing ethylene after reacting for a certain time, cooling to below 0 ℃, evacuating the pressure in the reaction kettle, adding acidified ethanol to stop the reaction, filtering, and collecting liquid to obtain the ethylene oligomerization product.
More specifically, in the method of the invention, the solvent is one or a mixture of two or more of toluene, n-hexane, cyclohexane, methylcyclohexane and n-heptane, preferably cyclohexane; the reaction temperature is 20-100 ℃, and preferably 40-50 ℃; the reaction pressure range is 0.1-10 MPa, and preferably 4-6 MPa; the reaction time is 10-120 min, preferably 30-60 min.
The invention has the advantages and positive effects that: the catalyst system of the invention is added with the chlorine-containing bridged silane accelerator, which can effectively increase the ethylene oligomerization reaction activity and the 1-octene selectivity.
Drawings
Detailed Description
The present invention is further illustrated by the following specific examples, which are intended to be illustrative, not limiting and are not intended to limit the scope of the invention.
Example 1
Heating 500ml reaction kettle to 120 ℃, keeping constant temperature for 1h, vacuumizing and supplementing N2And thirdly, cooling to 45 ℃, vacuumizing, filling ethylene for two times, and keeping the ethylene environment. 50mL of dehydrated deoxygenated cyclohexane was added, and after the temperature was constant methylaluminoxane (6mL of a 1.0M hexane solution) and Cl were added in this order3SiCH2SiCl3(56.6mg，0.2mmol)、Ph2PN(iPr)PPh2(8.6mg，20μmol)、Cr(acac)3(7.0mg, 20. mu. mol), raising the ethylene pressure to 5MPa for oligomerization reaction, stopping introducing ethylene after 30min of reaction, reducing the temperature to 0 ℃, releasing the pressure in the reaction kettle, adding 1ml of acidified ethanol, and filtering to obtain 216.40g of liquid.
Example 2
Heating 500ml reaction kettle to 120 ℃, keeping constant temperature for 1h, vacuumizing and supplementing N2And thirdly, cooling to 45 ℃, vacuumizing, filling ethylene for two times, and keeping the ethylene environment. 50mL of dehydrated deoxygenated cyclohexane was added, and after the temperature was constant methylaluminoxane (6mL of a 1.0M hexane solution) and Cl were added in this order3SiCH2CH2SiCl3(59.4mg，0.2mmol)、Ph2PN(iPr)PPh2(8.6mg，20μmol)、Cr(acac)3(7.0mg, 20. mu. mol), raising the ethylene pressure to 5MPa for oligomerization reaction, stopping introducing ethylene after 30min of reaction, reducing the temperature to 0 ℃, releasing the pressure in the reaction kettle, adding 1ml of acidified ethanol, and filtering to obtain 209.12g of liquid.
Example 3
Heating 500ml reaction kettle to 120 ℃, keeping constant temperature for 1h, vacuumizing and supplementing N2And thirdly, cooling to 45 ℃, vacuumizing, filling ethylene for two times, and keeping the ethylene environment. 50mL of dehydrated and deoxygenated cyclohexane was added, and after the temperature was kept constant, methylaluminoxane (6mL of a 1.0M hexane solution), (CH) was added in this order3)3SiC(Cl2)Si(CH3)3(44.2mg，0.2mmol)、Ph2PN(iPr)PPh2(8.6mg，20μmol)、Cr(acac)3(7.0mg, 20 mu mol), increasing the ethylene pressure to 5MPa for oligomerization reaction, stopping introducing ethylene after 30min of reaction, reducing the temperature to 0 ℃, discharging the pressure in the reaction kettle, adding 1ml of acidified ethanol, and filtering to obtain 204.44g of liquid.
Example 4
Heating 500ml reaction kettle to 120 ℃, keeping constant temperature for 1h, vacuumizing and supplementing N2And thirdly, cooling to 45 ℃, vacuumizing, filling ethylene for two times, and keeping the ethylene environment. 50mL of dehydrated deoxygenated cyclohexane was added, and after the temperature was constant methylaluminoxane (6mL of a 1.0M hexane solution) and Cl were added in this order3SiC(Cl2)SiCl3(68.8mg，0.2mmol)、Ph2PN(iPr)PPh2(8.6mg，20μmol)、Cr(acac)3(7.0mg, 20. mu. mol), raising the ethylene pressure to 5MPa for oligomerization reaction, stopping introducing ethylene after 30min of reaction, reducing the temperature to 0 ℃, releasing the pressure in the reaction kettle, adding 1ml of acidified ethanol, and filtering to obtain 191.44g of liquid.
Example 5
Heating 500ml reaction kettle to 120 ℃, keeping constant temperature for 1h, vacuumizing and supplementing N2And thirdly, cooling to 45 ℃, vacuumizing, filling ethylene for two times, and keeping the ethylene environment. 50mL of dehydrated and deoxygenated cyclohexane was added, and after the temperature was kept constant, methylaluminoxane (6mL of a 1.0M hexane solution), (CH) was added in this order3)3SiOSiCl3(45.3mg，0.2mmol)、Ph2PN(iPr)PPh2(8.6mg，20μmol)、Cr(acac)3(7.0mg, 20. mu. mol), raising the ethylene pressure to 5MPa for oligomerization reaction, stopping introducing ethylene after 30min of reaction, reducing the temperature to 0 ℃, releasing the pressure in the reaction kettle, adding 1ml of acidified ethanol, and filtering to obtain 180.52g of liquid.
Comparative example 1
Heating 500ml reaction kettle to 120 ℃, keeping constant temperature for 1h, vacuumizing and supplementing N2And thirdly, cooling to 45 ℃, vacuumizing, filling ethylene for two times, and keeping the ethylene environment. 50mL of dehydrated deoxygenated cyclohexane was added, and after the temperature was constant methylaluminoxane (6mL of a 1.0M hexane solution) and Ph were added in this order2PN(iPr)PPh2(8.6mg，20μmol)、Cr(acac)3(7.0mg, 20. mu. mol), raising the ethylene pressure to 5MPa for oligomerization reaction, stopping introducing ethylene after 30min of reaction, reducing the temperature to 0 ℃, releasing the pressure in the reaction kettle, adding 1ml of acidified ethanol, and filtering to obtain 165.96g of liquid.
The ethylene oligomerization activities and liquid product composition distributions of examples 1-5 and comparative example 1 are shown in Table I.
In one example, the distribution of oligomerization activity and products
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various changes and modifications can be made without departing from the inventive concept, and these changes and modifications are all within the scope of the present invention.
Claims (10)
1. A catalyst system for preparing linear alpha-olefin mixture by ethylene oligomerization is composed of A, B, C, D four parts, wherein a catalyst component A is a chromium-containing metal compound, a catalyst component B is a diphosphine amine ligand, a catalyst component C is an aluminum-containing alkyl compound, and a catalyst component D is chlorine-containing bridged silane.
2. The catalyst system of claim 1, characterized in that the chromium-containing compound is CrCl3(THF)3、Cr(acac)3、Cr(CH3COO)3One kind of (1).
3. Catalyst system according to claim 1, characterized in that the bisphosphine ligand is Ph2PN(R1)PPh2Wherein R1 is methyl, isopropyl, tert-butyl, cyclopentyl, cyclohexyl or phenyl.
4. The catalyst system of claim l, wherein the aluminum alkyl-containing compound is one or a mixture of methyl aluminoxane, ethyl aluminoxane, and isobutyl aluminoxane.
5. The catalyst system according to claim 1, wherein the chlorine-containing bridged silane is R2mCl3- mSiR3SiCl3-nR4nM is 0, 1, 2, 3, n is 0, 1, 2, 3, R2 is-CH3、-CH2CH3R3 is-O-, -CH2-、-CH2CH2-、-CH2CH2CH2-、-C(Cl2) -, R4 is-CH3、-CH2CH3。
6. The catalyst system of claim 1, wherein the molar ratio of component A to component B is from 1: 0.8 to 1: 1.2.
7. The catalyst system of claim 1, wherein the molar ratio of component A to C is from 1: 10 to 1: 1000.
8. The catalyst system of claim 1, wherein the molar ratio of component A to component D is from 1: 0.1 to 1: 50.
9. The catalyst system as set forth in claim 1, characterized in that component A, B, C, D may be added to the reaction system either as a physical pre-mixture or as a batch-wise addition directly to the reaction system.
10. A method of catalyzing a catalyst according to any one of claims 1 to 9, comprising: heating the reaction kettle to 120 ℃ before reaction, keeping the temperature for 1h at constant temperature, vacuumizing and supplementing N2Three times, then reducing the temperature to the preset temperature, vacuumizing and filling ethylene twice and maintaining the ethylene environment. Adding a solvent, starting a stirrer, adding the catalyst component C, the catalyst component D, the catalyst component B and the catalyst component A in sequence after the temperature is constant, or adding the catalyst component A, B, C, D in one step after premixing, and carrying out ethylene oligomerization under a certain ethylene pressure. Stopping introducing ethylene after reacting for a certain time, cooling to below 0 ℃, evacuating the pressure in the reaction kettle, adding acidified ethanol to stop the reaction, filtering, and collecting liquid to obtain the ethylene oligomerization product.
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