CN111889142A - Catalyst system for selective oligomerization of ethylene, reaction method and application thereof - Google Patents
Catalyst system for selective oligomerization of ethylene, reaction method and application thereof Download PDFInfo
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- CN111889142A CN111889142A CN202010717943.1A CN202010717943A CN111889142A CN 111889142 A CN111889142 A CN 111889142A CN 202010717943 A CN202010717943 A CN 202010717943A CN 111889142 A CN111889142 A CN 111889142A
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- Prior art keywords
- compound
- catalyst system
- ethylene
- oligomerization
- alkyl
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- 239000003054 catalyst Substances 0.000 title claims abstract description 73
- 238000006384 oligomerization reaction Methods 0.000 title claims abstract description 63
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000005977 Ethylene Substances 0.000 title claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 12
- 239000003446 ligand Substances 0.000 claims abstract description 26
- 150000003623 transition metal compounds Chemical class 0.000 claims abstract description 25
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 16
- 125000003118 aryl group Chemical group 0.000 claims abstract description 12
- 150000002736 metal compounds Chemical group 0.000 claims abstract description 4
- 239000011651 chromium Substances 0.000 claims description 27
- 150000001875 compounds Chemical class 0.000 claims description 27
- 239000012190 activator Substances 0.000 claims description 20
- -1 alkyl aluminum compound Chemical class 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 11
- 229910052804 chromium Inorganic materials 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 7
- 239000012442 inert solvent Substances 0.000 claims description 6
- 230000003213 activating effect Effects 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 4
- 239000002608 ionic liquid Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 3
- 125000006736 (C6-C20) aryl group Chemical group 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 150000001639 boron compounds Chemical class 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 239000000047 product Substances 0.000 abstract description 37
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 abstract description 12
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 abstract description 12
- 239000004711 α-olefin Substances 0.000 abstract description 12
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract description 6
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 4
- 238000007172 homogeneous catalysis Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 33
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 23
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 4
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 4
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 4
- NFJPEKRRHIYYES-UHFFFAOYSA-N methylidenecyclopentane Chemical compound C=C1CCCC1 NFJPEKRRHIYYES-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical group [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 3
- 239000011636 chromium(III) chloride Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910021554 Chromium(II) chloride Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 125000005234 alkyl aluminium group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001845 chromium compounds Chemical class 0.000 description 2
- XBWRJSSJWDOUSJ-UHFFFAOYSA-L chromium(ii) chloride Chemical compound Cl[Cr]Cl XBWRJSSJWDOUSJ-UHFFFAOYSA-L 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- GYQSSCGWAJWHCK-UHFFFAOYSA-N dimethylaminophosphanium;chloride Chemical compound [Cl-].CN(C)[PH3+] GYQSSCGWAJWHCK-UHFFFAOYSA-N 0.000 description 2
- 229940069096 dodecene Drugs 0.000 description 2
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000005829 trimerization reaction Methods 0.000 description 2
- WCFQIFDACWBNJT-UHFFFAOYSA-N $l^{1}-alumanyloxy(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]O[Al] WCFQIFDACWBNJT-UHFFFAOYSA-N 0.000 description 1
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- FZTHAJKHQAMAJM-UHFFFAOYSA-N C1(=CC=CC=C1)OC1=CC=CC=C1.[Cr] Chemical compound C1(=CC=CC=C1)OC1=CC=CC=C1.[Cr] FZTHAJKHQAMAJM-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021581 Cobalt(III) chloride Inorganic materials 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- VURFVHCLMJOLKN-UHFFFAOYSA-N Diphosphine Natural products PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- GYVCVTQHUUFHPO-UHFFFAOYSA-N [Cr]C1=CC=CC=C1 Chemical compound [Cr]C1=CC=CC=C1 GYVCVTQHUUFHPO-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- FRBFQWMZETVGKX-UHFFFAOYSA-K chromium(3+);6-methylheptanoate Chemical compound [Cr+3].CC(C)CCCCC([O-])=O.CC(C)CCCCC([O-])=O.CC(C)CCCCC([O-])=O FRBFQWMZETVGKX-UHFFFAOYSA-K 0.000 description 1
- RPBPCPJJHKASGQ-UHFFFAOYSA-K chromium(3+);octanoate Chemical compound [Cr+3].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O RPBPCPJJHKASGQ-UHFFFAOYSA-K 0.000 description 1
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 description 1
- XEHUIDSUOAGHBW-UHFFFAOYSA-N chromium;pentane-2,4-dione Chemical compound [Cr].CC(=O)CC(C)=O.CC(=O)CC(C)=O.CC(=O)CC(C)=O XEHUIDSUOAGHBW-UHFFFAOYSA-N 0.000 description 1
- 150000004700 cobalt complex Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000010689 synthetic lubricating oil Substances 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
- B01J31/2414—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom comprising aliphatic or saturated rings
-
- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/5022—Aromatic phosphines (P-C aromatic linkage)
-
- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/5045—Complexes or chelates of phosphines with metallic compounds or metals
-
- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/505—Preparation; Separation; Purification; Stabilisation
-
- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/505—Preparation; Separation; Purification; Stabilisation
- C07F9/5054—Preparation; Separation; Purification; Stabilisation by a process in which the phosphorus atom is not involved
-
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Biochemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a catalyst system for selective oligomerization of ethylene, a reaction method and application thereof, belonging to the technical field of homogeneous catalysis. The catalyst system comprises: a ligand a; a transition metal compound b, wherein the transition metal compound b is a metal compound of IVB-VIII groups; wherein, the structural general formula of the ligand a is shown as the formula (I):
R1、R2、R3、R4、R5which may be the same or different from each other,each independently selected from alkyl or aryl. The catalyst system is used for selective oligomerization of ethylene, and has the characteristics of high catalytic activity, high product linear alpha-olefin selectivity, low 1-butene content, high 1-hexene + 1-octene selectivity and few byproducts.
Description
Technical Field
The invention belongs to the technical field of homogeneous catalysis, and particularly relates to a catalyst system for selective oligomerization of ethylene, a reaction method and application thereof.
Background
With the continuous development of global economy and the demand for high performance of synthetic materials, the application of higher linear alpha-olefins such as 1-hexene and 1-octene in the fields of high performance polyolefins, high-end synthetic lubricating oils, and the like is increasing, and the demand thereof is continuously increasing. Ethylene oligomerization is the principal process for producing high purity, linear alpha-olefins such as 1-hexene, 1-octene, 1-decene and 1-dodecene, and generally involves non-selective ethylene oligomerization and selective ethylene oligomerization.
For non-selective ethylene oligomerization technology, several novel ligand-coordinated metal chromium-based homogeneous catalysts have been reported for the synthesis of linear alpha-olefins with a broad carbon number distribution. For example, the Sasol company Overett et al reported that a chromium catalyst system of PCP framework ligands was used to catalyze the non-selective oligomerization of ethylene, and the product composition followed the Schulz-Flory distribution (. alpha. ═ 0.55) (J.mol.Catal.A: Chem,2008,283,114). Gambarotta et al reported that pyridine-backbone ligand-derived N, P-coordinated chromium catalysts catalyze ethylene oligomerization under methylaluminoxane activation, but the product distribution is different from Schulz-Flory distribution, C6-C12The mass fraction of (2) is up to 60-75%, and the linearity is high (Organometallics, 2013,32, 7107; 2014,33, 1602). Subsequently, Danopoulos et al reported that a chromium-based catalyst of similar structure catalyzed oligomerization of ethylene under activation by methylaluminoxane to yield C6-C12The mass fraction of (A) is up to 71% (Organometallics,2016,35, 4044). In addition to chromium complexes, complexes of metals such as iron, cobalt, nickel, palladium, titanium and the like can also be used for ethyleneOligomerization, such as the late transition metal iron and cobalt complex catalysts found by Brookhart, Gibson et al, have high activity for the oligomerization of ethylene and very high selectivity for linear alpha-olefins (Brookhart, M et al, J.Am.chem.Soc.1998,120, 7143; Gibson, V.C. et al, J.chem.Commun.1998,849), but have high 1-butene contents (C.E.)>10％)、C6～C12Low selectivity of linear alpha-olefins.
The ethylene selective oligomerization can generate high-grade linear alpha-olefin such as 1-hexene, 1-octene, 1-decene, 1-dodecene and the like with high selectivity, and has the advantages of good atom economy, simple process route and the like. The activity of the catalyst system and the selectivity of the desired product are key to the evaluation of the advancement of this technology, and the structure of the ligand in the catalyst system plays an important role in this. Researchers of the Sasol company in south africa in 2004 made minor changes on the basis of ethylene trimerization diphosphine amine (PNP) ligands (chem. commun.,2002,858-859) developed by professor Wass, even though the original catalytic system was changed from ethylene trimerization to ethylene tetramerization. Then, many chemical companies and scientists in the world carry out follow-up research, such as PNP ligands disclosed by Chinese patents CN1741850A (WO2004/056478A1), CN1741849A (WO2004/056479A1), CN101032695A, CN101351424A, CN101415494A, CN1651142A, CN101291734A and US2006/0128910A1, Korean SK energy companies CN201880057196.4, CN201780043063.7, CN201780032874.7, CN201380014632.7, CN201080003564.0, CN201080003564.0, CN200880002464.9, CN200880002464.9 and CN200780100280.1, and form a catalytic system with Cr and MAO for ethylene tetramerization, so that the catalytic system has high catalytic activity and long-term stability. However, the content of the byproduct methyl cyclopentane and methylene cyclopentane in the catalytic system is high, and the total selectivity of linear alpha-olefin is low.
Disclosure of Invention
The invention aims to provide high catalytic activity and high C by finely adjusting the electronic property and steric hindrance of a catalyst ligand substituent6～C8A linear alpha-olefin selective ethylene oligomerization catalyst system to solve the problem of C in ethylene oligomerization reaction6～C8Total selectivity of linear alpha-olefinsHigh problems.
The invention provides a catalyst system for selective oligomerization of ethylene, which comprises:
a ligand a;
a transition metal compound b, wherein the transition metal compound b is a metal compound of IVB-VIII groups;
an activator c, the activator c being a compound containing a group IIIA metal;
wherein, the structural general formula of the ligand a is shown as the formula (I):
R1、R2、R3、R4、R5may be the same or different and are each independently selected from alkyl or aryl groups.
Further, alkyl is C1-C10Alkyl groups of (a); preferably, the alkyl group is selected from methyl, ethyl, n-propyl, isopropyl, cyclopentyl, cyclohexyl.
Further, aryl is C6-C20Aryl groups of (a) and derivatives thereof; preferably, aryl is selected from phenyl, substituted phenyl.
Further, the transition metal compound b is a compound of chromium, molybdenum, tungsten, cobalt, titanium, tantalum, vanadium, zirconium, iron, nickel, or palladium.
Further, the activating agent c is one or a mixture of more than two of an alkyl aluminum compound, an alkyl aluminoxane compound and an organic boron compound; wherein the alkylaluminoxane compound includes an alkylaluminoxane compound having a volatile component removed.
Further, the activator c is a mixture of an alkylaluminum compound and a volatile component-removing alkylaluminoxane compound, wherein the alkylaluminum compound is triethylaluminum, and the aluminoxane compound is volatile component-removing methylaluminoxane.
Further, the molar ratio of the ligand a, the transition metal compound b and the activator c is 1: 0.5-100: 0.1-5000.
The invention provides a reaction method for selective oligomerization of ethylene, which comprises the oligomerization of ethylene in the presence of any one of the catalyst systems.
Further, the reaction is carried out in an inert solvent, wherein the inert solvent is one or a mixture of more than two of alkane, arene, alkene or ionic liquid; the reaction temperature is 0-200 ℃; the reaction pressure is 0.1 MPa-50 MPa.
The invention also provides the use of any of the above catalyst systems in the selective oligomerization of ethylene.
The invention has the following advantages:
the catalyst system provided by the invention has high catalytic activity, the total selectivity of the target product 1-hexene + 1-octene is high, and the selectivity of the by-products methylcyclopentane and methylene cyclopentane is low.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The embodiments and features of the embodiments of the present invention may be combined with each other without conflict.
The catalyst system of the present invention is described below.
Note that, in this text, "C" is used6～C12Linear alpha-olefin Total selectivity "means C6～C12The total amount of linear alpha-olefins in the total product (all linear alpha-olefins and by-products).
The embodiment of the invention provides a catalyst system for selective oligomerization of ethylene, which comprises a ligand a, a transition metal compound b and an activator c. Wherein, the structural general formula of the ligand a is shown as a formula (I) and contains a ligand of phosphorus atoms and nitrogen atoms; the transition metal compound b is a metal compound of IVB-VIII groups, and is a central metal atom; the activator c is a compound containing a group IIIA metal;
wherein, the structural general formula of the ligand a is shown as the formula (I):
R1、R2、R3、R4、R5may be the same or different and are each independently selected from alkyl or aryl groups.
In one embodiment of the present invention, the alkyl group is C1-C10Alkyl group of (1). Preferably, the alkyl group is selected from methyl, ethyl, n-propyl, isopropyl, cyclopentyl, cyclohexyl. More preferably, the alkyl group is selected from methyl, ethyl, n-propyl, and the like.
In one embodiment of the present invention, aryl is C6-C20Aryl groups of (1) and derivatives thereof. Preferably, aryl is selected from phenyl, substituted phenyl. More preferably, aryl is selected from phenyl, 4-methylphenyl, 4-methoxyphenyl, and the like. The aryl derivatives may be selected from naphthyl, substituted naphthyl, fluorenyl and the like.
In an embodiment of the present invention, the transition metal compound b is a compound of chromium, molybdenum, tungsten, cobalt, titanium, tantalum, vanadium, zirconium, iron, nickel or palladium. Preferably, the transition metal compound b is CrCl3(THF)3、CrCl2(THF)2、CoCl3、NiBr2One kind of (1). More preferably, the transition metal compound b is a chromium-containing transition metal compound. Alternative chromium compounds include those of the formula CrRnA compound of the formula wherein RnBeing an organic negative ion or neutral molecule, RnWherein the carbon atoms are usually 1-10 carbon atoms, n is an integer of 0-6, and the valence of chromium is 0-6. Specific RnThe group is an organic matter containing carboxyl, beta-diketone group and alkyl or the group thereof. From the viewpoint of easy dissolution and easy handling, more suitable chromium compounds include chromium acetate, chromium isooctanoate, chromium n-octanoate, chromium acetylacetonate, chromium diisoprenate, chromium diphenyloxide, CrCl3(THF)3、CrCl2(THF)2One of (phenyl) chromium tricarbonyl and chromium hexacarbonyl.
Further, the activating agent c is one or a mixture of more than two of an alkyl aluminum compound, an alkyl aluminoxane compound and an organic boron compound; wherein the alkylaluminoxane compound includes an alkylaluminoxane compound having a volatile component removed.
Specifically, the activator c may be a compound containing a group IIIA metal. Such as alkylaluminum compounds, alkylaluminoxane compounds. The alkylaluminum compound can be various trialkylaluminums, such as Triethylaluminum (TEAL), triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum or tri-n-octylaluminum; the alkylaluminum compound can also be an alkylaluminum halide, alkylaluminum hydride or alkylaluminum sesquichloride, such as diethylaluminum monochloride (AlEt)2Cl) and triethylaluminum trichloride (A1)2Et3Cl3) (ii) a The alkylaluminoxane compound may be selected from Methylaluminoxane (MAO), ethylaluminoxane, isobutylaluminoxane, modified aluminoxane, methylaluminoxane DMAO from which volatile components are removed, and the like. The activator c may be a mixture of an alkylaluminum compound and an alkylaluminoxane for removing volatile components, wherein the alkylaluminum compound is TEAL and the alkylaluminoxane compound is DMAO. Preferably, the molar ratio of TEAL to DMAO is 0.01-100, preferably 0.1-10.
In the present invention, the TEAL alkylation capacity is relatively weak, and is more adaptable to the catalyst system proposed by the present invention; and simultaneously, DMAO can shield the influence of volatile components such as toluene on the catalyst complexing process, so that the activity of the catalyst system is improved, and the dosage of the activating agent can be further reduced by mixing the DMAO and the catalyst.
Further, the activator c is a mixture of an alkylaluminum compound and a volatile component-removed alkylaluminoxane compound, wherein the alkylaluminum compound is triethylaluminum, and the aluminoxane compound is volatile component-removed methylaluminoxane; the molar ratio of triethyl aluminum to methylaluminoxane for removing volatile components is 0.01 to 100, preferably 0.1 to 10.
Further, the molar ratio of the ligand a, the transition metal compound b and the activator c is 1: 0.5-100: 0.1-5000.
Further, the molar ratio of the ligand a, the transition metal compound b and the activator c is 1: 0.5-100: 0.1-200.
Further, the molar ratio of the transition metal compound b to the activator c is 1:1 to 500.
Further, the molar ratio of the transition metal compound b to the activator c is 1: 1-200.
The preparation of the catalyst system of the present invention is further illustrated below.
In an embodiment of the present invention, the preparation method of the ligand a may include the steps of:
(1) preparation of Ph2PR1NLi
Taking a certain amount of Ph2PR1NH, adding a small amount of n-hexane, and cooling in a refrigerator for 10-20 minutes for later use. Adding a certain amount of n-BuLi into a small amount of n-hexane, cooling in a refrigerator for 10-15 min, taking out the two medicines, slowly dripping n-BuLi into the standby solution, naturally heating to room temperature, stirring for reacting for about 12-24h, filtering with a sand core funnel, washing with n-hexane for 2 times, and vacuum drying to obtain white Ph2PR1NLi solid.
(2) Preparation of Ph2PR1NPR2R3
Taking a certain amount of Ph2PR1Adding NLi into a proper amount of normal hexane, putting the mixture into a refrigerator for later use, and taking ClPNR2R3NR4R5Adding appropriate amount of n-hexane, placing in refrigerator, taking out the above solution after 15-20 min, and adding ClPNR2R3NR4R5Slowly adding into the above solution, stirring overnight, filtering, vacuum drying to obtain white or yellow oil, adding appropriate amount of n-hexane, stirring, mixing, and recrystallizing in refrigerator. Overnight, the n-hexane solvent was filtered off and dried under vacuum to give the product as a white or pale yellow solid powder.
In one embodiment of the present invention, the preparation method of the catalyst system may include the following steps:
the components a, b and c are mixed in advance or directly added into a reaction system for in-situ synthesis. That is, the catalyst is prepared by mixing the ligand a, the transition metal compound b, and the activator c in advance; or directly adding the ligand a, the transition metal compound b and the activator c into a reaction system for in-situ synthesis;
the ligand a, the transition metal compound b and the activator c in the formula (I) can be reacted in a liquid phase reaction, for example, in the presence of a solvent, and optionally a solvent such as toluene, benzene and derivatives thereof; or by solid phase reaction; the catalyst may also be generated by an in situ reaction during the oligomerization reaction. The reaction here may be a reaction between one, two or three compounds of the above-mentioned ligand, transition metal compound and metal organic activator. The course of this reaction is also the aging (pre-complexing) of the catalyst.
The method of the catalyst system of the present invention for oligomerization of ethylene is further described below.
The invention also provides an ethylene oligomerization reaction method, which comprises the ethylene oligomerization reaction carried out in the presence of the catalyst system.
In one embodiment of the present invention, the reaction is performed in an inert solvent, wherein the inert solvent is one or more than two of alkane, arene, alkene or ionic liquid. Typical solvents include, but are not limited to, benzene, toluene, xylene, cumene, n-heptane, n-hexane, methylcyclohexane, cyclohexane, 1-hexene, 1-octene, ionic liquids, and the like, with methylcyclohexane being preferred.
In one embodiment of the invention, the reaction temperature is 0-200 ℃. Preferably from 45 ℃ to 100 ℃.
In one embodiment of the present invention, the pressure of the ethylene oligomerization reaction can be performed at a pressure of 0.1MPa to 50MPa, preferably 1.0MPa to 10 MPa.
In one embodiment of the present invention, the concentration of the catalyst in the reaction system may be from 0.01. mu. mol metal/L to 1000. mu. mol metal/L, preferably from 0.1. mu. mol metal/L to 10. mu. mol metal/L. Note that the metal here is a transition metal in the transition metal compound b.
The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples.
Example 1
1. Preparation of N- (dimethylamino) phosphine-N- (diphenylphosphino) cyclopentylamine (L1):
adding 0.9019g (3.3 mmol) of lithium cyclopentyl (diphenylphosphine) amine into a proper amount of n-hexane for standby, then adding 0.51g (3.3 mmol) of dimethylamino phosphonium chloride into a proper amount of n-hexane for standby, putting the mixture into a refrigerator, taking out the solution after 15-20 minutes, and slowly adding the dimethylamino phosphonium chloride solution into the standby solution. Stirring overnight, filtering, vacuum drying to obtain yellow oily substance, adding appropriate amount of n-hexane, stirring, mixing, and recrystallizing in refrigerator. Overnight, the n-hexane solvent was filtered off and dried under vacuum to give a white solid powder.
The products obtained by the experiment are verified to have correct structures through nuclear magnetic spectrograms.
2. Preparation of the catalyst
In the warp of N2A well-replaced stirred 100mL reactor was charged with non-dehydrated methylcyclohexane (20mL), N- (dimethylamino) phosphine-N- (diphenylphosphino) cyclopentylamine (L1) (0.98mg) (2.53. mu. mol), CrCl3·(THF)3(0.9mg, 2.4. mu. mol), and reacted at room temperature for 5 min.
3. Oligomerization of ethylene
A100 mL low-pressure autoclave was evacuated for 20 minutes, purged with nitrogen several times, charged with ethylene, heated to a predetermined temperature, and charged with non-dehydrated methylcyclohexane (20mL), 0.87mL of MAO and the above catalyst. Carrying out oligomerization reaction at 30 ℃ under the pressure of 1MPa, cooling by using ice bath after reacting for 30min, releasing pressure, and terminating the reaction by using acidified ethanol with the mass fraction of 10%. To obtain 1.01g of oligomerization product and the activity of the catalyst is 0.84 multiplied by 106g oligomer/mol Cr.h. The distribution of the oligomerization products is shown in table 1, and the experimental conditions and catalyst activity are shown in table 2.
Example 2
The same as in example 1. With the difference that R2、R3Is ethyl, R4、R5Is ethyl. Obtain 0.86g of oligomerization product and the activity of the catalyst is 0.72 multiplied by 106g oligomer/mol Cr.h. The distribution of the oligomerization products is shown in table 1, and the experimental conditions and catalyst activity are shown in table 2.
Example 3
The same as in example 1. With the difference that R2、R3Methyl, R4、R5Is ethyl. To obtain 1.24g of oligomerization product and the activity of the catalyst is 1.03 multiplied by 106g oligomer/mol Cr.h. The distribution of the oligomerization products is shown in table 1, and the experimental conditions and catalyst activity are shown in table 2.
Example 4
The same as in example 1. With the difference that R2、R3Is n-propyl, R4、R5Is n-propyl. Obtain 0.78 g of oligomerization product and the activity of the catalyst is 0.65 multiplied by 106g oligomer/mol Cr.h. The distribution of the oligomerization products is shown in table 1, and the experimental conditions and catalyst activity are shown in table 2.
Example 5
The same as in example 1. With the difference that R2、R3Is isopropyl, R4、R5Is isopropyl. To obtain 0.64 g of oligomerization product and 0.53X 10 of catalyst activity6g oligomer/mol Cr.h. The distribution of the oligomerization products is shown in table 1, and the experimental conditions and catalyst activity are shown in table 2.
Example 6
The same as in example 1. With the difference that R2、R3Is cyclopentyl, R4、R5Is methyl. Obtain 0.73g of oligomerization product and the activity of the catalyst is 0.61 multiplied by 106g oligomer/mol Cr.h. The distribution of the oligomerization products is shown in table 1, and the experimental conditions and catalyst activity are shown in table 2.
Example 7
The same as in example 1. With the difference that R2、R3Is cyclohexyl, R4、R5Is n-propyl. Obtain 0.36 g of oligomerization product and 0.30 multiplied by 10 of catalyst activity6g oligomer/mol Cr.h. The distribution of the oligomerization products is shown in table 1, and the experimental conditions and catalyst activity are shown in table 2.
Example 8
The same as in example 1. With the difference that R2、R3Is phenyl, R4、R5Is phenyl. Obtain oligomerization product 0.37g, catalyst activity 0.31X 106g oligomer/mol Cr.h. The distribution of the oligomerization products is shown in table 1, and the experimental conditions and catalyst activity are shown in table 2.
Example 9
The same as in example 1. Except that the reaction temperature was 50 ℃. Obtain 0.76g of oligomerization product and the activity of the catalyst is 0.63 multiplied by 106g oligomer/mol Cr.h. The distribution of the oligomerization products is shown in Table 1, and the experimental conditions and catalyst activities are shown in Table 2.
Example 10
The same as in example 1. Except that the reaction temperature was 70 ℃. Obtain 0.58g of oligomerization product and the activity of the catalyst is 0.48 multiplied by 106g oligomer/mol Cr.h. The distribution of the oligomerization products is shown in table 1, and the experimental conditions and catalyst activity are shown in table 2.
Example 11
The same as in example 9. Except that the reaction temperature was 90 ℃. Obtain 0.43g of oligomerization product and the activity of catalyst is 0.36X 106g oligomer/mol Cr.h. The distribution of the oligomerization products is shown in Table 1, and the experimental conditions and catalyst activities are shown in Table 2.
Example 12
The same as in example 11. Except that the amount of MAO added was 0.58 mL. Obtain 0.92g of oligomerization product and the activity of catalyst is 0.77X 106g oligomer/mol Cr.h. The distribution of the oligomerization products is shown in Table 1, and the experimental conditions and catalyst activities are shown in Table 2.
Example 13
The same as in example 1. Except that the ethylene oligomerization reaction is carried out in a 1.0L stainless steel reaction kettle, the adding amount of the methylcyclohexane is 200mL, the reaction pressure is 6.0MPa, and the hydrogen partial pressure is 0.5 MPa. 47g of oligomerization product is obtained, and the catalyst activity is 3.92 multiplied by 107g oligomer/mol Cr.h. The distribution of the oligomerization products is shown in Table 1, and the experimental conditions and catalyst activities are shown in Table 2.
Example 14
The same as in example 1. Except that the reaction pressure was 3.0 MPa. 3.05g of oligomerization product is obtained, and the activity of the catalyst is 2.54 multiplied by 106g oligomer/mol Cr.h. Distribution of oligomerization productsSee table 1, experimental conditions and catalyst activity see table 2.
Comparative example 1
The same as in example 1. Except that the ligands differ in structure as shown in the following formula:
obtain 0.19g of oligomerization product and the activity of catalyst is 0.16X 106g oligomer/mol Cr.h. The distribution of the oligomerization products is shown in table 1, and the experimental conditions and catalyst activity are shown in table 2.
Claims (10)
1. A catalyst system for selective oligomerization of ethylene, comprising:
a ligand a;
a transition metal compound b, wherein the transition metal compound b is a metal compound of IVB-VIII groups;
an activator c, the activator c being a compound containing a group IIIA metal;
wherein, the structural general formula of the ligand a is shown as the formula (I):
R1、R2、R3、R4、R5may be the same or different and are each independently selected from alkyl or aryl groups.
2. The catalyst system according to claim 1,
the alkyl group is C1-C10Alkyl groups of (a);
preferably, the alkyl group is selected from methyl, ethyl, n-propyl, isopropyl, cyclopentyl, cyclohexyl.
3. The catalyst system according to claim 1,
said aryl group is C6-C20Aryl groups of (a) and derivatives thereof;
preferably, the aryl group is selected from phenyl, substituted phenyl.
4. The catalyst system according to claim 1,
the transition metal compound b is a compound of chromium, molybdenum, tungsten, cobalt, titanium, tantalum, vanadium, zirconium, iron, nickel or palladium.
5. The catalyst system according to claim 1,
the activating agent c is one or a mixture of more than two of an alkyl aluminum compound, an alkyl aluminoxane compound and an organic boron compound; wherein the alkylaluminoxane compound comprises an alkylaluminoxane compound having a volatile component removed.
6. The catalyst system according to claim 1 or 5,
the activating agent c is a mixture of an alkyl aluminum compound and an alkyl aluminoxane compound for removing volatile components, wherein the alkyl aluminum compound is triethyl aluminum, and the aluminoxane compound is methylaluminoxane for removing volatile components.
7. The catalyst system according to claim 1,
the molar ratio of the ligand a to the transition metal compound b to the activator c is 1: 0.5-100: 0.1-5000.
8. A reaction method of ethylene selective oligomerization is characterized in that,
comprising an oligomerization of ethylene carried out in the presence of a catalyst system according to any of claims 1 to 7.
9. The method of claim 8,
the reaction is carried out in an inert solvent, wherein the inert solvent is one or a mixture of more than two of alkane, arene, alkene or ionic liquid;
the reaction temperature is 0-200 ℃;
the reaction pressure is 0.1 MPa-50 MPa.
10. Use of a catalyst system according to any one of claims 1 to 7 for the selective oligomerization of ethylene.
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| CN114160199B (en) * | 2021-11-02 | 2024-01-16 | 浙江智英石化技术有限公司 | Catalytic system for selectively trimerizing and tetramerizing ethylene and application thereof |
| CN115124575A (en) * | 2022-06-23 | 2022-09-30 | 中国五环工程有限公司 | Preparation method of PNP ligand structure Cr (III) metal catalyst |
| CN115124575B (en) * | 2022-06-23 | 2024-02-27 | 中国五环工程有限公司 | Preparation method of PNP ligand structure Cr (III) metal catalyst |
| CN114956939A (en) * | 2022-07-01 | 2022-08-30 | 万华化学集团股份有限公司 | Ethylene oligomerization regulation and control method |
| CN114956939B (en) * | 2022-07-01 | 2024-02-02 | 万华化学集团股份有限公司 | Ethylene oligomerization regulation and control method |
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