CN107282114B - Catalyst composition for ethylene trimerization and application thereof - Google Patents
Catalyst composition for ethylene trimerization and application thereof Download PDFInfo
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- CN107282114B CN107282114B CN201610196060.4A CN201610196060A CN107282114B CN 107282114 B CN107282114 B CN 107282114B CN 201610196060 A CN201610196060 A CN 201610196060A CN 107282114 B CN107282114 B CN 107282114B
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- aluminum
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- transition metal
- ethylene
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000005977 Ethylene Substances 0.000 title claims abstract description 46
- 239000000203 mixture Substances 0.000 title claims abstract description 46
- 238000005829 trimerization reaction Methods 0.000 title claims abstract description 38
- 239000003054 catalyst Substances 0.000 title claims abstract description 36
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 150000003623 transition metal compounds Chemical class 0.000 claims abstract description 29
- 239000003446 ligand Substances 0.000 claims abstract description 24
- 150000001451 organic peroxides Chemical class 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 18
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- 125000003118 aryl group Chemical group 0.000 claims abstract description 6
- 150000002430 hydrocarbons Chemical group 0.000 claims abstract description 4
- 239000003960 organic solvent Substances 0.000 claims description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- -1 alkyl aluminum compound Chemical class 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 150000001845 chromium compounds Chemical class 0.000 claims description 3
- CYOMBOLDXZUMBU-UHFFFAOYSA-K chromium(3+);oxolane;trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3].C1CCOC1.C1CCOC1.C1CCOC1 CYOMBOLDXZUMBU-UHFFFAOYSA-K 0.000 claims description 3
- 239000003426 co-catalyst Substances 0.000 claims description 3
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 150000008282 halocarbons Chemical class 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002506 iron compounds Chemical class 0.000 claims description 3
- 239000005078 molybdenum compound Substances 0.000 claims description 3
- 150000002752 molybdenum compounds Chemical class 0.000 claims description 3
- 150000002816 nickel compounds Chemical class 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 150000003609 titanium compounds Chemical class 0.000 claims description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 3
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 150000003755 zirconium compounds Chemical class 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
- IIFFFBSAXDNJHX-UHFFFAOYSA-N 2-methyl-n,n-bis(2-methylpropyl)propan-1-amine Chemical compound CC(C)CN(CC(C)C)CC(C)C IIFFFBSAXDNJHX-UHFFFAOYSA-N 0.000 claims description 2
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 238000004364 calculation method Methods 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
- 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 claims description 2
- 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 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[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
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 claims description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 2
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 claims description 2
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 claims description 2
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 13
- 230000000977 initiatory effect Effects 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 16
- 239000011651 chromium Substances 0.000 description 15
- 238000006384 oligomerization reaction Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 7
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 6
- 239000004711 α-olefin Substances 0.000 description 6
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 5
- 150000004696 coordination complex Chemical class 0.000 description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 150000001844 chromium Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- IYABWNGZIDDRAK-UHFFFAOYSA-N allene Chemical group C=C=C IYABWNGZIDDRAK-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 238000006317 isomerization reaction Methods 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
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 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
- 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
- B01J31/226—Sulfur, e.g. thiocarbamates
-
- 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
- B01J31/1805—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 nitrogen
-
- 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
-
- 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
- C07C2/14—Catalytic processes with inorganic acids; with salts or anhydrides of acids
- C07C2/20—Acids of halogen; Salts thereof ; Complexes thereof with organic compounds
- C07C2/22—Metal halides; Complexes thereof with organic compounds
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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
- 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
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
-
- 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
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
- B01J2531/0244—Pincer-type complexes, i.e. consisting of a tridentate skeleton bound to a metal, e.g. by one to three metal-carbon sigma-bonds
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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
- 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
- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/22—Organic complexes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Polyethers (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a catalyst composition for ethylene trimerization, which comprises an SNS ligand shown in a formula (1), a transition metal compound, an aluminum-containing cocatalyst and an organic peroxide;
wherein R is1Is alkyl, aryl, alkyl derivative or aryl derivative; r2Is C1‑C15A hydrocarbon group of (1). The invention also discloses a method for ethylene trimerization by using the catalyst composition. The catalyst composition is used for ethylene trimerization, has higher trimerization activity in the presence of organic peroxide such as tert-butyl hydroperoxide, and has the advantages of rapid reaction initiation, stable operation and good repeatability, thereby obtaining beneficial effects.
Description
Technical Field
The invention relates to the field of ethylene oligomerization, in particular to a catalyst composition for ethylene trimerization. The invention also relates to a process for the trimerization of ethylene.
Background
More specifically, a number of chromium-based catalysts have been developed and used for the oligomerization of olefins, primarily α -to produce α -olefins, wherein the trimerization of ethylene to 1-hexene and the tetramerization of ethylene to 1-octene is of particular interest, LLDPE resins copolymerized from 1-hexene, 1-octene are significantly superior in tensile strength, impact strength, tear resistance and durability compared to copolymers of 1-butene, and are particularly suitable for packaging films and agricultural cover films for greenhouses, sheds and the like, and in α -olefin as a comonomer, 1-hexene and 1-octene have been gradually substituted for 1-butene to produce high performance PE products.
α -olefin production method mainly comprises wax cracking method, ethylene oligomerization method, extraction separation method, fatty alcohol dehydrogenation method, internal olefin isomerization method, etc., wherein, the ethylene oligomerization method becomes one of the important paths of α -olefin production because the α -olefin produced by the ethylene oligomerization method has the characteristics of high purity, good selectivity, high raw material utilization rate, etc.
Continuing with John R.Briggs in J.chem.Soc., chem.Commun., 1989,674-675, a route to selectively produce 1-hexene by ethylene trimerization using homogeneous, ternary chromium-based catalysts has been reported, 1-hexene production technology has been greatly developed, in order to make more reasonable use of petroleum feedstocks, efforts have been made to develop efficient oligomerization catalysts, in the hope of obtaining high purity, high-grade α -olefins, in numerous explorations, heteroatom ligands have reacted with chromium-based compounds and used for their olefin oligomerization as a new research hotspot in the field, CN1606539A discloses a complex containing an aluminoxane and a chromium salt of a coordinating multidentate phosphine, arsenic and/or antimony, and in the course of ethylene oligomerization.
Disclosure of Invention
In view of the application of the sulfur and nitrogen heteroatom-containing ligand in the ethylene trimerization reaction, the inventors of the present application have conducted extensive and intensive research in the field of catalysts for ethylene trimerization, and surprisingly found that ethylene trimerization in a composition comprising a tridentate ligand represented by formula i, a transition metal compound, an aluminum-containing cocatalyst and an organic peroxide (such as t-butyl hydroperoxide) has better catalytic activity, rapid reaction initiation, smooth operation, good repeatability and the like. The tert-butyl hydroperoxide is used as organic peroxide to promote the reaction, thereby overcoming the technical prejudice of the technicians in the field and achieving unexpected technical effects.
The first object of the present invention is to provide a catalyst composition for ethylene trimerization comprising a tridentate ligand represented by formula I, a transition metal compound, an aluminum-containing cocatalyst and an organic peroxide,
in the formula: r1Is alkyl, aryl, an alkyl derivative or an aryl derivative; r2Is C1-C15The alkylene group of (1).
According to a particular embodiment of the composition according to the invention, R1Is selected from C5-C15Aryl or its derivative and C1-C10Or a derivative thereof. For example, R1May be selected from phenyl, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl and decyl. Wherein R is2Is C2-C10An alkylene group of (a). The alkyl groups in the present invention include straight-chain or branched alkyl groups. As R2Examples of (3) are methylene, ethylene, n-propylene, isopropylene, n-butylene or isobutylene and the like.
According to a preferred embodiment of the present invention, the composition further comprises an organic solvent. Wherein the organic solvent comprises at least one of hydrocarbons and derivatives thereof, aromatic hydrocarbons, halogenated hydrocarbons, ethers, alcohols and amines. Any organic solvent available in the art can be used in the present application. Hydrocarbons and derivatives thereof, aromatic hydrocarbons, halogenated hydrocarbons may have any number of carbon atoms, but typically contain less than 20 carbon atoms due to commercial availability and end use thereof. In a specific example, the organic solvent includes at least one of diethyl ether, methanol, ethanol, tetrahydrofuran, triethylamine, tripropylamine, triisobutylamine, benzene, toluene, xylene, and dichloromethane. The organic solvent is preferably the following compound: benzene, toluene, xylene, ethylbenzene, 1,3, 5-trimethylbenzene, heptane, nonane, cyclohexane, methylcyclohexane, 1-hexene, or chlorobenzene, but is not limited thereto. The amount of solvent is not critical, and generally the catalyst concentration is selected so that the activity and selectivity of the catalyst is maximized, typically because the catalyst activity tends to be higher at lower initial reaction mixture concentrations (typically 0.001 to 0.1mmol transition metal per 100ml reaction mixture).
In a preferred embodiment of the present invention, the catalyst composition comprises an organic peroxide in an amount of 25-1000ppm by weight, such as 150-1000ppm by weight, such as 250-1000ppm by weight, based on the weight of the organic solvent. In one embodiment, the organic peroxide is present in an amount of 150-800ppm, such as 150-500ppm, such as 250-500ppm, by weight. Within the weight content range, the composition herein has higher activity.
In some preferred embodiments of the present invention, the transition metal compound may be a transition metal compound commonly used in the art, such as a chromium compound, a molybdenum compound, an iron compound, a titanium compound, a zirconium compound, or a nickel compound. The transition metal compound includes at least one of a chromium compound, a molybdenum compound, an iron compound, a titanium compound, a zirconium compound, and a nickel compound. In a preferred embodiment, the transition metal compound includes at least one of chromium chloride, chromium acetylacetonate, chromium isooctanoate, chromium tris (tetrahydrofuran) trichloride, and the like.
According to some preferred embodiments of the invention, the organic peroxide comprises tert-butyl hydroperoxide.
In a preferred embodiment of the present invention, the amount of the ligand and transition metal in the catalyst composition is conventional in the art. In a specific embodiment, the SNS tridentate ligand is present in an amount of 2 to 500. mu. mol/L, based on the volume of the organic solvent; the content of the transition metal compound is 2-500 mu mol/L. Among them, it is preferable that the SNS tridentate ligand content is 5 to 100. mu. mol/L, or that the transition metal compound content is 5 to 100. mu. mol/L. Within this range, the compositions herein all have better activity.
In some embodiments of the invention, the aluminum-containing cocatalyst is selected from the group consisting of alkyl aluminum compounds and alkoxy aluminum compounds. The amounts of cocatalyst and transition metal compound are those conventionally used in the art. In one embodiment, the molar ratio of aluminum in the cocatalyst of the present invention to the metal in the transition metal compound is from 30:1 to 1500:1, such as from 100:1 to 1000:1, such as from 200:1 to 800: 1. Within the range of the molar ratio, the composition has better activity.
In some embodiments of the invention, the aluminum alkoxide is C1-C4An alkylaluminoxane. It is further preferred that the alkylaluminoxane includes at least one of methylaluminoxane, modified methylaluminoxane, ethylaluminoxane and isobutylaluminoxane.
In some embodiments of the invention, the alkylaluminum compound has the general formula AlWnYmWherein n is an integer from 1 to 3, m is an integer from 0 to 2, and m + n is equal to 3; when a plurality of W's are present, they may be the same or different and are each independently C1-C8An alkyl group; when a plurality of Y are present, they may be the same or different, and are each independently selected from halogen. Y may preferably be chlorine and/or bromine. It is further preferred that the alkyl aluminum compound comprises at least one of trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diethylaluminum monochloride and ethylaluminum dichloride.
In the ethylene trimerization reaction of the present invention, any two or three of the SNS ligand, the transition metal compound, the cocatalyst and the organic peroxide (e.g., t-butyl hydroperoxide) in the catalyst composition may be previously mixed and then added to the reaction system together with another one or two; or directly adding four components of the SNS ligand, the transition metal compound, the cocatalyst and the organic peroxide (such as tert-butyl hydroperoxide) into the reaction system; alternatively, the SNS ligand, the transition metal compound, the cocatalyst and the organic peroxide (e.g., t-butyl hydroperoxide) may be premixed and then directly added to the reaction system as a mixture. Wherein the organic solvent may be added during any mixing process of any of the above mixing modes. Further, it is also possible to dissolve the SNS ligand, the transition metal compound, the co-catalyst and the organic peroxide (e.g., t-butyl hydroperoxide) of the above-mentioned catalyst in an organic solvent, respectively, or dissolve the SNS ligand, the transition metal compound, the co-catalyst and the organic peroxide (e.g., t-butyl hydroperoxide) of the above-mentioned catalyst in an organic solvent in an arbitrary order. The mixing temperature of the catalyst components can be carried out at any temperature between 0 and 150 ℃.
A second object of the present invention relates to an ethylene trimerization process comprising carrying out the ethylene trimerization reaction in the presence of the above catalyst composition.
In a preferred embodiment of the present invention, the reaction temperature for the ethylene trimerization reaction is in the range of from 0 to 200 ℃, such as preferably from 20 to 180 ℃, more preferably from 60 to 120 ℃. The reaction pressure is 0.1-20MPa, preferably 2-10 MPa. In general, the polymerization activity increases with increasing ethylene pressure.
In the ethylene trimerization process, the diphosphine ligand and the transition metal compound can also form a metal complex (as shown in formula II, at the moment, the transition metal compound is a transition metal halide), any two of the metal complex, the cocatalyst and the organic peroxide (such as tert-butyl hydroperoxide) are mixed in advance, and then the mixture and the other one are added into the reaction system; or directly adding the three components of the metal complex, the cocatalyst and the organic peroxide (such as tert-butyl hydroperoxide) into the reaction system; or the metal complex, the cocatalyst and the organic peroxide (such as tert-butyl hydroperoxide) are premixed and then directly added into the reaction system in the form of a mixture. Wherein, the organic solvent can be added in any mixing process of one mixing mode.
In the present invention, the metal complex (formula II) can be prepared by reacting an SNS ligand of formula I with a transition metal compound by conventional chemical reactions, wherein M is a transition metal, X is selected from halogens, and q is an integer of 1 to 3. The halogen is selected from fluorine, chlorine, bromine and iodine, with fluorine, chlorine and bromine being particularly preferred.
In the invention, especially in the pilot-scale test and industrial production process of ethylene trimerization, the catalyst composition can effectively catalyze the ethylene trimerization reaction, has ultrahigh polymerization reaction activity, and has quick reaction initiation, stable operation and good repeatability.
After the polymerization reaction is finished, the obtained product is mainly C6, its content is greater than 95%, and its others are small quantity of C4, C8, C10 and C12 α -olefine, and the result shows that its catalyst activity can be up to 300Kg of oligomerization product g (Cr)-1·h-1. The ethylene trimerization reaction carried out by the method has few high molecular polymers.
According to the catalyst composition provided by the invention, ethylene is subjected to trimerization reaction under the action of the catalyst composition comprising the SNS ligand shown in the formula I, a transition metal compound, an aluminum-containing cocatalyst, an organic peroxide (such as tert-butyl hydroperoxide) and an organic solvent. The reaction condition of the reported ethylene trimerization or oligomerization catalyst system is usually required to be carried out under the anhydrous and oxygen-free conditions, but the catalyst disclosed by the invention has higher trimerization activity in the presence of organic peroxide such as tert-butyl hydroperoxide, and has the advantages of rapid reaction initiation, stable operation, good repeatability and beneficial effect.
Detailed Description
The present invention will be described in detail with reference to examples, but the present invention is not limited to the examples.
In an embodiment of the invention: the ligand is prepared from hydrochloride of haloalkylamine and mercaptan under alkaline condition.
The nuclear magnetic resonance was detected by an AV400MHz nuclear magnetic resonance spectrometer of Bruker, Switzerland.
The gas chromatography was performed using a Hewlett packard 5890 chromatograph.
The mass spectrum was detected by a Trace DSQ type gas chromatograph-mass spectrometer (Philippine corporation, USA).
Example 1
The polymerization was carried out in a 500ml stainless steel polymerizer. Firstly, a pressure maintaining test is carried out on the reaction kettle, and high-purity nitrogen is used for replacing three times and ethylene is used for replacing three times under high pressure under the condition that the reaction kettle is determined to be well sealed. 3. mu. mol of SNS ligand (wherein R is1、R2All are ethyl), a complex of chromium salt (chromium trichloride tris (tetrahydrofuran), a quantitative cocatalyst of triethylaluminum, tert-butyl hydroperoxide and a solvent of toluene, until the total volume of the mixed solution is 100ml, the weight of the organic solvent is taken as a calculation reference, the content of the tert-butyl hydroperoxide is 250ppm, the molar ratio of Al to Cr is 300, the reaction pressure is controlled to be 5.0MPa, the system temperature is 80 ℃, ethylene is introduced, and the ethylene trimerization reaction is initiated. After the reaction is finished for 0.5 hour, the temperature is reduced to room temperature, the gas product is put in a gas metering tank, the liquid product is collected in a conical flask, the gas chromatographic analysis is carried out after the metering, and the trimerization reaction result is shown in table 1. Wherein, catalyst activity is defined as: and the total amount of ethylene oligomerization products generated per gram of metal chromium per hour is Kg products per g.Cr/hour.
Example 2
The same as example 1 except that the content of t-butyl hydroperoxide was 25ppm, the ethylene trimerization reaction results were as shown in the attached Table 1.
Example 3
The same as example 1 except that the content of t-butyl hydroperoxide was 150ppm, the ethylene trimerization reaction results were as shown in the attached Table 1.
Example 4
The same as example 1 except that the content of t-butyl hydroperoxide was 500ppm, the results are shown in Table 1.
Example 5
The same as example 1, except that the content of t-butyl hydroperoxide was 1000ppm, the results are shown in Table 1.
Example 6
The same as example 1, except that the content of t-butyl hydroperoxide was 500ppm and the Al/Cr ratio was 500, the results are shown in Table 1.
Example 7
The difference from example 1 is that the content of t-butyl hydroperoxide was 500ppm, the Al/Cr ratio was 200, and the results are shown in Table 1.
Example 8
The difference from example 1 is that the content of t-butyl hydroperoxide was 500ppm, the Al/Cr ratio was 800, and the results are shown in Table 1.
Example 9
The same as example 1 except that the content of t-butyl hydroperoxide was 500ppm and the reaction temperature was 60 ℃ as shown in Table 1.
Example 10
The same as example 1 except that the content of t-butyl hydroperoxide was 500ppm and the reaction temperature was 120 ℃ and the results of the experiment are shown in Table 1.
Example 11
The same as example 1, except that the cocatalyst was diethylaluminum monochloride, the content of t-butyl hydroperoxide was 500ppm, the Al/Cr ratio was 800, and the experimental results are shown in Table 1.
Example 12
The same as example 1, except that the cocatalyst was diethylaluminum monochloride and t-butylhydroperoxide, the content was 500ppm, the reaction temperature was 130 deg.C, and the experimental results are shown in Table 1.
Example 13
The same as example 1, except that triisobutylaluminum was used as the cocatalyst, the Al/Cr ratio was 500, the reaction temperature was 120 ℃ and the experimental results are shown in Table 1.
Example 14
The same as example 1, except that the cocatalyst was t-butylhydroperoxide in an amount of 500ppm, the Al/Cr ratio was 800, the reaction pressure was 3MPa, and the results are shown in Table 1.
Example 15
The same as example 1, except that the cocatalyst was t-butylhydroperoxide in an amount of 500ppm, the Al/Cr ratio was 800, the reaction pressure was 7MPa, and the results are shown in Table 1.
Example 16
The same as example 1, except that R in the SNS ligand is1Is phenyl, R2The amount of t-butyl hydroperoxide was 400ppm, which was ethyl. The results of the ethylene oligomerization reaction are shown in the attached Table 1.
Example 17
The same as example 1, except that R in the SNS ligand is1Is decyl, R2The amount of t-butyl hydroperoxide was 400ppm, which was ethyl. The results of the ethylene oligomerization reaction are shown in the attached Table 1.
Comparative example 1
The difference from example 1 is that the content of t-butyl hydroperoxide was 0ppm and the Al/Cr ratio was 500, and the results are shown in Table 1.
TABLE 1
As can be seen from the data in Table 1, according to the catalyst composition provided by the invention, ethylene trimerization reaction is carried out under the action of SNS ligand shown in formula I, transition metal compound, aluminum-containing cocatalyst and organic peroxide (such as tert-butyl hydroperoxide), and instead, the catalyst composition has higher trimerization reaction activity, high C6 product content and high 1-hexene selectivity. The catalytic activity of the catalyst composition provided by the invention is 2 x 102Kg/(gCr. h) can reach 3.13 × 102Kg/(gCr. h), the selectivity to 1-hexene is over 99%. Compared with the catalyst of the comparative example 1, the catalyst composition provided by the invention has obviously improved catalyst activity, and can be improved by more than one order of magnitude.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (20)
1. A catalyst composition for ethylene trimerization comprises an SNS ligand represented by formula (1), a transition metal compound, an aluminum-containing cocatalyst and an organic peroxide;
wherein R is1Is alkyl, aryl, alkyl derivative or aryl derivative; r2Is C1-C15The organic peroxide comprises tert-butyl hydroperoxide, the composition also comprises an organic solvent, and the weight content of the organic peroxide is 25-1000ppm by weight based on the weight of the organic solvent;
the molar ratio of the aluminum in the cocatalyst to the metal in the transition metal compound is 30:1-1500: 1;
the content of the SNS tridentate ligand is 2-500 mu mol/L by taking the volume of the organic solvent as a calculation reference; the content of the transition metal compound is 2-500 mu mol/L.
2. The composition of claim 1, wherein R is1Is selected from C5-C15Aryl or its derivative and C1-C10Alkyl or a derivative thereof; and/or R2Is C2-C10An alkylene group of (a).
3. The composition of claim 2, wherein the composition is characterized byIn, R1Selected from phenyl, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl or decyl.
4. The composition as claimed in any one of claims 1 to 3, wherein the organic peroxide is present in an amount of 150-800ppm by weight.
5. The composition as claimed in claim 4, wherein the organic peroxide is present in an amount of 250-500ppm by weight.
6. The composition of any one of claims 1-3, wherein the transition metal compound comprises at least one of a chromium compound, a molybdenum compound, an iron compound, a titanium compound, a zirconium compound, and a nickel compound.
7. The composition of claim 6, wherein the transition metal compound comprises at least one of chromium chloride, chromium acetylacetonate, chromium isooctanoate, and chromium tris (tetrahydrofuran) trichloride.
8. The composition of any one of claims 1-3, wherein the aluminum-containing co-catalyst comprises at least one of an alkyl aluminum compound and an alkoxy aluminum compound.
9. The composition of claim 8, wherein the aluminum alkoxide is C1-C4Alkylaluminoxane; and/or
The alkyl aluminum compound has a general formula of AlWnYmWherein n is an integer from 1 to 3, m is an integer from 0 to 2, and m + n is equal to 3; when a plurality of W's are present, they may be the same or different and are each independently C1-C8An alkyl group; when a plurality of Y are present, they may be the same or different, and are each independently selected from halogen.
10. The composition of claim 9, wherein the alkylaluminoxane comprises at least one of methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, and isobutylaluminoxane; and/or
The alkyl aluminum compound comprises at least one of trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisobutyl aluminum, tri-n-hexyl aluminum, tri-n-octyl aluminum, diethyl aluminum monochloride and ethyl aluminum dichloride.
11. Composition according to claim 9, characterized in that, when a plurality of Y is present, it may be the same or different, each being independently selected from chlorine and/or bromine.
12. A composition according to any one of claims 1 to 3, wherein the molar ratio of aluminium in the cocatalyst to the metal in the transition metal compound is in the range 100:1 to 1000: 1.
13. The composition of claim 12, wherein the molar ratio of aluminum in the cocatalyst to the metal in the transition metal compound is from 200:1 to 800: 1.
14. The composition of any of claims 1-3, wherein the SNS tridentate ligand is present in an amount of 5 to 100 μmol/L, based on the volume of organic solvent; the content of the transition metal compound is 5-100 mu mol/L.
15. The composition according to any one of claims 1 to 3, wherein the organic solvent comprises at least one of hydrocarbons and derivatives thereof, aromatic hydrocarbons, halogenated hydrocarbons, ethers, alcohols, and amines.
16. The composition of claim 15, wherein the organic solvent comprises at least one of diethyl ether, methanol, ethanol, tetrahydrofuran, triethylamine, tripropylamine, triisobutylamine, benzene, toluene, xylene, and methylene chloride.
17. A process for the trimerization of ethylene comprising carrying out the trimerization of ethylene in the presence of the catalyst composition for the trimerization of ethylene according to any one of claims 1 to 16.
18. The method according to claim 17, wherein the reaction temperature of the ethylene trimerization reaction is 0-200 ℃; the reaction pressure is 0.1-20 MPa.
19. The method as claimed in claim 18, wherein the reaction temperature of the ethylene trimerization reaction is 20-180 ℃; the reaction pressure is 2-10 MPa.
20. The process according to claim 18, wherein the ethylene trimerization reaction is carried out at a reaction temperature of 60-130 ℃.
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