CN116328839A - Supported main catalyst for oligomerization of ethylene, catalyst composition for oligomerization of ethylene and application - Google Patents
Supported main catalyst for oligomerization of ethylene, catalyst composition for oligomerization of ethylene and application Download PDFInfo
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- CN116328839A CN116328839A CN202111600339.1A CN202111600339A CN116328839A CN 116328839 A CN116328839 A CN 116328839A CN 202111600339 A CN202111600339 A CN 202111600339A CN 116328839 A CN116328839 A CN 116328839A
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- Prior art keywords
- ethylene
- catalyst
- procatalyst
- ethylene oligomerization
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- 239000003054 catalyst Substances 0.000 title claims abstract description 89
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 239000005977 Ethylene Substances 0.000 title claims abstract description 85
- 238000006384 oligomerization reaction Methods 0.000 title claims abstract description 62
- 239000000203 mixture Substances 0.000 title claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 239000002808 molecular sieve Substances 0.000 claims abstract description 34
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 34
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 22
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 16
- 239000013110 organic ligand Substances 0.000 claims abstract description 13
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical group CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011651 chromium Substances 0.000 claims abstract description 12
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 8
- 101150061900 Ambn gene Proteins 0.000 claims abstract description 7
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 6
- 150000003624 transition metals Chemical class 0.000 claims abstract description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052736 halogen Chemical group 0.000 claims abstract description 3
- 125000005843 halogen group Chemical group 0.000 claims abstract description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 3
- 239000011733 molybdenum Substances 0.000 claims abstract description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 3
- 239000010937 tungsten Substances 0.000 claims abstract description 3
- -1 alkylaluminum compound Chemical class 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 238000005829 trimerization reaction Methods 0.000 claims description 7
- 241000269350 Anura Species 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical group CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 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 3
- 125000001153 fluoro group Chemical group F* 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 3
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 claims description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 2
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 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
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- JYLPOJPHFDVWCY-UHFFFAOYSA-K oxolane;trichlorochromium Chemical group [Cl-].[Cl-].[Cl-].[Cr+3].C1CCOC1 JYLPOJPHFDVWCY-UHFFFAOYSA-K 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
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 claims description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-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
- 230000000694 effects Effects 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 5
- 239000002815 homogeneous catalyst Substances 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000002638 heterogeneous catalyst Substances 0.000 abstract description 2
- 230000008929 regeneration Effects 0.000 abstract description 2
- 238000011069 regeneration method Methods 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 description 48
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 21
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 16
- 239000000047 product Substances 0.000 description 13
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 238000005481 NMR spectroscopy Methods 0.000 description 11
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 239000007787 solid Substances 0.000 description 8
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000004440 column chromatography Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 125000004198 2-fluorophenyl group Chemical group [H]C1=C([H])C(F)=C(*)C([H])=C1[H] 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 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 4
- 150000001925 cycloalkenes Chemical class 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 3
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 125000003963 dichloro group Chemical group Cl* 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 2
- NPDACUSDTOMAMK-UHFFFAOYSA-N 4-Chlorotoluene Chemical compound CC1=CC=C(Cl)C=C1 NPDACUSDTOMAMK-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- HPJPYHWZJQJKLM-UHFFFAOYSA-N chloro-bis(2-fluorophenyl)phosphane Chemical compound FC1=CC=CC=C1P(Cl)C1=CC=CC=C1F HPJPYHWZJQJKLM-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 150000001924 cycloalkanes Chemical class 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical group NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 229940117389 dichlorobenzene Drugs 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- BMTAFVWTTFSTOG-UHFFFAOYSA-N Butylate Chemical group CCSC(=O)N(CC(C)C)CC(C)C BMTAFVWTTFSTOG-UHFFFAOYSA-N 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- FRBFQWMZETVGKX-UHFFFAOYSA-K chromium(3+);6-methylheptanoate Chemical group [Cr+3].CC(C)CCCCC([O-])=O.CC(C)CCCCC([O-])=O.CC(C)CCCCC([O-])=O FRBFQWMZETVGKX-UHFFFAOYSA-K 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000002743 phosphorus functional group Chemical group 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical group CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 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
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/2247—At least one oxygen and one phosphorous atom present as complexing atoms in an at least bidentate or bridging ligand
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
- B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
-
- B01J35/19—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/26—Catalytic processes with hydrides or organic compounds
- C07C2/32—Catalytic processes with hydrides or organic compounds as complexes, e.g. acetyl-acetonates
-
- 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
-
- 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
- B01J2531/64—Molybdenum
-
- 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
- B01J2531/66—Tungsten
-
- 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
-
- 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
Abstract
The invention discloses a supported ethylene oligomerization main catalyst and an ethylene oligomerization catalyst composition and application. The supported ethylene oligomerization main catalyst comprises a molecular sieve and a metal complex supported on the molecular sieve, wherein the metal complex is a metal complex of AMBn shown in a general formula (I); wherein A is an organic ligand of the formula (II) wherein (Ar) 1 )(Ar 2 )PN(R)P(Ar 3 )(Ar 4 ) Wherein Ar is 1 、Ar 2 、Ar 3 、Ar 4 Each independently is phenyl or halogen substituted phenyl; wherein M is a transition metal selected from chromium, molybdenum or tungsten; wherein B is selected from acetylacetone, tetrahydrofuran, and isooctanoic acidThe method comprises the steps of carrying out a first treatment on the surface of the Wherein n=1 to 3. The invention combines the advantages of high activity and high selectivity of the homogeneous catalyst, easy regeneration and easy separation of the heterogeneous catalyst, and the like by adopting the proper carrier, realizes the heterogeneous phase of the homogeneous catalyst, prolongs the service life of the catalyst, reduces the consumption of the cocatalyst and ensures that the catalytic activity of a reaction system is released stably.
Description
Technical Field
The invention relates to the field of ethylene polymerization, in particular to the field of ethylene oligomerization, ethylene trimerization or ethylene tetramerization, and more particularly relates to a supported ethylene oligomerization main catalyst, an ethylene oligomerization catalyst composition containing the supported ethylene oligomerization main catalyst and application thereof.
Background
Alpha-olefins are important organic raw materials and chemical intermediates, and are mainly applied to the fields of producing high-quality Polyethylene (PE), lubricating oil base oil, plasticizer, detergent and the like. Ethylene oligomerization is one of the most important reactions in the olefin polymerization industry, by which inexpensive small molecule ethylene can be converted into products with high added value, i.e., different long chain alpha-olefins. Since the 70 s of the last century, research on the polymerization and oligomerization of olefins catalyzed by transition metal complexes has been increasingly receiving attention from scientists, and efforts have been made to develop new catalysts and to improve existing catalysts, to increase the activity of the catalysts and the selectivity of the catalytic products. Among the many studies that have been carried out the earliest and most rapidly, the more concentrated are nickel-based cationic catalytic systems, as reported earlier in U.S. Pat. nos. 3686351a and 3676523a, and the shell corporation SHOP process based on this patent technology. O-P bridged ligand is involved in shell company SHOP process, but the catalyst contains toxic organic phosphorus group, and has complex synthesis steps and poor stability. A number of patents such as JP11060627, WO9923096A1, CN1401666A, CN1769270A and the like have been developed for O-O, P-N, P-P and N-N type complex nickel catalysts. However, the catalysts obtained from the above patents have the disadvantage of being relatively complex in terms of the preparation process.
Patent WO2004056478A1 by Sasol discloses a PNP framework catalyst having a C8 component selectivity of about 66wt% and a C6 component selectivity of about 21wt% in ethylene tetramerization, wherein the content of 1-hexene in the C6 component is only 82%, and the total selectivity of 1-hexene and 1-octene is about 84%. In US20100137669A1 patent a PCCP symmetric framework catalyst is disclosed which is more stable than the PNP system in ethylene tetramerization reactions, with a total selectivity of 1-hexene and 1-octene of no more than 85%. The prior art also attempts to increase the reaction temperature to increase the 1-hexene content in the C6 component, but tends to result in a rapid decrease in the 1-octene content of the most predominant target product.
In these reaction systems, the byproducts such as cycloolefin and cyclized product present in the C6 product can be removed by separation and purification, but the economy of the whole process is disadvantageous. Thus, it is of some challenging importance how to increase the content of 1-hexene in the C6 component while maintaining a higher 1-octene content in the reaction product, thereby increasing the economics of the process.
On the other hand, the reaction systems are basically homogeneous catalysis, and the related technologies of the supported ethylene oligomerization catalyst are less, and mainly the selection of the carrier is difficult. The acidity and alkalinity of the support, the particle size, the pore size and pore distribution, the specific surface area, etc., determine its bond and ability to the catalyst active component.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a novel supported ethylene oligomerization main catalyst, an ethylene oligomerization catalyst composition containing the supported ethylene oligomerization main catalyst and application thereof. The invention combines the advantages of high activity and high selectivity of the homogeneous catalyst, easy regeneration and easy separation of the heterogeneous catalyst, and the like by adopting the proper carrier, realizes the heterogeneous phase of the homogeneous catalyst, prolongs the service life of the catalyst, reduces the consumption of the cocatalyst and ensures that the catalytic activity of a reaction system is released stably.
The invention provides a supported ethylene oligomerization main catalyst, which comprises a molecular sieve and a metal complex supported on the molecular sieve, wherein the metal complex is a metal complex of AMBn in a general formula (I),
wherein A is an organic ligand of the formula (II) wherein (Ar) 1 )(Ar 2 )PN(R)P(Ar 3 )(Ar 4 ) Wherein Ar is 1 、Ar 2 、Ar 3 、Ar 4 Each independently is phenyl or halogen substituted phenyl;
wherein M is a transition metal selected from chromium, molybdenum or tungsten;
wherein B is selected from acetylacetone, tetrahydrofuran, and isooctanoic acid;
wherein n=1 to 3.
According to some embodiments of the invention, the molecular sieve is selected from the group consisting of SAPO molecular sieves, preferably at least one selected from the group consisting of SAPO-5 molecular sieves, SAPO-11 molecular sieves, SAPO-31 molecular sieves, SAPO-34 molecular sieves and SAPO-41 molecular sieves.
According to some embodiments of the invention, ar linked to P in formula (II) 1 、Ar 2 、Ar 3 、Ar 4 And a phenyl group having one or more ortho-positions which are fluorine atoms or fluorinated substituents.
According to some embodiments of the invention, in formula (II), R is selected from substituted or unsubstituted C 1 -C 20 Alkyl, substituted or unsubstituted C 3 -C 20 Cycloalkyl and substituted or unsubstituted C 6 -C 30 At least one of aryl groups of (a); preferably, R is selected from substituted or unsubstituted C 1 -C 10 Alkyl, substituted or unsubstituted C 3 -C 10 Cycloalkyl and substituted or unsubstituted C 6 -C 20 At least one of aryl groups of (a); more preferably, R is selected from methyl, ethyl, propyl, isopropyl, butylAt least one of isobutyl, cyclopropyl, cyclopentyl, cyclohexyl, phenyl, and substituted phenyl.
According to some embodiments of the invention, preferably, formula (II) is selected from (Ph) 2 PN( i Pr)P(Ph)(2-F-Ph)、(Ph) 2 PN( i Pr)P(2-F-Ph) 2 、(2-F-Ph)(Ph)PN( i Pr)P(Ph)(2-F-Ph)、(2-F-Ph)(Ph)PN( i Pr)P(2-F-Ph) 2 、(Ph) 2 PN( t Bu)P(Ph)(2-F-Ph)、(Ph) 2 PN(C y )P(Ph)(2-F-Ph)、(Ph) 2 At least one of PN (Ph) P (Ph) (2-F-Ph).
According to some embodiments of the invention, M is selected from the transition metals of chromium in formula (I).
According to some embodiments of the invention, in formula (I), B is selected from acetylacetone.
According to some embodiments of the invention, in formula (I), n represents a number satisfying the valence of M, for example n is selected from 1, 2 or 3, preferably n is 3.
According to some embodiments of the invention, the weight ratio of metal complex to molecular sieve is from 1:1 to 3000, preferably from 1:10 to 2000, more preferably from 1:100 to 1000.
In a second aspect, the invention provides an ethylene oligomerization catalyst composition comprising the main catalyst and an organoaluminum cocatalyst as described above.
According to some embodiments of the invention, the organoaluminum co-catalyst is selected from at least one of an alkylaluminum compound, an alkylaluminum compound and an alkylaluminum chloride compound, more preferably from at least one of methylaluminoxane, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diethylaluminum chloride, ethylaluminum dichloride, ethylaluminoxane and modified methylaluminoxane. In the present invention, the modified methylaluminoxane may be an alkyl modified methylaluminoxane, such as alkyl modified methylaluminoxane MMAO which is conventional in the art.
According to some embodiments of the invention, the molar ratio of procatalyst to cocatalyst, calculated as metal M, is from 1:1 to 2000, preferably from 1:10 to 1000, more preferably from 1:100 to 600.
In a third aspect, the invention provides a process for the oligomerization of ethylene comprising: ethylene oligomerization is carried out in an organic solvent in the presence of the above-described procatalyst or the above-described ethylene oligomerization catalyst composition.
According to some embodiments of the invention, the concentration of the catalyst composition is 0.1 to 10. Mu. Mol/L on a metal basis, calculated on the volume of the organic solvent.
According to some embodiments of the invention, the reaction conditions may be those commonly used in the art. Preferably, the ethylene oligomerization reaction is carried out at a reaction temperature of from 0 to 75 ℃, preferably at a reaction temperature of from 30 to 75 ℃, more preferably at a reaction temperature of from 40 to 65 ℃. The supported ethylene oligomerization main catalyst or the ethylene oligomerization catalyst composition can be used for oligomerization reaction at a lower temperature and has good effect.
According to some embodiments of the invention, the reaction conditions may be those commonly used in the art. Preferably, the ethylene oligomerization reaction has an ethylene pressure of 0.1 to 20.0MPa, preferably 0.5 to 5.0MPa, more preferably 2.0 to 5.0MPa.
According to some embodiments of the invention, the organic solvent comprises aliphatic hydrocarbon compounds and/or aromatic hydrocarbon compounds.
According to some embodiments of the invention, the aliphatic hydrocarbon compound is selected from at least one of linear alkanes, branched alkanes, and cycloalkanes; more preferably at least one of pentane, heptane, hexane, cyclohexane and methylcyclohexane.
According to some embodiments of the invention, the aromatic compound is selected from at least one of benzene, toluene, xylene, monochlorobenzene, dichlorobenzene, trichlorobenzene, monochlorotoluene and derivatives thereof.
According to some embodiments of the present invention, in the above reaction, the supported procatalyst and the cocatalyst may be premixed and then added together into the reaction system, or both components of the supported procatalyst and the cocatalyst may be added separately into the reaction system.
In a fourth aspect the invention provides a process for trimerising or tetramerising ethylene comprising: ethylene trimerization or ethylene tetramerization is carried out in an organic solvent in the presence of a procatalyst according to the above or an ethylene oligomerization catalyst composition as described above.
According to some embodiments of the invention, the concentration of the catalyst composition is 0.1 to 10. Mu. Mol/L on a metal basis, calculated on the volume of the organic solvent.
According to some embodiments of the invention, the reaction conditions may be those commonly used in the art. Preferably, the reaction temperature of the ethylene trimerization or ethylene tetramerization reaction is from 0 to 75 ℃, preferably from 30 to 75 ℃, more preferably from 40 to 65 ℃. The supported ethylene oligomerization main catalyst or the ethylene oligomerization catalyst composition can be used for ethylene trimerization or ethylene tetramerization reaction at a lower temperature, and has good effect.
According to some embodiments of the invention, the reaction conditions may be those commonly used in the art. Preferably, the ethylene pressure of the ethylene trimerization or ethylene tetramerization reaction is from 0.1 to 20.0MPa, preferably from 0.5 to 5.0MPa, more preferably from 2.0 to 5.0MPa.
According to some embodiments of the invention, the organic solvent comprises aliphatic hydrocarbon compounds and/or aromatic hydrocarbon compounds.
According to some embodiments of the invention, the aliphatic hydrocarbon compound is selected from at least one of linear alkanes, branched alkanes, and cycloalkanes; more preferably at least one of pentane, heptane, hexane, cyclohexane and methylcyclohexane.
According to some embodiments of the invention, the aromatic compound is selected from at least one of benzene, toluene, xylene, monochlorobenzene, dichlorobenzene, trichlorobenzene, monochlorotoluene and derivatives thereof.
According to some embodiments of the present invention, in the above reaction, the supported procatalyst and the cocatalyst may be premixed and then added together into the reaction system, or both components of the supported procatalyst and the cocatalyst may be added separately into the reaction system.
The invention has the beneficial effects that:
(1) According to the supported ethylene oligomerization main catalyst and the catalyst composition, the metal complex is supported on the weakly acidic SAPO molecular sieve, so that the stability of the catalyst is improved, the economical efficiency of industrial application is better, and the cost is lower. With the catalyst composition provided by the invention, the catalytic activity is preferably more than 2X 10 8 g·mol(Cr) -1 ·h -1 Up to 6X 10 8 g·mol(Cr) -1 ·h -1 Under different conditions, the total selectivity of 1-hexene and 1-octene is more than 93 wt%, the highest selectivity can exceed 96 wt%, byproducts such as cycloolefin, cyclized products and the like are obviously reduced, oligomerization can last for more than 2 hours, and the using amount of a cocatalyst is also obviously reduced. Therefore, the catalyst composition provided by the invention has the characteristics of high catalytic activity, high selectivity, high stability and the like, and has good industrial application prospect and economic value.
(2) The supported main catalyst has better stability, novel structure, simple preparation and lower cost. The catalyst has long activity duration and low cocatalyst consumption.
(3) The catalyst composition can effectively catalyze ethylene oligomerization, especially ethylene oligomerization, ethylene trimerization and ethylene tetramerization, and has high catalyst activity and good product selectivity; and the byproducts such as cycloolefin, cyclized product and the like in the C6 product are obviously reduced.
(4) The catalyst composition provided by the invention has the characteristics of high catalytic activity, high selectivity and the like, and has good industrial application prospect and economic value.
Detailed Description
In order that the invention may be more readily understood, the invention will be described in detail below with reference to the following examples, which are given by way of illustration only and are not limiting of the scope of application of the invention.
The test method and the equipment used in the test are as follows:
(1) In the embodiment of the invention, nuclear magnetic resonance is detected by using a Bruker AV400 type nuclear magnetic resonance apparatus, wherein the detection conditions of nuclear magnetic resonance are as follows: deuterated chloroform is used as solvent.
(2) The room temperature test gas chromatograph adopts an Agilent 7890 chromatograph to detect, wherein the detection conditions of the gas chromatograph are as follows: a chromatographic column SE-54, a high-purity nitrogen carrier gas and a FID detector; the column temperature adopts two-stage temperature programming.
In the present invention, t bu is a tertiary butyl group, and the amino acid is a tertiary butyl group, i pr is isopropyl, cy is cyclohexyl, ph is phenyl, ar is substituted aryl, acac is acetylacetone, 2-EHA is isooctanoic acid, and THF is tetrahydrofuran.
[ PREPARATION EXAMPLE 1 ]
Preparation of organic ligand A 1 ：(Ph) 2 PN( i Pr)P(Ph)(2-F-Ph)
(o-fluorophenyl) phenylphosphorous chloride (10 mmol) was added dropwise to a solution of isopropylamine (12.5 mmol) and triethylamine (5 mL) in methylene chloride (10 mL) at 0deg.C and stirred for 30 min, then warmed to room temperature and stirred overnight, the mixture was drained of the solvent, then dehydrated ether (20 mL) was added to form a suspension, and the filtrate was obtained by filtration and was drained under reduced pressure to give an oil. The oily substance (2.0 g) was dissolved in methylene chloride (10 mL), triethylamine (0.5 mL) was added, followed by dropwise addition of diphenylphosphorus chloride (3.3 g,15.2 mmol), and after completion of the addition, the mixture was stirred at room temperature overnight, the solvent was drained, and white solid powder A was obtained by basic alumina column chromatography 1 。 1 H NMR(400MHz,CDCl 3 )δ＝7.52-7.41(m,1H),7.42-7.22(m,16H),7.11(t,1H),6.99(td,1H),3.87-3.69(m,1H),1.30(d,3H),1.02(d,3H)。
[ PREPARATION EXAMPLE 2 ]
Preparation of organic ligand A 2 ：(Ph) 2 PN( i Pr)P(2-F-Ph) 2
Di (o-fluorophenyl) phosphorus chloride (10 mmol) was added dropwise to a solution of isopropylamine (12.5 mmol) and triethylamine (5 mL) in dichloromethane (10 mL) at 0deg.C and stirred for 30 min, then warmed to room temperature and stirred overnight, the mixture was drained of solvent, then anhydrous diethyl ether (20 mL) was added to form a suspension, and the filtrate was filtered and drained under reduced pressure to give an oily crude product. The crude product, 0.5g, was dissolved in dichloromethane (10 mL) and triethylamine @ was added0.5 mL), followed by dropwise addition of diphenylphosphorus chloride (0.8 g,3.6 mmol), stirring overnight at room temperature after completion of the dropwise addition, pumping the mixture solvent to dryness, and subjecting to basic alumina column chromatography to obtain white solid powder A 2 。 1 H NMR(400MHz,CDCl 3 )δ＝7.42-7.27(m,14H),7.09(t,2H),6.99(td,2H),3.93-3.77(m,1H),1.18(d,6H)。
[ PREPARATION EXAMPLE 3 ]
Preparation of organic ligand A 3 ：(2-F-Ph)(Ph)PN( i Pr)P(Ph)(2-F-Ph)
(o-fluorophenyl) phenylphosphorous chloride (10 mmol) was added dropwise to a solution of isopropylamine (4 mmol) and triethylamine (5 mL) in methylene chloride (10 mL) at 0deg.C and stirred for 30 min, then warmed to room temperature and stirred overnight, the mixture was dried by pumping the solvent, and ligand A was obtained as a white solid by basic alumina column chromatography 3 。 1 H NMR(400MHz,CDCl 3 )δ7.45(m,1H),7.39-7.20(m,13H),7.10(m,2H),6.97(m,2H),3.91-3.70(m,1H),1.40(d,1.5H),1.17(d,3H),0.90(d,1.5H)。
[ PREPARATION EXAMPLE 4 ]
Preparation of organic ligand A 4 ：(2-F-Ph)(Ph)PN( i Pr)P(2-F-Ph) 2
Di (o-fluorophenyl) phosphorus chloride (10 mmol) was added dropwise to a solution of isopropylamine (12.5 mmol) and triethylamine (5 mL) in dichloromethane (10 mL) at 0deg.C and stirred for 30 min, then warmed to room temperature and stirred overnight, the mixture was drained of solvent, then anhydrous diethyl ether (20 mL) was added to form a suspension, and the filtrate was filtered and dried under reduced pressure to give an oil. Dissolving oily substance (1.8 g) in n-hexane, cooling to-60 ℃, adding n-butyllithium (6.3 mmol), slowly heating to room temperature, stirring for 30 min, cooling to-60 ℃ again, dropwise adding (o-fluorophenyl) phenylphosphorous chloride (1.7 g,7.0 mmol), stirring for 30 min, shifting to room temperature, reacting overnight, pumping the mixture solvent, and obtaining white solid powder A by basic alumina column chromatography 4 。 1 H NMR(400MHz,CDCl 3 )δ7.33(m,11H),7.18-7.04(m,3H),7.05-6.87(m,3H),3.86(m,1H),1.33(d,6H)。
[ PREPARATION EXAMPLE 5 ]
Preparation of organic ligand A 5 ：(Ph) 2 PN( t Bu)P(Ph)(2-F-Ph)
The preparation method is the same as in preparation example 1, except that isopropylamine is replaced with t-butylamine. 1 H NMR(400MHz,CDCl 3 )δ＝7.49-7.40(m,1H),7.38-7.20(m,16H),7.09(t,1H),6.98(td,1H),1.20(s,9H)。
[ PREPARATION EXAMPLE 6 ]
Preparation of organic ligand A 6 ：(Ph) 2 PN(C y )P(Ph)(2-F-Ph)
The preparation method is the same as in preparation example 1, except that isopropylamine is replaced with cyclohexylamine. 1 H NMR(400MHz,CDCl 3 )δ＝7.50-7.43(m,1H),7.40-7.25(m,16H),7.11(t,1H),7.00(td,1H),2.90(m,1H),1.60-1.40(m,10H)。
[ PREPARATION EXAMPLE 7 ]
Preparation of organic ligand A 7 ：(Ph) 2 PN(Ph)P(Ph)(2-F-Ph)
The preparation method is the same as in preparation example 1, except that isopropylamine is replaced with aniline. 1 H NMR(400MHz,CDCl 3 )δ＝7.35-6.90(m,24H)。
[ PREPARATION EXAMPLE 8 ]
Preparation of organic ligand A 8 ：(Ph) 2 PN(Ph)P(Ph) 2 (i.e., phenyl group having no ortho-position to the fluorine atom or fluorinated substituent)
Diphenyl phosphorus chloride (10 mmol) was added dropwise to a solution of aniline (5 mmol) and triethylamine (5 mL) in dichloromethane (10 mL) at 0 ℃ and stirred for 30 min, then the mixture was stirred at room temperature overnight, the solvent was drained off, then anhydrous diethyl ether (20 mL) was added to form a suspension, and the filtrate was obtained by filtration and drained off under reduced pressure to give an oil. Subjecting the oily matter to basic alumina column chromatography to obtain white solid powder A 8 。 1 H NMR(400MHz,CDCl 3 )δ＝7.40-6.85(m,25H)。
Synthesis examples 1 to 9
The preparation method of the metal complex AMBn comprises the following steps: under nitrogen protection, 5mmol of organic ligand A were respectively reacted 1 -A 7 (prepared in preparation examples 1-7, respectively) and 5mmol of chromium acetylacetonate were transferred to a Schlenk tube, 50mL of toluene solution was added, and then the mixture was stirred at 80℃for 8 hours. Will beCooling the reaction solution to room temperature, performing suction filtration, washing the obtained solid with toluene and n-hexane respectively, and vacuum drying to obtain corresponding metal complex AMBn, namely C 1 -C 7 。
Metal complex C 8 The preparation method of (2) is the same as in synthesis example 7, except that chromium acetylacetonate is replaced with chromium isooctanoate.
Metal complex C 9 The preparation method of (2) is the same as that of synthesis example 1, except that chromium acetylacetonate is replaced with chromium tetrahydrofuran chloride.
Synthesis example 10
The preparation method of the metal complex AMBn comprises the following steps: under nitrogen protection, 5mmol of organic ligand A were respectively reacted 8 (prepared in preparation example 8) and 5mmol of chromium acetylacetonate were transferred to a Schlenk tube, 50mL of toluene solution was added, and then the mixture was stirred at 80℃for 8 hours. Cooling the reaction solution to room temperature, performing suction filtration, washing the obtained solid with toluene and n-hexane respectively, and vacuum drying to obtain corresponding metal complex AMBn, namely C 10 。
[ Supported procatalyst preparation example 1 ]
Preparation of the Supported main catalyst S5-1:
50g of SAPO-5 molecular sieve was added to a reaction flask under nitrogen protection, 200mL of cyclohexane was added, and 0.05g of metal complex C was added with stirring 1 The temperature was raised from room temperature to 60℃and stirred overnight. Stopping the reaction, and removing the solvent from the reaction solution by using a rotary evaporator to obtain solid powder, namely the supported main catalyst S5-1.
[ Supported procatalyst preparation example 2 ]
Preparation of the Supported procatalyst S11-1.
Preparation example 1 of the same supported procatalyst was performed except that the SAPO-5 molecular sieve was replaced with a SAPO-11 molecular sieve.
[ Supported procatalyst preparation example 3 ]
Preparation of the Supported procatalyst S34-2.
Preparation example 1 of the same supported procatalyst except that the SAPO-5 molecular sieve was replaced with a SAPO-34 molecular sieve, and the metal complex C 1 Replacement by metal complexes C 2 。
[ Supported procatalyst preparation example 4 ]
Preparation of the Supported procatalyst S41-3.
Preparation example 1 of the same supported procatalyst except that the SAPO-5 molecular sieve was replaced with a SAPO-41 molecular sieve, and the metal complex C was reacted 1 Replacement by metal complexes C 3 。
[ Supported procatalyst preparation examples 5-12 ]
Preparation of Supported procatalysts S5-2 to S5-9.
Preparation example 1 of the same supported procatalyst, except that the metal complex C was reacted 1 Respectively replaced by metal complexes C 2 -C 9 。
[ Supported procatalyst preparation example 13 ]
Preparation of the supported main catalyst S5-10.
Preparation example 1 of the same supported procatalyst, except that the metal complex C was reacted 1 Replacement by metal complexes C 10 。
[ example 1 ]
The ethylene oligomerization reaction is carried out by adopting a supported main catalyst S5-1.
A300 mL stainless steel polymerizer was used. The autoclave was heated to 100 ℃, evacuated, replaced several times with nitrogen, then replaced by ethylene and cooled to the set temperature. Then methylcyclohexane was added at 70℃with 0.1. Mu. Mol of procatalyst S5-1 (calculated as chromium metal) and cocatalyst-Modified Methylaluminoxane (MMAO) added, the total volume of the mixture being 100mL, wherein the molar ratio of procatalyst S5-1 (calculated as chromium metal) to cocatalyst was 1:600, ethylene is introduced under the reaction pressure of 3MPa and the temperature of 70 ℃ to carry out ethylene oligomerization.
After the reaction was continued for 2 hours, the reaction was completed, the system was cooled to room temperature, the gas phase product was collected in a gas metering tank, the liquid phase product was collected in a conical flask, and 1mL of ethanol was added as a terminator to terminate the reaction. The gas-liquid phase product was measured and analyzed by gas chromatography (chromatograph is Hewlett-packard 5890). The data results are shown in Table 1.
[ example 2 ]
The ethylene oligomerization reaction is carried out by adopting a supported main catalyst S11-1.
The same as in example 1 was found to be different in that the main catalyst S5-1 was replaced with a main catalyst S11-1. The data results are shown in Table 1.
[ example 3 ]
The ethylene oligomerization reaction is carried out by adopting a supported main catalyst S34-2.
The same as in example 1 was found to be different in that the main catalyst S5-1 was replaced with a main catalyst S34-2. The data results are shown in Table 1.
[ example 4 ]
The ethylene oligomerization reaction is carried out by adopting a supported main catalyst S41-3.
The same as in example 1 was found to be different in that the main catalyst S5-1 was replaced with a main catalyst S41-3. The data results are shown in Table 1.
[ example 5 ]
The ethylene oligomerization reaction is carried out by adopting a supported main catalyst S5-1.
The procedure is as in example 1, except that the modified methylaluminoxane is replaced by triethylaluminum. The data results are shown in Table 1.
[ example 6 ]
The ethylene oligomerization reaction is carried out by adopting a supported main catalyst S5-1.
The procedure of example 1 was repeated except that the reaction temperature was changed from 70℃to 30 ℃. The data results are shown in Table 1.
[ example 7 ]
The ethylene oligomerization reaction is carried out by adopting a supported main catalyst S5-1.
The procedure is as in example 1, except that the reaction temperature is replaced by 40℃from 70 ℃. The data results are shown in Table 1.
[ example 8 ]
The ethylene oligomerization reaction is carried out by adopting a supported main catalyst S5-1.
The procedure of example 1 was repeated except that the reaction temperature was changed from 70℃to 75 ℃. The data results are shown in Table 1.
[ example 9 ]
The ethylene oligomerization reaction is carried out by adopting a supported main catalyst S5-1.
The same as in example 1 was found to be different in that the reaction pressure was replaced with 5MPa from 3 MPa. The data results are shown in Table 1.
[ example 10 ]
The ethylene oligomerization reaction is carried out by adopting a supported main catalyst S5-1.
The difference from example 1 is that the molar ratio of the procatalyst S5-1 to the cocatalyst is replaced by 1:600 by 1:100. The data results are shown in Table 1.
Examples 11 to 18
The ethylene oligomerization reaction is carried out by using the supported main catalysts S5-2 to S5-9 respectively.
The difference from example 1 is that the main catalyst S5-1 is replaced with S5-2 to S5-9, respectively. The data results are shown in Table 1.
[ example 19 ]
The procedure is as in example 1, except that the molar ratio of procatalyst S5-1 to cocatalyst is 1:1000. The data results are shown in Table 1.
[ example 20 ]
The ethylene oligomerization reaction is carried out by adopting a supported main catalyst S5-1.
The procedure is as in example 1, except that the molar ratio of procatalyst S5-1 to cocatalyst is 1:2000. The data results are shown in Table 1.
[ example 21 ]
The ethylene oligomerization reaction is carried out by adopting a supported main catalyst S5-1.
The procedure of example 1 was repeated except that the reaction temperature was changed from 40℃to 100 ℃. The data results are shown in Table 1.
[ example 22 ]
The ethylene oligomerization reaction is carried out by adopting a supported main catalyst S5-1.
The procedure of example 1 was repeated except that the reaction temperature was changed from 40℃to 80 ℃. The data results are shown in Table 1.
Example 23
And carrying out ethylene oligomerization reaction by adopting a supported main catalyst S5-10.
The difference is that S5-1 is replaced by a metal complex S5-10 as in example 1. The data results are shown in Table 1.
Comparative example 1
The compound bis [ (S, S) - (phenyl) is adopted 2 PCH (Me) CH (Me) P (phenyl) 2 Dichloro (mu-chloro) chromium]Ethylene oligomerization is carried out.
The method of implementation was as described in comparative example 2 in CN104169003 a. The data results are shown in Table 1.
Comparative example 2
Using the compound bis [ (S, S) - (o-fluoro-phenyl) 2 PCH (Me) CH (Me) P (o-fluoro-phenyl) 2 Dichloro (mu-chloro) chromium]Ethylene oligomerization is carried out.
The procedure was as described in example 4 of CN104169003 a. The data results are shown in Table 1.
[ comparative example 3 ]
The compound of comparative example 2 bis [ (S, S) - (o-fluoro-phenyl) 2 PCH (Me) CH (Me) P (o-fluoro-phenyl) 2 Dichloro (mu-chloro) chromium]The method is carried on a SAPO-5 molecular sieve, and the method is the same as that of the preparation example 1 of the supported main catalyst. The supported main catalyst S5-D1 is obtained.
Ethylene oligomerization was carried out using a supported procatalyst S5-D1 in the same manner as in example 1. The data results are shown in Table 1.
TABLE 1
As can be seen from the data in Table 1, the preferred supported catalyst compositions provided by the present invention exhibit catalytic activity in excess of 2X 10 at polymerization temperatures below 75 DEG C 8 g·mol(Cr) -1 ·h -1 Up to 6.4X10 8 g·mol(Cr) -1 ·h -1 Under different conditions, the total selectivity of 1-hexene and 1-octene is more than 92 wt% and can be up to more than96% by weight. In contrast to examples 21 and 22, the catalyst compositions provided by the present invention have significantly higher catalyst activity and selectivity to 1-octene at moderate reaction temperatures (below 75 ℃). Compared with the homogeneous catalyst of comparative example 1, the SAPO molecular sieve supported catalyst composition provided by the invention has the advantages that the catalyst activity is improved by several times or even more than 10 times, the high 1-octene selectivity is maintained, the content of 1-hexene in C6 is greatly improved, and byproducts such as cycloolefin, cyclized products and the like are obviously reduced. The catalyst after being loaded by the molecular sieve has improved stability, the catalytic activity can be kept for more than 2 hours, the used cocatalyst dosage is obviously reduced, and the catalyst can react even under the condition of low cocatalyst dosage. The catalyst composition disclosed by the invention has better performance, the SAPO molecular sieve can improve the dispersity of the metal complex, the specific surface area of the metal and the activity and stability of the catalyst composition.
The selectivity of the 1-octene in the invention is obviously improved. Because of the polyolefin field, in particular POE, C8-LLDPE, PAO new materials and the like, there is a need for a copolymerization grade of high purity 1-octene, which is not in demand in the market, is completely imported in China, and has a price obviously higher than other long chain alpha-olefins; therefore, the process technology with higher 1-octene selectivity has obvious economic benefit and social value.
The supported ethylene oligomerization catalyst composition can effectively catalyze ethylene polymerization reaction, and has the advantages of high catalyst activity, rapid reaction initiation, stable operation, good repeatability, strong practicability and wide industrial prospect.
What has been described above is merely a preferred example of the present invention. It should be noted that other equivalent modifications and improvements will occur to those skilled in the art, and are intended to be within the scope of the present invention, as a matter of common general knowledge in the art, in light of the technical teaching provided by the present invention.
Claims (10)
1. A supported ethylene oligomerization main catalyst, comprising a molecular sieve and a metal complex supported on the molecular sieve, wherein the metal complex is a metal complex of AMBn of the general formula (I);
wherein A is an organic ligand of the formula (II) wherein (Ar) 1 )(Ar 2 )PN(R)P(Ar 3 )(Ar 4 ) Wherein Ar is 1 、Ar 2 、Ar 3 、Ar 4 Each independently is phenyl or halogen substituted phenyl;
wherein M is a transition metal selected from chromium, molybdenum or tungsten;
wherein B is selected from acetylacetone, tetrahydrofuran, and isooctanoic acid;
wherein n=1 to 3.
2. The procatalyst of claim 1 wherein the molecular sieve is selected from SAPO molecular sieves, preferably at least one selected from SAPO-5 molecular sieves, SAPO-11 molecular sieves, SAPO-31 molecular sieves, SAPO-34 molecular sieves, and SAPO-41 molecular sieves.
3. Procatalyst according to claim 1 or 2, characterized in that in formula (II) Ar linked to P 1 、Ar 2 、Ar 3 、Ar 4 And a phenyl group having one or more ortho-positions which are fluorine atoms or fluorinated substituents.
4. A procatalyst according to any of claims 1-3, characterized in that in formula (II), R is selected from substituted or unsubstituted C 1 -C 20 Alkyl, substituted or unsubstituted C 3 -C 20 Cycloalkyl and substituted or unsubstituted C 6 -C 30 At least one of aryl groups of (a); preferably, R is selected from substituted or unsubstituted C 1 -C 10 Alkyl, substituted or unsubstituted C 3 -C 10 Cycloalkyl and substituted or unsubstituted C 6 -C 20 At least one of aryl groups of (a); more preferably, R is selected from at least one of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, cyclopropyl, cyclopentyl, cyclohexyl, phenyl, and substituted phenyl.
5. The procatalyst according to any one of claims 1-4Characterized in that the general formula (II) is selected from (Ph) 2 PN( i Pr)P(Ph)(2-F-Ph)、(Ph) 2 PN( i Pr)P(2-F-Ph) 2 、(2-F-Ph)(Ph)PN( i Pr)P(Ph)(2-F-Ph)、(2-F-Ph)(Ph)PN( i Pr)P(2-F-Ph) 2 、(Ph) 2 PN( t Bu)P(Ph)(2-F-Ph)、(Ph) 2 PN(C y )P(Ph)(2-F-Ph)、(Ph) 2 At least one of PN (Ph) P (Ph) (2-F-Ph).
6. Procatalyst according to any of claims 1-5, characterized in that M in general formula (I) is selected from the group of transition metals of chromium; and/or B is selected from acetylacetone or tetrahydrofuran chromium chloride; and/or n is selected from 1, 2 or 3, preferably n is 3.
7. Procatalyst according to any of claims 1-6, characterized in that the weight ratio of metal complex to molecular sieve is 1:1-3000, preferably 1:10-2000, more preferably 1:100-1000.
8. An ethylene oligomerization catalyst composition comprising the procatalyst of any of claims 1-7 and an organoaluminum cocatalyst;
preferably, the organoaluminum cocatalyst is selected from at least one of an alkylaluminum compound, and an alkylaluminum chloride compound, more preferably from at least one of methylaluminoxane, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diethylaluminum monochloride, ethylaluminum dichloride, ethylaluminoxane, and modified methylaluminoxane;
preferably, the molar ratio of procatalyst to cocatalyst, calculated as metal M, is from 1:1 to 2000, preferably from 1:10 to 1000, more preferably from 1:100 to 600.
9. A process for oligomerization of ethylene comprising: carrying out an ethylene oligomerization reaction in an organic solvent in the presence of the procatalyst according to any of claims 1-7 or the ethylene oligomerization catalyst composition according to claim 8;
preferably, the concentration of the procatalyst or catalyst composition is 0.1 to 10. Mu. Mol/L, calculated as metal M, based on the volume of the organic solvent;
preferably, the ethylene oligomerization reaction is carried out at a reaction temperature of 0-75 ℃, preferably at a reaction temperature of 30-75 ℃, more preferably at 40-65 ℃;
preferably, the ethylene oligomerization reaction has an ethylene pressure of 0.1 to 20.0MPa, preferably 0.5 to 5.0MPa, more preferably 2.0 to 5.0MPa.
10. A process for trimerization or tetramerization of ethylene comprising: ethylene trimerisation or ethylene tetramerisation in an organic solvent in the presence of a procatalyst according to any of claims 1-7 or an ethylene oligomerization catalyst composition according to claim 8.
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