CN114011469B - Catalyst composition for ethylene oligomerization - Google Patents
Catalyst composition for ethylene oligomerization Download PDFInfo
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- CN114011469B CN114011469B CN202111418435.4A CN202111418435A CN114011469B CN 114011469 B CN114011469 B CN 114011469B CN 202111418435 A CN202111418435 A CN 202111418435A CN 114011469 B CN114011469 B CN 114011469B
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000005977 Ethylene Substances 0.000 title claims abstract description 51
- 239000003054 catalyst Substances 0.000 title claims abstract description 37
- 238000006384 oligomerization reaction Methods 0.000 title claims abstract description 21
- 239000000203 mixture Substances 0.000 title claims abstract description 14
- 239000003446 ligand Substances 0.000 claims abstract description 45
- 150000003623 transition metal compounds Chemical class 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 7
- 125000005234 alkyl aluminium group Chemical group 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 150000001875 compounds Chemical class 0.000 claims description 26
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 20
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 9
- 238000005829 trimerization reaction Methods 0.000 claims description 8
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 229910007926 ZrCl Inorganic materials 0.000 claims description 3
- BULLHRADHZGONG-UHFFFAOYSA-N [cyclopenta-2,4-dien-1-ylidene(phenyl)methyl]benzene Chemical compound C1=CC=CC1=C(C=1C=CC=CC=1)C1=CC=CC=C1 BULLHRADHZGONG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 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
- 239000012467 final product Substances 0.000 claims description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 3
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 3
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 claims description 3
- 239000012044 organic layer Substances 0.000 claims description 3
- 239000012074 organic phase Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 239000011877 solvent mixture Substances 0.000 claims description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 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
- 230000035484 reaction time Effects 0.000 claims description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-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
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 abstract description 44
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract description 22
- -1 compound benzhydryl (cyclopentadienyl) (9-fluorenyl) zirconium dichloride Chemical class 0.000 abstract description 14
- 239000004698 Polyethylene Substances 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 229920000573 polyethylene Polymers 0.000 abstract description 7
- 239000006227 byproduct Substances 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000013110 organic ligand Substances 0.000 abstract description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000004711 α-olefin Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000005086 pumping Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000004700 high-density polyethylene Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- RMBPEFMHABBEKP-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2C3=C[CH]C=CC3=CC2=C1 RMBPEFMHABBEKP-UHFFFAOYSA-N 0.000 description 3
- 229920001903 high density polyethylene Polymers 0.000 description 3
- 229920006124 polyolefin elastomer Polymers 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229920000092 linear low density polyethylene Polymers 0.000 description 2
- 239000004707 linear low-density polyethylene Substances 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000007790 scraping Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910001868 water Inorganic materials 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- IKMQPGOYCLXVSL-UHFFFAOYSA-L [Cl-].[Cl-].C1(C=CC=C1)[Zr+2]C1C2=CC=CC=C2C=2C=CC=CC1=2 Chemical compound [Cl-].[Cl-].C1(C=CC=C1)[Zr+2]C1C2=CC=CC=C2C=2C=CC=CC1=2 IKMQPGOYCLXVSL-UHFFFAOYSA-L 0.000 description 1
- RLFRULMEJWRTQH-UHFFFAOYSA-L [Cl-].[Cl-].C1=CC=CC=2C3=CC=CC=C3C(C12)[Zr+2].C1(=CC=CC=C1)C(C1=CC=CC=C1)=C1C=CC=C1 Chemical group [Cl-].[Cl-].C1=CC=CC=2C3=CC=CC=C3C(C12)[Zr+2].C1(=CC=CC=C1)C(C1=CC=CC=C1)=C1C=CC=C1 RLFRULMEJWRTQH-UHFFFAOYSA-L 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- 229920004889 linear high-density polyethylene Polymers 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- VMRZYTKLQVKYKQ-UHFFFAOYSA-N lithium;1,9-dihydrofluoren-1-ide Chemical class [Li+].C1=C[C-]=C2CC3=CC=CC=C3C2=C1 VMRZYTKLQVKYKQ-UHFFFAOYSA-N 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010689 synthetic lubricating oil Substances 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 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
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2291—Olefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
- B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
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- 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
-
- 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
- C07C2/30—Catalytic processes with hydrides or organic compounds containing metal-to-carbon bond; Metal hydrides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/20—Olefin oligomerisation or telomerisation
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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
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/48—Zirconium
-
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention provides a catalyst composition for ethylene oligomerization, which comprises ligand compound benzhydryl (cyclopentadienyl) (9-fluorenyl) zirconium dichloride, transition metal compound and alkyl aluminum cocatalyst. The metal organic ligand benzhydryl (cyclopentadiene) (9-fluorenyl) zirconium dichloride is used as a ligand of an ethylene tetramerization catalyst, can effectively form a bimetallic center in the catalytic process, improves the selectivity of 1-octene, and can effectively inhibit the generation of polyethylene byproducts.
Description
Technical Field
The invention belongs to the field of ethylene oligomerization preparation, and particularly relates to a metal organic compound ligand and application thereof in ethylene oligomerization.
Background
In recent years, with the wide use of Linear Low Density Polyethylene (LLDPE) and High Density Polyethylene (HDPE), the consumption of linear alpha-olefin (LAO) monomers such as 1-hexene and 1-octene for synthesizing LLDPE and HDPE has also increased greatly, wherein the LLDPE needs to be added with 1-hexene or 1-octene to reach 8% -10%, and the HDPE needs to be added with alpha-olefin of about 2%. Furthermore, the alpha-olefin content in polyolefin elastomers (POE) needs to be up to 30%. Although POE is not yet industrialized in China at present, few enterprises report pilot-scale results at present, and industrialization is expected to be realized in the near future. It is predicted that the total alpha-olefin demand in 2023 China will reach 120 ten thousand tons/year, while the current supply of 7.5 ten thousand tons/year 1-hexene in China can not meet the market demand far, which will seriously affect the updating iteration of polyethylene products. Meanwhile, with the development of the automobile industry and precision machining machinery, the demand for high-end lubricating oil is greatly increased, wherein synthetic lubricating oil base oil (PAO) produced by using 1-decene oligomerization has an ultrahigh viscosity temperature index, and the PAO becomes the product with the most market value, and the demand for 1-decene in the market is continuously increased.
However, the 1-octene used in the industry today is still mainly prepared by non-selective oligomerization of ethylene, and the alpha-olefins produced by such processes are C 4 -C 20 The product is in accordance with Schulz-Flory distribution, so that pure 1-octene can be obtained by continuous rectification at the end of the process, and a large amount of energy is consumed. Ethylene selective oligomerization is a process for preparing alpha olefin contrary to non-selective oligomerization, and the process selectively generates one to two alpha olefins, and at present, the dimerization of ethylene to prepare 1-butene and the trimerization to prepare 1-hexene are all industrialized by the key technology in China. However, the technology for preparing 1-octene by ethylene tetramerization only announces that the first ethylene tetramerization device for producing 1-octene is built in Lake Charles in Louisiana in U.S.A. in Sasol in 2014, the production scale is 10 ten thousand tons/year 1-octene (8 ten thousand tons/year) and 1-hexene (2 ten thousand tons/year), the running condition of a factory is not reported in detail, industrialization has not been realized so far in China, and a key technology is not realized yetStill being mastered abroad.
At present, the development of ethylene selective tetramerization catalyst is based on a chromium/PNP ligand catalytic system with high activity and high selectivity. From the disclosure of the patent, sasol corporation, shell corporation, middle petrochemicals, middle petroleum, micheles, universities of Tianjin technology, etc., and the universities of universities, etc., are representative of the patents disclosed in the selective tetramerization of ethylene. For example, patent nos. PTCZA200300187, PTCZA200300188, PCTZA2003000186 and PCTZA2003000185 from Sasol are all catalysts of Cr/PNP/alkylaluminoxane system, and the 1-octene selectivity is about 70%. PCT/EP2006061425 by SHELL corporation uses two ligands with 1-octene selectivity up to 69.4%. Domestic scientific institutions also make a great deal of contribution in ethylene tetramerization, wherein patents CN108097322A, CN108607612A, CN108607613A, CN109174190A, CN109174191A, CN109331878A, CN110449186A, WO2019113748A1 and CN106582851B, CN105289742B, CN110368994A published by Tianjin technology university are all catalysts for protecting different types, and the 1-octene selectivity can reach 75 percent at most. Researches on the selective tetramerization of ethylene on the petrochemical industry are quite well established, and CN102040624B, CN102451758B, CN102451759B and the like relate to a synthesis method of ligands for ethylene trimerization or tetramerization catalysts, wherein the selectivity of 1-octene is 60% -75%. Related patents such as CN 108686706A, CN 100443178C and CN 101450326B are also researched and filed on the aspect of ethylene oligomerization, and are all catalysts for protecting ethylene selective oligomerization, wherein the selectivity of 1-octene can be more than 70%.
According to a number of published patents or reports, the prior art still has the problem of high levels of by-product polyolefin, resulting in ethylene tetramerization that is difficult to achieve continuous production. From the above analysis, it is known that the key to the technology of preparing 1-octene by ethylene tetramerization is to select a proper ligand to provide proper electron donating ability and space configuration, thereby facilitating the synthesis of 1-octene. However, the current mainstream technology is to use PNP (bis (diarylphosphino) -amine) or similar derivatives disclosed by SASOL company as ligand (US 7511183) to form ethylene tetramerization catalyst system with organochromium and MAO. The present invention aims to obtain ethylene selective oligomerization properties superior to PNP by synthesizing novel ligands.
Disclosure of Invention
In order to solve the technical problems, the invention provides an application of a metal organic compound of benzhydryl (cyclopentadiene) (9-fluorenyl) zirconium dichloride in ethylene tetramerization, and the metal organic ligand disclosed by the invention is used as a ligand of an ethylene tetramerization catalyst, can effectively form a bimetallic center in a catalytic process to improve the selectivity of 1-octene, and can effectively inhibit the generation of polyethylene byproducts. The catalyst has the advantages of high catalyst activity, high selectivity of 1-octene in the product, less polyethylene byproducts and the like when catalyzing ethylene oligomerization.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a catalyst composition for oligomerization of ethylene, comprising a ligand compound represented by formula (I), a transition metal compound and an alkyl aluminum cocatalyst, the ligand compound having the structure shown below:
the alkyl aluminum cocatalyst is one of methylaluminoxane, modified methylaluminoxane, triethylaluminum, trimethylaluminum and triisobutylaluminum; the transition metal compound is selected from at least one of chromium compounds, molybdenum compounds, iron compounds, titanium compounds, zirconium compounds, and nickel compounds.
Further, the preparation method of the ligand compound comprises the following steps:
step one: the white compound ligand is prepared by the salt elimination reaction of fluorenyl lithium salt and cyclopentadiene phosphine compound;
step two: under the action of butyl lithium, extracting hydrogen on cyclopentadiene in the white compound ligand to obtain a metal lithium compound of the ligand, and then carrying out a salt elimination reaction with zirconium tetrachloride to finally obtain a target product ligand compound.
Further, the preparation method of the ligand compound specifically comprises the following steps:
step one: fluorene and THF were added to the reaction vessel, then an ether solution of methyllithium in equimolar amount to fluorene was added at room temperature for 30 minutes, the resulting dark red solution was stirred for several hours until complete gas evolution ceased, then 6, 6-diphenylfulvene dissolved in THF was added dropwise thereto, the resulting red THF solution was stirred overnight, then saturated aqueous ammonium chloride solution was added for treatment and stirring for 10 minutes, the organic layer was extracted several times with ether, the combined organic phases were dried over magnesium sulfate, the ether was removed and the solid recrystallized from methanol/chloroform solvent mixture to give a white compound ligand;
step two: adding anhydrous pentane and the white compound ligand prepared in the step one into a reaction vessel, and then adding ZrCl with the same molar quantity as the white compound ligand 4 The powder was stirred for 6 hours, after the reaction was completed, the pentane solvent was removed, the remaining red solid was extracted with dichloromethane to remove lithium chloride, and the extract was cooled to-20 ℃ to give the final product ligand compound.
Further, the transition metal compound is at least one of chromium acetylacetonate, chromium isooctanoate, and chromium tri (tetrahydrofuran) trichloride (CAS number: 10170-68-0).
Further, the molar ratio of the transition metal compound, the ligand compound and the aluminum alkyl cocatalyst is 1:0.1-10:100-1000.
Application: the catalyst composition is used for ethylene trimerization and/or tetramerization in an aliphatic or aromatic hydrocarbon solvent.
Further, the solvent is n-hexane, cyclohexane, n-heptane or toluene, preferably cyclohexane.
Further, in the ethylene trimerization and/or tetramerization reaction, the reaction temperature is 0-200 ℃, the ethylene pressure is 0.1-20.0MPa, and the reaction time is 0.5-4 h. Preferably, the reaction temperature is 30-100 ℃ and the ethylene pressure is 0.5-6.0MPa.
The application of the catalyst composition in ethylene oligomerization, the specific method comprises the following steps:
(1) The reactor body and the lining are placed in an oven 120 before the reaction o C oven dried overnight and connected to evaluationThe system is sealed and heated to 100 under the condition of vacuum pumping o C is kept at the constant temperature for 1h (the tail gas valve is closed) to remove residual water, oxygen and oxygen-containing impurities. Then the temperature is set as the reaction temperature, so that the reaction temperature is naturally reduced, nitrogen is filled, and then the vacuum pumping is carried out for three times, so that the air is ensured to be replaced completely. Then pumping nitrogen by a vacuum pump, filling with ethylene, repeating for three times, and ensuring that the kettle body is full of ethylene.
(2) Opening an exhaust valve, sequentially injecting a dehydrated and deoxidized solvent and a certain amount of cocatalyst by using an injector under the stirring condition, injecting a transition metal compound and a ligand by using the injector after the temperature is stabilized to the reaction temperature, closing the exhaust valve, adjusting a pressure reducing valve, starting timing after the pressure is increased to a preset pressure value, recording data of a mass flowmeter, adding an aluminum alkyl auxiliary agent, closing ethylene gas after a certain period of reaction, recording data of the mass flowmeter, stopping the reaction, closing an air inlet valve, removing a reaction kettle body, and soaking in an ice water bath to cool the reaction kettle to 10 o And C or less.
(3) And after the reaction kettle is opened, weighing the total weight of liquid and solid as soon as possible, filling a proper amount of quartz cotton into a syringe, taking 1-2 ml of liquid sample, filtering, transferring to a sample bottle, and analyzing the components and the proportion of the product by GC-MS. Filtering the rest sample, weighing filter paper in advance, recording the mass, scraping the polymer on a stirring paddle by a spoon, cleaning the polymer in a beaker by using a solvent, and placing all the polymer in a vacuum oven for 60 percent o C, drying overnight, weighing respectively, and calculating to obtain pure quality. The liquid product composition can be calibrated by MS. The individual component selectivities can be calculated by combining the total liquid and solid weights, the solid mass and GC results, and the catalyst activities can be calculated by combining the catalyst usage amounts.
The invention has the advantages that:
(1) The catalyst system is formed by using benzhydryl (cyclopentadiene) (9-fluorenyl) zirconium dichloride as a ligand of a tetramerization catalyst and a metal center for the first time for ethylene selective oligomerization;
(2) The selectivity of 1-octene in the product is high;
(3) The polyethylene content in the product is very low.
(4) The metal organic ligand disclosed by the invention is used as a ligand of an ethylene tetramerization catalyst, can effectively form a bimetallic center in the catalytic process to improve the selectivity of 1-octene, and can effectively inhibit the generation of polyethylene byproducts.
(5) The ligand of the tetramerization catalyst is diphenylmethylene (cyclopentadiene) (9-fluorenyl) zirconium dichloride, which can improve the selectivity of 1-octene and reduce the action principle of polyethylene byproduct generation:the ligand contains a rigid group fluorenyl, so that the selectivity in polymerization can be improved; />The conjugation degree of the ligand is high, and the activity of the central metal can be reduced, so that the chain transfer of the catalyst can be effectively controlled, and the generation of polymers is reduced; />The ligand has moderate size, and can stabilize the formation of transition state eight-membered ring, thereby generating 1-octene directionally.
Drawings
FIG. 1 is a nuclear magnetic spectrum of the ligand compound benzhydryl (cyclopentadienyl) (9-fluorenyl) zirconium dichloride.
Detailed Description
The following examples are provided to illustrate the above features and advantages of the present invention. The method of the invention is a conventional method in the art unless specifically stated otherwise.
Example 1 preparation of benzhydryl (cyclopentadiene) (9-fluorenyl) zirconium dichloride:
synthetic route for white compound ligand
1) To a round bottom flask equipped with side arms, addition funnel and magnetic stirring bar was added 2.5 g (0.015 mol) fluorene and 50 ml THF. An equimolar amount of methyllithium in diethyl ether (1.4, M) was added over 30 minutes at room temperature. The resulting dark red solution was stirred for several hours until the evolution of gas was completely stopped. Then 3.4 g (0.015 mol) of 6, 6-diphenylfulvene dissolved in 100 mL of THF was added dropwise thereto, and the resulting red THF solution was stirred overnight, followed by treatment with 30 mL of saturated aqueous ammonium chloride solution and stirring for 10 minutes. The organic layer was extracted several times with 50 ml of diethyl ether and the combined organic phases were dried over magnesium sulfate. After removal of the ether and recrystallisation of the solid from a methanol/chloroform solvent mixture, 3.2. 3.2 g (54.5%) of the white compound ligand was obtained.
Synthetic route of metal organic catalyst
2) 200 ml of anhydrous pentane and 1.0 g (0.0025 mol) of the above white compound ligand were charged into a 250 mL three neck round bottom flask equipped with a magnetic stirring bar, and then ZrCl was added to the suspension of the above anhydrous pentane in an amount equimolar to the white compound ligand 4 The powder and mixture were stirred at ambient temperature for 6 hours. After completion of the reaction, the slurry turned red in color, the pentane solvent was removed, the remaining red solid was extracted with methylene chloride to remove lithium chloride, and the extract was cooled to-20 ℃ to give the final product ligand compound benzhydrylene (cyclopentadienyl) (9-fluorenyl) zirconium dichloride 1.3. 1.3 g in 92.8% yield.
The nuclear magnetic spectrum is shown in the attached figure 1.
Application examples and comparative examples:
ethylene oligomerization was carried out in a 300 mL autoclave. The reaction kettle body is put into an oven 120 before the reaction o C, drying overnight, connecting to an evaluation system, sealing, and heating to 100 under the condition of vacuum pumping o C constant temperature 1h (off-gas valve closed) to remove residual water, oxygen and oxygen-containing impurities. Then the temperature is set as the reaction temperature, so that the reaction temperature is naturally reduced, nitrogen is filled, and then the vacuum pumping is carried out for three times, thereby ensuring the airHas been replaced clean. Then pumping nitrogen by a vacuum pump, filling with ethylene, repeating for three times, and ensuring that the kettle body is full of ethylene. The off-gas valve was opened and 90 mL cyclohexane solvent, an amount of methylaluminoxane (methylaluminoxane is a toluene solution of 1.5 mol/L) and an amount of ligand compound solution were sequentially injected using an injector under stirring, and after the temperature had stabilized to the set temperature, the transition metal compound solution was injected into the reaction vessel, followed by washing the injector with 10 mL cyclohexane to ensure that all the catalyst components had been injected into the reactor. After stirring for 3-5 min, closing an exhaust valve, regulating a pressure reducing valve, starting timing after the pressure rises to a set pressure, closing ethylene gas after reacting for a certain time, recording data of a mass flowmeter, stopping the reaction, closing an air inlet valve, removing a reaction kettle body, and soaking in an ice water bath to cool the reaction kettle to 10 o And C or less. And after the reaction kettle is opened, weighing the total weight of liquid and solid as soon as possible, filling a proper amount of quartz cotton into a syringe, taking 1-2 ml of liquid sample, filtering, transferring to a sample bottle, and placing on a GC-MS to analyze the components and the proportion of the product. Filtering the rest sample, weighing filter paper in advance, recording the mass, scraping the polymer on a stirring paddle by a spoon, cleaning the polymer in a beaker by using a solvent, and placing all the polymer in a vacuum oven for 60 percent o C, drying overnight, weighing respectively, and calculating to obtain pure quality. The liquid product composition can be calibrated by MS. The individual component selectivities can be calculated by combining the total liquid and solid weights, the solid mass and GC results, and the catalyst activities can be calculated by combining the catalyst usage amounts. The reaction conditions related to examples 1 to 4 and comparative example 1 are summarized in Table 1.
Table 1 example reaction conditions summary table
TABLE 2 catalyst systems of examples 1-4 and comparative example 1 of the present invention for ethylene oligomerization activity and product distribution
Note that: application examples 1-4 the catalyst systems corresponding to examples 1-4, respectively, were used for ethylene oligomerization.
From the results of the analysis in combination with tables 1 and 2, it is clear that the catalyst composition of the present invention is used in ethylene trimerization and/or tetramerization reaction, the catalyst activity is obviously higher than that of the conventional catalyst, the 1-octene selectivity is equivalent to that of the conventional catalyst, and in addition, the polymer content is obviously reduced, which is favorable for long-period operation of ethylene oligomerization reaction and hopefully realizes continuous operation of ethylene trimerization and/or tetramerization reaction.
The foregoing description is only of the preferred embodiments of the invention, and all changes and modifications that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (5)
1. A catalyst composition for oligomerization of ethylene, the catalyst composition comprising a ligand compound of formula (I), a transition metal compound and an alkyl aluminum cocatalyst, the ligand compound having the structure shown below:(1)
The alkyl aluminum cocatalyst is one of methylaluminoxane, modified methylaluminoxane, triethylaluminum, trimethylaluminum and triisobutylaluminum;
the transition metal compound is at least one of chromium acetylacetonate, chromium isooctanoate and chromium tri (tetrahydrofuran) trichloride;
the molar ratio of the transition metal compound to the ligand compound to the aluminum alkyl cocatalyst is 1:0.1-10:100-1000;
the preparation method of the ligand compound specifically comprises the following steps:
step one: fluorene and THF were added to the reaction vessel, then an ether solution of methyllithium in equimolar amount to fluorene was added at room temperature for 30 minutes, the resulting dark red solution was stirred for several hours until complete cessation of gas evolution, then 6, 6-diphenylfulvene in THF was added to the reaction vessel, the resulting red THF solution was stirred overnight, then saturated aqueous ammonium chloride solution was added and stirred for 10 minutes, the organic layer was extracted several times with ether, the combined organic phases were dried over magnesium sulfate, the ether was removed and the solid recrystallized from methanol/chloroform solvent mixture to give a white compound ligand;
step two: adding anhydrous pentane and the white compound ligand prepared in the step one into a reaction vessel, and then adding ZrCl with the same molar quantity as the white compound ligand 4 The powder was stirred for 6 hours, after the reaction was completed, the pentane solvent was removed, the remaining red solid was extracted with dichloromethane to remove lithium chloride, and the extract was cooled to-20 ℃ to give the final product ligand compound.
2. Use of a catalyst composition according to claim 1, characterized in that the catalyst composition is used for ethylene trimerisation and/or tetramerisation in an aliphatic or aromatic hydrocarbon solvent.
3. Use according to claim 2, characterized in that the solvent is n-hexane, cyclohexane, n-heptane or toluene.
4. The use according to claim 2, wherein in the trimerization and/or tetramerization reaction of ethylene, the reaction temperature is 0-200 ℃, the ethylene pressure is 0.1-20.0MPa, and the reaction time is 0.5-4 h.
5. The process according to claim 4, wherein the ethylene trimerization and/or tetramerization is carried out at a temperature of 30 to 100℃and an ethylene pressure of 0.5 to 6.0MPa.
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