CN114011469A - Catalyst composition for ethylene oligomerization - Google Patents
Catalyst composition for ethylene oligomerization Download PDFInfo
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- CN114011469A CN114011469A CN202111418435.4A CN202111418435A CN114011469A CN 114011469 A CN114011469 A CN 114011469A CN 202111418435 A CN202111418435 A CN 202111418435A CN 114011469 A CN114011469 A CN 114011469A
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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 40
- 238000006384 oligomerization reaction Methods 0.000 title claims abstract description 21
- 239000000203 mixture Substances 0.000 title claims abstract description 17
- 239000003446 ligand Substances 0.000 claims abstract description 49
- 150000001875 compounds Chemical class 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 15
- 150000003623 transition metal compounds Chemical class 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 9
- -1 polyethylene Polymers 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 41
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 18
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 11
- 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 9
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims description 8
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 7
- 238000002360 preparation method Methods 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
- 238000001035 drying Methods 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
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 4
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 4
- 238000003379 elimination reaction Methods 0.000 claims description 4
- 150000002642 lithium compounds Chemical class 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 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
- 230000009471 action Effects 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- 239000007864 aqueous solution Substances 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 150000001845 chromium compounds 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
- 238000001816 cooling Methods 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 150000002506 iron compounds Chemical class 0.000 claims description 2
- 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 claims description 2
- 239000005078 molybdenum compound Substances 0.000 claims description 2
- 150000002752 molybdenum compounds Chemical class 0.000 claims description 2
- 150000002816 nickel compounds Chemical class 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 150000003609 titanium compounds Chemical class 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
- 150000003755 zirconium compounds Chemical class 0.000 claims description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 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
- 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 compound [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 abstract description 8
- 239000004698 Polyethylene Substances 0.000 abstract description 7
- 229920000573 polyethylene Polymers 0.000 abstract description 7
- 239000006227 byproduct Substances 0.000 abstract description 6
- 239000013110 organic ligand Substances 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 229910052782 aluminium Inorganic materials 0.000 abstract 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 7
- 239000004711 α-olefin Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 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
- RMBPEFMHABBEKP-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2C3=C[CH]C=CC3=CC2=C1 RMBPEFMHABBEKP-UHFFFAOYSA-N 0.000 description 4
- 239000004700 high-density polyethylene Substances 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
- 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
- 239000012494 Quartz wool Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000010438 heat treatment 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
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007789 sealing Methods 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
- 238000005303 weighing Methods 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 229920004889 linear high-density polyethylene Polymers 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010689 synthetic lubricating oil Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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- 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
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- 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
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/20—Olefin oligomerisation or telomerisation
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Abstract
The invention provides a catalyst composition for ethylene oligomerization, which comprises a ligand compound, namely diphenylmethylene (cyclopentadiene) (9-fluorenyl) zirconium dichloride, a transition metal compound and an aluminum alkyl cocatalyst. The metal organic ligand diphenylmethylene (cyclopentadiene) (9-fluorenyl) zirconium dichloride is used as a ligand of an ethylene tetramerization catalyst, can effectively form a bimetallic center in a catalysis process to improve 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 widespread 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 used for synthesizing LLDPE and HDPE has also increased greatly, wherein 1-hexene or 1-octene is required to be added into LLDPE to 8-10%, and the addition of alpha-olefin into HDPE is about 2%. In addition, the polyolefin elastomer (POE) needs to have an alpha-olefin content of up to 30%. Although POE is not industrialized at home at present, a few enterprises report pilot-plant results at present, and industrialization is expected to be realized in the near future. The total demand of alpha-olefin in our country is predicted to reach 120 ten thousand tons/year in 2023, while the existing supply of 1-hexene of 7.5 ten thousand tons/year in China is far from meeting the market demand, which seriously affects the updating iteration of polyethylene products. Meanwhile, with the development of the automobile industry and precision processing machinery, the demand of high-end lubricating oil is greatly increased, wherein the synthetic lubricating oil base oil (PAO) produced by oligomerization of 1-decene has an ultrahigh viscosity-temperature index, becomes the product with the highest market value in the PAO, and the demand of the market on 1-decene is continuously increased.
However, the 1-octene used in industry at present is still mainly obtained by non-selective oligomerization of ethylene, and the alpha olefin produced by the process is C4-C20The product of the mixture is in accordance with Schulz-Flory distribution, so that continuous rectification is needed at the end of the processTo obtain pure 1-octene, a large amount of energy is consumed. The selective oligomerization of ethylene is a process for preparing alpha olefin opposite to non-selective oligomerization, the process selectively generates one to two kinds of alpha olefin, and the preparation of 1-butene by ethylene dimerization and the preparation of 1-hexene by trimerization are realized by domestic key technology. However, until now, the technology for preparing 1-octene by ethylene tetramerization is only published in 2014 by Sasol to build a first set of device for producing 1-octene by ethylene tetramerization in Lake Charles, Louisiana, the production scale is 10 ten thousand tons/year of 1-octene (8 ten thousand tons/year) and 1-hexene (2 ten thousand tons/year), the operation condition of a factory is not reported in detail, industrialization is not realized at home so far, and the key technology is still mastered abroad.
Currently, the development of ethylene selective tetramerisation catalysts is based on a high activity and high selectivity chromium/PNP ligand catalytic system. From the disclosed patents, the patents disclosed by the Sasol corporation, Shell corporation, petrochemistry, petroleum, marylar, tianjin science and technology university, college, etc. are representative in terms of ethylene selective tetramerization. Patents such as PTCZA200300187, PTCZA200300188, PCTZA2003000186, PCTZA2003000185 from Sasol are all Cr/PNP/alkylaluminoxane system catalysts, and the selectivity of 1-octene is around 70%. PCT/EP2006061425 from SHELL corporation uses two ligands, with a 1-octene selectivity of 69.4%. Domestic scientific research institutions also make great contributions in ethylene tetramerization, wherein patents CN108097322A, CN108607612A, CN108607613A, CN109174190A, CN109174191A, CN109331878A, CN110449186A, WO2019113748A1, CN106582851B, CN105289742B and CN110368994A published by Tianjin scientific and technical university protect different types of catalysts, and the selectivity of 1-octene can reach 75% at most. Researches on selective tetramerization of ethylene by medium petrochemical are well established, CN102040624B, CN102451758B, CN102451759B and the like relate to a synthetic method of a ligand for an ethylene trimerization or tetramerization catalyst, and the selectivity of 1-octene is 60-75%. The medium petroleum oil has been studied and applied for the ethylene oligomerization, for example, CN 108686706A, CN 100443178C and CN 101450326B are all catalysts for ethylene selective oligomerization, wherein the selectivity of 1-octene can be more than 70%.
According to a large number of published patents or reports, the prior art still has the problem of high content of by-product polyolefin, resulting in difficulty in continuous production of ethylene tetramer. From the above analysis, the key to the technology of preparing 1-octene by ethylene tetramerization is to select a proper ligand to provide a proper electron donating ability and steric 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 as ligand (US 7511183) to form ethylene tetramerization catalyst system with organochromium and MAO. The present invention aims to obtain more excellent ethylene selective oligomerization performance than PNP by synthesizing a novel ligand.
Disclosure of Invention
In order to solve the technical problems, the invention provides an application of a metal organic compound, namely diphenylmethylene (cyclopentadiene) (9-fluorenyl) zirconium dichloride in ethylene tetramerization, and the metal organic ligand claimed by the invention is used as a ligand of an ethylene tetramerization catalyst, can effectively form a bimetallic center in a catalytic process, improve the selectivity of 1-octene, and simultaneously can effectively inhibit the generation of polyethylene byproducts. When the catalyst is used for catalyzing ethylene oligomerization, the catalyst has the advantages of high catalyst activity, high selectivity of 1-octene in the product, less polyethylene byproducts and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
a catalyst composition for ethylene oligomerization comprises a ligand compound shown as a formula (I), a transition metal compound and an alkyl aluminum cocatalyst, wherein the ligand compound has the following structure:
the alkyl aluminum cocatalyst is one of methylaluminoxane, modified methylaluminoxane, triethylaluminum, trimethylaluminum and triisobutylaluminum; the transition metal compound is at least one selected from the group consisting of a chromium compound, a molybdenum compound, an iron compound, a titanium compound, a zirconium compound, and a nickel compound.
Further, the preparation method of the ligand compound comprises the following steps:
the method comprises the following steps: preparing a white compound ligand by performing a salt elimination reaction on a fluorenyl lithium salt and a cyclopentadienylphosphine compound;
step two: under the action of butyl lithium, hydrogen on cyclopentadiene in the white compound ligand is extracted to obtain a metal lithium compound of the ligand, and then the metal lithium compound and zirconium tetrachloride undergo a salt elimination reaction to finally obtain a target product ligand compound.
Further, the preparation method of the ligand compound specifically comprises the following steps:
the method comprises the following steps: adding fluorene and THF into a reaction container, adding an ether solution of methyllithium with an equal molar amount to the fluorene at room temperature within 30 minutes, stirring the obtained dark red solution for several hours until gas escape completely stops, then dropwise adding 6, 6-diphenyl fulvene dissolved in THF into the dark red solution, stirring the obtained red THF solution overnight, then adding saturated aqueous solution of ammonium chloride, stirring for 10 minutes, extracting the organic layer with ether for several times, drying the combined organic phase with magnesium sulfate, removing ether, and recrystallizing the solid from a methanol/chloroform solvent mixture to obtain 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 molar quantity equal to that of the white compound ligand4And (3) stirring the powder for 6 hours, removing the pentane solvent after the reaction is finished, extracting the residual red solid with dichloromethane to remove lithium chloride, and cooling the extract to-20 ℃ to obtain the final product, namely the ligand compound.
Further, the transition metal compound is at least one of chromium acetylacetonate, chromium isooctanoate, and chromium tris (tetrahydrofuran) trichloride (CAS number: 10170-68-0).
Furthermore, the molar ratio of the transition metal compound, the ligand compound and the alkyl aluminum cocatalyst is 1: 0.1-10: 100-1000.
The application comprises the following steps: the catalyst composition is used for ethylene trimerization and/or tetramerization in aliphatic hydrocarbon or aromatic hydrocarbon solvents.
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 0.5-6.0 MPa.
The application of the catalyst composition in the oligomerization of ethylene comprises the following steps:
(1) before reaction, the kettle body and the lining of the reaction kettle are firstly placed in an oven 120oC drying overnight, connecting to evaluation system, sealing, heating to 100 degree under vacuum conditionoAnd C, keeping the temperature constant for 1h (closing a tail gas valve), and removing 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 at the same time, and then the reaction is vacuumized and repeated for three times to ensure that the air is completely replaced. Then the nitrogen gas is pumped out by a vacuum pump, the filling is carried out by ethylene, and the process is repeated for three times, so that the kettle body is ensured to be full of ethylene.
(2) Opening a tail gas valve, sequentially injecting a dehydrated and deoxidized solvent and a certain amount of cocatalyst by using an injector under the stirring condition, after the temperature is stabilized to the reaction temperature, injecting a transition metal compound and a ligand by using the injector, closing the tail gas valve, adjusting a pressure reducing valve, starting timing after the pressure is increased to a preset pressure value, recording mass flow meter data, adding an alkyl aluminum auxiliary agent, closing ethylene gas after reacting for a certain time, recording mass flow meter data, stopping the reaction, closing a gas inlet valve, detaching a reaction kettle body, soaking the reaction kettle body into an ice water bath to cool the reaction kettle to 10 DEG CoC is below.
(3) After the reaction kettle is opened, the total weight of liquid and solid is weighed as soon as possible, a proper amount of quartz wool is plugged into an injector, 1-2 ml of liquid sample is filtered and then transferred to a sample bottle, and the components and the proportion of the product are analyzed by GC-MS. The remaining sample was filtered, the filter paper weighed in advance and the mass recorded, then the polymer on the paddle was scraped off with a spoon, washed into a beaker with solvent, and all the polymer was placed in a vacuum oven 60oDrying overnight, weighing respectively, and calculating to obtain pure mass. The liquid product composition can be calibrated by MS. The selectivity of each component can be calculated by combining the total weight of liquid and solid, the mass of solid and the GC result, and the catalyst activity can be calculated by combining the catalyst usage amount.
The invention has the advantages that:
(1) diphenylmethylene (cyclopentadiene) (9-fluorenyl) zirconium dichloride is used as a ligand of a tetramerization catalyst for the first time to form a catalyst system with a metal center 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 claimed by the invention is used as a ligand of an ethylene tetramerization catalyst, can effectively form a bimetallic center in a catalysis process, improves the selectivity of 1-octene, and can effectively inhibit the generation of polyethylene byproducts.
(5) The diphenyl methylene (cyclopentadiene) (9-fluorenyl) zirconium dichloride is used as a ligand of a tetramerization catalyst, can improve the selectivity of 1-octene and reduce the action principle of polyethylene byproduct generation:
the ligand contains rigid group fluorenyl, so that the selectivity during 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 a moderate size, and can stabilize the formation of a transition eight-membered ring, so that the 1-octene is directionally generated.
Drawings
FIG. 1 shows the nuclear magnetic spectrum of diphenylmethylene (cyclopentadiene) (9-fluorenyl) zirconium dichloride as a ligand compound.
Detailed Description
In order to make the aforementioned and other features and advantages of the invention more comprehensible, embodiments accompanied with figures are described in detail below. The method of the present invention is a method which is conventional in the art unless otherwise specified.
Example 1 preparation of diphenylmethylene (cyclopentadiene) (9-fluorenyl) zirconium dichloride:
synthetic route to white compound ligands
1) To a round bottom flask equipped with a side arm, addition funnel and magnetic stir bar was added 2.5 grams (0.015 mole) of fluorene and 50 ml of THF. An ether solution of methyllithium (1.4M) in equimolar amount to the fluorene was added at room temperature over 30 minutes. The resulting dark red solution was stirred for several hours until gas evolution completely ceased. Then 3.4 g (0.015 mol) of 6, 6-diphenylfulvene dissolved in 100 mL of THF were added dropwise thereto, and the resulting red THF solution was stirred overnight, followed by addition of 30 mL of a saturated aqueous solution of ammonium chloride and stirring for 10 minutes. The organic layer was extracted several times with 50 ml of ether and the combined organic phases were dried over magnesium sulfate. After removal of the ether and recrystallization of the solid from a methanol/chloroform solvent mixture, 3.2 g (54.5%) of the white compound ligand are obtained.
Synthetic route of metal organic catalyst
2) To a 250 mL three necked round bottom flask equipped with a magnetic stir bar was added 200 mL of anhydrous pentane and 1.0 g (0.0025 mol) of the above white compound ligand, and then to the suspension of the above anhydrous pentane was added ZrCl in an equimolar amount to the white compound ligand4Powder, mixture was stirred at ambient temperature for 6 hours. After the reaction was completed, the color of the slurry was changed to red, 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 obtain 1.3 g of the final product, diphenylmethylene (cyclopentadiene) (9-fluorenyl) zirconium dichloride, in a yield of 1.3 g92.8%。
The nuclear magnetic spectrum is shown in the attached figure 1.
Application examples and comparative examples:
the ethylene oligomerization reaction was carried out in a 300 mL autoclave. Before reaction, the kettle body of the reaction kettle is firstly placed in an oven 120oC drying overnight, connecting to evaluation system, sealing, heating to 100 degree under vacuum conditionoAnd C, keeping the temperature constant for 1h (closing a tail gas valve), and removing 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 at the same time, then the reaction is vacuumized, and the steps are repeated for three times, so that the air is completely replaced. Then the nitrogen gas is pumped out by a vacuum pump, the filling is carried out by ethylene, and the process is repeated for three times, so that the kettle body is ensured to be full of ethylene. The tail gas valve is opened, 90 mL of cyclohexane solvent, a certain amount of methylaluminoxane (methylaluminoxane is a 1.5 mol/L toluene solution) and a certain amount of ligand compound solution are injected in sequence by using an injector under the stirring condition, after the temperature is stabilized to the set temperature, the transition metal compound solution is injected into the reaction kettle, and then the injector is washed by using 10 mL of cyclohexane to ensure that all catalyst components are injected into the reactor. Stirring for 3-5 min, closing the tail gas valve, adjusting the pressure reducing valve, starting timing after the pressure rises to a set pressure, closing the ethylene gas after reacting for a certain time, recording the data of the mass flow meter, stopping the reaction, closing the gas inlet valve, detaching the reaction kettle body, soaking the reaction kettle in ice-water bath to cool the reaction kettle to 10 DEGoC is below. After the reaction kettle is opened, the total weight of liquid and solid is weighed as soon as possible, a proper amount of quartz wool is plugged into an injector, 1-2 ml of liquid sample is filtered and transferred to a sample bottle, and the sample bottle is placed on a GC-MS (gas chromatography-Mass spectrometer) for analyzing the components and the proportion of the product. The remaining sample was filtered, the filter paper weighed in advance and the mass recorded, then the polymer on the paddle was scraped off with a spoon, washed into a beaker with solvent, and all the polymer was placed in a vacuum oven 60oC, drying overnight, respectively weighing, and calculating to obtain pure mass. The liquid product composition can be calibrated by MS. The selectivity of each component can be calculated by combining the total weight of liquid and solid, the mass of solid and the GC result, and the catalyst activity can be calculated by combining the catalyst usage amount. The relevant reaction conditions in examples 1 to 4 and comparative example 1 are summarized in Table 1.
Table 1 example reaction conditions summary table
Table 2 the catalyst systems of examples 1 to 4 of the invention and comparative example 1 were used for ethylene oligomerization activity and product distribution
Note: the catalyst systems of examples 1 to 4, which correspond to examples 1 to 4, respectively, were used for the oligomerization of ethylene.
The results in Table 1 and Table 2 show that when the catalyst composition of the present invention is used in the ethylene trimerization and/or tetramerization reaction, the catalyst activity is significantly higher than that of the conventional catalyst, the 1-octene selectivity is equivalent to that of the conventional catalyst, and the polymer content is significantly reduced, which is beneficial to the long-term operation of the ethylene oligomerization reaction, and is expected to realize the continuous operation of the ethylene trimerization and/or tetramerization reaction.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (9)
1. A catalyst composition for ethylene oligomerization is characterized by comprising a ligand compound shown as a formula (I), a transition metal compound and an alkyl aluminum cocatalyst, wherein the ligand compound has the following structure:
formula (1)
The alkyl aluminum cocatalyst is one of methylaluminoxane, modified methylaluminoxane, triethylaluminum, trimethylaluminum and triisobutylaluminum;
the transition metal compound is at least one selected from the group consisting of a chromium compound, a molybdenum compound, an iron compound, a titanium compound, a zirconium compound, and a nickel compound.
2. The catalyst composition of claim 1, wherein the ligand compound is prepared by a process comprising the steps of:
the method comprises the following steps: preparing a white compound ligand by performing a salt elimination reaction on a fluorenyl lithium salt and a cyclopentadienylphosphine compound;
step two: under the action of butyl lithium, hydrogen on cyclopentadiene in the white compound ligand is extracted to obtain a metal lithium compound of the ligand, and then the metal lithium compound and zirconium tetrachloride undergo a salt elimination reaction to finally obtain a target product ligand compound.
3. The catalyst composition according to claim 2, wherein the process for the preparation of the ligand compound comprises in particular the steps of:
the method comprises the following steps: adding fluorene and THF into a reaction vessel, adding an ether solution of methyllithium in an equimolar amount with fluorene at room temperature within 30 minutes, stirring the obtained dark red solution for several hours until gas escape completely stops, adding 6, 6-diphenylfulvene dissolved in THF into the reaction vessel, stirring the obtained red THF solution overnight, adding saturated aqueous solution of ammonium chloride, stirring for 10 minutes, extracting the organic layer with ether for several times, drying the combined organic phases with magnesium sulfate, removing ether, and recrystallizing the solid from a methanol/chloroform solvent mixture to obtain 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 molar quantity equal to that of the white compound ligand4And (3) stirring the powder for 6 hours, removing the pentane solvent after the reaction is finished, extracting the residual red solid with dichloromethane to remove lithium chloride, and cooling the extract to-20 ℃ to obtain the final product, namely the ligand compound.
4. The catalyst composition of claim 1, wherein the transition metal compound is at least one of chromium acetylacetonate, chromium isooctanoate, and chromium tris (tetrahydrofuran) trichloride.
5. The catalyst composition of claim 1, wherein the transition metal compound, the ligand compound, and the alkylaluminum cocatalyst are present in a molar ratio of 1:0.1 to 10:100 to 1000.
6. Use of a catalyst composition according to claim 1, characterized in that it is used for ethylene trimerization and/or tetramerization reactions in aliphatic or aromatic hydrocarbon solvents.
7. Use according to claim 6, characterized in that the solvent is n-hexane, cyclohexane, n-heptane or toluene.
8. The use of claim 6, wherein 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.
9. Use according to claim 8, wherein the ethylene trimerization and/or tetramerization reaction is carried out at a temperature of 30-100 ℃ and an ethylene pressure of 0.5-6.0 MPa.
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