CN114988980A - Method for producing 1-octene by ethylene high-activity oligomerization - Google Patents
Method for producing 1-octene by ethylene high-activity oligomerization Download PDFInfo
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- CN114988980A CN114988980A CN202210678627.7A CN202210678627A CN114988980A CN 114988980 A CN114988980 A CN 114988980A CN 202210678627 A CN202210678627 A CN 202210678627A CN 114988980 A CN114988980 A CN 114988980A
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- Prior art keywords
- octene
- ethylene
- reaction
- cocatalyst
- material flow
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- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 title claims abstract description 56
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000005977 Ethylene Substances 0.000 title claims abstract description 53
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- 238000006384 oligomerization reaction Methods 0.000 title claims abstract description 14
- 230000000694 effects Effects 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 110
- 239000000463 material Substances 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 20
- 125000005234 alkyl aluminium group Chemical group 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 127
- 239000011651 chromium Substances 0.000 claims description 16
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 13
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 12
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 11
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 10
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 10
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 9
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- -1 alicyclic hydrocarbon Chemical class 0.000 claims description 6
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- DMEGYFMYUHOHGS-UHFFFAOYSA-N cycloheptane Chemical compound C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 4
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 239000003446 ligand Substances 0.000 claims description 3
- UWZODPYTQSSIEQ-UHFFFAOYSA-N 2-tert-butyloxaluminane Chemical compound CC(C)(C)[Al]1CCCCO1 UWZODPYTQSSIEQ-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- HQMRIBYCTLBDAK-UHFFFAOYSA-M bis(2-methylpropyl)alumanylium;chloride Chemical compound CC(C)C[Al](Cl)CC(C)C HQMRIBYCTLBDAK-UHFFFAOYSA-M 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 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
- 150000008282 halocarbons Chemical class 0.000 claims description 2
- 239000001282 iso-butane Substances 0.000 claims description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-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
- 239000008096 xylene Substances 0.000 claims description 2
- 230000037048 polymerization activity Effects 0.000 abstract description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 54
- 239000000243 solution Substances 0.000 description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 18
- 229910052782 aluminium Inorganic materials 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 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 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 229910014299 N-Si Inorganic materials 0.000 description 9
- 229910052804 chromium Inorganic materials 0.000 description 9
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- WCFQIFDACWBNJT-UHFFFAOYSA-N $l^{1}-alumanyloxy(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]O[Al] WCFQIFDACWBNJT-UHFFFAOYSA-N 0.000 description 3
- 125000003542 3-methylbutan-2-yl group Chemical group [H]C([H])([H])C([H])(*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 238000004891 communication Methods 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 238000005829 trimerization reaction Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002431 hydrogen Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection 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
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003613 toluenes Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/26—Catalytic processes with hydrides or organic compounds
- C07C2/36—Catalytic processes with hydrides or organic compounds as phosphines, arsines, stilbines or bismuthines
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
-
- 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
-
- 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
-
- 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention discloses a method for producing 1-octene by ethylene high-activity oligomerization, which comprises the following steps: a. forming a first material flow at least consisting of a main catalyst and an aluminoxane cocatalyst; b. forming a second stream consisting at least of an alkylaluminum-based cocatalyst; c. separately supplying the first and second streams to at least one reaction zone comprising ethylene monomer dissolved in a process solvent; d. polymerizing ethylene monomer in at least one reaction zone in the presence of the main catalyst, the aluminoxane cocatalyst and the alkylaluminum cocatalyst to produce 1-octene. The invention can ensure higher polymerization activity under the condition of reducing the dosage of the aluminoxane by a unique feeding mode, and can really realize the reduction of the cost.
Description
Technical Field
The invention relates to an ethylene oligomerization method, in particular to a method for producing 1-octene by ethylene high-activity oligomerization.
Background
α -olefins (e.g., 1-hexene, 1-octene) are used in large amounts as comonomers for polyolefin polymerization as products of ethylene oligomerization, and in recent years, the market demand for α -olefins has been sharply increased with the development of high-end polyolefins such as POE, POP, and m-LLDPE.
At present, the production of 1-hexene in industry mainly depends on an ethylene selective trimerization process, the selectivity of 1-hexene is up to more than 96 percent, and for example, Phillips, medium petroleum and medium petrochemical industries have ethylene selective trimerization devices. However, 1-octene is mainly prepared by ethylene non-selective oligomerization, alpha-olefin produced by the traditional process is a mixture of C4-C20, the product conforms to Schulz-Flory distribution, the selectivity of 1-octene is generally 20-30%, continuous rectification and separation are needed for obtaining pure 1-octene, and the energy consumption is high. Sasol in south Africa developed a selective tetramerization process for ethylene in the presence of trivalent chromium compounds and i PrN(PPh 2 ) 2 the 1-octene is produced by selective tetramerisation of ethylene in the presence of a catalytic system comprising Methylaluminoxane (MAO) as co-catalyst, with 1-octene selectivity being up to over 70% (Journal of the American Chemical Society,126(2004) 14712). Sasol builds a first set of ethylene selective tetramerization device in 2014, and the production scale is 10 ten thousand tons per year.
However, the catalytic system developed by Sasol has a disadvantage in that the catalytic performance can be achieved only when an excessive amount of the expensive cocatalyst Methylaluminoxane (MAO) is used, that is, the Al/Cr molar ratio is 300-.
In order to reduce the production cost, it is currently common to use a combination of aluminoxane and aluminum alkyl to reduce the amount of MAO cocatalyst, for example, in the ethylene oligomerization process provided in CN109476779A, a cocatalyst mixture containing at least two different aluminum compounds (aluminoxane and aluminum alkyl) is used. CN106061607A combines the use of modified methylaluminoxane (MMAO-3a) and Triethylaluminum (TEA), which is believed to provide a cost effective cocatalyst system using MMAO-3a and TEA in combination. However, the above-mentioned method can not achieve a true economical efficiency because it can reduce the production cost and also cause a decrease in polymerization activity and product selectivity.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for producing 1-octene by ethylene high-activity oligomerization, which can ensure higher polymerization activity under the condition of reducing the dosage of aluminoxane by a unique feeding mode and can really realize the reduction of cost.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for producing 1-octene by ethylene high-activity oligomerization comprises the following steps:
a. forming a first material flow at least consisting of a main catalyst and an aluminoxane cocatalyst;
b. forming a second stream consisting at least of an alkylaluminum-based cocatalyst;
c. separately supplying the first and second streams to at least one reaction zone comprising ethylene monomer dissolved in a process solvent;
d. polymerizing ethylene monomers in at least one reaction zone in the presence of the main catalyst, the aluminoxane cocatalyst and the alkylaluminum cocatalyst to prepare a reaction solution containing 1-octene.
In the continuous research, the invention discovers that the activation effect of the alkyl aluminum cocatalyst on metal in the ethylene oligomerization reaction is far lower than that of the aluminoxane cocatalyst, so that the reduction of the dosage of the aluminoxane by directly mixing the alkyl aluminum and the aluminoxane can be at the expense of the reaction activity, and the cost reduction effect cannot be really achieved. Surprisingly, the invention can remarkably improve the polymerization activity under the condition of keeping lower dosage of the aluminoxane, is more beneficial to improving the yield of the 1-octene and further improves the economical efficiency of the device by mixing the main catalyst and the aluminoxane cocatalyst to form a first material flow and then respectively feeding the first material flow and a second material flow consisting of the alkylaluminum cocatalyst into the reaction zone.
In a preferred embodiment of the present invention, the first stream and the second stream each independently comprise a portion of the process solvent with or without ethylene monomer present.
In a preferred embodiment of the present invention, no ethylene monomer or only a low concentration of ethylene monomer, for example a mass concentration of 10% or less, is present in the first stream and in the second stream.
In a preferred embodiment of the present invention, the mixing time of the procatalyst and the aluminoxane based cocatalyst in the first stream before entering the reaction zone is from 30s to 30min, preferably from 5 to 10 min.
In a preferred embodiment of the present invention, the first stream comprises from 20 to 99% by weight of the total mass of the process solvent; the content of the process solvent in the second material flow accounts for 30-98% of the total mass of the second material flow.
In a preferred embodiment of the present invention, the process solvent is a non-coordinating inert liquid and/or a liquid olefin such as ethylene, 1-hexene, 1-octene serving as a monomer or reaction product, wherein the non-coordinating inert liquid is preferably a mixture of any one or more of isoparaffin, linear and branched aliphatic hydrocarbon, alkyl substituted or unsubstituted alicyclic hydrocarbon, halogenated hydrocarbon, aromatic hydrocarbon, nitrile, more preferably isoparaffin, isobutane, n-butane, n-pentane, isopentane, n-hexane, isohexane, n-heptane, n-octane, n-nonane, dodecane, cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, perfluorinated C-containing hydrocarbon 4-10 Any one or more of alkane, chlorobenzene, dichloromethane, benzene, toluene, mesitylene, xylene and acetonitrile.
In a preferable scheme provided by the invention, the polymerization reaction temperature in the reaction zone is 40-60 ℃, the reaction pressure is 3.0-6.0MPa, and the reaction time is 1-120min, preferably 30-60 min.
The reaction zone may be one or more reaction zones present in one reactor or one or more reactors combined with each other to form one or more reaction zones, and the definition of the reaction zone in the present invention is merely to provide a place for carrying out the ethylene polymerization reaction, and there is no particular limitation on the type and number of reactors involved.
The reactor type may be any one or a combination of more of a continuous stirred tank reactor, a tubular reactor, and a tower reactor.
In a preferred embodiment of the present invention, the main catalyst is a complex of chromium metal and a ligand;
the procatalyst may be one or more chromium metal complex catalysts and suitable ligands may be represented by the following formula I:
in formula I, A represents one or more of elements C, N, B, Si; r represents hydrogen, an alkyl group, a silyl group, or the like, which is bonded to A via a single bond or a double bond. Or, in the formula I, A-R represents a bridging group containing a skeleton structure such as-N-Si-, C-C-, C-C-, etc., wherein, the symbol only refers to a connecting position, and no specific meaning is provided.
As a preferred specific example, the main catalyst may be selected from:
(phenyl group) 2 PN (isopropyl) P (phenyl) 2 ;
(phenyl group) 2 PN (tert-butyl) P (phenyl) 2 ;
(phenyl group) 2 PN (1, 2-dimethylpropyl) P (phenyl) 2 ;
(phenyl group) 2 P (tert-butyl) C ═ CHP (phenyl) 2 ;
(phenyl group) 2 P (isopropyl) C ═ CHP (phenyl) 2 ;
(phenyl group) 2 P (n-butyl) C ═ CHP (phenyl) 2 ;
(phenyl group) 2 P (N-butyl) N-Si (methyl) 2 P (phenyl) 2 ;
(phenyl group) 2 P (isopropyl) N-Si (methyl) 2 P (phenyl) 2 ;
(phenyl group) 2 P (tert-butyl) N-Si (methyl) 2 P (phenyl) 2 。
In the first material flow, the dosage of the main catalyst and the aluminoxane cocatalyst is 1 (100) -300 in terms of the molar ratio of Cr/Al;
the feeding ratio of the first material flow and the second material flow is 1 (0.3-3) in terms of molar ratio of the aluminoxane cocatalyst to the alkylaluminum cocatalyst.
In a preferred embodiment provided by the present invention, the aluminoxane based cocatalyst is selected from C 1-5 The alkylaluminoxane or modified aluminoxane is preferably at least one of methylaluminoxane, ethylaluminoxane, propylaluminoxane, isobutylaluminoxane, isopropylaluminoxane, t-butylaluminoxane, modified methylaluminoxane, modified ethylaluminoxane and modified propylaluminoxane.
In a preferred embodiment of the present invention, the aluminum alkyl cocatalyst is C 1-30 Aluminum alkyls or C 1-30 The halogenated species of the alkyl aluminum is preferably at least one selected from the group consisting of trimethyl aluminum, triethyl aluminum, tri-n-hexyl aluminum, triisobutyl aluminum, tri-n-octyl aluminum, diethyl aluminum chloride, diisobutyl aluminum chloride and ethyl aluminum dichloride.
The invention can ensure higher polymerization activity under the condition of reducing the dosage of the aluminoxane by a unique feeding mode, and can really realize the reduction of the cost.
Detailed Description
The present invention is further illustrated by the following specific examples, which are intended to be illustrative of the invention and are not to be construed as limiting the scope of the invention.
The source information of the main raw materials in the following examples:
(phenyl group) 2 PN (isopropyl) P (phenyl) 2 : synthesized according to the Journal of the American Chemical Society (2004),126(45), 14712-;
(phenyl group) 2 PN (tert-butyl) P (phenyl) 2 : synthesized according to the Journal of the American Chemical Society (2004),126(45), 14712-;
(phenyl group) 2 PN (1, 2-dimethylpropyl) P (phenyl) 2 : synthesized according to the Journal of the American Chemical Society (2004),126(45), 14712-;
(phenyl group) 2 P (tert-butyl) C ═ CHP (phenyl) 2 : synthesized according to the literature Catalysis Communications (2019),121, 15-18;
(phenyl group) 2 P (isopropyl) C ═ CHP (phenyl) 2 : synthesized according to the literature Catalysis Communications (2019),121, 15-18;
(phenyl group) 2 P (n-butyl) C ═ CHP (phenyl) 2 : synthesized according to the literature Catalysis Communications (2019),121, 15-18;
(phenyl group) 2 P (isopropyl) N-Si (methyl) 2 P (phenyl) 2 : according to the Catalysis Science&Technology (2017),7(21), 5011-5018;
(phenyl group) 2 P (2, 6-diisopropylphenyl) N-Si (methyl) 2 P (phenyl) 2 : according to the Catalysis Science&Technology (2017),7(21), 5011-5018;
(phenyl group) 2 P (cyclopentyl) N-Si (methyl) 2 P (phenyl) 2 : according to the Catalysis Science&Technology (2017),7(21), 5011-5018;
modified methylaluminoxane (MMAO-3 a): 7 wt% Al in n-heptane, Nomoon Chemicals International Inc.;
methylaluminoxane (MAO): 10.0 wt% Al in toluene, Nomoon Chemicals International Inc.;
ethyl Aluminoxane (EAO): 25 wt% Al in hexane, Beijing YinoKay science Co., Ltd;
isobutylaluminoxane (IBAO): 10 wt% Al in toluene, Beijing YinoKai science and technology Co., Ltd;
triethyl aluminum (TEA): 16.9 wt% Al in n-hexane, Beijing Yinokay science and technology Co., Ltd;
triisobutylaluminum (TIBA): 25.0 wt% Al in toluene, Beijing YinuoKai science and technology Co., Ltd;
trimethylaluminum (TMA): 16.5 wt% Al in toluene, Ikonyka technologies, Beijing;
chromium acetylacetonate: 98%, Beijing Yinaoka science and technology Co., Ltd;
toluene: 99%, kyo illinois technologies ltd;
secondly, the following test method is adopted in each example of the invention:
the liquid phase products are characterized by gas chromatography, so that the mass of each liquid phase product is obtained, and the solid products are separated, dried and weighed;
analysis conditions for gas chromatography: sample injection temperature: 250 ℃; the temperature of the column box is 35 ℃;
temperature rising procedure: firstly keeping the temperature at 35 ℃ for 10 minutes, then increasing the temperature to 250 ℃ at the speed of 10 ℃/min, then keeping the temperature at 250 ℃ for 10 minutes, and then beginning to cool until the room temperature;
detector temperature: 250 ℃; carrier: 1.0 Mpa; air: 0.03 MPa; hydrogen gas: 0.03 MPa;
the product was characterized by nonane as an internal standard and calculated as follows:
wherein m1 represents the mass of a certain substance in the product, m is the mass of nonane, a1 is the peak area of the substance measured in GC, a is the peak area of nonane measured in GC, and k is the correction coefficient.
The present invention will be described in detail with reference to examples, but the present invention is not limited to the examples.
Preparing a main catalyst a-1:
873.3mg (2.50mmol) of chromium acetylacetonate and 1602mg (3.75mmol) (phenyl) are weighed out 2 PN (isopropyl) P (phenyl) 2 Dissolved in 500ml of a toluene solution to prepare a toluene solution having a concentration of 5.0. mu. mol/ml (in terms of chromium).
The main catalyst a-2 is configured:
873.3mg (2.50mmol) of chromium acetylacetonate and 1655mg (3.75mmol) (phenyl) 2 PN (tert-butyl) P (phenyl) 2 Dissolved in 500ml of a toluene solution to prepare a toluene solution having a concentration of 5.0. mu. mol/ml (in terms of chromium).
Preparing a main catalyst a-3:
873.3mg (2.50mmol) of chromium acetylacetonate and 1708mg (3.75mmol) (phenyl) are weighed out 2 PN (1, 2-dimethylpropyl) P (phenyl) 2 Dissolving in 500ml toluene solution, and preparingIn the form of a toluene solution with a concentration of 5.0. mu. mol/ml (calculated as chromium).
Configuring a main catalyst a-4:
873.3mg (2.50mmol) of chromium acetylacetonate and 1644mg (3.75mmol) (phenyl) are weighed out 2 P (isopropyl) C ═ CHP (phenyl) 2 Dissolved in 500ml of a toluene solution to prepare a toluene solution having a concentration of 5.0. mu. mol/ml (in terms of chromium).
Configuring a main catalyst a-5:
873.3mg (2.50mmol) of chromium acetylacetonate and 1696mg (3.75mmol) (phenyl) are weighed out 2 P (tert-butyl) C ═ CHP (phenyl) 2 Dissolved in 500ml of a toluene solution to prepare a toluene solution having a concentration of 5.0. mu. mol/ml (in terms of chromium).
Configuring a main catalyst a-6:
873.3mg (2.50mmol) of chromium acetylacetonate and 1794mg (3.75mmol) (phenyl) are weighed out 2 P (n-butyl) C ═ CHP (phenyl) 2 Dissolved in 500ml of a toluene solution to prepare a toluene solution having a concentration of 5.0. mu. mol/ml (in terms of chromium).
Configuring a main catalyst a-7:
873.3mg (2.50mmol) of chromium acetylacetonate and 1821mg (3.75mmol) (phenyl) are weighed out 2 P (isopropyl) N-Si (methyl) 2 P (phenyl) 2 Dissolved in 500ml of a toluene solution to prepare a toluene solution having a concentration of 5.0. mu. mol/ml (in terms of chromium).
Configuring a main catalyst a-8:
873.3mg (2.50mmol) of chromium acetylacetonate and 2264mg (3.75mmol) (phenyl) are weighed out 2 P (2, 6-diisopropylphenyl) N-Si (methyl) 2 P (phenyl) 2 Dissolved in 500ml of a toluene solution to prepare a toluene solution having a concentration of 5.0. mu. mol/ml (in terms of chromium).
The main catalyst a-9 is configured:
873.3mg (2.50mmol) of chromium acetylacetonate and 1918mg (3.75mmol) (phenyl) are weighed out 2 P (cyclopentyl) N-Si (methyl) 2 P (phenyl) 2 Dissolved in 500ml of a toluene solution to prepare a toluene solution having a concentration of 5.0. mu. mol/ml (in terms of chromium).
[ example 1 ]
Before reaction, a 500ml reaction kettle is heated to 120 ℃, vacuumized for 2 hours, replaced by nitrogen, replaced by ethylene for 3 times after being cooled to normal temperature, and 100ml toluene is added into the reaction kettle. 1ml of procatalyst a-1 and 0.23ml of MMAO-3a (Al/Cr ═ 100) were mixed for 5min to form a first stream, 0.75ml of TMA as a second stream; adding the first material flow and the second material flow into a reaction kettle respectively, adding 100ml of toluene into the reaction kettle, raising the temperature in the reaction kettle to 40 ℃, and introducing 4.0MPa of ethylene to start reaction. After the reaction for 20min, 10mL of ethanol containing 10 vol% aqueous hydrochloric acid was added to the reaction solution to terminate the reaction.
The molar ratio of the alumoxane in the first stream to the aluminum alkyl in the second stream is designated as Ali/aiii, where Ali/aiii is 1:3 in this example.
[ examples 2 to 27 ]
Ethylene polymerization was carried out by referring to substantially the same method as in example 1 except for the difference in reaction conditions shown in Table 1.
The following comparative examples 1 to 4 were compared with example 1:
comparative example 1
Before reaction, a 500ml reaction kettle is heated to 120 ℃, vacuumized for 2 hours, replaced by nitrogen, replaced by ethylene for 3 times after being cooled to normal temperature, and added with 100ml toluene. 1ml of main catalyst a-1, 0.23ml of MMAO-3a (Al/Cr ═ 100) and 0.75ml of TMA are added into a reaction kettle in sequence, 100ml of toluene is added into the reaction kettle, then the temperature in the reaction kettle is raised to 40 ℃, and 4.0MPa of ethylene is introduced to start the reaction. After the reaction for 20min, 10mL of ethanol containing 10 vol% aqueous hydrochloric acid was added to the reaction solution to terminate the reaction.
Comparative example 2
Before reaction, a 500ml reaction kettle is heated to 120 ℃, vacuumized for 2 hours, replaced by nitrogen, replaced by ethylene for 3 times after being cooled to normal temperature, and 100ml toluene is added into the reaction kettle. 1ml of procatalyst a-1 and 0.75ml of TMA were mixed for 5min to form a first stream, 0.23ml of MMAO-3a was used as a second stream; adding the first material flow and the second material flow into a reaction kettle respectively, adding 100ml of toluene into the reaction kettle, raising the temperature in the reaction kettle to 40 ℃, and introducing 4.0MPa of ethylene to start reaction. After the reaction for 20min, 10mL of ethanol containing 10 vol% aqueous hydrochloric acid was added to the reaction solution to terminate the reaction.
Comparative example 3
Before reaction, a 500ml reaction kettle is heated to 120 ℃, vacuumized for 2 hours, replaced by nitrogen, replaced by ethylene for 3 times after being cooled to normal temperature, and 100ml toluene is added into the reaction kettle. Mixing 0.23ml MMAO-3a and 0.75ml TMA for 5min to form a first stream, and using 1ml main catalyst a-1 as a second stream; and respectively adding the first material flow and the second material flow into a reaction kettle, adding 100ml of methylbenzene into the reaction kettle, raising the temperature in the reaction kettle to 40 ℃, and introducing 4.0MPa of ethylene to start reaction. After the reaction for 20min, 10mL of ethanol containing 10 vol% aqueous hydrochloric acid was added to the reaction solution to terminate the reaction.
Comparative example 4
Before reaction, a 500ml reaction kettle is heated to 120 ℃, vacuumized for 2 hours, replaced by nitrogen, replaced by ethylene for 3 times after being cooled to normal temperature, and added with 100ml toluene. Premixing 1ml of main catalyst a-1, 0.23ml of MMAO-3a (Al/Cr is 100) and 0.75ml of TMA for 5min, adding the premixed materials into a reaction kettle at one time, supplementing 100ml of toluene to the reaction kettle, raising the temperature in the reaction kettle to 40 ℃, and introducing 4.0MPa of ethylene to start reaction. After the reaction for 20min, 10mL of ethanol containing 10 vol% aqueous hydrochloric acid was added to the reaction solution to terminate the reaction.
The following comparative examples 5-8 were compared with example 6:
comparative example 5
Before reaction, a 500ml reaction kettle is heated to 120 ℃, vacuumized for 2 hours, replaced by nitrogen, replaced by ethylene for 3 times after being cooled to normal temperature, and 100ml toluene is added into the reaction kettle. 1ml of main catalyst a-2, 0.69ml of MMAO-3a (Al/Cr is 300) and 0.75ml of TEA are added into a reaction kettle in sequence, 100ml of toluene is added into the reaction kettle, then the temperature in the reaction kettle is raised to 50 ℃, and 4.0MPa of ethylene is introduced to start the reaction. After the reaction for 20min, 10mL of ethanol containing 10 vol% aqueous hydrochloric acid was added to the reaction solution to terminate the reaction.
Comparative example 6
Before reaction, a 500ml reaction kettle is heated to 120 ℃, vacuumized for 2 hours, replaced by nitrogen, replaced by ethylene for 3 times after being cooled to normal temperature, and 100ml toluene is added into the reaction kettle. 1ml of procatalyst a-2 and 0.75ml of TEA were mixed for 7min to form a first stream, 0.69ml of MMAO-3a was used as the second stream; adding the first material flow and the second material flow into a reaction kettle respectively, adding 100ml of toluene into the reaction kettle, raising the temperature in the reaction kettle to 50 ℃, and introducing 4.0MPa of ethylene to start reaction. After the reaction for 20min, 10mL of ethanol containing 10 vol% aqueous hydrochloric acid was added to the reaction solution to terminate the reaction.
Comparative example 7
Before reaction, a 500ml reaction kettle is heated to 120 ℃, vacuumized for 2 hours, replaced by nitrogen, replaced by ethylene for 3 times after being cooled to normal temperature, and 100ml toluene is added into the reaction kettle. 0.69ml of MMAO-3a and 0.75ml of TEA were mixed for 7min to form a first stream, and 1ml of procatalyst a-2 was used as the second stream; adding the first material flow and the second material flow into a reaction kettle respectively, adding 100ml of toluene into the reaction kettle, raising the temperature in the reaction kettle to 50 ℃, and introducing 4.0MPa of ethylene to start reaction. After the reaction for 20min, 10mL of ethanol containing 10 vol% aqueous hydrochloric acid was added to the reaction solution to terminate the reaction.
Comparative example 8
Before reaction, a 500ml reaction kettle is heated to 120 ℃, vacuumized for 2 hours, replaced by nitrogen, replaced by ethylene for 3 times after being cooled to normal temperature, and 100ml toluene is added into the reaction kettle. Premixing 1ml of main catalyst a-2, 0.69ml of MMAO-3a and 0.75ml of TEA for 7min, adding the premixed catalyst into a reaction kettle at one time, adding 100ml of toluene into the reaction kettle, raising the temperature in the reaction kettle to 50 ℃, and introducing 4.0MPa of ethylene to start reaction. After the reaction for 20min, 10mL of ethanol containing 10 vol% aqueous hydrochloric acid was added to the reaction solution to terminate the reaction.
The reactivity and the product selectivity in each example and comparative example were measured, and the results are shown in table 1. The experimental result shows that the feeding mode of the invention can ensure higher catalytic activity under the condition of lower dosage of aluminoxane, thereby really realizing the reduction of production cost.
Reaction conditions in Table 1, examples and comparative examples
Claims (10)
1. A method for producing 1-octene by ethylene high-activity oligomerization is characterized by comprising the following steps:
a. forming a first material flow at least consisting of a main catalyst and an aluminoxane cocatalyst;
b. forming a second stream consisting at least of an alkylaluminum-based cocatalyst;
c. separately supplying the first and second streams to at least one reaction zone comprising ethylene monomer dissolved in a process solvent;
d. polymerizing ethylene monomers in at least one reaction zone in the presence of the main catalyst, the aluminoxane cocatalyst and the alkylaluminum cocatalyst to prepare a reaction solution containing 1-octene.
2. The method for producing 1-octene according to claim 1, wherein the first material flow and the second material flow each independently comprise a portion of the process solvent and with or without ethylene monomer.
3. The method for producing 1-octene according to claim 2, wherein no ethylene monomer or only a low concentration of ethylene monomer, such as mass concentration less than or equal to 10%, is present in the first and second streams.
4. A process for the high-activity oligomerization of ethylene to 1-octene according to any one of claims 1-3, characterized in that the mixing time of the procatalyst and the aluminoxane cocatalyst in the first stream before entering the reaction zone is 30s-30min, preferably 5-10 min.
5. The method for producing 1-octene according to claim 2, wherein the content of process solvent in the first material flow is 20-99% of the total mass; the content of the process solvent in the second material flow accounts for 30-98% of the total mass of the second material flow.
6. The method for producing 1-octene by oligomerization of ethylene with high activity according to claim 2, wherein the process solvent is a non-coordinated inert liquid and/or liquid olefin serving as monomer or reaction product, such as ethylene, 1-hexene, 1-octene, wherein the non-coordinated inert liquid is preferably a mixture of any one or more of isoparaffin, linear and branched aliphatic hydrocarbon, alkyl substituted or unsubstituted alicyclic hydrocarbon, halogenated hydrocarbon, aromatic hydrocarbon, nitrile, more preferably isoparaffin, isobutane, n-butane, n-pentane, isopentane, n-hexane, isohexane, n-heptane, n-octane, n-nonane, dodecane, cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, perfluorinated C-olefin 4-10 Any one or more of alkane, chlorobenzene, dichloromethane, benzene, toluene, mesitylene, xylene and acetonitrile.
7. The method for producing 1-octene according to any one of claims 1-6, wherein the polymerization temperature in the reaction zone is 40-60 ℃, the reaction pressure is 3.0-6.0MPa, and the reaction time is 1-120min, preferably 30-60 min.
8. The method for producing 1-octene according to any one of claims 1-7, wherein the main catalyst is a complex of chromium metal and ligand;
in the first material flow, the dosage of the main catalyst and the aluminoxane cocatalyst is 1 (100) -300 in terms of the molar ratio of Cr/Al;
the feeding ratio of the first material flow and the second material flow is 1 (0.3-3) in terms of molar ratio of the aluminoxane cocatalyst to the alkylaluminum cocatalyst.
9. The method for producing 1-octene according to claim 8, wherein said aluminoxane based cocatalyst is selected from C 1-5 The alkylaluminoxane or modified aluminoxane is preferably at least one of methylaluminoxane, ethylaluminoxane, propylaluminoxane, butylaluminoxane, isopropylaluminoxane, t-butylaluminoxane, modified methylaluminoxane, modified ethylaluminoxane and modified propylaluminoxane.
10. The method for producing 1-octene according to claim 8, wherein said alkylaluminium cocatalyst is C 1-30 Alkyl aluminium or C 1-30 The halogenated species of the alkyl aluminum is preferably at least one selected from the group consisting of trimethyl aluminum, triethyl aluminum, tri-n-hexyl aluminum, triisobutyl aluminum, tri-n-octyl aluminum, diethyl aluminum chloride, diisobutyl aluminum chloride and ethyl aluminum dichloride.
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FR3140775A1 (en) * | 2022-10-17 | 2024-04-19 | IFP Energies Nouvelles | New catalytic composition based on supported chromium or titanium |
CN118290214A (en) * | 2024-04-07 | 2024-07-05 | 广东众和工程设计有限公司 | Method for preparing linear alpha-olefin by ethylene high-selectivity oligomerization |
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WO2018012793A1 (en) * | 2016-07-14 | 2018-01-18 | Sk Innovation Co., Ltd. | Oligomerization of ethylene |
CN111774098A (en) * | 2020-07-21 | 2020-10-16 | 万华化学集团股份有限公司 | Ethylene oligomerization catalyst system, preparation method and application thereof |
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US20060223960A1 (en) * | 2005-04-01 | 2006-10-05 | Nova Chemicals (International) S.A. | Modified (MAO + aluminum alkyl) activator |
WO2018012793A1 (en) * | 2016-07-14 | 2018-01-18 | Sk Innovation Co., Ltd. | Oligomerization of ethylene |
CN111774098A (en) * | 2020-07-21 | 2020-10-16 | 万华化学集团股份有限公司 | Ethylene oligomerization catalyst system, preparation method and application thereof |
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FR3140775A1 (en) * | 2022-10-17 | 2024-04-19 | IFP Energies Nouvelles | New catalytic composition based on supported chromium or titanium |
WO2024083616A1 (en) * | 2022-10-17 | 2024-04-25 | IFP Energies Nouvelles | Novel chromium- or titanium-based supported catalytic composition |
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