CN114988980B - Method for producing 1-octene by high-activity oligomerization of ethylene - Google Patents
Method for producing 1-octene by high-activity oligomerization of ethylene Download PDFInfo
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- CN114988980B CN114988980B CN202210678627.7A CN202210678627A CN114988980B CN 114988980 B CN114988980 B CN 114988980B CN 202210678627 A CN202210678627 A CN 202210678627A CN 114988980 B CN114988980 B CN 114988980B
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- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 title claims abstract description 68
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000005977 Ethylene Substances 0.000 title claims abstract description 66
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000006384 oligomerization reaction Methods 0.000 title claims abstract description 27
- 230000000694 effects Effects 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 113
- 238000000034 method Methods 0.000 claims abstract description 34
- 125000005234 alkyl aluminium group Chemical group 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 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 129
- 239000011651 chromium Substances 0.000 claims description 18
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 12
- 229910052804 chromium Inorganic materials 0.000 claims description 12
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 10
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-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
- 239000007788 liquid Substances 0.000 claims description 7
- 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
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 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
- -1 alicyclic hydrocarbons Chemical class 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
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003446 ligand Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 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
- 239000004411 aluminium Substances 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
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 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
- 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
- 239000003426 co-catalyst Substances 0.000 claims 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims 1
- 150000004820 halides Chemical class 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 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
- 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
- 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
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 10
- 229910014299 N-Si Inorganic materials 0.000 description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 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
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000004891 communication Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000203 mixture Substances 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
- 238000003786 synthesis reaction Methods 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
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000005829 trimerization reaction Methods 0.000 description 2
- UWZODPYTQSSIEQ-UHFFFAOYSA-N 2-tert-butyloxaluminane Chemical compound CC(C)(C)[Al]1CCCCO1 UWZODPYTQSSIEQ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect 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
- 238000004364 calculation method Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012967 coordination catalyst Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002431 hydrogen Chemical group 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 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
- 238000000926 separation method Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 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)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for producing 1-octene by oligomerization of ethylene with high activity, which comprises the following steps: a. forming a first stream consisting of at least a procatalyst, an aluminoxane-based cocatalyst; b. forming a second stream consisting at least of an alkylaluminum-based cocatalyst; c. separately feeding the first stream and the second stream 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, an aluminoxane-based cocatalyst, and an alkylaluminum-based cocatalyst to produce 1-octene. The invention can ensure higher polymerization activity under the condition of reduced aluminoxane consumption by a unique feeding mode, and can truly realize cost reduction.
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
Alpha-olefins (e.g., 1-hexene, 1-octene) are used in large amounts as comonomers for polyolefin polymerization as products of ethylene oligomerization, and the market demand for alpha-olefins has increased dramatically in recent years with the development of higher polyolefins such as POE, POP and m-LLDPE.
At present, the industrial production of 1-hexene mainly depends on an ethylene selective trimerization process, wherein the 1-hexene selectivity is up to more than 96%, and ethylene selective trimerization devices are arranged in Phillips, medium petroleum and medium petrochemical industries. However, the 1-octene is mainly prepared by ethylene nonselective oligomerization, alpha-olefin produced by the traditional process is a mixture of C4-C20, the product accords with Schulz-Flory distribution, the selectivity of the 1-octene is generally 20-30%, continuous rectification separation is needed for obtaining the pure product of the 1-octene, and the energy consumption is high. Sasol in south Africa developed an ethylene selective tetramerization process on trivalent chromium compounds and i PrN(PPh 2 ) 2 ethylene selective tetramerization is carried out with Methylaluminoxane (MAO) as a cocatalyst in the presence of a constitutive catalytic system to produce 1-octene, wherein the 1-octene selectivity is up to more than 70% (Journal of the American Chemical Society,126 (2004) 14712). Sasol built the first ethylene selective tetramerization device in 2014,production scale is 10 ten thousand tons/year.
However, the catalytic system developed by Sasol has a disadvantage in that catalytic performance can be achieved only when an excessive amount of expensive promoter Methylaluminoxane (MAO) is used, that is, a molar ratio of Al/Cr of 300 to 500 shows high activity, and has very high production cost compared to other alkylaluminum-based promoters widely used in industry.
In order to reduce the production cost, it is currently common to use a method of compounding aluminoxane and alkylaluminum to reduce the amount of MAO-type cocatalyst, for example, in the ethylene oligomerization method provided in CN109476779A, a cocatalyst mixture containing at least two different aluminum compounds (aluminoxane and alkylaluminum) is used. CN106061607a uses a combination of modified methylaluminoxane (MMAO-3 a) and Triethylaluminum (TEA), which is believed to provide a cost effective cocatalyst system. However, the above-mentioned method can reduce the production cost and simultaneously lead to the decrease of polymerization activity and product selectivity, and cannot realize the true economical efficiency.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for producing 1-octene by oligomerization of ethylene with high activity, which can ensure higher polymerization activity under the condition of reduced aluminoxane consumption by a unique feeding mode, and can truly realize cost reduction.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a method for producing 1-octene by high-activity oligomerization of ethylene, which comprises the following steps:
a. forming a first stream consisting of at least a procatalyst, an aluminoxane-based cocatalyst;
b. forming a second stream consisting at least of an alkylaluminum-based cocatalyst;
c. separately feeding the first stream and the second stream 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, aluminoxane-based cocatalyst and alkylaluminum-based cocatalyst to obtain a reaction solution containing 1-octene.
In the continuous research, the invention discovers that the activating effect of the alkyl aluminum cocatalyst on metals in the ethylene oligomerization reaction is far lower than that of the aluminoxane cocatalyst, so that the direct mixing of the alkyl aluminum and the aluminoxane can reduce the dosage of the aluminoxane at the expense of the reaction activity, and the invention can not really achieve the effect of reducing the cost. Surprisingly, the polymerization activity can be significantly improved while maintaining a low aluminoxane level by mixing the procatalyst with an aluminoxane-based cocatalyst to form a first stream and separately feeding the first stream to the reaction zone with a second stream of an alkylaluminum-based cocatalyst, which is more conducive to improving the yield of 1-octene and thus the economics of the apparatus.
In a preferred embodiment provided by the present invention, the first stream and the second stream each independently comprise a portion of the process solvent and are present with or without ethylene monomer.
In a preferred embodiment provided by the invention, no ethylene monomer or only a low concentration, e.g. less than or equal to 10% by mass, of ethylene monomer is present in either the first stream or the second stream.
In a preferred embodiment provided by the present invention, the mixing time of the procatalyst and the aluminoxane cocatalyst in the first stream is from 30s to 30min, preferably from 5 to 10min, before entering the reaction zone.
In a preferred embodiment of the present invention, the process solvent content of the first stream is 20-99% of its total mass; the second stream contains process solvent in an amount of 30-98% of its total mass.
In a preferred embodiment provided by the present invention, the process solvent is a non-coordinating inert liquid and/or a liquid olefin such as ethylene, 1-hexene, 1-octene acting as a monomer or reaction product, wherein the non-coordinating inert liquid is preferably a mixture of any one or more of isoparaffins, straight and branched aliphatic hydrocarbons, alkyl substituted or unsubstituted alicyclic hydrocarbons, halogenated hydrocarbons, aromatic hydrocarbons, nitriles, more preferably isoparaffins,Isobutane, n-butane, n-pentane, isopentane, n-hexane, isohexane, n-heptane, n-octane, n-nonane, dodecane, cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, perfluorinated C 4-10 Any one or more of alkane, chlorobenzene, dichloromethane, benzene, toluene, mesitylene, xylene and acetonitrile.
In a preferred embodiment of the present invention, 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 30-60min.
The reaction zone may be one or more reaction zones existing in one reactor, or one or more reaction zones may be formed by combining one or more reactors with each other, and the definition of the reaction zone in the present invention is merely to provide a place for realizing the polymerization of ethylene, and there is no particular limitation on the type and number of the reactors involved.
Suitable reactor types may be any one or a combination of a plurality of continuous stirred tank reactors, tubular reactors, tower reactors.
In a preferred embodiment provided by the present invention, the procatalyst is a complex of metallic chromium and a ligand;
the procatalyst may be one or more metal chromium coordination catalysts and suitable ligands may be represented by formula I:
in formula I, a represents one or more of the elements C, N, B, si; r represents hydrogen, alkyl, silyl or the like which is linked to A by a single bond or a double bond. Alternatively, a-R in formula I represents a bridging group comprising a backbone structure of-N-Si-, C-, c=c-, etc., wherein x is only the linker and has no specific meaning.
As a preferred specific example, the main catalyst may be selected from:
(phenyl) 2 PN (isopropyl) P (phenyl) 2 ；
(phenyl)) 2 PN (tertiary butyl) P (phenyl) 2 ；
(phenyl) 2 PN (1, 2-dimethylpropyl) P (phenyl) 2 ；
(phenyl) 2 P (tert-butyl) c=chp (phenyl) 2 ；
(phenyl) 2 P (isopropyl) c=chp (phenyl) 2 ；
(phenyl) 2 P (n-butyl) c=chp (phenyl) 2 ；
(phenyl) 2 P (N-butyl) N-Si (methyl) 2 P (phenyl) 2 ；
(phenyl) 2 P (isopropyl) N-Si (methyl) 2 P (phenyl) 2 ；
(phenyl) 2 P (t-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 Cr/Al molar ratio;
the feed ratio of the first stream to the second stream, calculated as the molar ratio of aluminoxane based cocatalyst to alkylaluminum based cocatalyst, is 1 (0.3-3).
In a preferred embodiment provided by the present invention, the aluminoxane based cocatalyst is selected from the group consisting of C 1-5 Alkyl aluminoxane or modified aluminoxane, preferably at least one of methyl aluminoxane, ethyl aluminoxane, propyl aluminoxane, isobutyl aluminoxane, isopropyl aluminoxane, t-butyl aluminoxane, modified methyl aluminoxane, modified ethyl aluminoxane, modified propyl aluminoxane.
In a preferred embodiment of the present invention, the alkylaluminum-based cocatalyst is C 1-30 Aluminium alkyls or C 1-30 The halogenated compound of the alkylaluminum is preferably at least one selected from trimethylaluminum, triethylaluminum, tri-n-hexylaluminum, triisobutylaluminum, tri-n-octylaluminum, diethylaluminum chloride, diisobutylaluminum chloride and ethylaluminum dichloride.
The invention can ensure higher polymerization activity under the condition of reduced aluminoxane consumption by a unique feeding mode, and can truly realize cost reduction.
Detailed Description
The invention will now be further illustrated by means of specific examples which are given solely by way of illustration of the invention and do not limit the scope thereof.
1. The main raw material source information in the following examples:
(phenyl) 2 PN (isopropyl) P (phenyl) 2 : according to document Journal of the American Chemical Society (2004), 126 (45), 14712-14713;
(phenyl) 2 PN (tertiary butyl) P (phenyl) 2 : according to document Journal of the American Chemical Society (2004), 126 (45), 14712-14713;
(phenyl) 2 PN (1, 2-dimethylpropyl) P (phenyl) 2 : according to document Journal of the American Chemical Society (2004), 126 (45), 14712-14713;
(phenyl) 2 P (tert-butyl) c=chp (phenyl) 2 : synthesized according to literature Catalysis Communications (2019), 121,15-18;
(phenyl) 2 P (isopropyl) c=chp (phenyl) 2 : synthesized according to literature Catalysis Communications (2019), 121,15-18;
(phenyl) 2 P (n-butyl) c=chp (phenyl) 2 : synthesized according to literature Catalysis Communications (2019), 121,15-18;
(phenyl) 2 P (isopropyl) N-Si (methyl) 2 P (phenyl) 2 : according to document Catalysis Science&Technology (2017), 7 (21), 5011-5018 synthesis;
(phenyl) 2 P (2, 6-diisopropylphenyl) N-Si (methyl) 2 P (phenyl) 2 : according to document Catalysis Science&Technology (2017), 7 (21), 5011-5018 synthesis;
(phenyl) 2 P (cyclopentyl) N-Si (methyl) 2 P (phenyl) 2 : according to document Catalysis Science&Technology (2017), 7 (21), 5011-5018 synthesis;
modified methylaluminoxane (MMAO-3 a): an n-heptane solution of 7wt% Al, noron chemical International Inc.;
methylaluminoxane (MAO): 10.0wt% Al in toluene, noron chemical International Inc.;
ethylaluminoxane (EAO): 25wt% Al in hexane, beijing enokic technologies Co., ltd;
isobutyl aluminoxane (IBAO): 10wt% Al in toluene, beijing enokic technologies Co., ltd;
triethylaluminum (TEA): 16.9wt% Al in n-hexane, beijing Inock technologies Co., ltd;
triisobutylaluminum (TIBA): 25.0wt% Al in toluene, beijing Inoci technologies Co., ltd;
trimethylaluminum (TMA): 16.5wt% Al in toluene, beijing Inocai technologies Co., ltd;
chromium acetylacetonate: 98%, beijing enoki technology Co., ltd;
toluene: 99%, beijing enoki technologies Co., ltd;
2. the following test methods are adopted in each example of the invention:
the liquid phase products are characterized by gas chromatography, so that the quality of each liquid phase product is obtained, and the solid products are separated, dried and weighed;
analysis conditions for gas chromatography: sample introduction temperature: 250 ℃; the temperature of the column box is 35 ℃;
heating program: firstly, keeping at 35 ℃ for 10 minutes, then raising the temperature to 250 ℃ at the speed of 10 ℃/min, then keeping at 250 ℃ for 10 minutes, and then starting to cool until the temperature reaches the room temperature;
detector temperature: 250 ℃; and (3) a carrier: 1.0Mpa; air: 0.03Mpa; hydrogen gas: 0.03Mpa;
characterization of the product with nonane as internal standard, the method of calculation is 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 factor.
The present invention will be described in detail with reference to examples, but the present invention is not limited to the following examples.
The main catalyst a-1 is configured:
873.3mg (2.50 mmol) of chromium acetylacetonate and 1602mg (3.75 mmol) of phenyl group were weighed out 2 PN (isopropyl) P (phenyl) 2 Dissolved in 500ml of toluene solution to prepare toluene solution with a concentration of 5.0. Mu. Mol/ml (calculated as chromium).
The main catalyst a-2 is configured:
873.3mg (2.50 mmol) of chromium acetylacetonate and 1655mg (3.75 mmol) of phenyl group were weighed out 2 PN (tertiary butyl) P (phenyl) 2 Dissolved in 500ml of toluene solution to prepare toluene solution with a concentration of 5.0. Mu. Mol/ml (calculated as chromium).
The main catalyst a-3 was configured:
873.3mg (2.50 mmol) of chromium acetylacetonate and 1708mg (3.75 mmol) of phenyl group were weighed out 2 PN (1, 2-dimethylpropyl) P (phenyl) 2 Dissolved in 500ml of toluene solution to prepare toluene solution with a concentration of 5.0. Mu. Mol/ml (calculated as chromium).
The main catalyst a-4 was configured:
873.3mg (2.50 mmol) of chromium acetylacetonate and 1644mg (3.75 mmol) of phenyl group were weighed out 2 P (isopropyl) c=chp (phenyl) 2 Dissolved in 500ml of toluene solution to prepare toluene solution with a concentration of 5.0. Mu. Mol/ml (calculated as chromium).
The main catalyst a-5 was configured:
873.3mg (2.50 mmol) of chromium acetylacetonate and 1696mg (3.75 mmol) of phenyl group were weighed out 2 P (tert-butyl) c=chp (phenyl) 2 Dissolved in 500ml of toluene solution to prepare toluene solution with a concentration of 5.0. Mu. Mol/ml (calculated as chromium).
Procatalyst a-6 configuration:
873.3mg (2.50 mmol) of chromium acetylacetonate and 1794mg (3.75 mmol) of phenyl group were weighed out 2 P (n-butyl) c=chp (phenyl) 2 Dissolved in 500ml of toluene solution to prepare toluene solution with a concentration of 5.0. Mu. Mol/ml (calculated as chromium).
Procatalyst a-7 configuration:
873.3mg (2.50 mmol) of chromium acetylacetonate and 1821mg (3.75 mmol) of phenyl group were weighed out 2 P (isopropyl) N-Si (methyl) 2 P (phenyl) 2 Dissolved in 500ml of toluene solution to prepare toluene solution with a concentration of 5.0. Mu. Mol/ml (calculated as chromium).
The main catalyst a-8 was configured:
873.3mg (2.50 mmol) of chromium acetylacetonate and 2264mg (3.75 mmol) of phenyl group were weighed out 2 P (2, 6-diisopropylphenyl) N-Si (methyl) 2 P (phenyl) 2 Dissolved in 500ml of toluene solution to prepare toluene solution with a concentration of 5.0. Mu. Mol/ml (calculated as chromium).
The main catalyst a-9 was configured:
873.3mg (2.50 mmol) of chromium acetylacetonate and 1918mg (3.75 mmol) of phenyl group were weighed out 2 P (cyclopentyl) N-Si (methyl) 2 P (phenyl) 2 Dissolved in 500ml of toluene solution to prepare toluene solution with a concentration of 5.0. Mu. Mol/ml (calculated as chromium).
[ example 1 ]
Before the reaction, 500ml of the 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 of toluene is added into the reaction kettle. Mixing 1ml of procatalyst a-1 and 0.23ml of MMAO-3a (Al/cr=100) for 5min to form a first stream, 0.75ml of TMA as a second stream; the first stream and the second stream were added to the reaction vessel, 100ml of toluene was added to the reaction vessel, the temperature in the reaction vessel was then raised to 40℃and 4.0MPa of ethylene was introduced to start the reaction. After 20min of reaction, 10mL of ethanol containing 10vol% aqueous hydrochloric acid was added to the reaction solution to terminate the reaction.
The molar ratio of alumoxane in the first stream to alkyl aluminum in the second stream is referred to as Ali/Alii, which in this example is indicated as Ali/alii=1:3.
[ examples 2 to 27 ]
Ethylene polymerization was carried out in substantially the same manner as in example 1 except that the reaction conditions shown in Table 1 were different.
The following comparative examples 1-4 are compared to example 1:
comparative example 1
Before the reaction, 500ml of the 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 of toluene is added into the reaction kettle. 1ml of main catalyst a-1, 0.23ml of MMAO-3a (Al/Cr=100) and 0.75ml of TMA are sequentially added into a reaction kettle, 100ml of toluene is added into the reaction kettle, the temperature in the reaction kettle is then increased to 40 ℃, and 4.0MPa of ethylene is introduced to start the reaction. After 20min of reaction, 10mL of ethanol containing 10vol% aqueous hydrochloric acid was added to the reaction solution to terminate the reaction.
Comparative example 2
Before the reaction, 500ml of the 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 of toluene is added into the reaction kettle. Mixing 1ml of procatalyst a-1 and 0.75ml of TMA for 5min to form a first stream and 0.23ml of MMAO-3a as a second stream; the first stream and the second stream were added to the reaction vessel, 100ml of toluene was added to the reaction vessel, the temperature in the reaction vessel was then raised to 40℃and 4.0MPa of ethylene was introduced to start the reaction. After 20min of reaction, 10mL of ethanol containing 10vol% aqueous hydrochloric acid was added to the reaction solution to terminate the reaction.
[ comparative example 3 ]
Before the reaction, 500ml of the 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 of toluene is added into the reaction kettle. Mixing 0.23ml MMAO-3a and 0.75ml TMA for 5min to form a first stream, and taking 1ml of main catalyst a-1 as a second stream; the first stream and the second stream were added to the reaction vessel, 100ml of toluene was added to the reaction vessel, the temperature in the reaction vessel was then raised to 40℃and 4.0MPa of ethylene was introduced to start the reaction. After 20min of reaction, 10mL of ethanol containing 10vol% aqueous hydrochloric acid was added to the reaction solution to terminate the reaction.
[ comparative example 4 ]
Before the reaction, 500ml of the 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 of toluene is added into the reaction kettle. 1ml of main catalyst a-1, 0.23ml of MMAO-3a (Al/Cr=100) and 0.75ml of TMA are premixed for 5min and then added into a reaction kettle at one time, 100ml of toluene is added into the reaction kettle, then the temperature in the reaction kettle is increased to 40 ℃, and ethylene with the pressure of 4.0MPa is introduced to start the reaction. After 20min of reaction, 10mL of ethanol containing 10vol% aqueous hydrochloric acid was added to the reaction solution to terminate the reaction.
The following comparative examples 5-8 are compared to example 6:
comparative example 5
Before the reaction, 500ml of the 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 of toluene is added into the reaction kettle. 1ml of main catalyst a-2, 0.69ml of MMAO-3a (Al/Cr=300) and 0.75ml of TEA are sequentially added into a reaction kettle, 100ml of toluene is added into the reaction kettle, the temperature in the reaction kettle is then increased to 50 ℃, and 4.0MPa of ethylene is introduced to start the reaction. After 20min of reaction, 10mL of ethanol containing 10vol% aqueous hydrochloric acid was added to the reaction solution to terminate the reaction.
[ comparative example 6 ]
Before the reaction, 500ml of the 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 of toluene is added into the reaction kettle. Mixing 1ml of procatalyst a-2 and 0.75ml of TEA for 7min to form a first stream and 0.69ml of MMAO-3a as a second stream; the first stream and the second stream were added to the reaction vessel, 100ml of toluene was added to the reaction vessel, the temperature in the reaction vessel was then raised to 50℃and 4.0MPa of ethylene was introduced to start the reaction. After 20min of reaction, 10mL of ethanol containing 10vol% aqueous hydrochloric acid was added to the reaction solution to terminate the reaction.
[ comparative example 7 ]
Before the reaction, 500ml of the 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 of toluene is added into the reaction kettle. Mixing 0.69ml MMAO-3a and 0.75ml TEA for 7min to form a first stream, and taking 1ml procatalyst a-2 as a second stream; the first stream and the second stream were added to the reaction vessel, 100ml of toluene was added to the reaction vessel, the temperature in the reaction vessel was then raised to 50℃and 4.0MPa of ethylene was introduced to start the reaction. After 20min of reaction, 10mL of ethanol containing 10vol% aqueous hydrochloric acid was added to the reaction solution to terminate the reaction.
Comparative example 8
Before the reaction, 500ml of the 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 of toluene is added into the reaction kettle. 1ml of main catalyst a-2, 0.69ml of MMAO-3a and 0.75ml of TEA are premixed for 7min and then added into a reaction kettle at one time, 100ml of toluene is added into the reaction kettle, then the temperature in the reaction kettle is increased to 50 ℃, and 4.0MPa of ethylene is introduced to start the reaction. After 20min of reaction, 10mL of ethanol containing 10vol% aqueous hydrochloric acid was added to the reaction solution to terminate the reaction.
The reactivity and product selectivity in each example, comparative example were tested and the test results are shown in table 1. The experimental result shows that the feeding mode can ensure higher catalytic activity under the condition of lower aluminoxane dosage, thereby truly realizing the reduction of production cost.
Reaction conditions in Table 1, examples and comparative examples
Claims (16)
1. A method for producing 1-octene by high-activity oligomerization of ethylene, which is characterized by comprising the following steps:
a. forming a first stream consisting of at least a procatalyst, an aluminoxane-based cocatalyst;
b. forming a second stream consisting at least of an alkylaluminum-based cocatalyst;
c. separately feeding the first stream and the second stream 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, an aluminoxane-based cocatalyst and an alkylaluminum-based cocatalyst to obtain a reaction solution containing 1-octene;
the procatalyst is a complex composed of metallic chromium and a ligand represented by the following formula I:
in formula I, a represents one or more of the elements C, N, B, si; r represents hydrogen, alkyl or silane groups linked to A by a single or double bond.
2. The process for producing 1-octene by high activity oligomerization of ethylene according to claim 1, characterized in that the first stream, the second stream each independently comprise a portion of the process solvent and ethylene monomers are present or not.
3. The process for producing 1-octene by high activity oligomerization of ethylene according to claim 2, characterized in that no ethylene monomer or only ethylene monomer with mass concentration less than or equal to 10% is present in both the first stream and the second stream.
4. A process for the production of 1-octene by high activity oligomerization of ethylene according to any of claims 1-3, characterised in that the mixing time of the procatalyst and the aluminoxane cocatalyst in the first stream is 30s-30min before entering the reaction zone.
5. The process for producing 1-octene by high activity oligomerization of ethylene according to claim 4, wherein the mixing time of the main catalyst and the aluminoxane co-catalyst in the first stream is 5-10min before entering the reaction zone.
6. The process for producing 1-octene by high activity oligomerization of ethylene according to claim 2, characterized in that the content of process solvent in the first stream is 20-99% of its total mass; the second stream contains process solvent in an amount of 30-98% of its total mass.
7. The process for the production of 1-octene by high activity oligomerization of ethylene according to claim 2, characterized in that the process solvent is a non-coordinating inert liquid and/or liquid olefins ethylene, 1-hexene, 1-octene acting as monomers or reaction products.
8. The process for producing 1-octene by high activity oligomerization of ethylene according to claim 7, wherein the non-coordinating inert liquid is selected from the group consisting of isoparaffins, straight and branched aliphatic hydrocarbons, alkyl substituted or unsubstituted alicyclic hydrocarbons, halogenated hydrocarbons, aromatic hydrocarbons, nitriles.
9. The process for producing 1-octene by high activity oligomerization of ethylene according to claim 8, wherein the non-coordinating inert liquid is selected from isoparaffins, isobutane, n-butane, n-pentane, isopentane, n-hexane, isohexane, n-heptane, n-octane, n-nonane, dodecane, cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, perfluorinated C 4-10 Any one or more of alkane, chlorobenzene, dichloromethane, benzene, toluene, mesitylene, xylene and acetonitrile.
10. A process for the production of 1-octene by high activity oligomerization of ethylene according to any of claims 1-3 or 6-9, characterized in that 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.
11. The process for producing 1-octene by high activity oligomerization of ethylene according to claim 10, characterized in that the reaction time is 30-60min.
12. A process for the production of 1-octene by high activity oligomerization of ethylene according to any of claims 1-3 or 6-9, characterized in that in said first stream the amount of procatalyst and alumoxane-based cocatalyst is 1 (100-300) calculated as Cr/Al molar ratio;
the feed ratio of the first stream to the second stream, calculated as the molar ratio of aluminoxane based cocatalyst to alkylaluminum based cocatalyst, is 1 (0.3-3).
13. The process for producing 1-octene by high activity oligomerization of ethylene according to claim 12, wherein said aluminoxane type cocatalyst is selected from the group consisting of C 1-5 Alkyl aluminoxanes or modified aluminoxanes.
14. The process for producing 1-octene by high activity oligomerization of ethylene according to claim 13, wherein the aluminoxane cocatalyst is at least one selected from the group consisting of methylaluminoxane, ethylaluminoxane, propylaluminoxane, butylaluminoxane, isopropylluminoxane, tert-butylaluminoxane, modified methylaluminoxane, modified ethylaluminoxane, and modified propylaluminoxane.
15. The process for producing 1-octene by high activity oligomerization of ethylene according to claim 12, wherein said alkylaluminum co-catalyst is C 1-30 Aluminium alkyls or C 1-30 A halide of an aluminum alkyl.
16. The process for producing 1-octene by high activity oligomerization of ethylene according to claim 15, wherein said alkylaluminum co-catalyst is at least one selected from trimethylaluminum, triethylaluminum, tri-n-hexylaluminum, triisobutylaluminum, tri-n-octylaluminum, diethylaluminum chloride, diisobutylaluminum chloride and ethylaluminum dichloride.
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