CN115555049A - Catalyst composition for ethylene trimerization and application thereof - Google Patents
Catalyst composition for ethylene trimerization and application thereof Download PDFInfo
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- CN115555049A CN115555049A CN202211159131.5A CN202211159131A CN115555049A CN 115555049 A CN115555049 A CN 115555049A CN 202211159131 A CN202211159131 A CN 202211159131A CN 115555049 A CN115555049 A CN 115555049A
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- ethylene
- catalyst composition
- ethylene trimerization
- trimerization
- chromium
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000005977 Ethylene Substances 0.000 title claims abstract description 38
- 239000003054 catalyst Substances 0.000 title claims abstract description 29
- 238000005829 trimerization reaction Methods 0.000 title claims abstract description 28
- 239000000203 mixture Substances 0.000 title claims abstract description 19
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims abstract description 32
- -1 1, 10-o-phenanthroline compound Chemical class 0.000 claims abstract description 22
- 125000005234 alkyl aluminium group Chemical group 0.000 claims abstract description 12
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical group ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 claims abstract description 8
- 241000501667 Etroplus Species 0.000 claims abstract description 8
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 6
- VHHHONWQHHHLTI-UHFFFAOYSA-N hexachloroethane Chemical compound ClC(Cl)(Cl)C(Cl)(Cl)Cl VHHHONWQHHHLTI-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003446 ligand Substances 0.000 claims abstract description 6
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical group CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims abstract description 6
- XEHUIDSUOAGHBW-UHFFFAOYSA-N chromium;pentane-2,4-dione Chemical compound [Cr].CC(=O)CC(C)=O.CC(=O)CC(C)=O.CC(=O)CC(C)=O XEHUIDSUOAGHBW-UHFFFAOYSA-N 0.000 claims abstract description 5
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims abstract description 4
- LQIIEHBULBHJKX-UHFFFAOYSA-N 2-methylpropylalumane Chemical compound CC(C)C[AlH2] LQIIEHBULBHJKX-UHFFFAOYSA-N 0.000 claims abstract description 3
- FRBFQWMZETVGKX-UHFFFAOYSA-K chromium(3+);6-methylheptanoate Chemical group [Cr+3].CC(C)CCCCC([O-])=O.CC(C)CCCCC([O-])=O.CC(C)CCCCC([O-])=O FRBFQWMZETVGKX-UHFFFAOYSA-K 0.000 claims abstract description 3
- JYLPOJPHFDVWCY-UHFFFAOYSA-K oxolane;trichlorochromium Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3].C1CCOC1 JYLPOJPHFDVWCY-UHFFFAOYSA-K 0.000 claims abstract description 3
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims abstract description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000012442 inert solvent Substances 0.000 claims description 5
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 150000001845 chromium compounds Chemical class 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 239000002815 homogeneous catalyst Substances 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 abstract description 8
- 229920000573 polyethylene Polymers 0.000 abstract description 8
- 239000000047 product Substances 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 6
- 239000006227 byproduct Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 26
- 229920000642 polymer Polymers 0.000 description 10
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 7
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 5
- 239000004711 α-olefin Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical class [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000004700 high-density polyethylene Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910001868 water Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229920004889 linear high-density polyethylene Polymers 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
- B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/26—Catalytic processes with hydrides or organic compounds
- C07C2/32—Catalytic processes with hydrides or organic compounds as complexes, e.g. acetyl-acetonates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/20—Olefin oligomerisation or telomerisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
- B01J2531/62—Chromium
-
- 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)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a catalyst composition for ethylene trimerization, which consists of a chromide, a 1, 10-o-phenanthroline compound, an alkyl aluminum auxiliary agent and an electron donor, wherein the molar ratio of the components is as follows: 1, 0.1 to 100, 1 to 1000, wherein the chromide is chromium isooctanoate, chromium acetylacetonate or chromium tetrahydrofuran chloride, and the alkyl aluminum auxiliary agent is triethyl aluminum, methyl Aluminoxane (MAO), trimethyl aluminum or isobutyl aluminum; the electron donor is tetrachloroethane or hexachloroethane; the ethylene trimerization catalyst system which takes the 1, 10-phenanthroline compound as the ligand has the advantages of high catalyst activity, high 1-hexene selectivity, less polyethylene byproducts in the product, capability of reducing the cost in industrialization and the like when used for catalyzing ethylene trimerization reaction.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a catalyst composition for ethylene trimerization and application thereof.
Background
The world alpha-olefin producers are mainly concentrated in developed countries and regions such as the United states, europe, south Africa and Japan, with a total production capacity of 2554kt/a in 2000 and a plant capacity of 520kt/a planned and built. Wherein 1-hexene accounted for 20.4% of the total amount of α -olefin. The world 1-hexene market is moving toward tight sources, short supply and high price. Therefore, it is imperative to home-produce high carbon alpha olefins such as 1-hexene, 1-octene, etc. High carbon alpha-olefin such as 1-hexene, 1-octene and the like is an important comonomer of polyethylene and is also an organic chemical raw material with wide application. 1-hexene is used as an important organic raw material and a chemical intermediate, and is mainly used for producing high-end Polyethylene (PE). At present, PE in China basically adopts 1-butene as a comonomer, but high-carbon alpha-olefin copolymer resin such as 1-hexene and the like has excellent performance which is difficult to compare with 1-butene copolymer resin, and the 1-butene copolymer is a product which is going to be rejected. Linear Low Density Polyethylene (LLDPE) and High Density Polyethylene (HDPE) produced by copolymerization of 1-hexene and ethylene have significant advantages in the mechanical processing, heat resistance, flexibility and transparency of polyethylene. Is particularly suitable for producing packaging films and agricultural covering films. Most countries around the world have used 1-hexene and 1-octene instead of 1-butene to produce LLDPE and HDPE. In the gas phase PE production process, the use of a coagulation process also enables production growth of more than 20% with minimal input. Many manufacturers in the world use this method to increase production efficiency.
The current mainstream technology for preparing 1-hexene by ethylene trimerization is a quaternary catalytic composition consisting of metal chromium salt, pyrrole compound, alkyl aluminum and halogenated hydrocarbon (mainly chlorinated hydrocarbon). Such as the patent CN102558107A of medium petrochemical and the patent CN03157351.7 of medium petroleum, the high selectivity of 1-hexene is realized by adopting the mode. On the basis of keeping the components of chromium metal salt, triethyl aluminum, tetrachloroethane or hexachloroethane unchanged, the invention uses 1, 10-phenanthroline compound as ligand for the first time to form a catalyst system. The ligand has low cost, the prepared catalyst has high activity and high selectivity of 1-hexene, and the generated polymer is few, thereby being beneficial to long-period operation.
Disclosure of Invention
In order to solve the above problems, the present invention provides a catalyst composition for ethylene trimerization, which comprises chromium metal salt, 1, 10-o-phenanthroline compound, alkyl aluminum and organic chloride, wherein 1-hexene in the reaction product has high selectivity, and compared with the disclosed catalyst (pyrrole compound is ligand), the catalyst composition has the advantages of very low content of byproduct polyethylene and higher activity; in industrialization, the ethylene trimerization reaction can be carried out through in-situ polymerization, and prepolymerization is not needed.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a catalyst composition for the trimerization of ethylene comprising the following components:
(1) Chromium compound: chromium isooctanoate, chromium acetylacetonate or chromium tetrahydrofuran chloride;
(2) Ligand: 1, 10-phenanthroline compound, having the following structural formula:
wherein R1, R2, R3, R4, R5, R6, R7 and R8 are the same or different and are selected from hydrogen, alkyl, alkoxy, cycloalkyl or halogen;
(3) An alkyl aluminum additive: triethylaluminum, methylaluminoxane, trimethylaluminum or isobutylaluminum;
(4) Electron donor: tetrachloroethane or hexachloroethane.
Further, the molar ratio of the chromide to the 1, 10-o-phenanthroline compound to the alkyl aluminum auxiliary agent to the electron donor is as follows: 1, 0.1 to 100, 1 to 1000; preferably 1.1 to 10; more preferably 1:1 to 8:1 to 100.
Use of the above catalyst composition for ethylene trimerization: the components of the catalyst composition for ethylene trimerization are respectively dissolved in an inert solvent, and are sequentially injected or uniformly mixed in advance in a homogeneous catalyst mode to an ethylene trimerization reaction system, and then the ethylene pressure is increased to fully contact with the catalyst to carry out ethylene trimerization reaction to obtain the 1-hexene.
Further, the conditions for the ethylene trimerization are: the temperature is 30 to 250 ℃, the pressure is 0.5 to 20MPa, and the time is 0.1 to 2h; the inert solvent comprises benzene, toluene, cyclohexane, methylcyclohexane, n-heptane or n-hexane.
Further, the application of the catalyst composition for ethylene trimerization of the present invention in catalyzing ethylene trimerization reaction specifically comprises the following steps:
(1) Preparation of catalyst composition for ethylene trimerization: dissolving each component in the catalyst composition for ethylene trimerization in an inert solvent subjected to water removal treatment to prepare four solutions of a chromide, a 1, 10-phenanthroline compound, an alkyl aluminum auxiliary agent and an electron donor for later use;
(2) Before reaction, firstly placing a reaction kettle body and a lining in an oven for drying overnight at 120 ℃, sealing after installing the reaction kettle on the reaction kettle, heating to 105 ℃ under a vacuum pumping condition, keeping the temperature for 1h, removing residual water, oxygen and oxygen-containing impurities, setting the temperature to be a reaction temperature, naturally cooling the reaction kettle, filling nitrogen, vacuumizing for three times, ensuring that air is completely replaced, pumping the nitrogen away by using a vacuum pump, filling ethylene, and repeating for three times to ensure that the kettle body is filled with ethylene;
(3) Injecting the alkyl aluminum auxiliary solution prepared in the step (1) by using an injector under the condition of stirring, after the temperature is stabilized to the reaction temperature, sequentially injecting a chromide solution, a 1, 10-phenanthroline compound solution and an electron donor solution by using the injector, closing an exhaust valve, adjusting a pressure reducing valve, starting timing after the pressure is increased to a preset pressure value, recording mass flow meter data, closing ethylene gas after the reaction is finished, stopping the reaction, closing an air inlet valve, detaching a reaction kettle body, and soaking the reaction kettle body in an ice water bath to cool the reaction kettle to below 10 ℃.
After opening the vent valve to allow pressure to escape, a quantity of 5 ml of 10% HCl/ethanol solution was injected under stirring to quench the aluminum alkyl adjuvant, and the weight was weighed and recorded. A small amount of the liquid phase product was taken and analyzed by GC-MS. The remaining sample was filtered, the filter paper weighed in advance to record the mass, then the polymer on the paddle was scraped off with a spoon, washed into a beaker with solvent, the resulting polymer was dried overnight in a vacuum oven at 60 ℃, weighed separately and the mass of the polymer calculated. The component types can be calibrated according to MS, and the selectivity and the catalyst activity of each product can be calculated according to GC results by combining the mass of the liquid phase product and the mass of the polymer.
Compared with the prior art, the invention has the following advantages: the benzene ring and the two adjacent nitrogen-containing six-membered rings in the 1, 10-phenanthroline compound form conjugation to form a large pi bond, the three six-membered rings have strong rigidity, are stable in structure in the coordination process and are not easy to rotate, can form a single active center with a metal center more stably, and can have a good effect with the active center. The compound has combined action with metal chromium, triethyl aluminum and chlorine-containing electron donors, can more flexibly adjust the performance of the monomer donor, efficiently catalyzes an ethylene molecule and metal to form a seven-membered ring, releases a 1-hexene molecule after beta dehydrogenation, and compared with a pyrrole compound, the 1, 10-o-phenanthroline compound has larger steric hindrance, can effectively reduce the generation of polymers, and is beneficial to long-period operation.
Detailed Description
The present invention is further illustrated, but is not limited, by the following specific examples.
Example 1
The ethylene oligomerization reaction is carried out in a high-pressure stainless steel reaction kettle. Before reaction, the high-pressure reaction kettle is heated to 100 ℃ under the condition of vacuum pumping, the temperature is kept for 1h, then the temperature is set to 80 ℃, the high-pressure reaction kettle is naturally cooled, nitrogen is replaced for a plurality of times, and then ethylene is replaced for a plurality of times, so that the kettle body is ensured to be filled with ethylene. Then the solvent cyclohexane and the catalyst were added thereto in this order, the molar ratio of chromium acetylacetonate: 1, 10-phenanthroline: triethyl aluminum: hexachloroethane = 1. Controlling the reaction pressure to be 4.5MPa, stopping the reaction after 1h of reaction, closing the air inlet valve, detaching the reaction kettle body, and soaking the reaction kettle body in ice-water bath to cool the reaction kettle to below 10 ℃. After opening the vent valve to allow pressure to escape, 5 mL of 10% HCl/ethanol solution was injected under stirring to quench the aluminum alkyl, which was then weighed and recorded. A small amount of the liquid phase product was taken and analyzed by GC-MS. The remaining sample was filtered, the filter paper weighed in advance to record the mass, then the polymer on the paddle was scraped off with a spoon, washed into a beaker with solvent, the resulting polymer was dried overnight in a vacuum oven at 60 ℃, weighed separately and the mass of the polymer calculated. The component types can be calibrated according to MS, and the selectivity and the catalyst activity of each product can be calculated according to GC results by combining the mass of the liquid phase product and the mass of the polymer. The data results are shown in table 1.
Example 2
The same as example 1 except that the reaction temperature was 130 deg.C, the data are shown in Table 1.
Example 3
The same as example 1 except that the reaction pressure was 6MPa, the data results are shown in Table 1.
Example 4
The same as example 1 except that the solvent was heptane, the data are shown in Table 1.
Example 5
The same as example 1 except that the ratio of chromium acetylacetonate to hexachloroethane was changed to 1.
Comparative example 1
The same as example 1 except that 1, 10-phenanthroline was changed to pyrrole, and the data results are shown in Table 1.
TABLE 1 summary of the reaction conditions and the reaction Performance for the examples of the invention and the comparative examples
The above examples are merely for clearly illustrating the present invention and the embodiments of the present invention are not limited thereto. Any modification, replacement, or improvement made without departing from the spirit and principle of the present invention shall fall within the protection scope of the present invention.
Claims (7)
1. A catalyst composition for the trimerization of ethylene characterized in that: comprises the following components:
(1) Chromium compound: chromium isooctanoate, chromium acetylacetonate or chromium tetrahydrofuran chloride;
(2) Ligand: 1, 10-phenanthroline compound, having the following structural formula:
wherein R1, R2, R3, R4, R5, R6, R7 and R8 are the same or different and are selected from hydrogen, alkyl, alkoxy, cycloalkyl or halogen;
(3) An alkyl aluminum additive: triethylaluminum, methylaluminoxane, trimethylaluminum or isobutylaluminum;
(4) Electron donor: tetrachloroethane or hexachloroethane.
2. Ethylene trimerization catalyst composition according to claim 1, characterized in that: the molar ratio of the chromide to the 1, 10-o-phenanthroline compound to the alkyl aluminum auxiliary to the electron donor is as follows: 1, 0.1 to 100, 1 to 1000.
3. The ethylene trimerization catalyst composition of claim 2, characterized in that: the molar ratio of the chromide to the 1, 10-o-phenanthroline compound to the alkyl aluminum auxiliary agent to the electron donor is 1.1 to 10.
4. The ethylene trimerization catalyst composition of claim 3, characterized in that: the molar ratio of the chromide to the 1, 10-o-phenanthroline compound to the alkyl aluminum auxiliary agent to the electron donor is 1:1 to 8:1 to 100 parts by weight.
5. Use of a catalyst composition for the trimerization of ethylene according to any of claims 1-4, characterized in that: the components of the catalyst composition for ethylene trimerization are respectively dissolved in an inert solvent, and are sequentially injected or uniformly mixed in advance in a homogeneous catalyst mode to an ethylene trimerization reaction system, and then the ethylene pressure is increased to fully contact with the catalyst to carry out ethylene trimerization reaction to obtain the 1-hexene.
6. Use according to claim 5, characterized in that: the conditions for the ethylene trimerization are as follows: the temperature is 30 to 250 ℃, the pressure is 0.5 to 20MPa, and the time is 0.1 to 2h.
7. Use according to claim 5, characterized in that: the inert solvent comprises benzene, toluene, cyclohexane, methylcyclohexane, n-heptane or n-hexane.
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