CN107149947B - Catalyst for ethylene oligomerization and application thereof - Google Patents
Catalyst for ethylene oligomerization and application thereof Download PDFInfo
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- CN107149947B CN107149947B CN201610124178.6A CN201610124178A CN107149947B CN 107149947 B CN107149947 B CN 107149947B CN 201610124178 A CN201610124178 A CN 201610124178A CN 107149947 B CN107149947 B CN 107149947B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 55
- 238000006384 oligomerization reaction Methods 0.000 title claims abstract description 36
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000005977 Ethylene Substances 0.000 title claims abstract description 30
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 8
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 5
- 150000002367 halogens Chemical class 0.000 claims abstract description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 5
- 125000003107 substituted aryl group Chemical group 0.000 claims abstract description 4
- 125000003118 aryl group Chemical group 0.000 claims abstract description 3
- 125000004429 atom Chemical group 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000011651 chromium Substances 0.000 claims description 13
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 11
- 229910052804 chromium Inorganic materials 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-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
- -1 alkyl aluminum compound Chemical class 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 5
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- 150000004945 aromatic 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
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- WCFQIFDACWBNJT-UHFFFAOYSA-N $l^{1}-alumanyloxy(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]O[Al] WCFQIFDACWBNJT-UHFFFAOYSA-N 0.000 claims description 2
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 claims description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 2
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-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
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 150000001924 cycloalkanes Chemical class 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- 229940117389 dichlorobenzene Drugs 0.000 claims description 2
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 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
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 229910052760 oxygen Chemical group 0.000 claims description 2
- 239000001301 oxygen Chemical group 0.000 claims description 2
- 239000010703 silicon Chemical group 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 claims description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 2
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 claims description 2
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 2
- 125000005418 aryl aryl group Chemical group 0.000 claims 1
- 239000003426 co-catalyst Substances 0.000 claims 1
- 229940037201 oris Drugs 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 7
- 238000009826 distribution Methods 0.000 abstract description 5
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 12
- 239000004711 α-olefin Substances 0.000 description 8
- 150000001336 alkenes Chemical class 0.000 description 7
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 6
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 238000005829 trimerization reaction Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229920006158 high molecular weight polymer Polymers 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 1
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical group [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000006317 isomerization reaction 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
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 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
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229930192474 thiophene Natural products 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
- B01J31/24—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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/14—Catalytic processes with inorganic acids; with salts or anhydrides of acids
- C07C2/20—Acids of halogen; Salts thereof ; Complexes thereof with organic compounds
- C07C2/22—Metal halides; Complexes thereof with organic compounds
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/24—Phosphines
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a catalyst for ethylene oligomerization, which comprises a main catalyst shown as a general formula (I) and an aluminum-containing cocatalyst,wherein one of A, B and D is S and the other two are independently selected from CR1And CR2(ii) a The R is1And R2The same or different, are respectively selected from hydrogen, alkyl, cycloalkyl and halogen, and the atoms on the alkyl and cycloalkyl groups are optionally substituted or unsubstituted by heteroatoms; ar is aryl or substituted aryl. The catalyst provided by the invention has the advantages of good oligomerization activity, excellent product distribution and the like.
Description
Technical Field
The invention relates to an oligomerization catalyst, in particular to an application of a thiophene oligomerization catalyst in ethylene oligomerization reaction, and also relates to an ethylene oligomerization process.
Background
The use of chromium-based catalysts for the oligomerization of olefins, primarily alpha-olefins, has been extensively studied. More specifically, a number of chromium-based catalysts have been developed and used for the oligomerization of olefins to produce alpha-olefins. Among them, the trimerization of ethylene to 1-hexene and the tetramerization of ethylene to 1-octene are of particular significance. Compared with the copolymer of 1-butene, the LLDPE resin copolymerized by 1-hexene and 1-octene has obviously excellent tensile strength, impact strength, tear resistance and durability, and is particularly suitable for packaging films, agricultural covering films for greenhouses, sheds and the like. In the context of alpha-olefins as comonomers, 1-hexene and 1-octene have been gradually substituted for 1-butene to produce high performance PE products.
The production method of alpha-olefin mainly includes wax cracking method, ethylene oligomerization method, extraction separation method, fatty alcohol dehydrogenation method and internal olefin isomerization method. Among them, the ethylene oligomerization method is one of the important ways of producing alpha-olefin because of its characteristics of high purity, good selectivity, high utilization rate of raw material, etc.
After a route for selectively preparing 1-hexene by ethylene trimerization by using a homogeneous ternary chromium-based catalyst is reported by John R.Briggs in J.chem.Soc., chem.Commun.,1989,674-675, a 1-hexene production technology is greatly developed. In order to make more rational use of petroleum feedstocks, efforts have been made to develop highly efficient oligomerization catalysts, with the expectation of obtaining high purity higher alpha-olefins. In many explorations, the interaction of heteroatom ligands with chromium-based compounds and their use for the oligomerization of olefins has become a new area of research in this field. CN1606539A discloses a coordination compound of multidentate ligand phosphine, arsenic and/or antimony containing aluminoxane and chromium salt, and the coordination compound is used in the ethylene oligomerization reaction process; WO2003053890 reports that a novel sulfur-nitrogen heteroatom ligand is used for olefin oligomerization, olefin oligomerization occurs under the action of a chromium compound and alkylaluminoxane, and the catalyst composition has the characteristics of high catalytic activity and high purity of 1-hexene as a product. The alkoxy aluminum (including methylaluminoxane, modified methylaluminoxane) and the like serving as cocatalysts have the problems of high cost, large using amount and the like, and the problem of high production cost is bound to be caused when the alkoxy aluminum is used for ethylene trimerization reaction on a large scale.
There is no doubt that there is still a need for a novel catalyst with excellent comprehensive performance in the field of olefin oligomerization. Attention is paid to the fact that novel ligand compounds for ethylene oligomerization catalysts are obtained, and therefore ethylene oligomerization catalysts with high activity and selectivity are developed.
Disclosure of Invention
The inventor of the application provides a novel ethylene oligomerization catalyst for ethylene oligomerization, and the catalyst has the advantages of high specific catalytic activity, excellent product distribution (high content of C6 and C8 products) and less high molecular polymer through intensive research. The invention also relates to the application of the ethylene polymerization catalyst.
According to one aspect of the invention, the catalyst for ethylene oligomerization comprises a main catalyst shown as a general formula (I) and an aluminum-containing cocatalyst,
wherein one of A, B and D is S and the other two are independently selected from CR1And CR2(ii) a The R is1And R2The same or different, are respectively selected from hydrogen, alkyl, cycloalkyl and halogen, and the atoms on the alkyl and cycloalkyl groups are optionally substituted or unsubstituted by heteroatoms; ar is aryl or substituted aryl.
The catalyst provided by the invention has a novel structure, is used for ethylene oligomerization, has good activity and excellent product distribution, has high product contents of C6 and C8, and has good industrial application prospect and economic value.
According to a preferred embodiment of the present invention, the procatalyst of formula (I) comprises a procatalyst of formula (II) and/or formula (III),
according to another preferred embodiment of the invention, R is1And R2Same or different, are respectively selected from hydrogen and C1-C10Alkyl radical, C3-C10Cycloalkyl and halogen, and the carbon atoms on the alkyl and cycloalkyl groups are optionally substituted or unsubstituted with heteroatoms. The heteroatoms in the present invention are selected, for example, from sulfur, silicon, nitrogen and oxygen. In a specific embodiment, R1And R2Selected from the group consisting of hydrogen, methyl, ethyl, butyl, hexyl, octyl, cyclopentyl, cyclohexyl, and trimethylsilyl. Preferably, Ar is C5-C20Preferably phenyl or substituted phenyl.
According to a preferred embodiment of the invention, the aluminium-containing cocatalyst is chosen from alkylaluminium compounds and alkoxyaluminium compounds. Preferably, the alkyl aluminum compound is selected from at least one of trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diethylaluminum chloride and ethylaluminum dichloride. Preferably, the aluminum alkoxide is selected from at least one of methylaluminoxane, modified methylaluminoxane, ethylaluminoxane and isobutylaluminoxane.
According to a preferred embodiment of the invention, the molar ratio of aluminum in the cocatalyst to chromium in the main catalyst is (20-1500):1, and the catalyst has better catalytic performance in the range. In a preferred embodiment, the molar ratio of aluminum in the cocatalyst to chromium in the procatalyst is (50-1000):1, for example (100-. Within the above range, there is a better catalytic performance.
According to another aspect of the present invention, there is provided a method for oligomerization of ethylene, comprising: the catalyst is adopted to carry out ethylene oligomerization reaction in an organic solvent.
The organic solvent in the present invention is an organic solvent commonly used in the art, and for example, the organic solvent contains an aliphatic hydrocarbon compound and/or an aromatic hydrocarbon compound. For example, the aliphatic hydrocarbon compound is selected from at least one of the following compounds: linear, branched and cyclic alkanes, more preferably at least one of pentane, heptane, hexane, cyclohexane and methylcyclohexane. The aromatic hydrocarbon compound is preferably at least one selected from the following compounds: benzene, toluene, xylene, monochlorobenzene, dichlorobenzene, trichlorobenzene, monochlorobenzene and derivatives thereof.
In a preferred embodiment of the above process, the amount of the catalyst used is not particularly limited. In one embodiment, the procatalyst concentration is from 2 to 500. mu. mol/L, preferably from 5 to 50. mu. mol/L, based on the volume of the organic solvent.
In another preferred embodiment of the above process, the reaction temperature of the reaction is in the range of from 0 to 200 deg.C, preferably from 20 to 150 deg.C, such as from 30 to 100 deg.C, such as from 30 to 90 deg.C. The reaction pressure is 0.1-20MPa, such as 1-10MPa, such as 1-5 MPa.
The main catalyst provided by the invention has the advantages of novel structure, simple preparation and lower cost, and the catalyst consisting of the main catalyst and the aluminum-containing cocatalyst can be used for carrying out ethylene oligomerization reaction. The obtained products mainly comprise C6 and C8, the content of the products is more than 80 percent, and the other products comprise a small amount of alpha-olefin such as C4, C10 and more. The highest activity of the catalyst can be more than 1000kg of oligomerization products g (Cr)-1·h-1The amount of the high molecular weight polymer is extremely small. Has the characteristics of high activity, excellent product distribution and the like, and has better industrial application prospect and economic value.
Detailed Description
The following examples are merely illustrative of the present invention in detail, but it should be understood that the scope of the present invention is not limited to these examples.
Wherein, the detection conditions of the gas chromatography are as follows: chromatographic column SE-54, high-purity nitrogen carrier gas and FID detector; the column temperature adopts two-step temperature programming.
Example 1
A stainless steel polymerizer is used. Heating the autoclave to 80 ℃, vacuumizing, replacing with nitrogen for a plurality of times, filling ethylene for replacement, and reducing to the reaction temperature. Then adding heptane at 60 deg.C while adding 10 μmol of main catalyst 1 (structure shown as formula II, wherein R is1＝R2H, Ar is phenyl) and a cocatalyst, triethylaluminum (AlEt3), the total volume of the mixed solution being 100mL, wherein the molar ratio of chromium in the main catalyst to aluminum in the cocatalyst is 1: 100, controlling the reaction pressure to be 1MPa, and introducing ethylene to carry out ethylene oligomerization.
And after the reaction is finished, cooling the system to room temperature, collecting the gas-phase product in a gas metering tank, collecting the liquid-phase product in a conical flask, and adding 1mL of ethanol as a terminator to terminate the ethylene oligomerization reaction. And (4) carrying out gas chromatographic analysis after the gas-liquid phase product is measured. The results show that the obtained products are mainly C6 and C8, the content of the products is more than 80 percent, and the others are small amount of C4, C10 and above alpha-olefin. The catalyst activity was about 363kg of oligomerization product g (Cr)-1·h-1The high molecular weight polymer is rare.
Example 2
The same as example 1 except that the reaction pressure was 5 MPa. The data results are shown in table 1.
Example 3
The same as example 1 except that the reaction temperature was 30 ℃. The data results are shown in table 1.
Example 4
The same as example 1 except that the reaction temperature was 90 ℃. The data results are shown in table 1.
Example 5
The difference from the example 1 is that the molar ratio of the chromium in the main catalyst and the aluminum in the cocatalyst is 1: 500. the data results are shown in table 1.
Example 6
The same as example 1 except that triethylaluminum was changed to Methylaluminoxane (MAO). The data results are shown in table 1.
Example 7
The difference from the example 1 is that the main catalyst 1 is changed into a main catalyst 2 (the structure is shown as a general formula II, wherein R is1＝SiMe3，R2Ar is phenyl). The data results are shown in table 1.
Example 8
The difference from the example 1 is that the main catalyst 1 is changed into a main catalyst 3 (the structure is shown as a general formula III, wherein R is1＝R2Ar is phenyl). The data results are shown in table 1.
TABLE 1
As can be seen from the data in Table 1, the catalyst with the novel structure provided by the invention is used for ethylene oligomerization, has good oligomerization activity and excellent product distribution, has high contents of C6 and C8 products, and has low yield of C4 and products above C10.
It should be noted that the above-mentioned embodiments are used for explaining the present invention and do not constitute any limitation to the present invention. The present invention has been described with reference to the exemplary embodiments illustrated above, but it is understood that all words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (21)
1. A catalyst for ethylene oligomerization comprises a main catalyst shown as a general formula (I) and an aluminum-containing cocatalyst,
wherein one of A, B and D is S and the other two are independently selected from CR1And CR2(ii) a The R is1And R2Identical or different, are independently selected from hydrogen, alkyl, cycloalkyl and halogen, and the atoms of the alkyl and cycloalkyl groups are optionally substituted by heteroatoms orIs not substituted; ar is aryl or substituted aryl.
2. The catalyst according to claim 1, wherein the main catalyst of formula (I) comprises a main catalyst of formula (II) and/or formula (III),
3. the catalyst of claim 1 or 2, wherein R is1And R2Same or different, are respectively selected from hydrogen and C1-C10Alkyl radical, C3-C10Cycloalkyl and halogen, and the carbon atoms on said alkyl and cycloalkyl groups are optionally substituted or unsubstituted with heteroatoms selected from sulfur, silicon, nitrogen and oxygen.
4. The catalyst of claim 1 or 2, wherein Ar is C5-C20Aryl or substituted aryl of (a).
5. The catalyst of claim 3, wherein R is1And R2Selected from the group consisting of hydrogen, methyl, ethyl, butyl, hexyl, octyl, cyclopentyl, cyclohexyl, and trimethylsilyl.
6. The catalyst of claim 4, wherein Ar is phenyl or substituted phenyl.
7. The catalyst according to claim 1 or 2, characterized in that the aluminium-containing cocatalyst is chosen from alkylaluminium compounds and alkoxyaluminium compounds.
8. The catalyst according to claim 7, characterized in that the alkyl aluminum compound is selected from at least one of trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diethylaluminum chloride and ethylaluminum dichloride; and/or, the alkoxy aluminum is selected from at least one of methylaluminoxane, modified methylaluminoxane, ethylaluminoxane and isobutylaluminoxane.
9. The catalyst of claim 1 or 2, wherein the molar ratio of aluminum in the cocatalyst to chromium in the procatalyst is (20-1500): 1.
10. The catalyst of claim 9, wherein the molar ratio of aluminum in the co-catalyst to chromium in the main catalyst is (50-1000): 1.
11. The catalyst as claimed in claim 9, wherein the molar ratio of aluminum in the cocatalyst to chromium in the main catalyst is (100-500): 1.
12. A process for oligomerization of ethylene, comprising: the use of the catalyst of any one of claims 1 to 11 for the oligomerization of ethylene in an organic solvent.
13. The method according to claim 12, wherein the organic solvent comprises an aliphatic hydrocarbon compound and/or an aromatic hydrocarbon compound.
14. The method of claim 13, wherein the aliphatic hydrocarbon compound is selected from at least one of the following compounds: straight-chain alkanes, branched alkanes, and cycloalkanes.
15. The method according to claim 13, wherein the aromatic hydrocarbon compound is selected from at least one of the following compounds: benzene, toluene, xylene, monochlorobenzene, dichlorobenzene, trichlorobenzene, monochlorobenzene and derivatives thereof.
16. The method of claim 13, wherein the aliphatic hydrocarbon compound is selected from at least one of pentane, heptane, hexane, cyclohexane, and methylcyclohexane.
17. The method according to claim 12 or 13, wherein the concentration of the main catalyst is 2-500 μmol/L based on the volume of the organic solvent.
18. The method of claim 17, wherein the procatalyst concentration is from 5 to 50 μmol/L based on the volume of the organic solvent.
19. The process according to any one of claims 12 to 16, wherein the reaction is carried out at a reaction temperature of 0 to 200 ℃; the reaction pressure is 0.1-20 MPa.
20. The method of claim 19, wherein the reaction temperature is 20-150 ℃ and the reaction pressure is 1-10 MPa.
21. The process of claim 19, wherein the reaction temperature of the reaction is 30-100 ℃.
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| CN1606539A (en) * | 2001-12-20 | 2005-04-13 | Sasol技术股份有限公司 | Trimerisation and oligomerisation of olefins using a chromium based catalyst |
| CN101500967A (en) * | 2006-05-30 | 2009-08-05 | Sasol技术股份有限公司 | Oligomerisation catalyst with pendant donor groups |
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| CN1606539A (en) * | 2001-12-20 | 2005-04-13 | Sasol技术股份有限公司 | Trimerisation and oligomerisation of olefins using a chromium based catalyst |
| CN101500967A (en) * | 2006-05-30 | 2009-08-05 | Sasol技术股份有限公司 | Oligomerisation catalyst with pendant donor groups |
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| Switchable Ethylene Tri-/Tetramerization with High Activity: Subtle Effect Presented by Backbone-Substituent of Carbon-Bridged Diphosphine Ligands;Jun Zhang等;《ACS Publications》;20130918;第3卷(第10期);第2311-2312页 * |
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