CN104624235A - Preparation and application of ethylene oligomerization catalyst composition - Google Patents
Preparation and application of ethylene oligomerization catalyst composition Download PDFInfo
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- CN104624235A CN104624235A CN201310552515.8A CN201310552515A CN104624235A CN 104624235 A CN104624235 A CN 104624235A CN 201310552515 A CN201310552515 A CN 201310552515A CN 104624235 A CN104624235 A CN 104624235A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 56
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000005977 Ethylene Substances 0.000 title claims abstract description 46
- 239000000203 mixture Substances 0.000 title claims abstract description 32
- 238000006384 oligomerization reaction Methods 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 239000012190 activator Substances 0.000 claims abstract description 12
- 150000002902 organometallic compounds Chemical class 0.000 claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 125000005843 halogen group Chemical group 0.000 claims abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 239000011651 chromium Substances 0.000 claims description 27
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 14
- -1 aluminium alkoxide compound Chemical class 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 229910052804 chromium Inorganic materials 0.000 claims description 13
- 150000002736 metal compounds Chemical class 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 5
- 238000011065 in-situ storage Methods 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000002608 ionic liquid Substances 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 238000010276 construction Methods 0.000 claims description 2
- 239000012442 inert solvent Substances 0.000 claims 1
- 239000003446 ligand Substances 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 125000005842 heteroatom Chemical group 0.000 abstract description 4
- 239000004711 α-olefin Substances 0.000 abstract 2
- 125000002950 monocyclic group Chemical group 0.000 abstract 1
- 230000003606 oligomerizing effect Effects 0.000 abstract 1
- 150000003623 transition metal compounds Chemical class 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- 230000000694 effects Effects 0.000 description 17
- 238000004458 analytical method Methods 0.000 description 11
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 11
- 238000004451 qualitative analysis Methods 0.000 description 11
- 238000004445 quantitative analysis Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 150000001845 chromium compounds Chemical class 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 125000005234 alkyl aluminium group Chemical group 0.000 description 6
- 235000010210 aluminium Nutrition 0.000 description 6
- 239000003426 co-catalyst Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 238000006073 displacement reaction Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001721 carbon Chemical class 0.000 description 3
- 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 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- KEVMYFLMMDUPJE-UHFFFAOYSA-N 2,7-dimethyloctane Chemical group CC(C)CCCCC(C)C KEVMYFLMMDUPJE-UHFFFAOYSA-N 0.000 description 2
- SDXAWLJRERMRKF-UHFFFAOYSA-N 3,5-dimethyl-1h-pyrazole Chemical compound CC=1C=C(C)NN=1 SDXAWLJRERMRKF-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 239000013638 trimer Substances 0.000 description 2
- 238000005829 trimerization reaction Methods 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- ICSNLGPSRYBMBD-UHFFFAOYSA-N 2-aminopyridine Chemical compound NC1=CC=CC=N1 ICSNLGPSRYBMBD-UHFFFAOYSA-N 0.000 description 1
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 description 1
- FQHYQCXMFZHLAE-UHFFFAOYSA-N 25405-85-0 Chemical compound CC1(C)C2(OC(=O)C=3C=CC=CC=3)C1C1C=C(CO)CC(C(C(C)=C3)=O)(O)C3C1(O)C(C)C2OC(=O)C1=CC=CC=C1 FQHYQCXMFZHLAE-UHFFFAOYSA-N 0.000 description 1
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 0 Cc1n[n](C)c(*)c1I Chemical compound Cc1n[n](C)c(*)c1I 0.000 description 1
- 241000555268 Dendroides Species 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- HVURSIGIEONDKB-UHFFFAOYSA-N benzene;chromium Chemical compound [Cr].C1=CC=CC=C1.C1=CC=CC=C1 HVURSIGIEONDKB-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- BRTALTYTFFNPAC-UHFFFAOYSA-N boroxin Chemical compound B1OBOBO1 BRTALTYTFFNPAC-UHFFFAOYSA-N 0.000 description 1
- VPCAAUUIFCAFRZ-UHFFFAOYSA-N butylalumane Chemical compound CCCC[AlH2] VPCAAUUIFCAFRZ-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- LXZNFQZTQSSCSQ-UHFFFAOYSA-N chromium;octanoic acid Chemical compound [Cr].CCCCCCCC(O)=O LXZNFQZTQSSCSQ-UHFFFAOYSA-N 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000004836 hexamethylene group Chemical class [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- IHLVCKWPAMTVTG-UHFFFAOYSA-N lithium;carbanide Chemical compound [Li+].[CH3-] IHLVCKWPAMTVTG-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- NXPHGHWWQRMDIA-UHFFFAOYSA-M magnesium;carbanide;bromide Chemical compound [CH3-].[Mg+2].[Br-] NXPHGHWWQRMDIA-UHFFFAOYSA-M 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- CMHHITPYCHHOGT-UHFFFAOYSA-N tributylborane Chemical compound CCCCB(CCCC)CCCC CMHHITPYCHHOGT-UHFFFAOYSA-N 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical group CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- LOFJKBAHPJENQS-UHFFFAOYSA-N tris(oxomethylidene)chromium Chemical compound O=C=[Cr](=C=O)=C=O LOFJKBAHPJENQS-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to an ethylene oligomerization catalyst composition; consists of a ligand containing hetero atoms, a transition metal compound (b) and an organometallic compound activator (c); the molar ratio of , (b) and (c) is 1: 0.5-100: 0.1 to 5000; the heteroatom-containing ligand is a compound corresponding to the following general formula (I): r1、R2、R3、R4Identical or different, selected from hydrogen, linear or branched alkyl; or selected from monocyclic and polycyclic aryl and derivatives thereof; or from a halogen atom; the catalyst composition is used for catalysisThe catalytic activity of the catalyst for preparing linear alpha-olefin by oligomerizing ethylene is greater than 4.63X 106g ethylene mol-1Cr·h-1In the product C6～C10Mass percent of linear alpha-olefins>Selectivity of 55% for linear a-olefins>98%。
Description
Technical field
The present invention relates to a kind of preparation method of ethylene oligomerisation catalyst composition and such carbon monoxide-olefin polymeric to be applied to catalyzed ethylene oligomerisation and to prepare linear a-alkene.This carbon monoxide-olefin polymeric is made up of a kind of pyrazole compound, a kind of chromium compound and a kind of alkyl aluminum or alumina alkane co-catalyst, and this carbon monoxide-olefin polymeric can be used for catalyzed ethylene oligomerisation and prepares high-grade linear a-alkene.
Technical background
Linear a-alkene has a wide range of applications in fields such as ethylene comonomer, synthesis of surfactant intermediate, plasticizer alcohol, synthetic lubricant fluid and oil dopes.In recent years, along with the development of polyolefin industry, the demand rapid development to high-grade linear a-alkene in world wide.Ethylene oligomerization is the main method preparing high-grade linear a-alkene, by oligomerisation reaction, the ethene of cheapness can be transformed into and have high value-added product.
The research that transient metal complex homogeneous catalyst is used for olefinic polymerization and oligomerisation is subject to people's attention always, and researcher makes great efforts research new catalyst and improves existing catalyst, improves the activity of catalyst and the selective of catalysate.Current research is more, develop ethylene oligomerisation catalyst faster mainly contains nickel system, iron system and chromium system etc.As US Patent No. 3686351 and US3676523 disclose a kind of O-P bridging type part Raney nickel for ethylene oligomerization, be developed into SHOP (the Shell Higher Olefin Process) technical process of shell (SHOP) company based on this patented technology.
1996, Brookhart group (people such as Brookhart, M, J.Am.Chem.Soc., 1998,120,7143 ~ 7144; W099/02472,1999), Gibson group (people such as Gibson, V.C., Chem.Commun., 1998,849 ~ 850; Chem.Eur.J., 2000,2221 ~ 2231) find that the trident pyridinimine complex of some Fe (II) and Co (II) can catalyzed ethylene oligomerisation respectively, not only the catalytic activity of catalyst is very high, and product linear a-alkene is selective also very high.Chinese patent CN101074244A, CN1364818A, CN1463799, CN1453069 and CN1850339A report the catalyst of a class for ethylene oligomerization, this catalyst is the complex compound of late transition metal Fe or Co of coordination, under the effect of co-catalyst MAO, this catalyst has good ethylene oligomerization catalysis performance as major catalyst, and wherein iron (II) complex shows very high oligomerization activity to ethene.Oligomerization product comprises C
4~ C
32selective up to more than 98% in, a-alkene; But obtain a certain amount of polymer in oligomerization, research shows that the polymer obtained is low-molecular-weight polyolefin and wax-like polyolefin.This low-molecular-weight polyolefin there will be the problem such as wall built-up and blocking pipeline in continuous polymerization process.
Chrome catalysts is used for ethylene oligomerization, mainly ethylene selectivity trimerization or four poly-preparation 1-hexenes, 1-octene.The four-way catalyst composition be made up of pyrrole ligand, chromium compound, co-catalyst alkyl aluminum and promoter as CN102407159A, CN103102237A and CN102107146A etc. are disclosed is used for ethylene trimer high selectivity and prepares 1-hexene, and Phillips company, CNPC and Sinopec etc. all develop the catalyst of ethylene trimerization composition of oneself and achieve suitability for industrialized production.Patent WO04/056479, US20090118117, US7906681, US7829749, US7511183, US7381857, US7297832 etc. are disclosed by using chromium-based catalysts to make ethylene tetramerization prepare 1-octene.Wherein said chromium-based catalysts contains phosphorus and nitrogen as heteroatomic heteroatom ligand.Patent CN101720253, CN101606605, CN101600722, CN101351424, CN101291734, CN1993180A, CN1741850A and CN1741849A etc. disclose the poly-method of alkene four, and described carbon monoxide-olefin polymeric all comprises heteroatom ligand, transistion metal compound and co-catalyst.
Disclosed in science and patent document, chrome catalysts is used for ethylene trimer and four and poly-usually has one or more lower column defects up to now: 1. product purity is low; 2. form polymer, this causes reactor plugs, is difficult to continuous long-term operation; 3. poor catalyst activity, co-catalyst cost are high; 4. severe reaction conditions, need high pressure, cause drop into, safeguard and energy cost high; 5. to the sensitive of co-catalyst quality.
A target of the present invention is to provide the carbon monoxide-olefin polymeric for ethylene oligomerization and method that overcome prior art defect.Especially regardless of process conditions, all can obtain higher linear a-olefine selective and avoid the formation of a large amount of wax and polymer.Under the appropriate reaction conditions, carbon monoxide-olefin polymeric of the present invention is used for ethylene oligomerization, and have the selective height of low-carbon alkene, product carbon number is adjustable, and catalytic activity is high, the selective high of linear a-alkene.
Summary of the invention
The object of this invention is to provide a kind of ethylene oligomerisation catalyst composition.It is by a kind of pyrazole compound, a kind of chromium compound and a kind of alkyl aluminum or alumina alkane activator composition.
Object of the present invention also provides a kind of synthetic method of above-mentioned ethylene oligomerisation catalyst composition.It can form before ethylene oligomerization reaction in complexing, also can synthesize at ethylene oligomerization course of reaction situ.
Object of the present invention also provides a kind of purposes of above-mentioned ethylene oligomerisation catalyst composition, and its feature prepares linear a-alkene for catalyzed ethylene oligomerisation, and carbon number distribution is adjustable, catalyst activity is high.
Object of the present invention can be achieved by the following measures: for the carbon monoxide-olefin polymeric of ethylene oligomerization, comprise a kind of catalyst system and catalyzing containing three components that heteroatomic part (a), a kind of transistion metal compound (b) and a kind of organo-metallic compound activator (c) form, described meets the compound shown in following general formula (I) containing heteroatomic part (a) being:
Wherein, R
1, R
2, R
3, R
4identical or different, be selected from the alkyl of hydrogen, straight or branched; Also monocycle and polyaromatic and derivative thereof is selected from; Also halogen atom is selected from; Described containing heteroatomic part (a), also can be meet construction unit shown in general formula (I) and couple together by group or chemical bond the noval chemical compound formed containing two or more; Described transistion metal compound (b) is the compound of chromium, molybdenum, tungsten, titanium, tantalum, vanadium, zirconium, iron, nickel, palladium; Described organo-metallic compound activator (c) is alkyl aluminum compound, aluminium alkoxide compound, organoboron compound, organic salt, inorganic acid and inorganic salts, also can be the mixture of one or more in them; In described carbon monoxide-olefin polymeric, the mol ratio of the component (a) comprised, (b) and (c) is (a): (b): (c)=1:0.5 ~ 100:0.1 ~ 5000; By three components that (a), (b) and (c) form, be pre-mixed; Or directly can join in reaction system and carry out fabricated in situ; Described catalytic component is used for ethylene oligomerization, and react and carry out in atent solvent, atent solvent can be selected from alkane, aromatic hydrocarbons, alkene, ionic liquid; The temperature 0 DEG C ~ 200 DEG C of reaction, reaction pressure 0.1MPa ~ 20MPa, obtained ethylene oligomerization product.
Describe the product that carbon monoxide-olefin polymeric contains following component in detail:
(1) at least one be selected from shown in general formula (I) containing heteroatomic part (a)
In formula, R
1, R
2, R
3, R
4identical or different, be selected from the alkyl of hydrogen, straight or branched; Also monocycle and polyaromatic and derivative thereof is selected from; Also halogen atom is selected from; (I) the heteroatomic part described in, also can be one or more unit as (I) formula structure, combined by group, chemical bond or intermolecular force etc., as obtained the compound of bridging, dendroid and star, it also can be the polymer being incorporated into the producing high-molecular that macromolecular chain is formed.
(2) a kind of transistion metal compound (b)
Selectable transistion metal compound has the compound of chromium, molybdenum, tungsten, titanium, tantalum, vanadium, zirconium, iron, nickel, palladium.Preferably chromium, zirconium, titanium compound, it is still further preferred that chromium compound.Selectable chromium compound comprises general formula CrR
n mthose shown compounds, R in formula
nfor organic negative ion or neutral molecule, R
nin usually containing 1 ~ 10 carbon atom, n is the integer of 0 ~ 6, and the valence state of chromium is 0 ~ 6 valency.Concrete R
ngroup is as the organic matter for containing carboxyl, b-diketo and alkyl or its group.Consider from the angle being easy to dissolve and be easy to operate, chromium compound preferably comprises chromic acetate, isooctyl acid chromium, caprylic acid chromium, chromium acetylacetonate, diisoamyl diene chromium, dibenzene-chromium, CrCl
3(THF)
3, (phenyl) tricarbonyl chromium, chromium carbonyl a kind of and or multiple mixture.Best chromium compound is CrCl
3(THF)
3, isooctyl acid chromium, chromium acetylacetonate.
(3) a kind of organo-metallic compound activating agent (c)
Selectable organo-metallic compound comprises alkyl aluminum compound, aluminium alkoxide compound, organoboron compound, organic salt, inorganic acid and inorganic salts.Specifically be selected from various trialkylaluminium and aluminium alkoxide compound, as the aikyiaiurnirsoxan beta etc. of triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, three just base aluminium, tri-n-octylaluminium, MAO, ethylaluminoxane, isobutyl aluminium alkoxide and modification.Also aluminum alkyl halide, alkyl aluminum hydride or alkylaluminium sesquichloride can be used, as AlEt
2cl and Al
2et
3cl
3, also can be the mixture with above-mentioned one or more alkyl aluminums of mentioning or aikyiaiurnirsoxan beta.Organic salt activator is as lithium methide, methyl-magnesium-bromide etc.; Inorganic acid and inorganic salts activator are as tetrafluoro boric acid etherate, tetrafluoroborate, hexafluoro antimonate etc.Organoboron compound comprises boroxin, sodium borohydride, boron triethyl, three (pentafluorophenyl group) boron, tri butyl boron hydrochlorate etc.
(I) reactive mode of the heteroatomic part described in, transistion metal compound and metal organic activator, can pass through liquid phase reactor, as reacted under the action of the solvent, selectable solvent is as toluene, benzene and its derivative etc.; Also solid phase reaction can be passed through; Also catalyst can be generated by carrying out reaction in-situ in oligomerisation reaction process.Reaction described here can be a kind of, the reaction between two kinds and three kinds of compounds of above-mentioned heteroatomic part, transistion metal compound and metal organic activator.The process of this reaction is also ageing (pre-complexing) process of catalyst.
Ethylene oligomerization reaction is mainly carried out in atent solvent.Selectable solvent comprises alkane, cycloalkane, aromatic hydrocarbons, halogenated hydrocarbons, alkene etc.Typical solvent includes, but are not limited to benzene,toluene,xylene, isopropylbenzene, normal heptane, n-hexane, hexahydrotoluene, cyclohexane, 1-hexene, 1-octene, ionic liquid etc.
The preparation of catalyst is pre-mixed containing heteroatomic part (a), transistion metal compound (b) and organo-metallic compound activator (c); Also fabricated in situ can be carried out directly joining in reaction system containing heteroatomic part (a), transistion metal compound (b) and organo-metallic compound activator (c);
The temperature of ethylene oligomerization reaction can be carried out in 0 DEG C ~ 200 DEG C, preferably 50 DEG C ~ 150 DEG C.The pressure of ethylene oligomerization reaction can carry out under the pressure of 0.1MPa ~ 20MPa, preferred 1.0MPa ~ 10MPa.In reaction system, the concentration of catalyst can from 0.01 μm of ol metal/L ~ 1000 μm ol metal/L, preferably 0.1 μm of ol metal/L ~ 20 μm ol metal/L.
Ternary catalyst systems of the present invention is used for ethylene oligomerization, and compared with prior art tool has the following advantages: catalyst activity is high, catalyst synthesis is simple, cost is low, catalyst life is long.C in product
6~ C
10the mass percentage >55% of linear a-alkene, selective >98%, the 1-C of linear a-alkene
4and polymerizate content is low.
Detailed description of the invention
Enumerate 11 embodiments below, the present invention is further illustrated, instead of be used for limiting the scope of the invention.
Embodiment 1
The autoclave of 500mL is heated to 200 DEG C and vacuumizes 2 hours, is filled with ethene, cools to 70 DEG C, add toluene 100mL, the toluene solution of MAO(10% after nitrogen displacement for several times) 5.6mL, stirs and adds rapidly Cr (THF) after 2 minutes
3cl
3major catalyst 19.2 μm of ol, reaction temperature be 70 DEG C, reaction pressure is 2.0MPa, mixing speed carries out oligomerisation reaction under being the condition of 650 revs/min, reacting and be cooled to 0 DEG C, release after 30 minutes, is the acidic ethanol cessation reaction of 10% with mass fraction.Obtain product 11.42g, catalyst activity is 1.19 × 10
6g/molCr.h.The composition of product is by GC-MS qualitative and quantitative analysis, and analysis result is in table 1.
Embodiment 2
The autoclave of 500mL is heated to 200 DEG C and vacuumizes 2 hours, after nitrogen displacement for several times, be filled with ethene, cool to 70 DEG C, add toluene 100mL, the toluene solution of MAO(10%) 5.6mL and pyrazoles 19.2 μm of ol, stirs and adds rapidly Cr (THF) after 2 minutes
3cl
3major catalyst 19.2 μm of ol, reaction temperature be 70 DEG C, reaction pressure is 2.0MPa, mixing speed carries out oligomerisation reaction under being the condition of 650 revs/min, reacting and be cooled to 0 DEG C, release after 30 minutes, is the acidic ethanol cessation reaction of 10% with mass fraction.Obtain product 22.84g, catalyst activity is 2.38 × 10
6g/mol Cr.h.The composition of product is by GC-MS qualitative and quantitative analysis, and analysis result is in table 1.
Embodiment 3
The autoclave of 500mL is heated to 200 DEG C and vacuumizes 2 hours, is filled with ethene, cools to 70 DEG C after nitrogen displacement for several times, add toluene 100mL, the toluene solution of MAO(10%) 5.6mL and 3,5-dimethyl pyrazole, 19.2 μm of ol, stirs and adds rapidly Cr (THF) after 2 minutes
3cl
3major catalyst 19.2 μm of ol, reaction temperature be 70 DEG C, reaction pressure is 1.0MPa, mixing speed carries out oligomerisation reaction under being the condition of 650 revs/min, reacting and be cooled to 0 DEG C, release after 30 minutes, is the acidic ethanol cessation reaction of 10% with mass fraction.Obtain product 21.02g, catalyst activity is 2.19 × 10
6g/mol Cr.h.The composition of product is by GC-MS qualitative and quantitative analysis, and analysis result is in table 1.
Embodiment 4
With embodiment 3, difference is that reaction pressure is 3.0MPa.Obtain product 41.1g, catalyst activity is 4.28 × 10
6g/mol Cr.h.The composition of product is by GC-MS qualitative and quantitative analysis, and analysis result is in table 1.
Embodiment 5
The autoclave of 500mL is heated to 200 DEG C and vacuumizes 2 hours, is filled with ethene, cools to 70 DEG C after nitrogen displacement for several times, add toluene 100mL, the toluene solution of MAO(10%) 5.6mL and 3,5-dimethyl pyrazole, 19.2 μm of ol, stirs and adds rapidly Cr (THF) after 2 minutes
3cl
3major catalyst 19.2 μm of ol, reaction temperature be 50 DEG C, reaction pressure is 2.0MPa, mixing speed carries out oligomerisation reaction under being the condition of 650 revs/min, reacting and be cooled to 0 DEG C, release after 30 minutes, is the acidic ethanol cessation reaction of 10% with mass fraction.Obtain product 28.6g, catalyst activity is 2.98 × 10
6g/mol Cr.h.The composition of product is by GC-MS qualitative and quantitative analysis, and analysis result is in table 1.
Embodiment 6
With embodiment 5, difference is that reaction temperature is 70 DEG C.Obtain product 39.36g, catalyst activity is 4.10 × 10
6g/mol Cr.h.The composition of product is by GC-MS qualitative and quantitative analysis, and analysis result is in table 1.
Embodiment 7
With embodiment 5, difference is that reaction temperature is 90 DEG C.Obtain product 16.32g, catalyst activity is 1.70 × 10
6g/mol Cr.h.The composition of product is by GC-MS qualitative and quantitative analysis, and analysis result is in table 1.
Embodiment 8
With embodiment 6, what difference was chromium compound is chromium acetylacetonate.Obtain product 14.98g, catalyst activity is 1.56 × 10
6g/mol Cr.h.The composition of product is by GC-MS qualitative and quantitative analysis, and analysis result is in table 1.
Embodiment 9
With embodiment 6, what difference was chromium compound is isooctyl acid chromium.Obtain product 1.64g, catalyst activity is 0.17 × 10
6g/mol Cr.h.The composition of product is by GC-MS qualitative and quantitative analysis, and analysis result is in table 1.
Embodiment 10
With embodiment 6, difference is that the solvent that ethylene oligomerization reacts is cyclohexane.Obtain product 0.15g, catalyst activity is 0.016 × 10
6g/mol Cr.h.The composition of product is by GC-MS qualitative and quantitative analysis, and analysis result is in table 1.
Embodiment 11
With embodiment 6, difference is that the solvent that ethylene oligomerization reacts is hexahydrotoluene.Obtain product 1.5g, catalyst activity is 0.16 × 10
6g/mol Cr.h.The composition of product is by GC-MS qualitative and quantitative analysis, and analysis result is in table 1.
Claims (6)
1. an ethylene oligomerisation catalyst composition, is characterized in that: comprise a kind of carbon monoxide-olefin polymeric containing three components that heteroatomic part (a), a kind of transistion metal compound (b) and a kind of organo-metallic compound activator (c) form; A the mol ratio of (), (b) and (c) is 1:0.5 ~ 100:0.1 ~ 5000;
Described meets the compound shown in following general formula (I) containing heteroatomic part (a) being:
Wherein, R
1, R
2, R
3, R
4identical or different, be selected from the alkyl of hydrogen, straight or branched; Or be selected from monocycle and polyaromatic and derivative thereof; Or be selected from halogen atom.
2. according to the ethylene oligomerisation catalyst composition of claim 1, it is characterized in that: described containing heteroatomic part (a), is meet the construction unit shown in general formula (I) and couple together by group or chemical bond the compound formed containing two or more.
3. according to the ethylene oligomerisation catalyst composition of claim 1, it is characterized in that: described transistion metal compound (b) is the compound of chromium, nickel or palladium.
4. according to the ethylene oligomerisation catalyst composition of claim 1, it is characterized in that: described organo-metallic compound activator (c) is aluminium alkoxide compound, organic salt, inorganic acid or inorganic salts; Or two or more the mixture in them.
5. according to a preparation method for the ethylene oligomerisation catalyst composition of claim 1, it is characterized in that: by (a), (b) and (c) three components, be pre-mixed; Or directly join in reaction system and carry out fabricated in situ.
6. according to an application for ethylene oligomerisation catalyst composition according to claim 1, it is characterized in that: prepare linear a-alkene for catalyzed ethylene oligomerisation, react and carry out in inert solvent, be selected from alkane, ionic liquid; The temperature of reaction is 0 DEG C ~ 200 DEG C, and reaction pressure is 0.1MPa ~ 20MPa, obtained ethylene oligomerization product.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110479381A (en) * | 2019-08-19 | 2019-11-22 | 迈瑞尔实验设备（上海）有限公司 | A kind of catalyst system and the preparation method and application thereof for ethylene selectivity oligomerisation |
| CN114409494A (en) * | 2020-10-28 | 2022-04-29 | 中国石油天然气股份有限公司 | Method for improving yield of alpha-olefin in ethylene oligomerization reaction |
| CN114471718A (en) * | 2020-10-27 | 2022-05-13 | 中国石油天然气股份有限公司 | Catalytic system for ethylene selective oligomerization and ethylene selective oligomerization method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020035029A1 (en) * | 2000-09-29 | 2002-03-21 | Tosoh Corporation | Catalyst for trimerization of ethylene and process for trimerizing ethylene using the catalyst |
| CN101450326A (en) * | 2007-12-05 | 2009-06-10 | 中国石油天然气股份有限公司 | Catalyst composition for ethylene oligomerization and application thereof |
| WO2013067620A1 (en) * | 2011-11-08 | 2013-05-16 | Nova Chemicals (International) S.A. | Ethylene oligomerization process with aliiminoxane/organoboron as activators using a halogenated aromatic solvent |
-
2013
- 2013-11-08 CN CN201310552515.8A patent/CN104624235A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020035029A1 (en) * | 2000-09-29 | 2002-03-21 | Tosoh Corporation | Catalyst for trimerization of ethylene and process for trimerizing ethylene using the catalyst |
| CN101450326A (en) * | 2007-12-05 | 2009-06-10 | 中国石油天然气股份有限公司 | Catalyst composition for ethylene oligomerization and application thereof |
| WO2013067620A1 (en) * | 2011-11-08 | 2013-05-16 | Nova Chemicals (International) S.A. | Ethylene oligomerization process with aliiminoxane/organoboron as activators using a halogenated aromatic solvent |
Non-Patent Citations (4)
| Title |
|---|
| SIMPHIWE M. NELANA ET AL: ""Ethylene polymerization catalyzed by substituted pyrazole nickel complexes"", 《JOURNAL OF ORGANOMETALLIC CHEMISTRY》 * |
| 曹军 等: ""乙烯齐聚均相铬系催化剂的研究进展"", 《石油化工》 * |
| 李山明 等: ""乙烯选择性齐聚催化剂研究进展"", 《石化技术与应用》 * |
| 王力博 等: ""铬(Ⅲ)系1-己烯催化剂的研究进展"", 《化工进展》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110479381A (en) * | 2019-08-19 | 2019-11-22 | 迈瑞尔实验设备（上海）有限公司 | A kind of catalyst system and the preparation method and application thereof for ethylene selectivity oligomerisation |
| CN110479381B (en) * | 2019-08-19 | 2022-04-29 | 迈瑞尔实验设备（上海）有限公司 | Catalyst system for selective oligomerization of ethylene and preparation method and application thereof |
| CN114471718A (en) * | 2020-10-27 | 2022-05-13 | 中国石油天然气股份有限公司 | Catalytic system for ethylene selective oligomerization and ethylene selective oligomerization method |
| CN114409494A (en) * | 2020-10-28 | 2022-04-29 | 中国石油天然气股份有限公司 | Method for improving yield of alpha-olefin in ethylene oligomerization reaction |
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