CN114409495A - Ethylene tetramerization method - Google Patents
Ethylene tetramerization method Download PDFInfo
- Publication number
- CN114409495A CN114409495A CN202011168968.7A CN202011168968A CN114409495A CN 114409495 A CN114409495 A CN 114409495A CN 202011168968 A CN202011168968 A CN 202011168968A CN 114409495 A CN114409495 A CN 114409495A
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- CN
- China
- Prior art keywords
- compound
- component
- alkyl
- aluminum
- ether
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000005977 Ethylene Substances 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 57
- 239000003054 catalyst Substances 0.000 claims abstract description 104
- 238000006243 chemical reaction Methods 0.000 claims abstract description 64
- 239000003112 inhibitor Substances 0.000 claims abstract description 62
- 150000001875 compounds Chemical class 0.000 claims abstract description 44
- 230000008569 process Effects 0.000 claims abstract description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 12
- 239000001301 oxygen Substances 0.000 claims abstract description 12
- 150000002989 phenols Chemical class 0.000 claims abstract description 11
- 150000002170 ethers Chemical class 0.000 claims abstract description 6
- 150000004053 quinones Chemical class 0.000 claims abstract description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- -1 quinone compound Chemical class 0.000 claims description 99
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 84
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 48
- 125000005842 heteroatom Chemical group 0.000 claims description 26
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 26
- 229910052757 nitrogen Inorganic materials 0.000 claims description 24
- 125000000217 alkyl group Chemical group 0.000 claims description 23
- 125000003118 aryl group Chemical group 0.000 claims description 19
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 14
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 13
- MJSNUBOCVAKFIJ-LNTINUHCSA-N chromium;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Cr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MJSNUBOCVAKFIJ-LNTINUHCSA-N 0.000 claims description 13
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 13
- 229910052698 phosphorus Inorganic materials 0.000 claims description 13
- 239000011574 phosphorus Substances 0.000 claims description 13
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 11
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 claims description 10
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 10
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- 229910052804 chromium Inorganic materials 0.000 claims description 10
- 239000011651 chromium Substances 0.000 claims description 10
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 10
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 claims description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 9
- JYLPOJPHFDVWCY-UHFFFAOYSA-K oxolane;trichlorochromium Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3].C1CCOC1 JYLPOJPHFDVWCY-UHFFFAOYSA-K 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- 125000004434 sulfur atom Chemical group 0.000 claims description 9
- 125000005023 xylyl group Chemical group 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 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 8
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- 125000003107 substituted aryl group Chemical group 0.000 claims description 8
- 150000001336 alkenes Chemical class 0.000 claims description 7
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims description 7
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 6
- 229930192627 Naphthoquinone Natural products 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052787 antimony Inorganic materials 0.000 claims description 6
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 6
- 229910052785 arsenic Inorganic materials 0.000 claims description 6
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052797 bismuth Inorganic materials 0.000 claims description 6
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 6
- 229910052796 boron Inorganic materials 0.000 claims description 6
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 6
- 125000001624 naphthyl group Chemical group 0.000 claims description 6
- 125000003944 tolyl group Chemical group 0.000 claims description 6
- WCFQIFDACWBNJT-UHFFFAOYSA-N $l^{1}-alumanyloxy(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]O[Al] WCFQIFDACWBNJT-UHFFFAOYSA-N 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 5
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 5
- WBKDDMYJLXVBNI-UHFFFAOYSA-K chromium(3+);2-ethylhexanoate Chemical compound [Cr+3].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O WBKDDMYJLXVBNI-UHFFFAOYSA-K 0.000 claims description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 5
- 239000012442 inert solvent Substances 0.000 claims description 5
- 239000003446 ligand Substances 0.000 claims description 5
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 5
- AZQWKYJCGOJGHM-UHFFFAOYSA-N para-benzoquinone Natural products O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 5
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 5
- KETQAJRQOHHATG-UHFFFAOYSA-N 1,2-naphthoquinone Chemical compound C1=CC=C2C(=O)C(=O)C=CC2=C1 KETQAJRQOHHATG-UHFFFAOYSA-N 0.000 claims description 4
- 229940105324 1,2-naphthoquinone Drugs 0.000 claims description 4
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 125000002541 furyl group Chemical group 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- DIIIISSCIXVANO-UHFFFAOYSA-N 1,2-Dimethylhydrazine Chemical compound CNNC DIIIISSCIXVANO-UHFFFAOYSA-N 0.000 claims description 3
- 125000002030 1,2-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([*:2])C([H])=C1[H] 0.000 claims description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 3
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 claims description 3
- 125000004429 atom Chemical group 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 3
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 claims description 3
- 150000004292 cyclic ethers Chemical class 0.000 claims description 3
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical group CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 3
- MGDOJPNDRJNJBK-UHFFFAOYSA-N ethylaluminum Chemical compound [Al].C[CH2] MGDOJPNDRJNJBK-UHFFFAOYSA-N 0.000 claims description 3
- 150000008282 halocarbons Chemical class 0.000 claims description 3
- 230000003993 interaction Effects 0.000 claims description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 3
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 3
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 3
- 239000001294 propane Substances 0.000 claims description 3
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 claims description 3
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 claims description 3
- 125000004076 pyridyl group Chemical group 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 claims description 3
- 125000001544 thienyl group Chemical group 0.000 claims description 3
- 125000004014 thioethyl group Chemical group [H]SC([H])([H])C([H])([H])* 0.000 claims description 3
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 claims description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 3
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 claims description 3
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims 2
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 claims 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims 2
- NUMQCACRALPSHD-UHFFFAOYSA-N tert-butyl ethyl ether Chemical compound CCOC(C)(C)C NUMQCACRALPSHD-UHFFFAOYSA-N 0.000 claims 2
- NKJOXAZJBOMXID-UHFFFAOYSA-N 1,1'-Oxybisoctane Chemical compound CCCCCCCCOCCCCCCCC NKJOXAZJBOMXID-UHFFFAOYSA-N 0.000 claims 1
- CUVLMZNMSPJDON-UHFFFAOYSA-N 1-(1-butoxypropan-2-yloxy)propan-2-ol Chemical compound CCCCOCC(C)OCC(C)O CUVLMZNMSPJDON-UHFFFAOYSA-N 0.000 claims 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 claims 1
- FQQBAHSCHMASLR-UHFFFAOYSA-N 2-(2-methoxyethoxy)-2-methylpropane Chemical compound COCCOC(C)(C)C FQQBAHSCHMASLR-UHFFFAOYSA-N 0.000 claims 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims 1
- YPWLZGITFNGGKW-UHFFFAOYSA-N 2-phenanthrol Chemical compound C1=CC=C2C3=CC=C(O)C=C3C=CC2=C1 YPWLZGITFNGGKW-UHFFFAOYSA-N 0.000 claims 1
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 claims 1
- NUZWLKWWNNJHPT-UHFFFAOYSA-N anthralin Chemical compound C1C2=CC=CC(O)=C2C(=O)C2=C1C=CC=C2O NUZWLKWWNNJHPT-UHFFFAOYSA-N 0.000 claims 1
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical compound CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 claims 1
- 229960002311 dithranol Drugs 0.000 claims 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims 1
- 150000003254 radicals Chemical class 0.000 claims 1
- 238000007086 side reaction Methods 0.000 abstract description 4
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 28
- 239000000203 mixture Substances 0.000 description 23
- 239000006227 byproduct Substances 0.000 description 22
- 239000007791 liquid phase Substances 0.000 description 12
- 239000002994 raw material Substances 0.000 description 10
- 235000010290 biphenyl Nutrition 0.000 description 8
- 239000004305 biphenyl Substances 0.000 description 8
- 125000006267 biphenyl group Chemical group 0.000 description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 8
- IBUWSVDQGMTMLO-UHFFFAOYSA-N C(C)(C)[P].[N].C1(=CC=CC=C1)[P]C1=CC=CC=C1 Chemical group C(C)(C)[P].[N].C1(=CC=CC=C1)[P]C1=CC=CC=C1 IBUWSVDQGMTMLO-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 4
- 238000009825 accumulation Methods 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- GTBXZWADMKOZQJ-UHFFFAOYSA-N 1-phenanthrol Chemical compound C1=CC2=CC=CC=C2C2=C1C(O)=CC=C2 GTBXZWADMKOZQJ-UHFFFAOYSA-N 0.000 description 2
- OGRAOKJKVGDSFR-UHFFFAOYSA-N 2,3,5-trimethylphenol Chemical group CC1=CC(C)=C(C)C(O)=C1 OGRAOKJKVGDSFR-UHFFFAOYSA-N 0.000 description 2
- AQZGPSLYZOOYQP-UHFFFAOYSA-N Diisoamyl ether Chemical compound CC(C)CCOCCC(C)C AQZGPSLYZOOYQP-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- RPBPCPJJHKASGQ-UHFFFAOYSA-K chromium(3+);octanoate Chemical compound [Cr+3].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O RPBPCPJJHKASGQ-UHFFFAOYSA-K 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- SOEVKJXMZBAALG-UHFFFAOYSA-N octylalumane Chemical compound CCCCCCCC[AlH2] SOEVKJXMZBAALG-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- WOAHJDHKFWSLKE-UHFFFAOYSA-N 1,2-benzoquinone Chemical compound O=C1C=CC=CC1=O WOAHJDHKFWSLKE-UHFFFAOYSA-N 0.000 description 1
- PZHIWRCQKBBTOW-UHFFFAOYSA-N 1-ethoxybutane Chemical compound CCCCOCC PZHIWRCQKBBTOW-UHFFFAOYSA-N 0.000 description 1
- NCCTVAJNFXYWTM-UHFFFAOYSA-N 2-tert-butylcyclohexa-2,5-diene-1,4-dione Chemical compound CC(C)(C)C1=CC(=O)C=CC1=O NCCTVAJNFXYWTM-UHFFFAOYSA-N 0.000 description 1
- QQOMQLYQAXGHSU-UHFFFAOYSA-N 236TMPh Natural products CC1=CC=C(C)C(O)=C1C QQOMQLYQAXGHSU-UHFFFAOYSA-N 0.000 description 1
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical group CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- RZVHIXYEVGDQDX-UHFFFAOYSA-N 9,10-anthraquinone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1 RZVHIXYEVGDQDX-UHFFFAOYSA-N 0.000 description 1
- 229940076442 9,10-anthraquinone Drugs 0.000 description 1
- LSRLLOZBJURIHL-UHFFFAOYSA-N C1(CCCCC1)[P].[N].C1(=CC=CC=C1)[P]C1=CC=CC=C1 Chemical group C1(CCCCC1)[P].[N].C1(=CC=CC=C1)[P]C1=CC=CC=C1 LSRLLOZBJURIHL-UHFFFAOYSA-N 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
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Classifications
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- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
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- 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
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- 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
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Abstract
The invention relates to a method for ethylene tetramerization, which is characterized in that an inhibitor and an ethylene tetramerization catalyst are added into a reaction system together, wherein the inhibitor is composed of more than two oxygen-containing compounds, and the oxygen-containing compounds are quinone compounds, ether compounds, phenol compounds or phenol group-containing compounds. The method can inhibit the side reaction which can generate oligomer in the ethylene tetramerization reaction on the premise of not changing the ethylene tetramerization essential reaction, and reduce the generation of the oligomer in the long-period operation process, thereby avoiding the phenomena of adhesive hanging and fouling caused by the oligomer.
Description
Technical Field
The invention relates to the technical field of petrochemical industry, in particular to a method for ethylene tetramerization by using an inhibitor.
Background
Octene-1 is an important organic chemical raw material and chemical intermediate, mainly used as comonomer of high-end Linear Low Density Polyethylene (LLDPE), and also as basic raw material of high value-added products such as plasticizer, detergent, synthetic oil, surfactant, etc.
The ethylene/octene-1 copolymer is a kind of high molecular material with excellent performance. Because the longer side chain provided by the octene-1 endows the polyethylene molecules with stronger binding force, the ethylene/octene-1 copolymer often has better toughness, tear resistance and heat sealability, along with the increasing improvement of the living quality of people, the requirements of high-end materials such as PE-RT (heat-resistant polyethylene), POE (elastomer) and the like are also driven, but currently, no industrial device for producing the octene-1 is provided in China, nearly 10 ten thousand tons of octene-1 need to be imported every year, the shortage of raw materials greatly limits the research and development process of high-end functional new materials in China, so that the technology for producing the octene-1 by ethylene tetramer is urgently developed in China and the industrial production is realized.
Patents WO04/056479, WO2013/168102, WO2009/060342, US20090118117, US7906681, US7829749, US7511183, US7381857, US7297832 disclose a method for preparing octene-1 by tetramerising ethylene using a chromium-based catalyst containing a heteroatom ligand having phosphorus and nitrogen as heteroatoms, such as (phenyl) 2PN (isopropyl) P (phenyl) 2 and the like, with octene-1 selectivity capable of reaching 69%.
Patents CN101720253, CN101606605, CN101600722, CN101351424, CN101291734, CN1993180A, CN1741850A and CN1741849A, etc. all disclose olefin tetramerization methods, the catalyst systems all include heteroatom ligands, transition metal compounds and cocatalysts, and other cocatalysts are mainly alkylaluminums, alkylaluminoxanes and boron compounds, etc. It is disclosed in the above ethylene tetramerization art that octene-1 having a selectivity of more than 70% can be prepared by tetramerizing ethylene using a chromium-based catalyst.
However, although the production method reported in the above patent can ensure high selectivity of octene-1, the yield of by-product oligomers is above 2%, and these by-products exist in a swollen form in the reaction vessel, which is large in volume, and seriously affects the mass transfer of the reaction and the continuity of the apparatus.
The method is characterized in that the heat exchanger wall in the reactor is usually coated with a glue, and it is determined that polymerization reaction can occur on the heat exchanger wall to generate a covered polymer film, and as the reaction proceeds, the glue coating phenomenon is formed by accumulation of polymers, so that the heat transfer efficiency is seriously influenced, and then the entering catalyst active center can proceed at a higher reaction temperature, and the accumulation of byproducts is more serious, so that the reaction is finally terminated. Therefore, there is a need to develop a process for ethylene tetramerization that avoids or minimizes by-product oligomers.
Disclosure of Invention
In view of the above-described problems of the prior art, it is an object of the present invention to provide a method for ethylene tetramerization using an inhibitor, in which the inhibitor is added to a reaction mixture or a catalyst system at the same time as an ethylene tetramerization catalyst system is added to a reaction vessel, thereby effectively inhibiting the production of by-produced oligomers.
The inhibitor is added into a reaction system of ethylene tetramerization, and consists of more than two oxygen-containing compounds, wherein the oxygen-containing compounds are quinone compounds, ether compounds, phenolic compounds or phenolic group-containing compounds, and preferably ether compounds or quinone compounds.
The adding time of the inhibitor is one of the following: (1) adding an inhibitor and a catalyst for ethylene tetramerization into a reaction system; (2) the inhibitor is added into a reaction system before the catalyst for ethylene tetramerization; (3) the inhibitor is added into the reaction system after the catalyst for ethylene tetramerization.
In the ethylene tetramerization method according to the present invention, the inhibitor is preferably a combination of two oxygen-containing compounds, more preferably a combination of an ether compound and a quinone compound, and a combination of an ether compound and a phenol compound.
In the ethylene tetramerization method according to the present invention, the quinone compound is preferably a benzoquinone compound, a naphthoquinone compound, a phenanthrenequinone compound, or an anthraquinone compound.
In the ethylene tetramerization method according to the present invention, the benzoquinone compound preferably has a general formula of:
wherein R is6To R9Each independently is H or an alkyl group which is a C1-C9 alkyl group, with particular further preference R6To R9Each independently is-H, methyl, ethyl, propyl, n-butyl, isobutyl, tert-butyl, n-hexyl, n-octyl, phenyl, tolyl, furyl, more preferably-H, propyl, n-butylButyl, tert-butyl, n-octyl, furyl.
In the ethylene tetramerization method, the naphthoquinone compound is preferably 1, 2-naphthoquinone or 1, 4-naphthoquinone; the aromatic ring substituent of the phenanthrenequinone compound is-H; the aromatic ring substituent of the anthraquinone compound is-H.
In the ethylene tetramerization method according to the present invention, the ether compound is preferably a symmetric, asymmetric or cyclic ether.
In the ethylene tetramerization method of the present invention, the phenolic compound is preferably naphthol, anthraphenol or phenanthrol.
In the ethylene tetramerization method according to the present invention, it is preferable that the phenolic compound has a general formula of:
wherein R is10To R14Each independently is H or alkyl, the alkyl is C1-C40 alkyl, R10To R14Are connected to each other.
In the ethylene tetramerization method, preferably, the catalyst comprises a component A, a component B and a component C, and the molar ratio of the component A to the component B is 1: 1-20: 1-1000, and the molar ratio of the inhibitor to the component A is 1: 1-20.
In the ethylene tetramerization method, it is further preferable that the catalyst comprises a component A, a component B and a component C, the molar ratio of the component A to the component B is 1: 1-10: 200-500, and the molar ratio of the inhibitor to the component A is 1: 1-10.
The process for ethylene tetramerization according to the present invention, wherein, preferably,
the component A is a chromium source;
the component B is a ligand component containing heteroatoms, which contains substituents formed by at least two structural units, and the general formula of the structural units is formula (3) or formula (4):
wherein, the group A and the group D are the same or different and are respectively and independently phosphorus, arsenic, antimony, bismuth, nitrogen or sulfur atoms, or groups containing at least one atom in the group consisting of phosphorus, arsenic, antimony, bismuth, nitrogen and sulfur;
when the group B exists, as shown in the formula (3), the group B is a connecting group or a heteroatom, the connecting group is alkyl, substituted alkyl containing the heteroatom, aryl, substituted aryl or substituted aryl containing the heteroatom, and the heteroatom is boron, silicon, phosphorus, nitrogen or sulfur atom; when group B is absent, as shown in formula (4), then R5Nor is it present;
R5selected from hydrogen, halogen, linear or branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl, alkylaryl or fused ring aryl (when R is5When a group, may contain a hetero atom, for example, a boron, silicon, phosphorus, nitrogen or sulfur atom),
R1、R2、R3、R4each independently selected from phenyl, substituted phenyl, phenyl derivatives or substituted phenyl derivatives;
the component C is an aluminum-containing compound.
The process for ethylene tetramerization according to the present invention, wherein it is further preferred,
the connecting group is methylene, dimethylmethylene, 1, 2-ethane, 1, 2-phenylene, 1, 2-propane, 1, 2-catechol or 1, 2-dimethylhydrazine;
R5is isopropyl, tert-butyl, cyclohexyl or aryl.
(in the original technology, R is5Selected from hydrogen, halogen, linear or branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl, alkylaryl or fused ring aryl, or is a heteroatom containing group, such as an N-containing group, a silicon containing group; r5Isopropyl, tert-butyl, cyclohexyl and aryl are preferred.
The ethylene tetramerization method of the present invention, wherein preferably, the chromium source is selected from one or two of tetrahydrofuran chromium (iii) trichloride, chromium (iii) octanoate, chromium (iii) trichloride, chromium (iii) acetylacetonate, chromium (iii) 2-ethylhexanoate, and chromium (iii) acetate; the aluminum-containing compound is at least one selected from the group consisting of an alkylaluminum compound, an aluminoxane compound, a modified aluminoxane compound, and a product of interaction of an alkylaluminum compound with an aluminoxane compound or a modified aluminoxane compound.
In the ethylene tetramerization method of the present invention, it is preferable that the chromium source is one or two selected from the group consisting of tetrahydrofuran chromium (iii) trichloride, chromium (iii) 2-ethylhexanoate, and chromium (iii) acetylacetonate.
The process for ethylene tetramerization according to the present invention, wherein R is preferably1、R2、R3、R4Each independently is benzyl, phenyl, tolyl, xylyl, 2, 4, 6-trimethylphenyl, 3, 5-xylylmethyl, bisphenyl, naphthyl, anthracenyl, methoxy, ethoxy, phenoxy, tolyloxy, dimethylamino, methylethylamino, thiophenyl, pyridyl, thioethyl, thiophenoxy, trimethylsilyl, methyl, ethyl, vinyl, propyl, butyl, propenyl, propynyl, cyclopentyl, cyclohexyl, ferrocenyl, tetrahydrofuranyl. Further preferably, R1、R2、R3、R4Each independently is phenyl, substituted phenyl, xylyl, bisphenyl, naphthyl, thiophenyl, or ethyl.
In the ethylene tetramerization method, it is preferable that the reaction system comprises an inert solvent, wherein the inert solvent is at least one selected from alkanes, aromatic hydrocarbons, halogenated hydrocarbons and olefins, and the alkanes are at least one selected from n-hexane, methylcyclohexane, cyclohexane, heptane and decane; the aromatic hydrocarbon is selected from at least one of benzene, toluene, xylene and cumene; the olefin is at least one selected from butene-1, hexene-1 and octene-1.
In the invention, the inhibitor is a substance, and the inhibitor is added into a reaction system, the oxygen-containing end of the inhibitor reacts with the component A in the catalyst provided by the invention, the active species of the byproduct oligomer is passivated, and the side reaction rate constant is reduced, so that the selectivity of ethylene tetramerization is ensured, and the purpose of inhibiting the byproduct oligomer is achieved.
The ethylene tetramerization method of the present invention is preferably that the alkyl aluminum compound is trialkyl aluminum compound, alkyl aluminum halide, alkyl aluminum hydride or alkyl aluminum polychloride; the aluminoxane compound is selected from at least one of methylaluminoxane, ethylaluminoxane and isobutylaluminoxane; the modified aluminoxane compound is selected from at least one of modified methylaluminoxane and modified ethylaluminoxane.
The modification process of the modified ethyl aluminoxane is to add another alkyl aluminum as a cohydrolysis raw material in a specific raw material in the synthesis process of the aluminoxane.
In the ethylene tetramerization method, preferably, the trialkyl aluminum compound is at least one selected from triethyl aluminum, triisobutyl aluminum, tri-n-butyl aluminum, tri-n-hexyl aluminum and tri-n-octyl aluminum; the alkyl aluminum double chloride is diethyl aluminum chloride AlEt2Cl or ethyl aluminum sesqui Al2Et3Cl3。
The method for ethylene tetramerization comprises the following specific steps:
adding a solvent into a kettle before a test by using a kettle type reactor, heating the kettle to 50-80 ℃ to obtain a preheating condition of a reaction device, respectively dissolving A, B, C components and an inhibitor of the catalyst into an inert solvent, preparing A, B, C components of the catalyst in advance according to a ratio of 1: 1-10: 200-500, adding the catalyst and the inhibitor when the temperature of the kettle reaches 50-80 ℃, stirring for 1-5 min, adding the inhibitor into the kettle according to a molar ratio of 1: 1-10 of the inhibitor to the catalyst A, introducing pressure, controlling the reaction pressure at 3-7 MPa, reacting for 0.5-5 h, collecting oligomers and products in the kettle after the reaction, and calculating the selectivity of each component.
The ethylene tetramerization method can inhibit the side reaction of partial generation of oligomer in the ethylene tetramerization reaction on the premise of not changing the ethylene tetramerization essential reaction, and reduce the phenomena of adhesive hanging and fouling caused by the generation of the oligomer in the long-period operation process. The inhibitor used in the invention can ensure the selectivity of ethylene tetramerization reaction and adjust the generation amount of byproducts.
Detailed Description
The following examples illustrate the invention in detail: the present example is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following examples, and the experimental methods without specific conditions noted in the following examples are generally performed according to conventional conditions.
According to the ethylene tetramerization method provided by the invention, the inhibitor and the ethylene tetramerization catalyst are added into the reaction system together, or the inhibitor is added into the reaction system before the ethylene tetramerization catalyst, wherein the inhibitor is composed of more than two oxygen-containing compounds, the oxygen-containing compounds are quinone compounds, ether compounds, phenolic compounds or phenolic group-containing compounds, and preferably ether compounds or quinone compounds.
In some embodiments, the inhibitor is a combination of two oxygen-containing compounds, more preferably a combination of an ether compound and a quinone compound, and a combination of an ether compound and a phenolic compound.
In some embodiments, the quinone compound is a benzoquinone compound, a naphthoquinone compound, a phenanthrenequinone compound, or an anthraquinone compound.
In some embodiments, the benzoquinone-like compound has the formula:
wherein R is6To R9Each independently is H or an alkyl group which is a C1-C9 alkyl group, with particular further preference R6To R9Each independently is-H, methyl, ethyl, propyl, n-butyl, isobutyl, tert-butyl, n-hexyl, n-octyl, phenyl, tolyl, furylFurther preferred are-H, propyl, n-butyl, tert-butyl, n-octyl and furyl.
In some embodiments, the naphthoquinone compound is 1, 2-naphthoquinone or 1, 4-naphthoquinone; the aromatic ring substituent of the phenanthrenequinone compound is-H; the aromatic ring substituent of the anthraquinone compound is-H.
In some embodiments, the ether compound is a symmetric, asymmetric, or cyclic ether.
In some embodiments, the phenolic compound is naphthol, anthraphenol, or phenanthrol.
In some embodiments, the phenolic compound has the general formula:
wherein R is10To R14Each independently is H or alkyl, the alkyl is C1-C40 alkyl, R10To R14Are connected to each other.
In some embodiments, the catalyst comprises component a, component B, and component C in a molar ratio of 1: 1-20: 1-1000, and the molar ratio of the inhibitor to the component A is 1: 1-20.
In some embodiments, the catalyst comprises component A, component B and component C in a molar ratio of 1:1 to 10:200 to 500, and the molar ratio of the inhibitor to component A is 1:1 to 10.
In some embodiments, the component a is a source of chromium;
the component B is a ligand component containing heteroatoms, which contains substituents formed by at least two structural units, and the general formula of the structural units is formula (3) or formula (4):
wherein, the group A and the group D are the same or different and are respectively and independently phosphorus, arsenic, antimony, bismuth, nitrogen or sulfur atoms, or groups containing at least one atom in the group consisting of phosphorus, arsenic, antimony, bismuth, nitrogen and sulfur;
when the group B exists, as shown in the formula (3), the group B is a connecting group or a heteroatom, the connecting group is alkyl, substituted alkyl containing the heteroatom, aryl, substituted aryl or substituted aryl containing the heteroatom, and the heteroatom is boron, silicon, phosphorus, nitrogen or sulfur atom; when group B is absent, as shown in formula (4), then R5Nor is it present;
R5selected from hydrogen, halogen, linear or branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl, alkylaryl or fused ring aryl (when R is5When a group, may contain a hetero atom, for example, a boron, silicon, phosphorus, nitrogen or sulfur atom),
R1、R2、R3、R4each independently selected from phenyl, substituted phenyl, phenyl derivatives or substituted phenyl derivatives;
the component C is an aluminum-containing compound.
In some embodiments, the linking group is methylene, dimethylmethylene, 1, 2-ethane, 1, 2-phenylene, 1, 2-propane, 1, 2-catechol, or 1, 2-dimethylhydrazine;
R5is isopropyl, tert-butyl, cyclohexyl or aryl.
(in the original technology, R is5Selected from hydrogen, halogen, linear or branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl, alkylaryl or fused ring aryl, or is a heteroatom containing group, such as an N-containing group, a silicon containing group; r5Isopropyl, tert-butyl, cyclohexyl and aryl are preferred.
In some embodiments, the chromium source is selected from one or two of tetrahydrofuran chromium (iii) trichloride, chromium (iii) octanoate, chromium (iii) trichloride, chromium (iii) acetylacetonate, chromium (iii) 2-ethylhexanoate, and chromium (iii) acetate; the aluminum-containing compound is at least one selected from the group consisting of an alkylaluminum compound, an aluminoxane compound, a modified aluminoxane compound, and a product of interaction of an alkylaluminum compound with an aluminoxane compound or a modified aluminoxane compound.
In some embodiments, the chromium source is selected from one or two of chromium (iii) tetrahydrofuran trichloride, chromium (iii) 2-ethylhexanoate, and chromium (iii) acetylacetonate.
In some embodiments, R1、R2、R3、R4Each independently is benzyl, phenyl, tolyl, xylyl, 2, 4, 6-trimethylphenyl, 3, 5-xylylmethyl, bisphenyl, naphthyl, anthracenyl, methoxy, ethoxy, phenoxy, tolyloxy, dimethylamino, methylethylamino, thiophenyl, pyridyl, thioethyl, thiophenoxy, trimethylsilyl, methyl, ethyl, vinyl, propyl, butyl, propenyl, propynyl, cyclopentyl, cyclohexyl, ferrocenyl, tetrahydrofuranyl. Further preferably, R1、R2、R3、R4Each independently is phenyl, substituted phenyl, xylyl, bisphenyl, naphthyl, thiophenyl, or ethyl.
In some embodiments, the reaction system comprises an inert solvent selected from at least one of an alkane selected from at least one of n-hexane, methylcyclohexane, cyclohexane, heptane, and decane, an aromatic hydrocarbon, a halogenated hydrocarbon, and an alkene; the aromatic hydrocarbon is selected from at least one of benzene, toluene, xylene and cumene; the olefin is at least one selected from butene-1, hexene-1 and octene-1.
In the invention, the inhibitor is a substance, and the inhibitor is added into a reaction system, the oxygen-containing end of the inhibitor reacts with the component A in the catalyst provided by the invention, the active species of the byproduct oligomer is passivated, and the side reaction rate constant is reduced, so that the selectivity of ethylene tetramerization is ensured, and the purpose of inhibiting the byproduct oligomer is achieved.
In some embodiments, the alkylaluminum compound is a trialkylaluminum compound, an alkylaluminum halide, an alkylaluminum hydride, or an alkylaluminum polychloride; the aluminoxane compound is selected from at least one of methylaluminoxane, ethylaluminoxane and isobutylaluminoxane; the modified aluminoxane compound is selected from at least one of modified methylaluminoxane and modified ethylaluminoxane.
The modification process of the modified ethyl aluminoxane is to add another alkyl aluminum as a cohydrolysis raw material in a specific raw material in the synthesis process of the aluminoxane.
In some embodiments, the trialkylaluminum compound is selected from at least one of triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum; the alkyl aluminum double chloride is diethyl aluminum chloride AlEt2Cl or ethyl aluminum sesqui Al2Et3Cl3。
Example 1:
200ml of cyclohexane was charged into the reactor, and the reaction system was heated to 60 ℃. The catalyst A component selects chromium (III) acetylacetonate, and is dissolved in a toluene solvent; the catalyst B component is (diphenyl) phosphorus nitrogen (isopropyl) phosphorus (diphenyl), and is dissolved in toluene; the catalyst C component is modified methylaluminoxane, the A, B, C component of the catalyst is prepared in advance according to the proportion of 1:2:500, the catalyst is added into a reactor after the temperature of a reaction system is stable, and the adding amount of the catalyst is 5 ppm; at the same time, an inhibitor is added to the reactor.
The preparation method of the modified methylaluminoxane comprises the step of adding triisobutyl aluminum into a trimethylaluminum raw material as a cohydrolysis raw material in the synthesis process of the aluminoxane, wherein the adding amount ratio of the triisobutyl aluminum to the trimethylaluminum is controlled to be 1: 3-10.
1, 2-naphthoquinone is selected as an inhibitor, the inhibitor is dissolved in cyclohexane, the mixture is added into a reactor according to the molar ratio of the inhibitor to the component A of the catalyst being 1:10, the yield of by-product oligomer in the reactor is collected after the reaction is carried out for 2 hours under the pressure of 5MPa, liquid phase products are collected, and the composition content of each product component is analyzed, and the result is shown in Table 1.
Example 2:
the reactor was evacuated at 120 ℃ for 1h, displaced 3 times with nitrogen, cooled to 100 ℃ and then charged with 200ml of toluene, the reaction system was brought to 60 ℃. The catalyst A component selects chromium (III) acetylacetonate, and is dissolved in a toluene solvent; the catalyst B component is (diphenyl) phosphorus nitrogen (cyclohexyl) phosphorus (diphenyl), and is dissolved in toluene; the catalyst C component is methylaluminoxane, the A, B, C component of the catalyst is prepared in advance according to the proportion of 1:2:400, and the catalyst is added into a reactor after the temperature of a reaction system is stable, wherein the adding amount of the catalyst is 5 ppm; at the same time, an inhibitor is added to the reactor.
The inhibitor is diethylene glycol monobutyl ether, is dissolved in toluene, is added into a reactor according to the molar ratio of the component A of the catalyst of 1:10, is reacted for 2 hours under 5MPa, the yield of the by-product oligomer in the reactor is collected, a liquid phase product is collected, and the composition content of each product component is analyzed, and the result is shown in Table 1.
Example 3:
the reactor was evacuated at 120 ℃ for 1h, displaced 3 times with nitrogen, cooled to 70 ℃ and then 200ml heptane was added and the reaction was heated to 60 ℃. The component A of the catalyst is tetrahydrofuran chromium trichloride which is dissolved in a toluene solvent; the catalyst B component is (xylyl) phosphorus nitrogen (tert-butyl) phosphorus (xylyl) and is dissolved in toluene; the catalyst C component is ethyl aluminoxane, the A, B, C component of the catalyst is prepared in advance according to the proportion of 1:2:300, and the catalyst is added into a reactor after the temperature of a reaction system is stable, wherein the adding amount of the catalyst is 5 ppm; at the same time, an inhibitor is added to the reactor.
The inhibitor is a mixture of diethylene glycol dimethyl ether and tetrahydrofuran, the mixture is dissolved in heptane, the mixture is added into the reaction vessel according to the molar ratio of 1:3:7 to the catalyst A component for reaction, the yield of by-product oligomer in the reaction vessel is collected after the reaction is carried out for 2 hours under 5MPa, liquid phase products are collected, and the composition content of each product component is analyzed, and the result is shown in Table 1.
Example 4:
the reactor was evacuated at 120 ℃ for 1h, displaced 3 times with nitrogen, cooled to 70 ℃ and then charged with 200ml of cyclohexane and the reaction system was heated to 60 ℃. The catalyst A component selects chromium (III) acetylacetonate, and is dissolved in a toluene solvent; the catalyst B component is (dithiophenyl) phosphorus nitrogen (isopropyl) phosphorus (dithiophenyl), and is dissolved in toluene; the catalyst C component is n-octyl aluminum modified methylaluminoxane, the A, B, C component of the catalyst is prepared in advance according to the proportion of 1:3:500, and the catalyst is added into a reactor after the temperature of a reaction system is stable, wherein the adding amount of the catalyst is 5 ppm; at the same time, an inhibitor is added to the reactor.
The preparation method of the modified methylaluminoxane comprises the step of adding n-octyl aluminum into a trimethylaluminum raw material as a cohydrolysis raw material in the synthesis process of the aluminoxane, wherein the adding amount ratio of the n-octyl aluminum to the trimethylaluminum is controlled to be 1: 3-10.
The inhibitor is selected from tetrahydrofuran, is dissolved in cyclohexane, and is prepared from the components A according to the mol ratio of 1: 7, reacting for 2 hours at 5MPa, collecting the yield of the by-product oligomer in the reactor, collecting liquid phase products, and analyzing the component content of each product, wherein the results are shown in Table 1.
Example 5:
the reactor was evacuated at 120 ℃ for 1h, displaced 3 times with nitrogen, cooled to 70 ℃ and then charged with 200ml of n-hexane, and the reaction system was heated to 60 ℃. The catalyst A component selects chromium (III) acetylacetonate, and is dissolved in a toluene solvent; the catalyst B component is (diphenyl) phosphorus nitrogen (isopropyl) phosphorus (diphenyl), and is dissolved in toluene; the catalyst C component is methylaluminoxane, the catalyst A, B, C component is prepared in advance according to the proportion of 1:3:400, and the catalyst is added into a reactor after the temperature of a reaction system is stable, wherein the adding amount of the catalyst is 5 ppm; at the same time, an inhibitor is added to the reactor.
The inhibitor is selected from p-tert-butylphenol, is dissolved in normal hexane, and is mixed with the component A of the catalyst according to the molar ratio of 1:10, and collecting the yield of the by-product oligomer in the reactor after reacting for 2 hours under 5MPa, collecting liquid phase products, and analyzing the component content of each product, wherein the results are shown in Table 1.
Example 6:
the reactor was evacuated at 120 ℃ for 1h, displaced 3 times with nitrogen, cooled to 70 ℃ and then charged with 200ml of cyclohexane and the reaction system was heated to 60 ℃. The component A of the catalyst is tetrahydrofuran chromium trichloride which is dissolved in a toluene solvent; the catalyst B component is (diphenyl) phosphorus nitrogen (p-methylphenyl) phosphorus (diphenyl), and is dissolved in toluene; the catalyst C component is isobutylaluminoxane, the A, B, C component of the catalyst is prepared in advance according to the proportion of 1:3:400, and the catalyst is added into the reactor after the temperature of the reaction system is stable, wherein the adding amount of the catalyst is 5 ppm; at the same time, an inhibitor is added to the reactor.
The inhibitor is 2,3, 5-trimethylphenol dissolved in cyclohexane and is prepared by mixing the components in a molar ratio of 1: 8, under 5MPa for 2 hours, collecting the yield of the by-product oligomer in the reactor, collecting the liquid phase product, and analyzing the component content of each product, wherein the results are shown in Table 1.
Example 7
The reactor was evacuated at 120 ℃ for 1h, displaced 3 times with nitrogen, cooled to 70 ℃ and then charged with 200ml of n-hexane, and the reaction system was heated to 50 ℃. The component A of the catalyst is tetrahydrofuran chromium trichloride which is dissolved in a toluene solvent; the catalyst B component is (diphenyl) phosphorus nitrogen (isobutyl) phosphorus (diphenyl), and is dissolved in toluene; the catalyst C component is methylaluminoxane, the A, B, C component of the catalyst is prepared in advance according to the proportion of 1:3:500, the catalyst is added into a reactor after the temperature of a reaction system is stable, and the adding amount of the catalyst is 3 ppm; at the same time, an inhibitor is added to the reactor.
1, 4-naphthoquinone is selected as an inhibitor, is dissolved in toluene, and is mixed with the component A of the catalyst according to the molar ratio of 1:10, and collecting the yield of the by-product oligomer in the reactor after reacting for 2 hours under 5MPa, collecting liquid phase products, and analyzing the component content of each product, wherein the results are shown in Table 1.
Example 8
The reactor was evacuated at 120 ℃ for 1h, displaced 3 times with nitrogen, cooled to 70 ℃ and then charged with 200ml of n-hexane, and the reaction system was heated to 50 ℃. The component A of the catalyst is tetrahydrofuran chromium trichloride which is dissolved in a toluene solvent; the catalyst B component is (diphenyl) phosphorus nitrogen (isobutyl) phosphorus (diphenyl), and is dissolved in toluene; the catalyst C component is methylaluminoxane, the A, B, C component of the catalyst is prepared in advance according to the proportion of 1:3:500, the catalyst is added into a reactor after the temperature of a reaction system is stable, and the adding amount of the catalyst is 3 ppm; at the same time, an inhibitor is added to the reactor.
The inhibitor is a mixture of 1, 4-naphthoquinone and isopropyl ether, is dissolved in toluene, is added into the mixture for reaction according to the molar ratio of the inhibitor to the component A of the catalyst being 1:5:10, and after the reaction is carried out for 2 hours under the pressure of 5MPa, the yield of the by-product oligomer in the reactor is collected, the liquid phase product is collected, and the composition content of each product component is analyzed, and the results are shown in Table 1.
Example 9
The reactor was evacuated at 120 ℃ for 1h, displaced 3 times with nitrogen, cooled to 70 ℃ and then charged with 200ml of cyclohexane and the reaction system was heated to 50 ℃. The catalyst A component selects chromium (III) acetylacetonate, and is dissolved in a toluene solvent; the catalyst B component is (xylyl) phosphorus nitrogen (cyclopentyl) sulfur (xylyl) and is dissolved in toluene; the catalyst C component is triisobutylaluminum modified methylaluminoxane, the A, B, C component of the catalyst is prepared in advance according to the proportion of 1:3:1000, and after the temperature of a reaction system is stable, the catalyst is added into a reactor, wherein the adding amount of the catalyst is 5 ppm; at the same time, an inhibitor is added to the reactor.
The inhibitor is a mixture of 9, 10-anthraquinone and ethyl butyl ether, the mixture is dissolved in toluene, the mixture is added into the toluene for reaction according to the molar ratio of the mixture to the component A of the catalyst being 1:3:5, the yield of the by-product oligomer in the reactor is collected after the reaction is carried out for 2 hours under 5MPa, the liquid phase product is collected, and the composition content of each product component is analyzed, and the result is shown in Table 1.
Example 10
The reactor was evacuated at 120 ℃ for 1h, displaced 3 times with nitrogen, cooled to 70 ℃ and then charged with 200ml of cyclohexane and the reaction system was heated to 50 ℃. The catalyst A component selects chromium (III) acetylacetonate, and is dissolved in a toluene solvent; the catalyst B component is (xylyl) phosphorus nitrogen (cyclopentyl) phosphorus (xylyl) and is dissolved in toluene; the catalyst C component is methylaluminoxane, the A, B, C component of the catalyst is prepared in advance according to the proportion of 1:3:600, the catalyst is added into a reactor after the temperature of a reaction system is stable, and the adding amount of the catalyst is 5 ppm; at the same time, an inhibitor is added to the reactor.
The inhibitor is a mixture of 1, 2-benzoquinone and tetrahydrofuran, is dissolved in toluene, is added into the mixture according to the molar ratio of 1:2:8 to the component A of the catalyst for reaction, the yield of the by-product oligomer in the reactor is collected after the reaction is carried out for 2 hours under 5MPa, liquid phase products are collected, and the composition content of each product component is analyzed, and the result is shown in Table 1.
Example 11
The reactor was evacuated at 120 ℃ for 1h, displaced 3 times with nitrogen, cooled to 70 ℃ and then charged with 200ml of cyclohexane and the reaction system was heated to 50 ℃. The catalyst A component selects chromium (III) acetylacetonate, and is dissolved in a toluene solvent; the catalyst B component is (diphenyl) phosphorus nitrogen (isopropyl) phosphorus (diphenyl), and is dissolved in toluene; the catalyst C component is tri-n-hexylaluminum modified methylaluminoxane, the A, B, C component of the catalyst is prepared in advance according to the proportion of 1:3:1000, and the catalyst is added into a reactor after the temperature of a reaction system is stable, wherein the adding amount of the catalyst is 5 ppm; at the same time, an inhibitor is added to the reactor.
The inhibitor is a mixture of isoamyl ether and m-diphenol, is dissolved in toluene, is added into the mixture for reaction according to the molar ratio of the isoamyl ether to the component A of the catalyst of 1:1:10, is reacted for 2 hours under the pressure of 5MPa, the yield of the by-product oligomer in the reactor is collected, liquid phase products are collected, and the composition content of each product component is analyzed, and the result is shown in Table 1.
Example 12
The reactor was evacuated at 120 ℃ for 1h, displaced 3 times with nitrogen, cooled to 70 ℃ and then charged with 200ml of cyclohexane and the reaction system was heated to 50 ℃. The catalyst A component selects chromium (III) acetylacetonate, and is dissolved in a toluene solvent; the catalyst B component is (diphenyl) phosphorus nitrogen (isopropyl) phosphorus (diphenyl), and is dissolved in toluene; the catalyst C component is tri-n-hexylaluminum modified methylaluminoxane, the A, B, C component of the catalyst is prepared in advance according to the proportion of 1:3:1000, and the catalyst is added into a reactor after the temperature of a reaction system is stable, wherein the adding amount of the catalyst is 5 ppm; at the same time, an inhibitor is added to the reactor.
The inhibitor is a mixture of tert-butyl p-benzoquinone and methyl tert-butyl ether, dissolved in toluene, added to react with the component A in a molar ratio of 1:2:8 at 5MPa for 2 hours, the yield of by-product oligomers in the reactor is collected, the liquid phase product is collected, and the composition content of each product component is analyzed, and the results are shown in Table 1.
Comparative example 1
The difference from example 1 is that no inhibitor was added.
TABLE 1
As can be seen from Table 1, according to the method provided by the invention, the content of by-product oligomers in the ethylene tetramerization reaction can be reduced by means of adding the inhibitor, the accumulation of the oligomers in the reactor and the problem of the hanging glue of the heat removing element are reduced, and the mass transfer effect and the heat transfer effect in the reactor are ensured. The method has wide application prospect for industrial amplification of ethylene tetramerization technology.
The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and it is therefore intended that all such changes and modifications as fall within the true spirit and scope of the invention be considered as within the following claims.
Claims (15)
1. The method for ethylene tetramerization is characterized in that an inhibitor is added into a reaction system of the ethylene tetramerization, wherein the inhibitor is composed of more than two oxygen-containing compounds, and the oxygen-containing compounds are quinone compounds, ether compounds, phenolic compounds or phenolic group-containing compounds.
2. The method of ethylene tetramerization according to claim 1, wherein the quinone compound is a benzoquinone compound, a naphthoquinone compound, a phenanthrenequinone compound, or an anthraquinone compound.
3. The method of claim 2, wherein the benzoquinone-like compound has the formula:
wherein R is6To R9Each independently is H or alkyl, the alkyl is C1-C9 alkyl;
the naphthoquinone compound is 1, 2-naphthoquinone or 1, 4-naphthoquinone;
the aromatic ring substituent of the phenanthrenequinone compound is-H;
the aromatic ring substituent of the anthraquinone compound is-H.
4. The process for the tetramerization of ethylene according to claim 3, wherein R in the general formula (1)6To R9Each independently-H, methyl, ethyl, propyl, n-butyl, isobutyl, tert-butyl, n-hexyl, n-octyl, phenyl, tolyl, furyl.
5. The process for the tetramerization of ethylene according to claim 1, wherein the ether-based compound is a symmetrical, asymmetrical or cyclic ether.
6. The method of claim 1, wherein the ether compound is at least one selected from the group consisting of diphenyl ether, dibenzyl ether, anisole, n-butyl ether, n-octyl ether, ethyl tert-butyl ether, methyl tert-butyl ether, isopropyl ether, ethylene glycol butyl ether, diethylene glycol butyl ether, ethylene glycol phenyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, ethylene glycol methyl tert-butyl ether, dipropylene glycol butyl ether, and tetrahydrofuran.
7. The method of claim 1, wherein the phenolic compound is naphthol, anthralin or phenanthrenol.
8. The process for the tetramerization of ethylene according to claim 1, wherein the phenolic compound has the general formula:
wherein R is10To R14Each independently is H or alkyl, the alkyl is C1-C40 alkyl, R10To R14Are connected to each other.
9. The process for the tetramerization of ethylene according to claim 8, wherein R in the general formula (2)10To R14At least two of which are independent and are C3-C30 alkyl groups.
10. The process for the tetramerization of ethylene according to claim 1, wherein the catalyst comprises component a, component B, and component C in a molar ratio of 1: 1-20: 1-1000, wherein the molar ratio of the inhibitor to the component A is 1: 1-20;
the component A is a chromium source, the component B is a ligand component containing heteroatoms, and the component C is an aluminum-containing compound.
11. The process for the tetramerization of ethylene according to claim 10,
the chromium source is selected from one or two of tetrahydrofuran chromium (III) trichloride, chromium (III) octoate, chromium (III) trichloride, chromium (III) acetylacetonate, chromium (III) 2-ethylhexanoate and chromium (III) acetate;
the component B contains a substituent formed by at least two structural units, and the general formula of the structural unit is formula (3) or formula (4):
wherein, the groups A and D are the same or different and are respectively and independently phosphorus, arsenic, antimony, bismuth, nitrogen or sulfur atoms, or groups containing at least one atom in the group consisting of phosphorus, arsenic, antimony, bismuth, nitrogen and sulfur;
when the radicals B andR5when the compound exists, as shown in the formula (3), the group B is a connecting group or a heteroatom, the connecting group is alkyl, substituted alkyl containing heteroatom, aryl, substituted aryl or substituted aryl containing heteroatom, and the heteroatom is boron, silicon, phosphorus, nitrogen or sulfur atom; r5Selected from hydrogen, halogen, linear or branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl, alkylaryl or fused ring aryl;
when the groups B and R5When the substituent B is absent, as shown in the formula (4), the group B is a connecting group or a heteroatom, the connecting group is alkyl, substituted alkyl containing a heteroatom, aryl, substituted aryl or substituted aryl containing a heteroatom, and the heteroatom is boron, silicon, phosphorus, nitrogen or sulfur atom;
R1、R2、R3、R4each independently selected from phenyl, substituted phenyl, phenyl derivatives or substituted phenyl derivatives;
the aluminum-containing compound is at least one selected from the group consisting of an alkylaluminum compound, an aluminoxane compound, a modified aluminoxane compound, and a product of interaction of an alkylaluminum compound with an aluminoxane compound or a modified aluminoxane compound.
12. The process for the tetramerization of ethylene according to claim 11,
the connecting group is methylene, dimethylmethylene, 1, 2-ethane, 1, 2-phenylene, 1, 2-propane, 1, 2-catechol or 1, 2-dimethylhydrazine;
R5is isopropyl, tert-butyl, cyclohexyl or aryl;
R1、R2、R3、R4each independently is benzyl, phenyl, tolyl, xylyl, 2, 4, 6-trimethylphenyl, 3, 5-xylylmethyl, bisphenyl, naphthyl, anthracenyl, methoxy, ethoxy, phenoxy, tolyloxy, dimethylamino, methylethylamino, thiophenyl, pyridyl, thioethyl, thiophenoxy, trimethylsilyl, methyl, ethyl, vinyl, propyl, butyl, propenyl, propynyl, cyclomethinyl, or the likePentyl, cyclohexyl, ferrocenyl, tetrahydrofuranyl.
13. The process for the tetramerisation of ethylene according to claim 11, wherein the alkyl aluminum compound is a trialkyl aluminum compound, an alkyl aluminum halide, an alkyl aluminum hydride or an alkyl aluminum polychloride; the aluminoxane compound is selected from at least one of methylaluminoxane, ethylaluminoxane and isobutylaluminoxane; the modified aluminoxane compound is selected from at least one of modified methylaluminoxane, modified ethylaluminoxane and modified isobutylaluminoxane.
14. The process for the tetramerization of ethylene according to claim 13,
R1、R2、R3、R4each independently is phenyl, substituted phenyl, xylyl, bisphenyl, naphthyl, thiophenyl, or ethyl;
the trialkyl aluminum compound is selected from at least one of triethyl aluminum, triisobutyl aluminum, tri-n-butyl aluminum, tri-n-hexyl aluminum and tri-n-octyl aluminum; the alkyl aluminum double chloride is diethyl aluminum chloride AlEt2Cl or ethyl aluminum sesqui Al2Et3Cl3。
15. The method of claim 1, wherein the reaction system comprises an inert solvent selected from at least one of an alkane selected from at least one of n-hexane, methylcyclohexane, cyclohexane, heptane, and decane, an aromatic hydrocarbon, a halogenated hydrocarbon, and an alkene; the aromatic hydrocarbon is selected from at least one of benzene, toluene, xylene and cumene; the olefin is at least one selected from butene-1, hexene-1 and octene-1.
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| CN101855015A (en) * | 2007-11-28 | 2010-10-06 | 林德股份公司 | Catalyst composition and process for oligomerization of ethylene |
| CN110785391A (en) * | 2017-06-16 | 2020-02-11 | Sk新技术株式会社 | Method for preventing fouling and method for oligomerizing olefins |
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| US20060229480A1 (en) * | 2002-12-20 | 2006-10-12 | Kevin Blann | Tetramerization of olefins |
| CN101855015A (en) * | 2007-11-28 | 2010-10-06 | 林德股份公司 | Catalyst composition and process for oligomerization of ethylene |
| CN110785391A (en) * | 2017-06-16 | 2020-02-11 | Sk新技术株式会社 | Method for preventing fouling and method for oligomerizing olefins |
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