CN111408404A - Catalyst composition, preparation method thereof and application thereof in reaction for synthesizing 1-butene through selective dimerization of ethylene - Google Patents
Catalyst composition, preparation method thereof and application thereof in reaction for synthesizing 1-butene through selective dimerization of ethylene Download PDFInfo
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- CN111408404A CN111408404A CN201910007609.4A CN201910007609A CN111408404A CN 111408404 A CN111408404 A CN 111408404A CN 201910007609 A CN201910007609 A CN 201910007609A CN 111408404 A CN111408404 A CN 111408404A
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- ether
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- 239000000203 mixture Substances 0.000 title claims abstract description 54
- 239000003054 catalyst Substances 0.000 title claims abstract description 45
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 36
- 238000006471 dimerization reaction Methods 0.000 title claims abstract description 33
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000005977 Ethylene Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 230000002194 synthesizing effect Effects 0.000 title abstract description 7
- -1 ether compound Chemical class 0.000 claims abstract description 107
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000654 additive Substances 0.000 claims abstract description 23
- 230000000996 additive effect Effects 0.000 claims abstract description 23
- 239000002879 Lewis base Substances 0.000 claims abstract description 22
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 22
- 150000007527 lewis bases Chemical class 0.000 claims abstract description 22
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 150000001399 aluminium compounds Chemical class 0.000 claims abstract 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 60
- 150000001875 compounds Chemical class 0.000 claims description 16
- 239000010936 titanium Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 13
- PJUOHDQXFNPPRF-UHFFFAOYSA-N 2,6-diphenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=N1 PJUOHDQXFNPPRF-UHFFFAOYSA-N 0.000 claims description 12
- 239000004305 biphenyl Substances 0.000 claims description 10
- 239000004215 Carbon black (E152) Substances 0.000 claims description 9
- 229930195733 hydrocarbon Natural products 0.000 claims description 9
- 150000002430 hydrocarbons Chemical class 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 claims description 4
- IIYSNNBEZBAQCQ-UHFFFAOYSA-N 1-butylpyrrole Chemical compound CCCCN1C=CC=C1 IIYSNNBEZBAQCQ-UHFFFAOYSA-N 0.000 claims description 4
- ARGCQEVBJHPOGB-UHFFFAOYSA-N 2,5-dihydrofuran Chemical compound C1OCC=C1 ARGCQEVBJHPOGB-UHFFFAOYSA-N 0.000 claims description 4
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 claims description 4
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 claims description 4
- HWWYDZCSSYKIAD-UHFFFAOYSA-N 3,5-dimethylpyridine Chemical compound CC1=CN=CC(C)=C1 HWWYDZCSSYKIAD-UHFFFAOYSA-N 0.000 claims description 4
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 claims description 4
- HJKGBRPNSJADMB-UHFFFAOYSA-N 3-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CN=C1 HJKGBRPNSJADMB-UHFFFAOYSA-N 0.000 claims description 4
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 claims description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 4
- KYMVBVBRCRFHIE-UHFFFAOYSA-N ethane-1,2-diimine Chemical compound N=CC=N KYMVBVBRCRFHIE-UHFFFAOYSA-N 0.000 claims description 4
- 125000005842 heteroatom Chemical group 0.000 claims description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 4
- 150000002460 imidazoles Chemical class 0.000 claims description 4
- 150000002466 imines Chemical class 0.000 claims description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 229920000768 polyamine Polymers 0.000 claims description 4
- 229920000570 polyether Polymers 0.000 claims description 4
- 239000001294 propane Substances 0.000 claims description 4
- 150000003222 pyridines Chemical class 0.000 claims description 4
- 150000003233 pyrroles Chemical class 0.000 claims description 4
- SMUQFGGVLNAIOZ-UHFFFAOYSA-N quinaldine Chemical group C1=CC=CC2=NC(C)=CC=C21 SMUQFGGVLNAIOZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000003248 quinolines Chemical class 0.000 claims description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical group CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 4
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical group CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- VDFVNEFVBPFDSB-UHFFFAOYSA-N 1,3-dioxane Chemical compound C1COCOC1 VDFVNEFVBPFDSB-UHFFFAOYSA-N 0.000 claims description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 2
- MCMFEZDRQOJKMN-UHFFFAOYSA-N 1-butylimidazole Chemical compound CCCCN1C=CN=C1 MCMFEZDRQOJKMN-UHFFFAOYSA-N 0.000 claims description 2
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical group CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 2
- UWKQJZCTQGMHKD-UHFFFAOYSA-N 2,6-di-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=N1 UWKQJZCTQGMHKD-UHFFFAOYSA-N 0.000 claims description 2
- NOIXNOMHHWGUTG-UHFFFAOYSA-N 2-[[4-[4-pyridin-4-yl-1-(2,2,2-trifluoroethyl)pyrazol-3-yl]phenoxy]methyl]quinoline Chemical compound C=1C=C(OCC=2N=C3C=CC=CC3=CC=2)C=CC=1C1=NN(CC(F)(F)F)C=C1C1=CC=NC=C1 NOIXNOMHHWGUTG-UHFFFAOYSA-N 0.000 claims description 2
- PCFUWBOSXMKGIP-UHFFFAOYSA-N 2-benzylpyridine Chemical compound C=1C=CC=NC=1CC1=CC=CC=C1 PCFUWBOSXMKGIP-UHFFFAOYSA-N 0.000 claims description 2
- MTAODLNXWYIKSO-UHFFFAOYSA-N 2-fluoropyridine Chemical compound FC1=CC=CC=N1 MTAODLNXWYIKSO-UHFFFAOYSA-N 0.000 claims description 2
- OKAMTPRCXVGTND-UHFFFAOYSA-N 2-methoxyoxolane Chemical compound COC1CCCO1 OKAMTPRCXVGTND-UHFFFAOYSA-N 0.000 claims description 2
- IWTFOFMTUOBLHG-UHFFFAOYSA-N 2-methoxypyridine Chemical compound COC1=CC=CC=N1 IWTFOFMTUOBLHG-UHFFFAOYSA-N 0.000 claims description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 2
- JTZSFNHHVULOGJ-UHFFFAOYSA-N 3-(trifluoromethyl)pyridine Chemical compound FC(F)(F)C1=CC=CN=C1 JTZSFNHHVULOGJ-UHFFFAOYSA-N 0.000 claims description 2
- LJPCNSSTRWGCMZ-UHFFFAOYSA-N 3-methyloxolane Chemical compound CC1CCOC1 LJPCNSSTRWGCMZ-UHFFFAOYSA-N 0.000 claims description 2
- OFDVABAUFQJWEZ-UHFFFAOYSA-N 3-pyridin-3-ylpyridine Chemical compound C1=CN=CC(C=2C=NC=CC=2)=C1 OFDVABAUFQJWEZ-UHFFFAOYSA-N 0.000 claims description 2
- XQABVLBGNWBWIV-UHFFFAOYSA-N 4-methoxypyridine Chemical compound COC1=CC=NC=C1 XQABVLBGNWBWIV-UHFFFAOYSA-N 0.000 claims description 2
- 239000005725 8-Hydroxyquinoline Substances 0.000 claims description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical class N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- BUDQDWGNQVEFAC-UHFFFAOYSA-N Dihydropyran Chemical compound C1COC=CC1 BUDQDWGNQVEFAC-UHFFFAOYSA-N 0.000 claims description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 2
- UQFQONCQIQEYPJ-UHFFFAOYSA-N N-methylpyrazole Chemical group CN1C=CC=N1 UQFQONCQIQEYPJ-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N anhydrous quinoline Natural products N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 2
- 229940111121 antirheumatic drug quinolines Drugs 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- ZDZHCHYQNPQSGG-UHFFFAOYSA-N binaphthyl group Chemical group C1(=CC=CC2=CC=CC=C12)C1=CC=CC2=CC=CC=C12 ZDZHCHYQNPQSGG-UHFFFAOYSA-N 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 239000001273 butane Substances 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 2
- 239000001282 iso-butane Substances 0.000 claims description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 2
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 claims description 2
- 229940078552 o-xylene Drugs 0.000 claims description 2
- 229960003540 oxyquinoline Drugs 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- GGHDAUPFEBTORZ-UHFFFAOYSA-N propane-1,1-diamine Chemical group CCC(N)N GGHDAUPFEBTORZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000003217 pyrazoles Chemical class 0.000 claims description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 2
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- HVZJRWJGKQPSFL-UHFFFAOYSA-N tert-Amyl methyl ether Chemical compound CCC(C)(C)OC HVZJRWJGKQPSFL-UHFFFAOYSA-N 0.000 claims description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 2
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims 1
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- 239000004411 aluminium Substances 0.000 claims 1
- 125000004430 oxygen atom Chemical group O* 0.000 claims 1
- 239000004698 Polyethylene Substances 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 10
- 229920000573 polyethylene Polymers 0.000 abstract description 10
- 239000000047 product Substances 0.000 description 10
- 239000012298 atmosphere Substances 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000003857 carboxamides Chemical class 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0201—Oxygen-containing compounds
- B01J31/0204—Ethers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0201—Oxygen-containing compounds
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- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
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Abstract
The present invention relates to a catalyst composition comprising a titanium compound, an aluminium compound and a lewis base type additive; wherein the Lewis base type additive comprises an ether compound and an amine compound. The invention also relates to a preparation method of the catalyst composition, which comprises the step of mixing the titanium compound, the aluminum compound, the ether compound and the amine compound to form the catalyst composition. In addition, the invention also relates to the application of the catalyst composition in the reaction of synthesizing 1-butene by ethylene dimerization. The invention can not only obtain higher 1-butene selectivity and polyethylene content approaching zero in the product, but also has higher catalyst activity and C4 content in the product, and has rapid reaction, stable operation and good repeatability.
Description
Technical Field
The invention belongs to the technical field of polymer synthesis, and particularly relates to a catalyst composition, a preparation method thereof and application thereof in reaction for synthesizing 1-butene through selective dimerization of ethylene.
Background
The catalytic systems reported so far for the selective dimerization of ethylene to 1-butene comprise catalytic systems based on vanadium, iron or cobalt, tungsten, tantalum, nickel, titanium. Of these systems, titanium-based catalytic systems are the best. Patent US2943125 to ziegler et al discloses a process for the dimerization of ethylene to 1-butene using a catalyst obtained by mixing a trialkylaluminum with a zirconium tetraalkoxide. During this reaction, a certain amount of high molecular weight polymer (i.e., polyethylene) is also formed; this has a rather detrimental effect on the implementation of the method. Patent CN1031364A discloses a process for the preparation of butene-1 comprising dimerization of ethylene in the presence of titanium tetraalkoxide-trialkylaluminum in a hydrocarbon solvent of a catalytic system, followed by distillation of the reactants resulting from the dimerization, in the presence of a compound selected from the group consisting of: mono-and diols, aliphatic and cyclic ethers, aliphatic ketones, carboxamides. The catalyst used in the method is expensive, and in the generated product, the selectivity of the butene-1 is low, only 70 percent, and a large amount of butene-2 is contained.
Therefore, there is a need to develop a catalyst composition with high activity and selectivity and low polyethylene content in the product, a preparation method thereof, and an application thereof in the reaction of ethylene selective dimerization to 1-butene.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a catalyst composition, a preparation method thereof and an application thereof in a reaction for synthesizing 1-butene by selective dimerization of ethylene, aiming at the defects of the prior art. The inventors of the present invention have found through repeated experimental studies that, when a mixture of an ether-based compound and an amine-based compound is used as a lewis base additive, a catalyst composition prepared without preparing a pre-prepared mixture with an aluminum compound in advance, i.e., a catalyst composition prepared in situ from components including a titanium compound, an aluminum compound, and a lewis base additive, is used in the selective dimerization of ethylene to 1-butene, the production of polyethylene can be minimized to a threshold value below the detection limit, while the dimerization activity of ethylene and the C4 content in the product are greatly improved.
To this end, a first aspect of the invention provides a catalyst composition comprising a titanium compound, an aluminum compound and a lewis base-type additive; wherein the Lewis base type additive comprises an ether compound and an amine compound.
In some embodiments, the ether compound is selected from the group consisting of monoethers and polyethers.
Preferably, the monoether is selected from one or more of diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, 2-methoxy-2-methylpropane, 2-methoxy-2-methylbutane, 2-methoxy-2, 2 propane, bis (ethyl-2-hexyloxy) -2,2 propane, 2, 5-dihydrofuran, tetrahydrofuran, 2-methoxytetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, 2, 3-dihydropyran, tetrahydropyran, and benzofuran. The polyether is selected from one or more of 1, 3-dioxane, 1, 4-dioxane, dimethoxyethane, bis (2-methoxyethyl) ether, glyme, and diglyme.
In other embodiments, the amine compound is selected from the group consisting of C, C1-C5Alkyl of (C)1-C5Alkoxy, halogen, C6-C12Aryl substituted or unsubstituted monoamines, polyamines, imines, pyridines, bipyridines, quinolines, imidazoles, pyrroles and pyrazoles.
Preferably, the substituted monoamine is selected from trimethylamine and/or triethylamine. The substituted polyamine is selected from propane diamine and/or butane diamine. The substituted imine is selected from the group consisting of benzoylimine, N '-dimethyl-ethane-1, 2-diimine, N' -diphenyl-butane-2, 3-diimine, N '-di-tert-butyl-butane-2, 3-diimine, N' -bis- (dimethyl-2, 6-diphenyl) ethane-1, 2-diimine, N '-bis- (diisopropyl-2, 6-diphenyl) ethane-1, 2-diimine, N' -bis- (dimethyl-2, 6-diphenyl) -butane-2, 3-diimine, and N, one or more of N' -bis- (diisopropyl-2, 6-diphenyl) -butane-2, 3 diimine. The substituted pyridine is selected from one or more of 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2-methoxypyridine, 3-methoxypyridine, 4-methoxypyridine, 2-fluoropyridine, 3-trifluoromethylpyridine, 2-phenylpyridine, 3-phenylpyridine, 2-benzylpyridine, 3, 5-dimethylpyridine, 2, 6-di-tert-butylpyridine and 2, 6-diphenylpyridine. The unsubstituted bipyridine is selected from one or more of 1,1 ' -bipyridine, 2 ' -bipyridine and 3,3 ' -bipyridine. The substituted quinoline is selected from 2-methylquinoline and/or 8-hydroxyquinoline. The substituted imidazole is selected from N-methylimidazole and/or N-butylimidazole. The substituted pyrroles are selected from N-methyl pyrrole and/or N-butyl pyrrole. The substituted pyrazole is N-methylpyrazole.
In some embodiments, the molar ratio of the ether compound to the amine compound is (0.05-20):1, preferably (0.2-10): 1.
The inventor of the invention researches and discovers that when a mixture of an ether compound and an amine compound is used as a Lewis base additive for selective dimerization of ethylene to 1-butene, the two compounds have synergistic effect, so that the activity of the catalyst and the content of C4 in a product are higher, and simultaneously, the content of polyethylene in the product is lower.
In some embodiments, the titanium compound is a compound of formula (I),
Ti(OR)4(I)
in the general formula (I), R is selected from C which is substituted or unsubstituted by a substituent containing or not containing a hetero atom2-C30Straight or branched alkanes or C6-C30Aryl of (a); preferably the heteroatoms are selected from nitrogen, phosphorus, sulfur and oxygen atomsOne or more of (a).
In some specific embodiments, in formula (I), R is selected from the group consisting of tetraethyl, tetraisopropyl, tetra-n-butyl, tetra-2-ethylhexyl, phenyl, 2-methylphenyl, 2, 6-dimethylphenyl, 2,4, 6-trimethylphenyl, 4-methylphenyl, 2-phenylphenyl, 2, 6-diphenylphenyl, 2,4, 6-triphenylphenyl, 4-phenylphenyl, 2-tert-butyl-6-phenylphenyl, 2, 4-di-tert-butyl-6-phenylphenyl, 2, 6-diisopropylphenyl, 2, 6-di-tert-butylphenyl, 4-methyl-2, 6-di-tert-butylphenyl, 2, 6-dichloro-4-tert-butylphenyl and 2, 6-dibromo-4-tert-butylphenyl, One or more of biphenyl, binaphthyl, and 1, 8-naphthalene-diyl.
In some embodiments, the aluminum compound is selected from a hydrocarbylaluminum compound and/or an aluminoxane compound. Optionally, the hydrocarbyl group in the hydrocarbylaluminum compound is substituted with a halogen, preferably the halogen is selected from chlorine or bromine. In some more preferred embodiments, the hydrocarbylaluminum compound is a trihydrocarbylaluminum compound. In some further preferred embodiments, the hydrocarbyl aluminum compound is triethylaluminum.
In some embodiments, the ratio of the number of moles of the lewis base additive to the number of moles of aluminum in the aluminum compound is (0.5-20):1, preferably (0.5-5.3):1, more preferably (1-5): 1.
In other specific embodiments, the molar ratio of the aluminum compound to the titanium compound, calculated as aluminum to titanium, is (1-100):1, preferably (1-30):1, more preferably (1-10): 1.
In a second aspect, the present invention provides a method for preparing the catalyst composition according to the first aspect, which comprises mixing a titanium compound, an aluminum compound, an ether compound and an amine compound to form the catalyst composition.
In some embodiments, the ether compound and the amine compound are added separately as a single component, or the ether compound and the amine compound are premixed and then added.
The method adopts the titanium compound, the aluminum compound and the Lewis base type additive containing the ether compound and the amine compound to prepare the catalyst composition in situ, and the catalyst composition prepared in situ has the advantages that: the generation of active species of the catalyst is facilitated; the method is beneficial to reducing the steps of synthesizing the catalyst and reducing the synthesis cost; is beneficial to the smooth initiation of the reaction.
In some embodiments, the titanium compound or any of the titanium compounds is used as a mixture with a hydrocarbon solvent. Preferably, the volume ratio of hydrocarbon solvent to the titanium compound in the mixture is (1-100):1, preferably (10-75): 1.
In some preferred embodiments, the hydrocarbon solvent is selected from C substituted or unsubstituted with halogen1-C7Alkane, C3-C7Cycloalkane of (2)6-C20One or more of (a) aromatic hydrocarbons.
In some more preferred embodiments, the hydrocarbon solvent is selected from one or more of n-butane, isobutane, n-hexane, n-heptane, cyclohexane, benzene, toluene, o-xylene, mesitylene, and ethylbenzene.
In a third aspect, the present invention provides the use of a catalyst composition according to the first aspect of the present invention or a process for the preparation of a catalyst composition according to the second aspect of the present invention in a reaction for the selective dimerization of ethylene to 1-butene.
In some embodiments, the dimerization temperature is 20 to 180 ℃, preferably 40 to 140 ℃. The total pressure of the dimerization reaction is 0.5 to 20MPa, preferably 0.5 to 15MPa, and more preferably 1 to 10 MPa. The dimerization reaction time is 10-120min, preferably 30-60 min.
In the present invention, the ethylene dimerization reaction is preferably performed under a lower total pressure, so that not only is the controllability of the dimerization reaction stronger, but also the content of polyethylene PE in the dimerization reaction product is ensured to be lower.
Compared with the prior art, the invention has the following beneficial effects:
when the mixture of the ether compound and the amine compound is used as the Lewis base type additive, the catalyst composition prepared on the premise of not preparing a prefabricated mixture with an aluminum compound in advance, namely the catalyst composition prepared by mixing the components including the titanium compound, the aluminum compound and the Lewis base type additive in situ is used for the reaction of synthesizing 1-butene through selective dimerization of ethylene, the generation of polyethylene can be minimized to be lower than the threshold value of a detection limit, and simultaneously, the dimerization activity of the ethylene and the content of C4 in a product are greatly improved. Moreover, the preparation method of the catalyst composition is simple, the ethylene dimerization reaction is rapid, the operation is stable, the repeatability is good, and the catalyst composition is more beneficial to industrial popularization and application.
Detailed Description
In order that the present invention may be more readily understood, the following detailed description of the invention is given by way of example only, and is not intended to limit the scope of the invention.
The test method or the calculation method provided by the invention is as follows:
the ethylene dimerization product is firstly qualitatively analyzed by combining gas chromatography and mass spectrometry to determine the peak quality of each product. Samples were routinely made for quantitative analysis by gas chromatography. The gas chromatograph is an Agilent 7890A, SE-54 type chromatographic column with a column length of 30m and an inner diameter of 0.2mm, the carrier gas is high-purity nitrogen, and the FID detector is adopted. The temperature program of the chromatogram is: the initial temperature is 40 ℃, the mixture stays for 3 minutes, then the temperature is raised to 50 ℃ at the speed of 30 ℃/min, the mixture stays for 1 minute, and then the temperature is raised to 280 ℃ at the speed of 40 ℃/min, and the mixture stays for 15 minutes.
(1) Method for calculating the catalyst activity (in g/gTi. h):
(Note: the molar mass of titanium is 48g/mol)
(2) Method for calculating C4 content (%) and 1-butene selectivity (%):
(3) the content of PE was measured by weighing the reaction solution after filtration, drying and drying.
Examples
Example 1
The dimerization reaction was carried out in a stainless steel reaction vessel having an effective volume of 300m L, equipped with mechanically driven stirring paddles and jacketed by water circulation to adjust the temperature, under an ethylene atmosphere and at ambient temperature, 50m L n-heptane and a solution of 5m L of titanium tetrabutoxide compound in n-heptane at a concentration of 0.085 mol/L, 7m L of AlEt at a concentration of 0.238 mol/L3In heptane (1m L AlEt with a density of 0.84g/m L3Dissolved in 30m L n-heptane) and a mixture of 0.39g 1, 4-dioxane (4.44mmol) and 1.03g 2, 6-diphenylpyridine (4.44mmol) were added to the reactor, and the dimerization of ethylene to 1-butene was carried out at a temperature of 55 ℃ and a pressure of 10MPa after 30min of reaction, the feed of ethylene was stopped, a sample was taken and the gas was analyzed by gas chromatography, the liquid phase in the reactor was then weighed, the polymer (if present) was recovered, dried and weighed, the specific reaction conditions and the results obtained are shown in table 1, the activity of which is the mass.% C of ethylene consumed per hour per gram of the titanium initially introduced4Corresponding to the amount of olefin containing 4 carbon atoms in the total product. % C4 =1Is shown in C4Selectivity to 1-butene in the fraction. The amount of polyethylene (% PE) corresponds to the mass of polyethylene recovered.
Example 2
The same as in example 1 except that 3.3m L0.085.085 mol/L of an n-heptane solution of titanium tetrabutoxide compound was added so that the Al/Ti molar ratio was 6 specific reaction conditions and results obtained are shown in Table 1.
Example 3
The same as in example 1, except that 3.3m L0.085.085 mol/L of an n-heptane solution of titanium tetrabutoxide compound was added so that the Al/Ti molar ratio was 6 while controlling the reaction time to 60 min.
Example 4
The same as in example 1, except that 3.3m L0.085.085 mol/L mol of an n-heptane solution of titanium tetrabutoxide compound was added so that the Al/Ti molar ratio was 6 while controlling the reaction time to 120 min.
Example 5
The same as example 1 except that 3.3m L0.085.085 mol/L of an n-heptane solution of titanium tetrabutoxide compound was added so that the Al/Ti molar ratio was 6, and 0.65g of 1, 4-dioxane (7.4mmol) and 0.34g of 2, 6-diphenylpyridine (1.48mmol) were added so that the molar ratio of 1, 4-dioxane to 2, 6-diphenylpyridine was 5:1 while controlling the reaction time to 60min specific reaction conditions and results obtained are shown in table 1.
Example 6
As in example 1, 3.3m L0.085.085 mol/L of an n-heptane solution of titanium tetrabutoxide compound was added so that the Al/Ti molar ratio was 6, and 0.13g of 1, 4-dioxane (1.48mmol) and 1.71g of 2, 6-diphenylpyridine (7.4mmol) were added so that the molar ratio of 1, 4-dioxane to 2, 6-diphenylpyridine was 0.2:1, while controlling the reaction time to 60 min. the specific reaction conditions and results obtained are shown in Table 1.
Example 7
The same as example 1 except that 3.3m L0.085 mol/L of an n-heptane solution of titanium tetrabutoxide compound was added so that the Al/Ti molar ratio was 6, and 0.73g 1, 4-dioxane (8.325mmol) and 0.13g2, 6-diphenylpyridine (0.555mmol) were added so that the molar ratio of 1, 4-dioxane to 2, 6-diphenylpyridine was 15:1 while controlling the reaction time to 60min specific reaction conditions and results obtained are shown in table 1.
Example 8
The same as in example 1 except that 0.66m L0.085 of a 0.085 mol/L n-heptane solution of titanium tetrabutoxide compound was added so that the Al/Ti molar ratio was 30 specific reaction conditions and results obtained are shown in Table 1.
Example 9
The same as in example 1 except that "a mixture of 0.39g of 1, 4-dioxane (4.44mmol) and 1.03g of 2, 6-diphenylpyridine (4.44 mmol)" in example 1 was replaced with "a mixture of 0.32g of tetrahydrofuran (4.44mmol) and 0.36g of n-methylpyrrole (4.44 mmol)". Specific reaction conditions and results obtained are shown in table 1.
Comparative example 1
The same as in example 1 except that the Lewis base type additive used was 1, 4-dioxane only, and the amount of 1, 4-dioxane added was 8.88 mmol. Specific reaction conditions and results obtained are shown in table 1.
Comparative example 2
The same as in example 1, except that only 2, 6-diphenylpyridine was used as the Lewis base type additive, and that the amount of 2, 6-diphenylpyridine added was 8.88 mmol. Specific reaction conditions and results obtained are shown in table 1.
Comparative example 3
AlEt having dissolved a concentration of 0.238 mol/L of 7m L was added under an inert atmosphere3In heptane (1m L AlEt with a density of 0.84g/m L3Dissolved in 30m L n-heptane) was introduced into a Schlenk flask, 0.78g of 1, 4-dioxane (8.88mmol) was added to the Schlenk flask described above, and the solution was stirred under a nitrogen atmosphere at room temperature for about 1 hour to form a lewis base additive with AlEt3The pre-formed mixture of (1).
The dimerization reaction was carried out in a stainless steel reaction vessel of effective volume 300m L, equipped with mechanically driven stirring paddles, jacketed by water circulation to adjust the temperature, 50m L n-heptane and 5m L0.085 mol/L of titanium tetrabutoxide in n-heptane were added to the reaction vessel under an ethylene atmosphere and at ambient temperature, the required amounts of Lewis base type additive and AlEt were introduced under ethylene pressure once the temperature of the reaction vessel reached 55 deg.C3The pre-formed mixture of (1). The ethylene pressure was maintained at 10MPa and the temperature at 55 ℃. After 30min of reaction, the ethylene feed was stopped and a sample was taken and the gas was analysed by gas chromatography. The liquid phase in the reactor is then weighed, the polymer (if present) recovered, dried and weighed. Specific reaction conditions and results obtained are shown in table 1.
Comparative example 4
AlEt having dissolved a concentration of 0.238 mol/L of 7m L was added under an inert atmosphere3In heptane (1m L Al with a density of 0.84g/m LEt3Dissolved in 30m L n-heptane) was introduced into a Schlenk flask, 2.05g of 2, 6-diphenylpyridine (8.88mmol) was further added to the above-mentioned Schlenk flask, and the solution was stirred under a nitrogen atmosphere at ordinary temperature for about 1 hour to form a Lewis base type additive and AlEt3The pre-formed mixture of (1).
The dimerization reaction was carried out in a stainless steel reaction vessel of effective volume 300m L, equipped with mechanically driven stirring paddles, jacketed by water circulation to adjust the temperature, 50m L n-heptane and 5m L0.085 mol/L of titanium tetrabutoxide in n-heptane were added to the reaction vessel under an ethylene atmosphere and at ambient temperature, the required amounts of Lewis base type additive and AlEt were introduced under ethylene pressure once the temperature of the reaction vessel reached 55 deg.C3The pre-formed mixture of (1). The ethylene pressure was maintained at 10MPa and the temperature at 55 ℃. After 30min of reaction, the ethylene feed was stopped and a sample was taken and the gas was analysed by gas chromatography. The liquid phase in the reactor is then weighed, the polymer (if present) recovered, dried and weighed. Specific reaction conditions and results obtained are shown in table 1.
As can be seen from table 1, when the catalyst composition using the lewis base additive comprising the ether compound and the amine compound according to the present invention is used in the reaction for selective dimerization of ethylene to 1-butene, the catalyst activity and the content of C4 in the product are both made higher while ensuring that the production of polyethylene is minimized to be below the threshold of detection limit, compared to the catalyst composition using a single ether compound or a single amine compound as the lewis base additive. In addition, compared with the prior art, the method of the invention omits the step of premixing the aluminum compound and the Lewis base type additive, is more beneficial to the generation of catalyst active species and the smooth initiation of reaction, further improves the catalyst activity and obtains better effect.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. A catalyst composition comprising a titanium compound, an aluminum compound, and a lewis base type additive; wherein the Lewis base type additive comprises an ether compound and an amine compound.
2. The catalyst composition according to claim 1, wherein the ether compound is selected from monoethers and/or polyethers;
preferably, the monoether is selected from one or more of diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, 2-methoxy-2-methylpropane, 2-methoxy-2-methylbutane, 2-methoxy-2, 2 propane, bis (ethyl-2-hexyloxy) -2,2 propane, 2, 5-dihydrofuran, tetrahydrofuran, 2-methoxytetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, 2, 3-dihydropyran, tetrahydropyran, and benzofuran; the polyether is selected from one or more of 1, 3-dioxane, 1, 4-dioxane, dimethoxyethane, bis (2-methoxyethyl) ether, glyme and diglyme;
the amine compound is selected from C1-C5Alkyl of (C)1-C5Alkoxy, halogen, C6-C12Aryl substituted or unsubstituted monoamines, polyamines, imines, pyridines, bipyridines, quinolines, imidazoles, pyrroles and pyrazoles;
preferably, the substituted monoamine is selected from trimethylamine and/or triethylamine; the substituted polyamine is selected from propane diamine and/or butane diamine; the substituted imine is selected from the group consisting of benzoylimine, N '-dimethyl-ethane-1, 2-diimine, N' -diphenyl-butane-2, 3-diimine, N '-di-tert-butyl-butane-2, 3-diimine, N' -bis- (dimethyl-2, 6-diphenyl) ethane-1, 2-diimine, N '-bis- (diisopropyl-2, 6-diphenyl) ethane-1, 2-diimine, N' -bis- (dimethyl-2, 6-diphenyl) -butane-2, 3-diimine, and N, one or more of N' -bis- (diisopropyl-2, 6-diphenyl) -butane-2, 3 diimine; the substituted pyridine is selected from one or more of 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2-methoxypyridine, 3-methoxypyridine, 4-methoxypyridine, 2-fluoropyridine, 3-trifluoromethylpyridine, 2-phenylpyridine, 3-phenylpyridine, 2-benzylpyridine, 3, 5-dimethylpyridine, 2, 6-di-tert-butylpyridine and 2, 6-diphenylpyridine; the unsubstituted bipyridine is selected from one or more of 1,1 ' -bipyridine, 2 ' -bipyridine and 3,3 ' -bipyridine; the substituted quinoline is selected from 2-methylquinoline and/or 8-hydroxyquinoline; the substituted imidazole is selected from N-methylimidazole and/or N-butylimidazole; the substituted pyrrole is selected from N-methyl pyrrole and/or N-butyl pyrrole; the substituted pyrazole is N-methylpyrazole.
3. The catalyst composition according to claim 1 or 2, wherein the molar ratio of the ether compound to the amine compound is (0.05-20):1, preferably (0.2-10): 1.
4. The catalyst composition according to any of claims 1 to 3, characterized in that the titanium compound is a compound of the general formula (I),
Ti(OR)4(I)
in the general formula (I), R is selected from C which is substituted or unsubstituted by a substituent containing or not containing a hetero atom2-C30Straight or branched alkanes or C6-C30Aryl of (a); preferably the heteroatoms are selected from one or more of nitrogen, phosphorus, sulphur and oxygen atoms.
5. The catalyst composition according to claim 4, wherein in the general formula (I), R is selected from the group consisting of tetraethyl group, tetraisopropyl group, tetra-n-butyl group, tetra-2-ethylhexyl group, phenyl group, 2-methylphenyl group, 2, 6-dimethylphenyl group, 2,4, 6-trimethylphenyl group, 4-methylphenyl group, 2-phenylphenyl group, 2, 6-diphenylphenyl group, 2,4, 6-triphenylphenyl group, 4-phenylphenyl group, 2-tert-butyl-6-phenylphenyl group, 2, 4-di-tert-butyl-6-phenylphenyl group, 2, 6-diisopropylphenyl group, 2, 6-di-tert-butylphenyl group, 4-methyl-2, 6-di-tert-butylphenyl group, 2, 6-dichloro-4-tert-butylphenyl group, 2, 6-dibromo-4-tert-butylphenyl, biphenyl, binaphthyl and 1, 8-naphthalene-diyl.
6. The catalyst composition according to any one of claims 1 to 5, characterized in that the aluminium compound is selected from hydrocarbylaluminium compounds and/or aluminoxane compounds; optionally, the hydrocarbyl group in the hydrocarbylaluminum compound is substituted with a halogen, preferably the halogen is selected from chlorine or bromine; more preferably, the hydrocarbylaluminum compound is a trihydrocarbylaluminum compound; further preferably, the hydrocarbyl aluminum compound is triethylaluminum.
7. The catalyst composition according to any one of claims 1 to 6, characterized in that the ratio of the number of moles of Lewis base additive to the number of moles of aluminium in the aluminium compound is (0.5-20) to 1, preferably (0.5-5.3) to 1, more preferably (1-5) to 1; and/or
The molar ratio of the aluminum compound to the titanium compound is (1-100):1, preferably (1-30):1, more preferably (1-10):1, in terms of aluminum: titanium.
8. A method of preparing the catalyst composition of any one of claims 1-7, comprising mixing a titanium compound, an aluminum compound, an ether compound, and an amine compound to form the catalyst composition.
9. The method according to claim 8, wherein the ether compound and the amine compound are added separately as a single component, or the ether compound and the amine compound are premixed and then added; and/or
Any one of the titanium compound and the aluminum compound is used as a mixture with a hydrocarbon solvent; preferably, the volume ratio of hydrocarbon solvent to the titanium compound in the mixture is (1-100) to 1, preferably (10-75) to 1;
preferably, the hydrocarbon solvent is selected from C substituted or unsubstituted by halogen1-C7Alkane, C3-C7Cycloalkane of (2)6-C20One or more of the aromatic hydrocarbons of (a); preferably, the hydrocarbon solvent is selected from one or more of n-butane, isobutane, n-hexane, n-heptane, cyclohexane, benzene, toluene, o-xylene, mesitylene and ethylbenzene.
10. Use of a catalyst composition according to any one of claims 1 to 7 or a method for preparing a catalyst composition according to claim 8 or 9 in a reaction for the selective dimerization of ethylene to 1-butene, wherein the dimerization reaction is carried out at a temperature of 20 to 180 ℃, preferably 40 to 140 ℃; the total pressure of the dimerization reaction is 0.5-20MPa, preferably 0.5-15MPa, and more preferably 1-10 MPa; the dimerization reaction time is 10-120min, preferably 30-60 min.
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