CN110201713B - 一种催化剂及其制备方法和在烯烃异构反应中的应用 - Google Patents
一种催化剂及其制备方法和在烯烃异构反应中的应用 Download PDFInfo
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- CN110201713B CN110201713B CN201910520057.7A CN201910520057A CN110201713B CN 110201713 B CN110201713 B CN 110201713B CN 201910520057 A CN201910520057 A CN 201910520057A CN 110201713 B CN110201713 B CN 110201713B
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- Prior art keywords
- catalyst
- reaction
- ionic liquid
- metal
- olefin
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- 239000003054 catalyst Substances 0.000 title claims abstract description 71
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 50
- 238000006317 isomerization reaction Methods 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000002608 ionic liquid Substances 0.000 claims abstract description 61
- 229910052751 metal Inorganic materials 0.000 claims abstract description 39
- 239000002184 metal Substances 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000010936 titanium Substances 0.000 claims abstract description 6
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052788 barium Inorganic materials 0.000 claims abstract description 5
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 5
- 239000011575 calcium Substances 0.000 claims abstract description 5
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 5
- 239000011651 chromium Substances 0.000 claims abstract description 5
- 239000010941 cobalt Substances 0.000 claims abstract description 5
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 239000010949 copper Substances 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 5
- 239000011777 magnesium Substances 0.000 claims abstract description 5
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 5
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 5
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 5
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 5
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 5
- 239000011701 zinc Substances 0.000 claims abstract description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract 3
- 238000006243 chemical reaction Methods 0.000 claims description 99
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 39
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 21
- 239000002994 raw material Substances 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 19
- 229910021645 metal ion Inorganic materials 0.000 claims description 15
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 15
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 14
- 230000035484 reaction time Effects 0.000 claims description 14
- 238000011068 loading method Methods 0.000 claims description 13
- QWXYZCJEXYQNEI-OSZHWHEXSA-N intermediate I Chemical compound COC(=O)[C@@]1(C=O)[C@H]2CC=[N+](C\C2=C\C)CCc2c1[nH]c1ccccc21 QWXYZCJEXYQNEI-OSZHWHEXSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 claims description 6
- 230000020477 pH reduction Effects 0.000 claims description 6
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 5
- GGQQNYXPYWCUHG-RMTFUQJTSA-N (3e,6e)-deca-3,6-diene Chemical compound CCC\C=C\C\C=C\CC GGQQNYXPYWCUHG-RMTFUQJTSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 3
- 229910001507 metal halide Inorganic materials 0.000 claims description 2
- 150000005309 metal halides Chemical group 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims 2
- ZSIAANIILFGLQH-UHFFFAOYSA-N C1(=CC=CC=C1)[ClH]P(=O)(Cl)[ClH]C1=CC=CC=C1 Chemical compound C1(=CC=CC=C1)[ClH]P(=O)(Cl)[ClH]C1=CC=CC=C1 ZSIAANIILFGLQH-UHFFFAOYSA-N 0.000 claims 1
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 11
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 66
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 28
- 238000005303 weighing Methods 0.000 description 16
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 15
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 11
- 238000005160 1H NMR spectroscopy Methods 0.000 description 11
- 238000004679 31P NMR spectroscopy Methods 0.000 description 11
- 238000000921 elemental analysis Methods 0.000 description 11
- 238000004949 mass spectrometry Methods 0.000 description 11
- 238000005406 washing Methods 0.000 description 11
- 239000004711 α-olefin Substances 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 9
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 8
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 8
- VAMFXQBUQXONLZ-UHFFFAOYSA-N n-alpha-eicosene Natural products CCCCCCCCCCCCCCCCCCC=C VAMFXQBUQXONLZ-UHFFFAOYSA-N 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 239000000395 magnesium oxide Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 4
- 229940106006 1-eicosene Drugs 0.000 description 4
- FIKTURVKRGQNQD-UHFFFAOYSA-N 1-eicosene Natural products CCCCCCCCCCCCCCCCCC=CC(O)=O FIKTURVKRGQNQD-UHFFFAOYSA-N 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 4
- 238000007323 disproportionation reaction Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 230000005311 nuclear magnetism Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical group CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 description 3
- LAAVYEUJEMRIGF-UHFFFAOYSA-N 2,4,4-trimethylpent-2-ene Chemical compound CC(C)=CC(C)(C)C LAAVYEUJEMRIGF-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
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- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000013067 intermediate product Substances 0.000 description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- -1 pentaerythritol tetrachloro, pentaerythritol Chemical compound 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- HPMGSGCDKVCZHC-UHFFFAOYSA-N 1,3-diiodo-2,2-bis(iodomethyl)propane Chemical compound ICC(CI)(CI)CI HPMGSGCDKVCZHC-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- AZFUOHYXCLYSQJ-UHFFFAOYSA-N [V+5].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O Chemical compound [V+5].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O AZFUOHYXCLYSQJ-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 229940069096 dodecene Drugs 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
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- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
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- 238000004451 qualitative analysis Methods 0.000 description 2
- DFCYEXJMCFQPPA-UHFFFAOYSA-N scandium(3+);trinitrate Chemical compound [Sc+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O DFCYEXJMCFQPPA-UHFFFAOYSA-N 0.000 description 2
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- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- PKXHXOTZMFCXSH-UHFFFAOYSA-N 3,3-dimethylbut-1-ene Chemical compound CC(C)(C)C=C PKXHXOTZMFCXSH-UHFFFAOYSA-N 0.000 description 1
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- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
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- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
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- 239000006227 byproduct Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
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- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 1
- 238000002451 electron ionisation mass spectrometry Methods 0.000 description 1
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- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000007037 hydroformylation reaction Methods 0.000 description 1
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- 239000011630 iodine Chemical group 0.000 description 1
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- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
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- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- RQIITWKDTBNDJW-UHFFFAOYSA-N trichloro(diphenyl)-$l^{5}-phosphane Chemical compound C=1C=CC=CC=1P(Cl)(Cl)(Cl)C1=CC=CC=C1 RQIITWKDTBNDJW-UHFFFAOYSA-N 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
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Abstract
Description
技术领域
本发明涉及一种催化剂及其制备方法,该催化剂可以作为烯烃双键异构反应的催化剂。
背景技术
双键异构化反应,也就是烯烃化合物中双键位置的转移,可以将相对价值较低或过剩的烯烃转化为更有价值或相对较少的异构体。
烯烃双键异构在工业化生产中有着非常重要的应用,比如乙烯与丁烯-2歧化生产丙烯过程中,需要将C4中的丁烯-1异构化为丁烯-2,二异丁烯与乙烯歧化生产3,3-二甲基-1-丁烯(辛己烯)过程中需要将2,4,4-三甲基1-戊烯异构化为2,4,4-三甲基-2-戊烯,乙烯齐聚生产α-烯烃的过程中,通常伴随有大量的异构体产生,需要通过双键异构化反应将内烯烃转化为α-烯烃,并且生产过程中需要将副产的长链α-烯烃异构化为内烯烃,然后与短链α-烯烃歧化,氢甲酰化反应中内烯烃位阻较大,反应速度远低于端位α-烯烃,通过双键异构将内烯烃转化为α-烯烃,将大大提高反应的效率,带来显著的经济效应。
碱土金属氧化物,氧化镁、氧化钙等,被报道在烯烃双键异构化反应中具有优异的催化性能,CN1511126使用的催化剂优选为高纯度氧化镁,烯烃异构化条件包括从约340到约500℃的温度。
CN104549212A公开了双键异构化催化剂的制备方法,依次包括如下步骤:1)将元素周期表ⅣA族元素所相应的盐、碱或氧化物溶于水中制成溶液I;2)将碱土金属相应的盐、碱或氧化物加入到溶液I制成溶液II;3)溶液II洗涤、抽滤后经干燥,焙烧得所需催化剂前驱体;4)对催化剂前驱体用卤素进行改性得到双键异构化催化剂。将上述异构化催化剂用于1-丁烯歧化制2-丁烯的方法,在反应温度200~400℃,反应压力1~4Mpa,1-丁烯质量空速0.1~20h-1的条件下,1-丁烯与所述的异构化催化剂接触反应生成2-丁烯。
CN104549295A涉及一种烯烃异构化催化剂,以重量份数计,包括以下组分:a)77-100份氧化镁;b)0.1-20份氧化钙;c)0.01-2份氧化铁;d)0-1份氧化镍,可用于烯烃异构化反应的工业生产。
CN1307552公开了用氧化硅-氧化铝负载的镍催化剂以最低程度骨架异构化将α-烯烃异构化成直链内烯的方法,其中氧化硅/氧化铝负载的镍催化剂用于在不明显增加支链烯烃含量的条件下使直链α-烯烃基本上完全异构成直链内烯烃。
CN1106367涉及含不超过20个碳原子的正烯烃的异构化的方法,它包括使含烯烃的进料与基于氧化铝的催化剂接触,所述氧化铝用明确定量的钛浸渍并用蒸汽处理。
目前关于烯烃异构的催化剂多为氧化铝、硅胶负载的氧化镁和过渡金属,这类催化剂表面会因为结焦等原因逐步丧失其反应活性,存在寿命时间短,活性低,反应条件苛刻的问题,为解决上述问题需要提供一种全新的催化剂满足催化剂寿命和高活性的反应要求。
发明内容
本发明的目的在于提供一种催化剂,该催化剂可以在较温和的工艺条件下高活性和高选择性的催化烯烃双键异构,且催化剂活性稳定,寿命时间长。
本发明的另一个目的在于提供所述的催化剂的制备方法。
本发明的再一个目的在于提供所述的催化剂在烯烃异构化反应中的应用。
为了实现上述发明目的,本发明采用的技术方案如下:
一种催化剂,包含离子液体和负载在其上的金属(金属以离子形式存在,与磺酸根结合),所述的离子液体结构如下:
其中,n=3或4,X-为Cl-,H2PO4 -,HSO4 -,CF3SO3 -或CF3COO-,优选Cl-,HSO4 -或CF3SO3 -。
本发明的催化剂中,负载的金属为镁,钙,锶,钡,钪,钛,钒,铬,锰,铁,钴,镍,铜,锌中的一种或多种。
本发明催化剂的制备方法,包含以下步骤:
离子液体的制备:(1)采用季戊四卤化物(例如:季戊四氯、季戊四溴或季戊四碘)与丁基锂反应,优选投料摩尔比为1:4-1:5,更优选1:4.4-1:4.8,采用己烷或甲苯为溶剂,溶剂用量为季戊四卤化物质量的50%-200%,反应温度-78至-20℃,反应时间2-4h后,滴加二苯基氯化磷,二苯基氯化磷与季戊四卤化物优选投料摩尔比为1:4-1:5,更优选1:4.4-1:4.8,搅拌反应1-2h,反应温度-20℃至60℃,反应结束后过滤,脱除溶剂,得到中间体I,反应过程如下:
X表示氯,溴或碘;
(2)中间体I和1,3-丙烷磺酸内酯或1,4-丁烷磺酸内酯反应,摩尔比1:10-1:4,优选1:4-1:5,优选采用己烷、甲苯或DMSO中的一种或多种为溶剂,溶剂用量为中间体I质量的50%-200%,反应温度20-100℃,优选50-80℃,反应时间1-4h,反应结束后,真空抽滤,并用无水乙醚洗涤产物数次,最终得到中间体II,反应方程式如下:
(3)以中间体II为原料,加入酸优选浓硫酸、三氟甲磺酸、三氟乙酸、磷酸、盐酸中的一种或多种进行酸化,中间体II与酸的反应摩尔比1:10-1:4,优选1:4-1:5,反应温度20-100℃,反应时间1-4h,得到了浅黄色透明粘稠液体。用无水乙醚和甲苯洗涤多次,真空干燥,后可得到离子液体,反应方程式如下:
X-为Cl-,H2PO4 -,HSO4 -,CF3SO3 -,CF3COO-,优选Cl-,HSO4 -,CF3SO3 -;n=3或4;
金属的负载:(4)使用一种或多种金属的化合物配制成单一或混合组分的水溶液,所用金属化合物为水溶性的金属卤化物、硫酸盐、硝酸盐中的一种或多种,金属离子总浓度为0.1mol/L-2mol/L,优选浓度1-2mol/L,将上述水溶液与离子液体搅拌混合,所用水溶液中的金属总摩尔数与离子液体的摩尔数之比为1.5-1,优选1.2-1,所述的金属为镁,钙,锶,钡,钪,钛,钒,铬,锰,铁,钴,镍,铜,锌中的一种或多种。混合温度20-80℃,混合时间1-4h,搅拌混合后放置分层,分离下层即为离子液体负载的金属离子催化剂。
本发明的催化剂可用于催化C4-C20直链内烯烃、C4-C20带有支链的内烯烃、C4-C20直链端位烯烃或C4-C20带有支链的端位烯烃的异构化反应;包括但不限于1-丁烯,2-丁烯,1-戊烯,2-戊烯,1-己烯,2-己烯,3-己烯,1-辛烯,1-癸烯,2,4,4-三甲基-1-戊烯,2,4,4-三甲基-2-戊烯等烯烃。该催化剂可以实现内烯烃与端位α烯烃相互异构,即既可将内烯烃异构为端位α烯烃,也可以将端位α烯烃异构为内烯烃,该催化剂可以在低温、低压温和条件下实现烯烃的双键异构,并且催化剂活性稳定,寿命时间长。
异构化反应过程如下:将离子液体负载的金属催化剂加入到反应釜中,加入烯烃原料,催化剂的用量为烯烃原料质量的0.1wt%-100wt%,优选1wt%-10wt%,反应温度20-80℃,优选40-60℃,反应压力为表压0.1-2MPa,反应时间0.1-4h,优选1-2h,反应结束后,静置分层,分离上层烯烃产品,将下层离子液体催化剂分离后继续套用,连续套用五次以上,活性无降低。
负载过程本质上是金属离子与磺酸基上的氢离子进行交换从而使金属负载于离子液体上,负载的金属可以为单一金属,也可为多种金属的混合物,由于磺酸中的氢离子被金属离子置换,催化剂的酸性和腐蚀性大大降低。目前关于烯烃异构的催化剂多为氧化铝、硅胶负载的氧化镁和过渡金属,这类催化剂表面会因为结焦等原因逐步丧失其反应活性,存在寿命时间短,活性低,反应条件苛刻的问题,离子液体负载的过渡金属催化剂催化烯烃异构反应温度低,长周期运转不会发生结焦,催化剂寿命时间长,并且活性高,选择性高,异构化效果好。
本发明与现有技术相比,有以下优点:
(1)催化剂不结焦,稳定性好,寿命时间长,多次重复套用活性基本无降低。
(2)异构化反应条件温和,催化剂活性高,转化率和产物选择性高。
具体实施方式:
下面结合实施例对本发明作进一步的详细说明,本发明的范围包括但不局限于此类实施例。
实例用分析仪器及方法如下:
核磁:Varian-NMR 300,化学位移以ppm标示;
气相色谱-质谱联机(EI-MS):Finnigan MAT 95,70eV;
元素分析仪:ThermoFisher Flash 2000 CHNS/O有机元素分析仪,含量以%表示。
气相色谱仪:Agilent-7820;
气相色谱柱:0.25mm×30m的DB-5毛细管柱,检测器FID,气化室温度280℃,柱箱温度280℃,FID检测器温度300℃,氩气载流量2.1mL/min,氢气流量30mL/min,空气流量400mL/min,进样量1.0μL。使用面积归一化法计算烯的转化率及产物的选择性。升温程序:预热至柱温40℃,保持5min,15℃/min的速率从40℃升至280℃,保持2min。
实施例1
(1)离子液体的制备
季戊四溴与丁基锂反应,投料摩尔比为1:4,己烷为溶剂,用量为季戊四溴质量的50wt%,反应温度-78℃,反应时间2h后,滴加二苯基氯化磷,二苯基膦与季戊四溴摩尔比1:4,搅拌反应1h,反应温度-20℃,反应结束后过滤,使用旋转蒸发仪水浴温度80℃脱除溶剂,得到中间体产物I,称重计算收率90%,反应方程式如下:
定性分析:核磁分析:1H NMR(500MHz,C6D6,TMS),δ(ppm):1.34(s,8H),7.38-7.45(m,40H);13C NMR(500MHz,C6D6,TMS),δ(ppm):13.2,45.5,132.7,138.9;31P NMR(500MHz,C6D6,TMS),δ(ppm):+12(s,4P)
质谱分析:438,439,440
元素分析(%):C,79.44;H,6.44;P,14.13
中间体I和1,3-丙烷磺酸内酯反应,摩尔比1:10,己烷为溶剂,用量为中间体I质量的50wt%,20℃反应1h,反应结束后,水泵抽滤,压力20Kpa,并用无水乙醚洗涤产物数次,最终得到中间体II,称重计算收率88%,反应方程式如下:
定性分析:核磁:1H NMR(500MHz,C6D6,TMS),δ(ppm):1.9(m,8H),2.4(s,8H),2.48-2.55(m,16H),7.38-7.45(m,40H);13C NMR(500MHz,C6D6,TMS),δ(ppm):13.2,28.2,38.1,45.5,132.7,138.9;31P NMR(500MHz,C6D6,TMS),δ(ppm):+450(s,4P)
质谱分析:1296,1297,1298,1299,1230
元素分析(%):C,60.17;H,5.59;O,14.80;P,9.55;S,9.89
以中间体II为原料,加入浓硫酸进行酸化,反应摩尔比1:10,反应温度20℃,反应时间1h,得到了浅黄色透明粘稠液体。用无水乙醚和甲苯洗涤多次,120℃,3Kpa,干燥2h后可得到离子液体,称重计算收率89%,反应方程式如下:
核磁分析:1H NMR(500MHz,C6D6,TMS),δ(ppm):1.92(m,8H),2.43(s,8H),2.48-2.55(m,16H),7.38-7.45(m,40H);13C NMR(500MHz,C6D6,TMS),δ(ppm):15.2,29.2,38.9,48.5,132.7,138.9;31P NMR(500MHz,C6D6,TMS),δ(ppm):+470(s,4P)
质谱分析:1688,1689,1690,1691
元素分析(%):C,46.20;H,4.77;O,26.51;P,7.33;S,15.18
(2)金属负载
称量氯化镁、硫酸镍、硫酸铁配制成混合溶液1L,其中氯化镁浓度为0.03mol/L、硫酸镍0.02mol/L、硫酸铁0.05mol/L,加入与金属离子总量等摩尔比的离子液体,20℃搅拌混合1h后放置分层,分离下层即为离子液体负载的金属催化剂,负载前后离子液体质量增加0.1wt%,即离子液体中金属负载量为0.1wt%。
(3)异构化反应
将离子液体负载的金属催化剂加入到反应釜中,加入丁烯-1原料,催化剂的用量为丁烯-1质量的0.1wt%,反应压力0.1Mpa,反应温度20℃,反应时间4h,反应结束后,静置分层,分离上层烯烃产品,将下层离子液体催化剂分离后继续套用,连续套用五次以上,结果如下:
套用次数 | 丁烯-1转化率(%) | 丁烯-2选择性(%) |
1 | 85 | 98 |
2 | 85 | 97 |
3 | 85 | 98 |
4 | 85 | 98 |
5 | 85 | 97 |
实施例2
(1)离子液体的制备
采用季戊四氯与丁基锂反应,投料摩尔比为1:5,甲苯为溶剂,用量为季戊四溴质量的200wt%,反应温度-20℃,反应时间4h后,滴加二苯基氯化磷,二苯基氯化膦与季戊四溴摩尔比1:5,搅拌反应2h,反应温度60℃,反应结束后过滤,使用旋转蒸发仪水浴温度120℃脱除溶剂,得到中间体产物I,称重计算收率92%,反应方程式如下:
核磁分析:1H NMR(500MHz,C6D6,TMS),δ(ppm):1.34(s,8H),7.38-7.45(m,40H);13CNMR(500MHz,C6D6,TMS),δ(ppm):13.2,45.5,132.7,138.9;31P NMR(500MHz,C6D6,TMS),δ(ppm):+12(s,4P)
质谱分析:438,439,440
元素分析(%):C,79.44;H,6.44;P,14.13
中间体I和1,4-丁烷磺酸内酯反应,摩尔比1:4,甲苯为溶剂,100℃反应4h,反应结束后,水泵抽滤,压力20Kpa,并用无水乙醚洗涤产物数次,最终得到中间体II,称重计算收率91%,反应方程式如下:
核磁分析:1H NMR(500MHz,C6D6,TMS),δ(ppm):1.9(m,8H),2.1(m,8H),2.4(s,8H),2.48-2.55(m,16H),7.38-7.45(m,40H);13C NMR(500MHz,C6D6,TMS),δ(ppm):15.2,29.2,38.8,45.5,132.7,137.9;31P NMR(500MHz,C6D6,TMS),δ(ppm):+460(s,4P)
质谱分析:1352,1353,1354,1355,1356
元素分析(%):C,61.23;H,5.96;O,14.18;P,9.15;S,9.48
以中间体II为原料,加入三氟乙酸进行酸化,反应摩尔比1:4,反应温度100℃,反应时间4h,得到了浅黄色透明粘稠液体。用无水乙醚和甲苯洗涤多次,120℃,3Kpa,干燥2h后可得到离子液体,称重计算收率92%,反应方程式如下:
核磁分析:1H NMR(500MHz,C6D6,TMS),δ(ppm):1.93(m,8H),2.18(m,8H),2.44(s,8H),2.48-2.55(m,16H),7.38-7.45(m,40H);13C NMR(500MHz,C6D6,TMS),δ(ppm):15.2,29.2,38.8,45.5,132.7,137.9;31P NMR(500MHz,C6D6,TMS),δ(ppm):+480(s,4P)
质谱分析:1808,1809,1810,1811,1812,1813
元素分析(%):C,51.11;H,4.68;F,12.60;O,17.68;P,6.85;S,7.09
(2)金属负载
称量氯化镁、氯化钙、硝酸钴、硝酸铜配制成混合溶液2L,其中氯化镁浓度为0.5mol/L、氯化钙浓度0.5mol/L、硝酸钴浓度0.5mol/L,硝酸铜浓度0.5mol/L,加入金属离子总量与离子液体摩尔比1.5:1,80℃搅拌4h后放置分层,分离下层即为离子液体负载的金属催化剂。负载前后离子液体质量增加10wt%,即离子液体中金属负载量为10wt%。
(3)烯烃异构反应
将离子液体负载的催化剂加入到反应釜中,加入丁烯-2原料,催化剂的用量为丁烯-2质量的1wt%,反应压力2Mpa,反应温度40℃,反应时间1h,反应结束后,静置分层,分离上层烯烃产品,将下层离子液体催化剂分离后继续套用,连续套用五次以上,结果如下:
套用次数 | 丁烯-2转化率(%) | 丁烯-1选择性(%) |
1 | 86 | 98 |
2 | 86 | 97 |
3 | 86 | 98 |
4 | 87 | 98 |
5 | 85 | 98 |
实施例3
(1)离子液体的制备
采用季戊四碘与丁基锂反应,投料摩尔比为1:4.4,己烷为溶剂,用量为季戊四溴质量的100wt%,反应温度-55℃,反应时间3h后,滴加二苯基氯化磷,二苯基氯化膦与季戊四溴摩尔比1:4.4,搅拌反应1.5h,反应温度45℃,反应结束后过滤,使用旋转蒸发仪水浴温度80℃脱除溶剂脱除溶剂,得到中间体产物I,称重计算收率95%,反应方程式如下:
核磁分析:1H NMR(500MHz,C6D6,TMS),δ(ppm):1.34(s,8H),7.38-7.45(m,40H);13CNMR(500MHz,C6D6,TMS),δ(ppm):13.2,45.5,132.7,138.9;31P NMR(500MHz,C6D6,TMS),δ(ppm):+12(s,4P)
质谱分析:438,439,440
元素分析(%):C,79.44;H,6.44;P,14.13
中间体I和1,4-丁烷磺酸内酯反应,摩尔比1:5,甲苯为溶剂,50℃反应2h,反应结束后,水泵抽滤,压力20Kpa,并用无水乙醚洗涤产物数次,最终得到中间体II,称重计算收率94%,反应如下:
核磁:1H NMR(500MHz,C6D6,TMS),δ(ppm):1.9(m,8H),2.1(m,8H),2.4(s,8H),2.48-2.55(m,16H),7.38-7.45(m,40H);13C NMR(500MHz,C6D6,TMS),δ(ppm):15.2,29.2,38.8,45.5,132.7,137.9;31P NMR(500MHz,C6D6,TMS),δ(ppm):+460(s,4P)
质谱分析:1352,1353,1354,1355,1356
元素分析(%):C,61.23;H,5.96;O,14.18;P,9.15;S,9.48
以中间体II为原料,加入三氟甲磺酸进行酸化,反应摩尔比1:5,反应温度70℃,反应时间2h,得到了浅黄色透明粘稠液体。用无水乙醚和甲苯洗涤多次,120℃,3Kpa,干燥2h后可得到离子液体,称重计算收率92%,反应方程式如下
核磁分析:1H NMR(500MHz,C6D6,TMS),δ(ppm):1.99(m,8H),2.28(m,8H),2.46(s,8H),2.58-2.61(m,16H),7.38-7.45(m,40H);13C NMR(500MHz,C6D6,TMS),δ(ppm):16.2,30.2,39.8,48.5,136.7,138.9;31P NMR(500MHz,C6D6,TMS),δ(ppm):+490(s,4P)
质谱分析:1896,1897,1898,1899,1900
元素分析(%):C,43.67;H,4.04;F,12.01;O,20.23;P,6.53;S,13.52
(2)金属负载
称量硝酸铁、硝酸镍、硝酸铜、硝酸锌配制成混合溶液500ml,其中硝酸铁浓度为0.2mol/L、硝酸镍浓度为0.2mol/L,硝酸铜浓度为0.3mol/L,硝酸锌浓度为0.3mol/L,加入金属离子总量与离子液体摩尔比1.2:1,50℃搅拌2h后放置分层,分离下层即为离子液体负载的金属催化剂。负载前后离子液体质量增加2wt%,即离子液体中金属负载量为2wt%。
(3)烯烃异构反应
将离子液体负载的催化剂加入到反应釜中,加入1-癸烯原料,催化剂的用量为1-癸烯质量的10wt%,反应温度60℃,反应压力1Mpa,反应时间2h,反应结束后,静置分层,分离上层烯烃产品,将下层离子液体催化剂分离后继续套用,连续套用五次以上,结果如下:
套用次数 | 1-癸烯转化率(%) | 直链C10内烯烃选择性(%) |
1 | 83 | 98 |
2 | 82 | 97 |
3 | 83 | 98 |
4 | 82 | 98 |
5 | 82 | 98 |
实施例4
(1)离子液体的制备:
以实施例1中的中间体II为原料,加入磷酸进行酸化,反应摩尔比1:6,反应温度80℃,反应时间3h,得到了浅黄色透明粘稠液体。用无水乙醚和甲苯洗涤多次,120℃,3Kpa,干燥2h后可得到离子液体,称重计算收率90%,反应方程式如下:
核磁分析:1H NMR(500MHz,C6D6,TMS),δ(ppm):2.28(m,8H),2.46(s,8H),2.58-2.61(m,16H),7.38-7.45(m,40H);13C NMR(500MHz,C6D6,TMS),δ(ppm):16.2,30.2,39.8,48.5,136.7,138.9;31P NMR(500MHz,C6D6,TMS),δ(ppm):+455(s,4P)
质谱分析:1952,1953,1954,1955,1956,
元素分析(%):C,44.88;H,4.33;F,11.67;O,19.65;P,6.34;S,13.13
(2)金属负载
称量硝酸钪、硝酸钛、硝酸钒、硝酸铬配制成混合溶液0.8L,其中硝酸钪浓度为0.4mol/L、硝酸钛浓度为0.3mol/L,硝酸钒浓度为0.3mol/L,硝酸铬浓度为0.5mol/L,加入金属离子总量与离子液体摩尔比1.1:1,35℃搅拌1.5h后放置分层,分离下层即为离子液体负载的金属催化剂。负载前后离子液体质量增加7wt%,即离子液体中金属负载量为7wt%。
(3)烯烃异构反应
将离子液体负载的催化剂加入到反应釜中,加入2,4,4-三甲基-2-戊烯原料,催化剂的用量为烯烃质量的100wt%,反应温度80℃,反应压力0.5Mpa,反应时间4h,反应结束后,静置分层,分离上层烯烃产品,将下层离子液体催化剂分离后继续套用,连续套用五次以上,结果如下:
实施例5
(1)离子液体的制备
以实施例2中的中间体II为原料,加入盐酸进行酸化,反应摩尔比1:7,反应温度70℃,反应时间2.5h,得到了浅黄色透明粘稠液体。用无水乙醚和甲苯洗涤多次,120℃,3Kpa,干燥2h后可得到离子液体,称重计算收率91%,反应如下:
核磁:1H NMR(500MHz,C6D6,TMS),δ(ppm):1.96(m,8H),2.44(s,8H),2.48-2.59(m,16H),7.48-7.55(m,40H);13C NMR(500MHz,C6D6,TMS),δ(ppm):16.2,29.2,39.9,47.5,136.7,139.9;31P NMR(500MHz,C6D6,TMS),δ(ppm):+370(s,4P)
质谱分析:1498,1499,1500,
元素分析(%):C,55.27;H,5.65;Cl,9.46;O,12.80;P,8.26;S,8.55
(2)金属负载
称量硫酸镁、硫酸镍、硫酸铁配制成混合溶液1.2L,其中硫酸镁浓度为0.1mol/L、硝酸铁浓度为0.2mol/L,硝酸镍浓度为0.1mol/L,加入金属离子总量与离子液体摩尔比1.2:1,70℃搅拌反应3.5h后放置分层,分离下层即为离子液体负载的金属催化剂。负载前后离子液体质量增加16wt%,即离子液体中金属负载量为16wt%。
(3)烯烃异构反应
将离子液体负载的催化剂加入到反应釜中,加入1-二十烯原料,催化剂的用量为1-二十烯质量的5wt%,反应温度50℃,反应压力0.2Mpa,反应时间1.5h,反应结束后,静置分层,分离上层烯烃产品,将下层离子液体催化剂分离后继续套用,连续套用五次以上,结果如下:
套用次数 | 1-二十烯转化率(%) | 直链二十碳内烯烃选择性(%) |
1 | 62 | 98 |
2 | 61 | 97 |
3 | 63 | 98 |
4 | 61 | 98 |
5 | 62 | 99 |
对比例:
采用氧化镁为催化剂,加入到反应釜中,加入丁烯-1为原料,氧化镁的加入量为丁烯-1的10wt%,升温至80℃,搅拌反应4h,取样分析丁烯-1无异构化反应;将原料切换为丁烯-2,1-癸烯,1-辛烯,1-十二烯,改变催化剂用量0.1%-100wt%,调整不同反应温度20-80℃,压力0.1-2Mpa,原料均无异构化。
催化剂加入量10wt%,将反应温度提高至200℃,加入丁烯-1为原料,表压10Mpa,反应时间2h,反应结束后,静置分层,分离上层烯烃产品,将下层催化剂分离后继续套用,连续套用五次以上,结果如下:
相同条件下将反应原料切换为丁烯-2,1-癸烯,2,4,4-三甲基-2-戊烯,1-十二烯,结果如下:
套用次数 | 丁烯-2转化率(%) | 丁烯-1选择性(%) |
1 | 36 | 85 |
2 | 36 | 84 |
3 | 32 | 85 |
4 | 30 | 82 |
5 | 30 | 81 |
套用次数 | 1-癸烯转化率(%) | 直链C10内烯烃选择性(%) |
1 | 25 | 85 |
2 | 25 | 84 |
3 | 25 | 85 |
4 | 24 | 82 |
5 | 22 | 80 |
套用次数 | 1-二十烯转化率(%) | 直链二十碳内烯烃选择性(%) |
1 | 25 | 86 |
2 | 26 | 86 |
3 | 24 | 85 |
4 | 23 | 84 |
5 | 22 | 85 |
Claims (18)
2.根据权利要求1所述的催化剂,其特征在于:X-为Cl-,HSO4 -或CF3SO3 -。
3.根据权利要求1或2所述催化剂,其特征在于:所述的负载的金属为镁,钙,锶,钡,钪,钛,钒,铬,锰,铁,钴,镍,铜,锌中的一种或多种;金属的负载量为0.1wt%-16wt%,基于离子液体质量。
4.根据权利要求1-3中任一项所述的催化剂的制备方法,其特征在于:包含以下步骤:(1)采用季戊四卤化物与丁基锂在溶剂存在下反应,反应温度-78至-20℃,反应时间2-4h后,加入二苯基氯化磷,搅拌反应1-2h,反应温度-20℃至60℃,反应结束后过滤,脱除溶剂,得到中间体I,
(2)中间体I和1,3-丙烷磺酸内酯或1,4-丁烷磺酸内酯反应,反应温度20-100℃,反应时间1-4h,反应结束后,真空抽滤,洗涤产物,最终得到中间体II,反应方程式如下:
(3)以中间体II为原料,加入酸进行酸化,得到离子液体,反应方程式如下:
(4)将金属可溶性盐溶液与离子液体搅拌混合;混合温度20-80℃,混合时间1-4h,搅拌混合后放置分层,分离下层即为离子液体负载的金属催化剂。
5.根据权利要求4所述的制备方法,其特征在于:步骤(2)反应温度为50-80℃,步骤(3)中酸为浓硫酸、三氟甲磺酸、三氟乙酸、磷酸、盐酸中的一种或多种,步骤(4)中金属可溶性盐溶液的金属为镁,钙,锶,钡,钪,钛,钒,铬,锰,铁,钴,镍,铜,锌中的一种或多种。
6.根据权利要求4所述的制备方法,其特征在于:步骤(1)中,季戊四卤化物与丁基锂投料摩尔比为1:4-1:5,溶剂为己烷或甲苯,溶剂用量为季戊四卤化物质量的50%-200%,二苯基氯化磷与季戊四卤化物投料摩尔比为1:4-1:5。
7.根据权利要求6所述的制备方法,其特征在于:步骤(1)中,季戊四卤化物与丁基锂投料摩尔比为1:4.4-1:4.8,二苯基氯化磷与季戊四卤化物投料摩尔比为1:4.4-1:4.8。
8.根据权利要求4-7中任一项所述的制备方法,其特征在于:步骤(2)中,中间体I与1,3-丙烷磺酸内酯或1,4-丁烷磺酸内酯的摩尔比1:10-1:4,反应采用己烷、甲苯、DMSO中的一种或多种为溶剂,溶剂用量为中间体I质量的50%-200%。
9.根据权利要求8所述的制备方法,其特征在于:步骤(2)中,中间体I与1,3-丙烷磺酸内酯或1,4-丁烷磺酸内酯的摩尔比1:4-1:5。
10.根据权利要求4-7中任一项所述的制备方法,其特征在于:步骤(3)中,中间体II与酸的摩尔比1:10-1:4,反应温度20-100℃,反应时间1-4h。
11.根据权利要求10所述的制备方法,其特征在于:步骤(3)中,中间体II与酸的摩尔比1:4-1:5。
12.根据权利要求4-7中任一项所述的制备方法,其特征在于:步骤(4)中,所用金属可溶性盐为金属卤化物、硫酸盐或硝酸盐,金属离子浓度为0.1mol/L-2mol/L;金属总摩尔数与离子液体的摩尔数之比为1.5-1。
13.根据权利要求12所述的制备方法,其特征在于:金属离子浓度为1-2mol/L;金属总摩尔数与离子液体的摩尔数之比为1.2-1。
14.根据权利要求1或2或3所述的催化剂或根据权利要求4-13中任一项制备方法得到的催化剂的应用,用于催化C4-C20直链内烯烃、C4-C20带有支链的内烯烃、C4-C20直链端位烯烃或C4-C20带有支链的端位烯烃的异构化反应。
15.根据权利要求14所述的应用,其特征在于:异构化反应过程如下:将催化剂加入到反应釜中,加入烯烃原料,反应温度20-80℃,反应压力为表压0.1-2MPa,反应时间0.1-4h,反应结束后,静置分层,分离上层烯烃产品,将下层离子液体催化剂分离后继续套用。
16.根据权利要求15所述的应用,其特征在于:反应温度40-60℃,反应时间1-2h。
17.根据权利要求15所述的应用,其特征在于,催化剂的用量为烯烃原料质量的0.1wt%-100wt%。
18.根据权利要求17所述的应用,其特征在于,催化剂的用量为烯烃原料质量的1wt%-10wt%。
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