CN107754793A - 多孔碳负载的费托合成催化剂及其制备方法和应用 - Google Patents
多孔碳负载的费托合成催化剂及其制备方法和应用 Download PDFInfo
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- CN107754793A CN107754793A CN201711182229.1A CN201711182229A CN107754793A CN 107754793 A CN107754793 A CN 107754793A CN 201711182229 A CN201711182229 A CN 201711182229A CN 107754793 A CN107754793 A CN 107754793A
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- Prior art keywords
- metal
- active phase
- fischer
- chloride
- catalyst
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 169
- 239000003054 catalyst Substances 0.000 title claims abstract description 119
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 229910052751 metal Inorganic materials 0.000 claims abstract description 138
- 239000002184 metal Substances 0.000 claims abstract description 135
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 69
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 67
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 37
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 36
- 239000010439 graphite Substances 0.000 claims abstract description 36
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002088 nanocapsule Substances 0.000 claims abstract description 13
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 5
- 150000003624 transition metals Chemical class 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims description 44
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 43
- 239000012298 atmosphere Substances 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 28
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 25
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 18
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 18
- 239000010941 cobalt Substances 0.000 claims description 18
- 229910017052 cobalt Inorganic materials 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 18
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 17
- 229910052742 iron Inorganic materials 0.000 claims description 17
- 239000002243 precursor Substances 0.000 claims description 17
- 229910052707 ruthenium Inorganic materials 0.000 claims description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 14
- 238000007598 dipping method Methods 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 13
- 150000002430 hydrocarbons Chemical class 0.000 claims description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 11
- 229910052786 argon Inorganic materials 0.000 claims description 11
- 238000003763 carbonization Methods 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 229930195733 hydrocarbon Natural products 0.000 claims description 9
- 229910052763 palladium Inorganic materials 0.000 claims description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 8
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 8
- -1 chlorauride Chemical compound 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000007493 shaping process Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 6
- 239000003575 carbonaceous material Substances 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 6
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 6
- 229910052734 helium Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000002082 metal nanoparticle Substances 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
- 238000005660 chlorination reaction Methods 0.000 claims description 5
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 5
- 239000001307 helium Substances 0.000 claims description 5
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- HTYQIJOJHXNLIU-UHFFFAOYSA-L dichlorocobalt;ethane-1,2-diamine Chemical compound Cl[Co]Cl.NCCN HTYQIJOJHXNLIU-UHFFFAOYSA-L 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 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 claims description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 claims description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 4
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 4
- 239000004323 potassium nitrate Substances 0.000 claims description 4
- 235000010333 potassium nitrate Nutrition 0.000 claims description 4
- RWRDJVNMSZYMDV-UHFFFAOYSA-L radium chloride Chemical compound [Cl-].[Cl-].[Ra+2] RWRDJVNMSZYMDV-UHFFFAOYSA-L 0.000 claims description 4
- 229910001630 radium chloride Inorganic materials 0.000 claims description 4
- 229910052704 radon Inorganic materials 0.000 claims description 4
- SYUHGPGVQRZVTB-UHFFFAOYSA-N radon atom Chemical compound [Rn] SYUHGPGVQRZVTB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 239000010948 rhodium Substances 0.000 claims description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052724 xenon Inorganic materials 0.000 claims description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 239000002028 Biomass Substances 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 240000007594 Oryza sativa Species 0.000 claims description 3
- 235000007164 Oryza sativa Nutrition 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 239000008246 gaseous mixture Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 235000011164 potassium chloride Nutrition 0.000 claims description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 3
- 235000009566 rice Nutrition 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 235000002639 sodium chloride Nutrition 0.000 claims description 3
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 3
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- 235000010344 sodium nitrate Nutrition 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- HYZQBNDRDQEWAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;manganese(3+) Chemical compound [Mn+3].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O HYZQBNDRDQEWAN-LNTINUHCSA-N 0.000 claims description 2
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- NGIISMJJMXRCCT-UHFFFAOYSA-N [Ru].[N+](=O)(O)[O-] Chemical compound [Ru].[N+](=O)(O)[O-] NGIISMJJMXRCCT-UHFFFAOYSA-N 0.000 claims description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 2
- WSLMHVFKYRAUMK-UHFFFAOYSA-N acetic acid;iridium Chemical compound [Ir].CC(O)=O WSLMHVFKYRAUMK-UHFFFAOYSA-N 0.000 claims description 2
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 2
- 239000001639 calcium acetate Substances 0.000 claims description 2
- 235000011092 calcium acetate Nutrition 0.000 claims description 2
- 229960005147 calcium acetate Drugs 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 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 claims description 2
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 2
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- PFQLIVQUKOIJJD-UHFFFAOYSA-L cobalt(ii) formate Chemical compound [Co+2].[O-]C=O.[O-]C=O PFQLIVQUKOIJJD-UHFFFAOYSA-L 0.000 claims description 2
- UMYVESYOFCWRIW-UHFFFAOYSA-N cobalt;methanone Chemical compound O=C=[Co] UMYVESYOFCWRIW-UHFFFAOYSA-N 0.000 claims description 2
- SZKXDURZBIICCF-UHFFFAOYSA-N cobalt;pentane-2,4-dione Chemical compound [Co].CC(=O)CC(C)=O SZKXDURZBIICCF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- QFEOTYVTTQCYAZ-UHFFFAOYSA-N dimanganese decacarbonyl Chemical group [Mn].[Mn].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] QFEOTYVTTQCYAZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 2
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 238000002386 leaching Methods 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 2
- 239000011654 magnesium acetate Substances 0.000 claims description 2
- 235000011285 magnesium acetate Nutrition 0.000 claims description 2
- 229940069446 magnesium acetate Drugs 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- 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 description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- 125000000018 nitroso group Chemical group N(=O)* 0.000 claims description 2
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- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
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- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 1
- WHRBSMVATPCWLU-UHFFFAOYSA-K iron(3+);triformate Chemical compound [Fe+3].[O-]C=O.[O-]C=O.[O-]C=O WHRBSMVATPCWLU-UHFFFAOYSA-K 0.000 description 1
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- ABMFBCRYHDZLRD-UHFFFAOYSA-N naphthalene-1,4-dicarboxylic acid Chemical class C1=CC=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1 ABMFBCRYHDZLRD-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
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- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
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- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
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- 150000003303 ruthenium Chemical class 0.000 description 1
- FZHCFNGSGGGXEH-UHFFFAOYSA-N ruthenocene Chemical compound [Ru+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 FZHCFNGSGGGXEH-UHFFFAOYSA-N 0.000 description 1
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
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Abstract
本发明公开了一种令多孔碳负载的费托合成催化剂及其制备方法和应用。所述费托合成催化剂包括活性相金属和多孔碳载体;多孔碳载体为多孔石墨或石墨烯纳米胶囊;活性相金属包载于多孔石墨或石墨烯纳米胶囊的腔体中;活性相金属选自第VIIIB族过渡金属中至少一种。本发明催化剂在费托合成应用中表现出优异的电子特性、高导热性、抗物理化学磨损性能、高水热稳定性和高机械强度,其丰富纳米孔道结构能够促进催化剂活性相的高度分散和反应物种的扩散,由此具有优异的费托合成反应性能:高活性、低甲烷选择性和长的运转寿命。
Description
技术领域
本发明涉及一种多孔碳负载的费托合成催化剂及其制备方法和应用,属于费托合成催化领域。
背景技术
合成气(含有CO和H2、少量CO2、甲烷和N2的混合气)在催化剂的作用下,可以转化为烃类化合物。这一反应被称为费托合成反应,第VIIIB族过渡金属铁、钴、镍、钌是常用于该反应的催化剂的活性成分。
费托合成反应是一种高温(150~350℃)、高压(10~50bar)、强放热(165kJ/mol)的反应。该反应的一种主要副产物是水。目前适用于费托合成反应的反应器主要有固定床、固定流化床和气-液-固三相浆态床。因此,费托合成催化剂在反应过程中会经历非常苛刻的机械和化学应力,这就要求催化剂具有非常高的抗磨损性能。
通常一些难熔氧化物,像氧化硅、氧化铝、氧化钛和氧化锆等,被用作费托合成催化剂的载体。但这些载体也给催化剂带来了一些难以避免的缺点,如低热导率、水热稳定性差、表面酸性强、机械强度不高和抗磨损能力差等。由于费托合成反应是强放热反应,催化剂的导热性差会导致反应过程中大量反应热滞留于催化剂颗粒内部,致使催化剂局部反应超温、目标产物选择性变差、更严重的会导致催化剂活性相烧结失去催化活性,因此及时移除催化剂颗粒内部释放出的大量反应热变得非常重要。另外,费托合成反应中的高的水分压对催化剂来讲也是非常致命的。文献(Journal of the Chemical Society-ChemicalCommunications,1984,10,第629-630页)报道了水对氧化铝负载的催化剂具有非常有害的影响,在低温、低水分压下,氧化铝载体会部分地转变为拟水勃姆石,后者会导致催化剂发生粉化。为提高费托合成催化剂的机械和化学稳定性,众多研究者尝试寻找具有高热导性、高传质效率的新型催化剂载体。
石墨或石墨烯是具有二维层状结构的材料,具有非常大的比表面积、超高的热导率(2000~5000W/m/K),且化学惰性、孔道可调,这些优点使得石墨或石墨烯成为理想的催化剂载体。但由于石墨或石墨烯与金属之间弱的相互作用,金属在石墨或石墨烯表面的均匀分散也存在一定困难。利用石墨或石墨烯的二维层状结构特点,将石墨或石墨烯卷曲成中空结构,在空腔中内嵌金属颗粒能够有效抑制金属粒子的团聚。Saito等通过电弧放电方式制备了中空石墨笼包覆的镧系或铁族金属颗粒复合材料(Yahachi Saito,TadanobuYoshikawa,et al.,Journal of Physics and Chemistry of Solids,54(1993)1849-1860)。这种方法制备的M@C复合材料具有中空的竹节状、链状、管状碳结构,金属颗粒内嵌于中空碳结构中,能够有效抑制金属颗粒的烧结团聚,但中空碳结构内外封闭,金属粒子的较大且尺寸不一,未见其在催化中的应用,同时电弧法产量小,不适合大规模生产。Chen等通过化学开笼法将铁纳米粒子植入碳纳米管(CNT)中(Wei Chen,Zhongli Fan,et al.,Journal of American Chemical Society 130(2008)9414-9419),这种Fe@CNT催化剂的铁纳米粒子尺寸均一,在费托合成反应中活性高、产物选择性优良,但该方法制备工艺路线长,生产成本高,也不适合大规模工业生产。
发明内容
本发明的目的是提供一种用于合成气制备烃类化合物的费托合成催化剂,所述费托合成催化剂在传质、传热和电子性质方面具有极大改进,由此其催化效率大大提升,克服了费托合成催化剂存在的上述缺陷。
本发明所提供的费托合成催化剂,包括活性相金属和多孔碳载体;
所述多孔碳载体具有非连续或独立的多孔石墨或石墨烯纳米胶囊的结构;
所述活性相金属包载于所述多孔石墨或石墨烯纳米胶囊的腔体中,其分散度很高,使所述费托合成催化剂表现出良好的催化剂活性;
所述活性相金属选自第VIIIB族过渡金属中的至少一种。
所述费托合成催化剂具有优良的传质和传热能力,能够大幅提高在列管式固定床反应中的费托合成性能。
所述活性相金属具体可为铁、钴、镍和钌中的至少一种;
所述多孔石墨纳米胶囊的石墨层数不大于10层;所述多孔石墨烯纳米胶囊的石墨烯为单层或双层;
所述多孔石墨或石墨烯纳米胶囊的腔体直径为1~30nm;
所述催化剂的比表面积不小于50m2/g;
所述活性相金属在所述多孔碳载体中的分散度(指的是表面金属原子占总的金属原子的百分比)为5%~75%,从而使催化剂具有更佳的催化活性。
所述活性相金属与所述多孔载体的质量比可为0.1~200:100,1.2~186:100、1.2:100、4.1:100、4.2:100、18.6:100、22.3:100、24.5:100、31:100、35.5:100或186:100。
所述费托合成催化剂还包括助剂金属;
所述助剂金属可为锰、铬、锌、钼、铜、铂、钯、铑、铱、金、银、镁、钙、锶、钡、钠或钾中的至少一种;
所述助剂金属与所述多孔碳载体的质量比可为0.002~30:100,具体可为0.01~21.8:100、0.1:100、1.14:100、1.8:100、2.9:100、4.1:100或21.8:100。
本发明还提供了所述费托合成催化剂的制备方法,包括如下步骤:
制备含碳和所述活性相金属的前驱物或含碳、所述活性相金属和所述助剂金属的前驱物,按照下述步骤(1)-(3)或(a)-(b)即得所述费托合成催化剂:
(1)所述前驱物在含碳气氛中进行碳化,得到分散的多孔石墨或石墨烯包覆的金属纳米粒子复合材料;
(2)将所述多孔石墨或石墨烯包覆的金属纳米粒子复合材料成型;
(3)在惰性气氛下,经成型后的所述多孔石墨或石墨烯包覆的金属纳米粒子复合材料经焙烧即得;
(a)将所述前驱物成型;
(b)经成型后的所述前驱物在含碳气氛中进行碳化即得。
上述的制备方法中,所述前驱物可为下述1)-6)种任一种或两种以上的混合物:
1)所述活性相金属的前驱体的溶液或所述活性相金属的前驱体和所述助剂金属的前驱体的溶液浸渍的碳材料前驱体;
2)所述活性相金属的前驱体的溶液或所述活性相金属的前驱体和所述助剂金属的前驱体的溶液与含碳胶体溶液的混合物(具有共聚物特征);
3)所述活性相金属的前驱体的溶液或所述活性相金属的前驱体和所述助剂金属的前驱体的溶液与生物质及其衍生物单体的混合物;
4)所述活性相金属的前驱体的溶液或所述活性相金属的前驱体和所述助剂金属的前驱体的溶液与有机羧酸的混合物(具有共聚物特征);
5)所述活性相金属的羧酸盐有机金属骨架化合物或所述助剂金属的前驱体的溶液浸渍的所述活性相金属的羧酸盐有机金属骨架化合物;
6)所述活性相金属的茂基配合物或所述助剂金属与所述活性相金属的茂基配合物的混合物。
上述的制备方法中,所述活性相金属的前驱体选自如下中任一种:
硝酸铁、氯化铁、氯化亚铁、硫酸亚铁、醋酸亚铁、乙酰丙酮铁(III)、羰基铁、二茂铁、硝酸钴、氯化钴、甲酸钴、醋酸钴、乙酰丙酮钴、羰基钴、三(乙二胺)氯化钴(III)三水合物、硝酸镍、氯化镍、硫酸镍、醋酸镍、乙酰丙酮镍、羰基镍、氯化钌、硝酸钌、三苯基膦氯化羰基钌、羰基氯化钌、氯化钌酸铵和亚硝酰硝酸钌;
所述助剂金属的前驱体选自如下中任一种:
硝酸锰、氯化锰、醋酸锰、乙酰丙酮锰、羰基锰、硝酸锌、氯化锌、硫酸锌、醋酸锌、乙酰丙酮锌、硝酸铬、氯化铬、硫酸铬、钼酸铵、氯化铂、硝酸铂、氯铂酸、氯铂酸铵、亚硝基二铵合铂、硝酸铑、氯化铑、硫酸铑、醋酸铑、三苯基膦氯化铑、乙酰丙酮三苯基膦羰基铑、硝酸钯、氯化钯、硫酸钯、醋酸钯、四氯钯酸铵、六氯钯酸铵、三苯基膦钯、氯铱酸、氯化铱、醋酸铱、氯铱酸铵、氯化金、氯金酸、氯金酸铵、硝酸银、醋酸银、碳酸银、硝酸镁、氯化镁、醋酸镁、硝酸钙、氯化钙、醋酸钙、硝酸锶、氯化锶、醋酸锶、硝酸钠、氯化钠、醋酸钠、氢氧化钠、碳酸钠、碳酸氢钠、硝酸钾、氯化钾、氢氧化钾、碳酸钾、碳酸氢钾和醋酸钾。
上述的制备方法中,1)中,所述碳材料前驱体可为活性碳、纳米碳纤维、碳纳米管或碳球等碳载体。
上述的制备方法中,2)中,所述含碳胶体溶液可为活性碳溶胶、纳米碳纤维溶胶、碳纳米管溶胶、氧化石墨烯溶胶、纳米木质素溶胶、甲基纤维素溶胶、乙基纤维素溶胶、丙基纤维素溶胶、甲基羟丙基纤维素溶胶或羧甲基纤维素溶胶等。
上述的制备方法中,3)中,所述生物质可为木质素、纤维素、半纤维素、蔗糖、葡萄糖或果糖等。
上述的制备方法中,4)中,所述有机羧酸可为乙酰丙酸、月桂酸、草酸、柠檬酸、1,3,5-苯三甲酸、1,4-苯二甲酸、富马酸、偶氮苯四甲酸、氨基-对苯二甲酸、2,5-二羟基对苯二甲酸、1,4-萘二羧酸、1,5-萘二羧酸或2,6-萘二羧酸等。
上述的制备方法中,5)中,所述活性相金属的羧酸盐有机金属骨架化合物可为1,3,5-苯三甲酸铁、1,3,5-苯三甲酸钴、1,3,5-苯三甲酸镍、1,3,5-苯三甲酸钌、1,4-对苯二甲酸铁、1,4-对苯二甲酸钴、1,4-对苯二甲酸镍、1,4-对苯二甲酸钌、富马酸铁、富马酸钴、富马酸镍、富马酸钌、偶氮苯四甲酸铁、偶氮苯四甲酸钴、偶氮苯四甲酸镍、偶氮苯四甲酸钌、氨基-对苯二甲酸铁、氨基-对苯二甲酸钴、氨基-对苯二甲酸镍、氨基-对苯二甲酸钌、2,5-二羟基对苯二甲酸铁、2,5-二羟基对苯二甲酸钴、2,5-二羟基对苯二甲酸镍、2,5-二羟基对苯二甲酸钌、1,4-萘二羧酸铁、1,4-萘二羧酸钴、1,4-萘二羧酸镍、1,4-萘二羧酸钌、1,5-萘二羧酸铁、1,5-萘二羧酸钴、1,5-萘二羧酸镍、1,5-萘二羧酸钌、2,6-萘二羧酸铁、2,6-萘二羧酸钴、2,6-萘二羧酸镍或2,6-萘二羧酸钌等。
上述的制备方法中,6)中,所述活性相金属的茂基配合物可为二茂铁、二茂钴、二茂镍或二茂钌等。
上述的制备方法中,所述前驱物可通过浸渍、共沉淀、水/溶剂热合成、化学气相沉积和/或原子层沉积等方法与含碳的前驱体混合制备。
作为浸渍方法的示例,所述活性相金属的前驱体和所述助剂金属的前驱体可通过共浸渍或分步浸渍的方法在适宜温度、例如室温(如15℃~40℃)下负载于含碳前驱体上。其中,示例性的共浸渍方法包括将所述活性相金属的前驱体和所述助剂金属的前驱体按它们在催化剂中的组成比例混合并溶解于溶剂中形成浸渍溶液,然后将浸渍溶液浸渍于含碳前驱体上。示例性的分步浸渍方法是将所述活性相金属的前驱体和所述助剂金属的前驱体分别溶解于溶剂中形成单独的浸渍溶液,然后分步浸渍于含碳前驱体上。其中,浸渍可以是等体积浸渍,也可以是过量浸渍。等体积浸渍是指浸渍溶液的体积与载体的饱和吸水体积相等;过量浸渍是指浸渍溶液的体积大于载体的饱和吸水体积。例如,可通过将活性碳、纳米碳纤维、碳纳米管、氧化石墨烯、有机金属骨架化合物或它们的混合物与由活性金属的前驱体和/或助剂金属的前驱体形成的浸渍溶液共浸渍或分步浸渍,而使所述活性相金属和所述助剂金属负载于含碳前驱体上。
形成所述浸渍溶液、溶胶、聚合物溶液的溶剂可为水、甲醇、甲胺、二甲胺、N,N-二甲基甲酰胺、N-甲基甲酰胺、甲酰胺、乙醇、乙二醇、乙醚、乙胺、乙腈、乙酰胺、丙醇、丙酮、丙腈、四氢呋喃、二氧六环、丁醇、吡啶、吗啉、喹啉、甲苯、二甲苯、庚烷中的一种或任意两种以上的混合物,但不仅限于此。
或者,可通过共沉淀方法将所述活性相金属的前驱体和所述助剂金属的前驱体转化为水合氢氧化物和氧化物形式而沉积于含碳前驱体上。其中,示例性的共沉淀方法包括将所述活性相金属的前驱体和所述助剂金属的前驱体按它们在催化剂中的组成比例混合并溶解于溶剂中形成混合盐溶液;将该混合盐溶液按催化剂组成比例与含碳前驱体粉末混合并搅拌,形成均匀分散的悬浊液;将悬浊液与碱性沉淀剂溶液混合、沉淀、静置、过滤、洗涤得到催化剂前驱体。例如,可通过将混合盐溶液与活性碳、纳米碳纤维、碳纳米管、氧化石墨烯、木质素、纤维素、半纤维素、甲基纤维素、乙基纤维素、丙基纤维素、甲基羟丙基纤维素、羧甲基纤维素、蔗糖、葡萄糖、果糖、乙酰丙酸、月桂酸、草酸、柠檬酸、1,3,5-苯三甲酸、1,4-苯二甲酸、富马酸、偶氮苯四甲酸、氨基-对苯二甲酸、2,5-二羟基对苯二甲酸、有机金属骨架化合物的一种或任意两种以上的混合物形成悬浊液,随后与碱性沉淀剂溶液共沉淀,而使活性金属和助剂金属与含碳前驱体均匀混合形成含碳-金属前驱物。
所述碱性沉淀剂溶液可以是碱金属氢氧化物溶液,例如氢氧化钠和/或氢氧化钾的水溶液;也可以是碱金属碳酸盐或碳酸氢盐溶液,如碳酸钠、碳酸氢钠、碳酸钾和/或碳酸氢钾的水溶液;还可以是氨水溶液、碳酸铵水溶液、碳酸氢铵水溶液;优选氨水溶液。
或者,可通过水/溶剂热合成方法将所述活性相金属的前驱体和所述助剂金属的前驱体转化为金属、水合金属氢氧化物、水合金属氧化物、金属羧酸盐等而沉积于含碳前驱体上。例如,可通过将所述活性相金属的前驱体和/或所述助剂金属的前驱体与活性碳、纳米碳纤维、碳纳米管、氧化石墨烯、木质素、纤维素、半纤维素、甲基纤维素、乙基纤维素、丙基纤维素、甲基羟丙基纤维素、羧甲基纤维素、蔗糖、葡萄糖、果糖、乙酰丙酸、月桂酸、草酸、柠檬酸、1,3,5-苯三甲酸、1,4-苯二甲酸、富马酸、偶氮苯四甲酸、氨基-对苯二甲酸、2,5-二羟基对苯二甲酸或它们的混合物在溶剂中形成混合液进行水/溶剂热合成,使活性相金属和助剂金属与含碳前驱体均匀混合,形成含碳-金属前驱物。
形成上述的混合盐溶液或碱金属氢氧化物溶液或碱金属碳酸盐溶液或碱金属碳酸氢盐溶液及在水/溶剂热合成方法中使用的溶剂可为水、甲醇、甲胺、二甲胺、N,N-二甲基甲酰胺、N-甲基甲酰胺、甲酰胺、乙醇、乙二醇、乙胺、乙腈、乙酰胺、丙醇、丙腈、四氢呋喃、二氧六环、丁醇、吡啶、吗啉、喹啉中的一种或任意两种以上的混合物,但不仅限于此。
或者,可通过化学气相沉积方法将活性相金属的前驱体和助剂金属的前驱体转化为金属、金属碳化物、金属氮化物、金属氧化物等而沉积于氮化物载体上。例如,可通过将含活性金属和助剂金属的有机金属化合物在高真空(10-1Pa~10-6Pa)或常压(即,一个大气压)条件下加热,并经化学气相沉积而使活性金属和助剂金属沉积于活性碳、纳米碳纤维、碳纳米管、氧化石墨烯、有机金属骨架化合物或它们的混合物上。
或者,可通过原子层沉积方法将活性相金属和助剂金属的前驱体转化为金属、金属碳化物、金属氮化物、金属氧化物等而沉积于氮化物载体上。例如,可通过在高真空(10- 1Pa~10-6Pa)舱室中交替吸附含活性金属和助剂金属的气体化合物与氧化剂,以原子层沉积方法将活性金属和助剂金属沉积于活性碳、纳米碳纤维、碳纳米管、氧化石墨烯、有机金属骨架化合物上。
上述的制备方法中,所述前驱物可采用物理研磨法进行破碎,优选碾压、冲击、磨剥、劈碎和折断中的至少一种,更优选冲击和/或磨剥;
研磨得到的粉末状含碳和金属的前驱物的颗粒尺寸优选小于100微米,更优选小于1微米。
上述的制备方法中,所述含碳气氛可为含碳气体与惰性气体的混合气;
所述含碳气体为甲烷、乙烷、乙烯、乙炔、丙烷、丙烯、CO和/或合成气(CO+H2);
所述含碳气氛中,所述含碳气体的体积浓度为0.5~100%;
所述惰性气体选自氮气、氦气、氩气、氙气和氡气中至少一种。
所述碳化的温度为350~1100℃,时间为1~10小时。
上述的制备方法中,所述惰性气氛为氮气、氦气、氩气、氙气和氡气中至少一种;
所述焙烧的温度为300~500℃,时间为1~10小时。
上述的制备方法中,步骤(2)或(a)中,所述成型步骤采用纤维素醚作为成型剂;
所述纤维素醚选自官能团取代的纤维素,所述官能团优选自羧酸基、羟基、烷基官能团以及它们的组合官能团,所述烷基官能团优选自甲基、乙基、丙基以及它们的组合官能团。
所述纤维素醚选自羧乙基纤维素、羧甲基纤维素、羧甲基羟乙基纤维素、羧乙基羟甲基纤维素、羟乙基纤维素、羟甲基纤维素、羟丙基纤维素、羟甲基-甲基纤维素、羟甲基-乙基纤维素、羟乙基-乙基纤维素、甲基纤维素、乙基纤维素、丙基纤维素、乙基-羧甲基纤维素、羟基-乙基纤维素中羟基-乙基-丙基纤维素中的一种。
步骤(2)或(a)中,所述成型步骤采用的成型方法可选用压缩成型、转动成型、挤条成型或油中成型等;成型后的催化剂前驱体形状可为颗粒状、微球状、片状、条状、柱状、环状、多孔片状或三叶草状。
本发明费托合成催化剂可用于费托合成反应中催化合成气制备烃类化合物。
作为优选的示例,在将本发明费托合成催化剂可以直接应用至费托合成反应,也可以在应用于费托合成反应之前,预先使该催化剂在还原气氛中进行还原。还原气氛可为纯氢气气氛、CO气氛、合成气气氛、氨气气氛、稀释的氢气气氛、稀释的CO气氛、稀释的合成气气氛、稀释的氨气气氛。合成气中的H2与CO的体积比为0.01:1至1000:1。稀释的各还原气氛中除相应的各还原气氛外还可进一步含有氮气、氩气、氦气、CO2和/或CH4,上述稀释的各气氛中的还原性气体的体积浓度大于10%、优选大于25%、更优选为50%、最优选为75%、最佳大于90%。所述费托合成催化剂经过进一步的预处理生成具有一定还原度(即,金属相、金属碳化物占全部活性相金属的百分数)的还原态费托合成催化剂,优选得到的还原态费托合成催化剂的还原度至少大于60%、优选大于75%、最佳大于85%。
费托合成反应的合成气中的H2与CO的体积比为0.5:1~3.0:1、优选1.0:1~2.5:1、更优选1.2:1~2.2:1、最优选1.5:1~2.0:1。费托合成反应能够以连续式或间歇式反应过程进行。费托合成反应可采用一台或多台固定床反应器、微通道反应器、连续搅拌浆态床釜式反应器、射流循环式反应器、浆态鼓泡塔反应器或流化床反应器进行。费托合成反应的压力为1.0~6.0MPa,温度为120~350℃。当费托合成反应以连续式反应过程进行时,反应重时空速为100~60000NL/Kg/h。
例如,当费托合成催化剂为钴催化剂时,合成气中的H2与CO的体积比为1.0:1~3.0:1、优选为1.5:1~2.5:1、最佳为1.8:1~2.2:1。费托合成反应的压力为1.0~6.0MPa、优选1.5~4.5MPa、最佳2.0~3.0MPa。费托合成反应的温度为180~280℃、优选200~260℃、最佳220~240℃。当费托合成反应以连续式反应过程进行时,反应重时空速为100~25000NL/Kg/h、优选1000~20000NL/Kg/h、最佳5000~15000NL/Kg/h。
或者,当费托合成催化剂为铁催化剂时,合成气中的H2与CO的体积比为0.5:1~3.0:1、优选1.0:1~2.5:1、更优选1.2:1~2.2:1、最优选1.5:1~2.0:1。优选费托合成反应的压力为1.0~6.0MPa、优选1.5~5.5MPa、更优选2.0~5.0MPa、最优选2.5~4.0MPa。费托合成反应的温度为220~350℃、优选240~330℃、最佳260~300℃。当费托合成反应以连续式反应过程进行时,反应重时空速为100~60000NL/Kg/h、优选1000~40000NL/Kg/h、最佳10000~20000NL/Kg/h。
或者,当费托合成催化剂为钌催化剂时,合成气中的H2与CO的体积比为0.5:1~3.0:1、优选1.0:1~2.5:1、更优选1.2:1~2.2:1、最优选1.5:1~2.0:1。费托合成反应的压力为1.0~10.0MPa、优选2.5~7.5MPa、更优选3.0~6.0MPa、最优选3.5~5.0MPa。费托合成反应的温度为120~280℃、优选150~240℃、最佳180~220℃。当费托合成反应以连续式反应过程进行时,反应重时空速为100~10000NL/Kg/h、优选500~8000NL/Kg/h、最佳1000~5000NL/Kg/h。
本发明所述的示例性方案具有如下特点:催化剂制备方法简单、原料廉价、生产成本低、重复性好;本发明的催化剂具有较大的比表面积(不小于50m2/g)、高的活性金属分散度(5%~75%)、较高的机械强度(磨损指数为1~2.0%·h-1)和优异的稳定性;本公开的催化剂在应用于费托合成反应时,比起直接化学合成制备的催化剂或包含常规载体(SiO2或Al2O3)的催化剂,具有更好的合成气转化活性、烃类化合物选择性和高温稳定性。
例如,本发明的多孔碳包覆的钴纳米粒子催化剂在反应温度为200~280℃且在反应重时空速为10000NL/Kg/h时,CO的转化率能维持在10%以上,C5 +烃的选择性大于75%,甲烷选择性小于13%。CO转化历经100h以上的稳定运行测试:初始反应温度为220℃,强化测试温度为250℃。该催化剂的转化稳定性维持在0.8以上、甚至大于0.9。再例如,本发明的多孔碳包覆的铁纳米粒子催化剂在反应温度为280~320℃且在反应重时空速在15000NL/Kg/h以上时,CO的转化率能够维持在10%以上,CO2选择性小于10%(甚至小于5%),C5 +烃的选择性大于90%,甲烷选择性小于5%。CO转化历经100h以上的稳定运行测试:初始反应温度为280℃,强化反应温度为300℃。该催化剂的转化稳定性维持在0.8以上、甚至大于0.9。再例如,本发明的多孔碳包覆的钌纳米粒子催化剂在反应温度为180~240℃且在反应重时空速在1000NL/Kg/h以上时,CO的转化率能够维持在10%以上,CO2选择性小于5%(甚至小于1%),C5 +烃的选择性大于90%,甲烷选择性小于5%。CO转化历经100h以上的稳定运行测试:初始反应温度为180℃,强化反应温度为240℃。该催化剂的转化稳定性维持在0.9以上、甚至大于0.98。
实验结果表明,将本发明提供的多孔碳负载钌基、钴基或铁基催化剂用于费托合成反应中,其具有明显增加的催化活性、长周期稳定性和灵活的可操作性,特别是将该费托合成催化剂应用于高温固定床费托合成反应时。本公开的催化剂具有优良的热量、质量传递能力,能够高选择性地制备目标烃类化合物(特别是C5 +烃类,即,碳原子数大于等于5的碳氢化合物),并表现出良好的机械和化学稳定性。因此,该催化剂非常适用于费托合成反应。该催化剂特别适用于在常规固定床反应器或列管反应器(具有壳-管换热器模式)中并在高空速条件下进行的费托合成反应。
本发明具有以下特点:
1、本发明催化剂中金属活性相被包覆于非连续或独立多孔石墨或石墨烯纳米胶囊的腔体中,金属活性相与石墨或石墨烯之间存在直接的电子相互作用,石墨或石墨烯具有优异的电子助剂特性。
2、本发明催化剂的制备方法中采用含碳气体为多孔石墨或石墨烯的生长碳源,石墨或石墨烯沿金属纳米粒子表面生长,避免了封闭型中空石墨或石墨烯胶囊的生成。
3、本发明催化剂在费托合成应用中表现出优异的电子特性、高导热性、抗物理化学磨损性能、高水热稳定性和高机械强度,催化剂的丰富纳米孔道结构能够促进催化剂活性相的高度分散和反应物种的扩散,由此催化剂具有优异的费托合成反应性能:高活性、低甲烷选择性和长的运转寿命。
附图说明
图1为本发明实施例1制备的多孔碳负载的钴催化剂的XRD图谱。
图2为本发明实施例4制备的多孔碳负载的铁催化剂的XRD图谱。
图3为本发明实施例1制备的多孔碳负载的钴催化剂的TEM照片。
图4为本发明实施例1制备的多孔碳负载的钴催化剂经酸洗后去除金属元素后剩余碳载体的TEM照片。
具体实施方式
下述实施例中所使用的实验方法如无特殊说明,均为常规方法。
下述实施例中所用的材料、试剂等,如无特殊说明,均可从商业途径得到。
实施例1、
称取44.7g对苯二甲酸(H2BDC)、1179g N,N-二甲基甲酰胺(DMF)、71.5g七水合硫酸钴和4.1g硫酸锰,混合,搅拌至溶解,移入水热合成釜中,150℃下水热合成36h,过滤、洗涤、干燥,得到CoMn-BDC有机羧酸共聚物前驱体(属于第4)种前驱物),其BET比表面积为331m2/g。称取硝酸钾1.5g与去离子水44g配制成溶液,将此溶液与所制CoMn-BDC有机羰酸共聚物前驱体混合均匀、干燥,在50%C2H4/50%N2气流中600℃碳化2h,得到碳包覆的CoMn纳米复合材料。将碳包覆的CoMn纳米复合材料与48.0g甲基纤维素混捏、挤压成直径为1mm的条型,在N2气氛中120℃干燥、400℃焙烧,得到催化剂,标记为Exam-1。催化剂元素质量组成为:Co/Mn/K/C=31:2.9:1.2:100,其织构性质、分散度、还原度和磨损指数列于表1中。
本实施例制备的催化剂的XRD图如图1所示,可以看出,催化剂中存在石墨或石墨烯的特征结构,钴的XRD衍射峰为高度弥散的面心立方相金属钴特征结构。
本实施例制备的催化剂的TEM照片如图3所示,可以看出,金属钴纳米晶粒均匀地镶嵌于碳基质中,而粒子周围包覆着几层非连续的石墨烯碳结构,表明包覆金属粒子的碳层为多孔石墨烯。
费托合成性能测试:分别取0.5g的上述各催化剂,并用2ml碳化硅稀释混合均匀,置于内径为10mm、恒温段长为50mm的固定床反应器中。催化剂在H2中于375℃下还原6小时,降温至160℃。然后将62%H2/31%CO/7%Ar(体积比)的合成气通入反应器中,压力为3.0MPa,将反应器温度按0.1℃/min的升温速率提高至220℃,调节反应空速为8000NL/Kg/h,保持反应100小时以上。然后将反应温度提高至260℃,调节空速为15000NL/Kg/h,保持此条件反应约50小时;然后再降温至220℃,调节空速为8000NL/Kg/h,反应维持24小时以上。反应期间用气相色谱分析反应器尾气的组成,并用于计算反应的CO转化率、产物选择性和稳定性。上述各催化剂的费托合成反应结果列于表2中。将反应后催化剂用甲苯萃取出吸附蜡,然后在稀盐酸中浸泡过夜以溶解催化剂中的金属元素、洗涤、过滤,留取滤样在氮气中干燥,其TEM照片如图4所示,可以看出,去除金属后的残余碳载体为多孔的石墨烯胶囊结构,中间空心部分为金属纳米粒子提供封装位,从而能够有效防止金属颗粒的聚集。
实施例2、
称取2,5-二羟基对苯二甲酸25.2g、四水合乙酸钴63.4g、四氢呋喃27.5g、去离子水18.3g,充分搅拌至溶解,移入水热合成釜中,110℃下晶化72h,所得产物经过滤、洗涤、干燥最终得到CPO-27-Co金属有机骨架材料前驱体(属于第5)种前驱物)。将CPO-27-Co前驱体在20%C2H6/80%Ar气流中850℃碳化1h,得到碳包覆的Co纳米复合材料。将碳包覆的Co纳米复合材料与25.0g乙基纤维素混捏、挤压成直径为1mm的条型,在N2气氛中120℃干燥、450℃焙烧,得到催化剂,标记为Exam-2。催化剂元素质量组成为:Co/C=24.5:100,其织构性质、分散度、还原度和磨损指数列于表1中。按照与实施例1相同的方法进行费托合成性能测试,结果列于表2中。
实施例3、
称取24.7g六水合硝酸钴、5.18g 50%硝酸锰溶液、0.01g氯化铂、50g淀粉、8g离子水(属于第3)种前驱物),充分搅拌混合得到金属与含碳物质的混合物前驱体,挤压成直径为1mm的条型,干燥,然后在20%C3H6/80%Ar气流中700℃碳化1h,得到催化剂,标记为Exam-3。催化剂的元素质量组成为:Co/Mn/Pt/C=35.5:1.1:0.04:100,其织构性质、分散度、还原度和磨损指数列于表1中。
按照与实施例1相同的方法进行费托合成性能测试,结果列于表2中。
实施例4、
称取六水合氯化铁482.5g、均苯三甲酸251.4g、去离子水375g配制溶液,常温搅拌溶解后放入聚四氟乙烯内衬的不锈钢反应釜中,反应溶液在140℃下反应12h,离心洗涤干燥后得到金属有机骨架材料前驱体Fe-MIL-100,其BET比表面积为1558m2/g。称取四水氯化锰70.7g、氯化钾1.1g、葡萄糖242.2、去离子水810g配制成溶液,将此溶液与所制金属有机骨架Fe-MIL-100混合均匀、干燥得含碳和金属的混合物,破碎至颗粒目数为10~20目的颗粒,即为前驱物(属于第5)种前驱物),然后在5%CO/95%N2气流中1000℃碳化3h,得到催化剂,标记为Exam-4。催化剂的元素质量组成为:Fe/Mn/K/C=186/19.5/2.3/100,其XRD图谱如图2所示,且织构性质、分散度、还原度和磨损指数列于表1中。
本实施例制备的催化剂的XRD图如图2所示,可以看出,催化剂中存在石墨或石墨烯的特征结构,铁的XRD衍射峰为χ-Fe5C2特征结构。
费托合成性能测试:分别取2g的上述催化剂,并用2ml碳化硅稀释混合均匀,置于内径为10mm、恒温段长为50mm的固定床反应器中。催化剂在98%H2/2%CO的合成气中于320℃下还原24小时,降温至220℃。然后将63%H2/37%CO的合成气通入反应器中,压力为3.0MPa,将反应器温度按0.1℃/min的升温速率提高至280℃,调节反应空速为12000NL/Kg/h,保持反应100小时以上。然后将反应温度提高至300℃,调节空速为25000NL/Kg/h,保持此条件反应约50小时;然后再降温至280℃,调节空速为12000NL/Kg/h,反应维持24小时以上。反应期间用气相色谱分析反应器尾气的组成,并用于计算反应的CO转化率、产物选择性和稳定性。费托合成反应结果列于表2中。
实施例5、
称取144.7g九水合硝酸铁、4.2g六水合硝酸锰、2.9g硝酸铜、3.7g硝酸钠,溶解于去离子水中。同时,称取100g活性碳载体颗粒(20~40目,BET表面积为740m2/g),按照金属盐混合溶液体积与活性碳吸水体积为1:1的比例,将金属盐混合溶液浸渍到活性碳载体上,静置8小时,在氮气气氛中于110℃过夜干燥,得到金属浸渍的碳材料前驱体(属于第1)种前驱物)。在2%C2H2/98%Ar气流中550℃碳化1h,得到催化剂,标记为Exam-5。催化剂的元素质量组成为:Fe/Mn/Cu/Na/C=18.6/0.9/1.0/1.0/100,其织构性质、分散度、还原度和磨损指数列于表1中。按照与实施例4相同的方法进行费托合成性能测试,结果列于表2中。
实施例6、
称取44.7g对苯二甲酸(H2BDC)、1179g N,N-二甲基甲酰胺(DMF)和46.7g醋酸亚铁,混合,搅拌至溶解,移入水热合成釜中,110℃下水热合成24h,过滤、洗涤、干燥,得到Fe-BDC金属有机羧酸共聚物前驱体,其BET比表面积为231m2/g。称取硝酸铜0.9g、硝酸钾1.5g、蔗糖13.5g、去离子水74g配制成溶液,将此溶液与所制Fe-BDC金属有机羧酸共聚物混合均匀、干燥、破碎,得到颗粒目数为10~20目的含碳和金属混合物前驱体(属于第4)种前驱物),在25%CO/5%H2/70%N2气流中900℃碳化1h,得到催化剂,标记为Exam-6。催化剂的元素质量组成为:Fe/Cu/K/C=22.3/0.6/1.2/100,其织构性质、分散度、还原度和磨损指数列于表1中。按照与实施例4相同的方法进行费托合成性能测试,结果列于表2中。
实施例7、
称取5.5g三氯化钌(Ru含量38%)溶解于去离子水中,称取40g活性碳载体颗粒(20~40目,BET表面积为740m2/g),按照金属盐混合溶液体积与活性碳吸水体积为1:1的比例,将钌盐溶液浸渍到活性碳载体上,静置8小时,在氮气气氛中于100℃过夜干燥,得到金属浸渍的碳材料前驱体(属于第1)种前驱物),在5%C2H2/95%He气流中650℃碳化1h,得到催化剂,标记为Exam-7。催化剂的元素质量组成为:Ru/C=4.1/100,其织构性质、分散度、还原度和磨损指数列于表1中其织构性质、还原度和分散度列于表1中。
费托合成性能测试:称取20g的上述催化剂Exam-7、320g正十六烷装入500ml浆态床搅拌釜中。搅拌釜搅拌桨的转速为800rpm,催化剂在H2中于200℃下还原6小时,降温至150℃。然后将62%H2/31%CO/7%Ar(体积比)的合成气通入反应器中,压力为10.0MPa,调节反应空速为2000NL/Kg/h,保持反应100小时以上。然后将反应温度提高至200℃,调节空速为8000NL/Kg/h,保持此条件反应约50小时;然后再降温至150℃,调节空速为5000NL/Kg/h,反应维持24小时以上。反应期间用气相色谱分析反应器尾气的组成,并用于计算反应的CO转化率、产物选择性和稳定性。上述各催化剂的费托合成反应结果列于表2中。
实施例8、
称取33.2g对苯二甲酸(H2BDC)、12.4g乙二醇、1179g N,N-二甲基甲酰胺(DMF)和11.3g三氯化钌(Ru含量38%)混合,搅拌至溶解,移入水热合成釜中,110℃下水热合成72h,过滤、洗涤、干燥,得到Ru-BDC金属有机羧酸共聚物前驱体(属于第4)种前驱物)。将Ru-BDC金属有机羧酸共聚物在10%C3H6/90%N2气流中700℃碳化5h,得到碳包覆的Ru纳米复合材料。将碳包覆的Ru纳米复合材料与87.0g甲基纤维素混捏、挤压成直径为1mm的条型,在N2气氛中120℃干燥、400℃焙烧,得到催化剂,标记为Exam-8。催化剂元素质量组成为:Ru/C=1.2/100,其织构性质、分散度、还原度和磨损指数列于表1中。
按照与实施例7相同的方法进行费托合成性能测试,结果列于表2中。
实施例9、
称取33.2g对苯二甲酸(H2BDC)、48.3g葡萄糖、16.8g氢氧化钾、16.5g氯钌酸铵(Ru含量31%)和300g去离子水混合,搅拌至溶解,移入水热合成釜中,120℃下水热合成24h,过滤、洗涤、干燥,得到含碳和Ru的混合物前驱体(属于第3)种前驱物)。将含碳和Ru的混合物前驱体在8%C2H2/92%Ar气流中500℃碳化3h,得到碳包覆的Ru纳米复合材料。将碳包覆的Ru纳米复合材料与63.0g甲基纤维素混捏、挤压成直径为1mm的条型,在N2气氛中120℃干燥、400℃焙烧,得到催化剂,标记为Exam-9。催化剂元素质量组成为:Ru/K/C=4.2/0.1/100,其织构性质、分散度、还原度和磨损指数列于表1中。
按照与实施例7相同的方法进行费托合成性能测试,结果列于表2中。
对比例1、
采用共沉淀法制备氧化铝负载的钴催化剂:称取24.71g六水合硝酸钴、5.18g50%硝酸锰溶液、0.01g氯化铂溶解于100ml去离子水中,然后再称取13.3g拟薄水铝石(山东铝厂出品,含干基氧化铝75wt%)与上述溶液混合,采用超声分散的方式形成均匀悬浊液。在搅拌状态下向上述悬浊液中滴加1mol/L的氨水溶液至pH值为8~9,形成沉淀。将沉淀过滤、洗涤,在空气中于120℃过夜干燥,在马弗炉中以1℃/min的升温速率加热至450℃并在该温度下焙烧5小时,得到处于催化剂的组成为:Co/Mn/Pt/Al2O3=50/10/0.06/100,标记为CE-1,其织构性质、还原度、分散度和磨损指数列于表1中。
按照与实施例4相同的方法进行费托合成性能测试,结果列于表2中。
表1实施例1-9和对比例1制备的催化剂织构性质、颗粒尺寸和还原度
表2实施例1-9和对比例1制备的催化剂的费托合成反应活性、选择性和稳定
性
如表2所示,本发明所述的多孔碳包覆的钴催化剂表现出非常高的费托合成催化活性和优良的C5 +烃选择性,在经历200多小时的长时间和220℃以上的高温苛刻反应后,大部分催化剂的活性仍能恢复到初始活性的90%以上。同时,与Al2O3负载的钴催化剂相比,所有多孔碳包覆的钴催化剂均显示优异的活性、抗磨损性能和反应稳定性。
与之相似,本发明中制备的多孔碳包覆的铁催化剂在更高的反应温度下,表现出更高的费托合成催化活性和同样优良的C5 +烃类选择性。在经历长周期和高温反应后,这些铁催化剂的活性均能恢复到初始活性的90%以上,说明本发明的催化剂具有优良的稳定性和催化活性。
与之相似,本发明中制备的多孔碳包覆的钌催化剂在较低的反应温度和较高的反应压力下,表现出非常高的费托合成催化活性和极高的C5 +烃类选择性。在经历长周期、高温、高压反应后,这些钌催化剂的活性几乎没有损失,说明本发明的催化剂具有优良的稳定性和催化活性。
由此可以看出,本发明公开的多孔碳为载体的VIIIB簇过渡金属催化剂能够实现非常优良的费托合成反应性能。
Claims (10)
1.一种费托合成催化剂,包括活性相金属和多孔碳载体;
所述多孔碳载体为多孔石墨或石墨烯纳米胶囊;
所述活性相金属包载于所述多孔石墨或石墨烯纳米胶囊的腔体中;
所述活性相金属选自第VIIIB族过渡金属中的至少一种。
2.根据权利要求1所述的费托合成催化剂,其特征在于:所述活性相金属为铁、钴、镍和钌中的至少一种;
所述多孔石墨纳米胶囊的石墨层数不大于10层;所述石墨烯纳米胶囊的石墨烯为单层或双层;
所述多孔石墨或石墨烯纳米胶囊的腔体直径为1~30nm;
所述活性相金属与所述多孔载体的质量比为0.1~200:100。
3.根据权利要求1或2所述的费托合成催化剂,其特征在于:所述费托合成催化剂还包括包载于所述多孔石墨或石墨烯纳米胶囊的腔体中的助剂金属;
所述助剂金属为锰、铬、锌、钼、铜、铂、钯、铑、铱、金、银、镁、钙、锶、钡、钠或钾中的至少一种;
所述助剂金属与所述多孔碳载体的质量比为0.002~30:100。
4.权利要求1-3中任一项所述费托合成催化剂的制备方法,包括如下步骤:
制备含碳和所述活性相金属的前驱物或含碳、所述活性相金属和所述助剂金属的前驱物,按照下述步骤(1)-(3)或(a)-(b)即得所述费托合成催化剂:
(1)所述前驱物在含碳气氛中进行碳化,得到分散的多孔石墨或石墨烯包覆的金属纳米粒子复合材料;
(2)将所述多孔石墨或石墨烯包覆的金属纳米粒子复合材料成型;
(3)在惰性气氛下,经成型后的所述多孔石墨或石墨烯包覆的金属纳米粒子复合材料经焙烧即得;
(a)将所述前驱物成型;
(b)经成型后的所述前驱物在含碳气氛中进行碳化即得。
5.根据权利要求4所述的制备方法,其特征在于:所述前驱物为下述1)-6)种任一种或两种以上的混合物:
1)所述活性相金属的前驱体的溶液或所述活性相金属的前驱体和所述助剂金属的前驱体的溶液浸渍的碳材料前驱体;
2)所述活性相金属的前驱体溶液或所述活性相金属的前驱体和所述助剂金属的前驱体溶液与含碳胶体溶液的混合物;
3)所述活性相金属的前驱体的溶液或所述活性相金属的前驱体和所述助剂金属的前驱体的溶液与生物质及其衍生物单体的混合物;
4)所述活性相金属的前驱体的溶液或所述活性相金属的前驱体和所述助剂金属的前驱体的溶液与有机羧酸的混合物;
5)所述活性相金属的羧酸盐有机金属骨架化合物或所述助剂金属的前驱体的溶液浸渍的所述活性相金属的羧酸盐有机金属骨架化合物;
6)所述活性相金属的茂基配合物或所述助剂金属与所述活性相金属的茂基配合物的混合物。
6.根据权利要求5所述的制备方法,其特征在于:所述活性相金属的前驱体选自如下中任一种:
硝酸铁、氯化铁、氯化亚铁、硫酸亚铁、醋酸亚铁、乙酰丙酮铁(III)、羰基铁、二茂铁、硝酸钴、氯化钴、甲酸钴、醋酸钴、乙酰丙酮钴、羰基钴、三(乙二胺)氯化钴(III)三水合物、硝酸镍、氯化镍、硫酸镍、醋酸镍、乙酰丙酮镍、羰基镍、氯化钌、硝酸钌、三苯基膦氯化羰基钌、羰基氯化钌、氯化钌酸铵和亚硝酰硝酸钌;
所述助剂金属的前驱体选自如下中任一种:
硝酸锰、氯化锰、醋酸锰、乙酰丙酮锰、羰基锰、硝酸锌、氯化锌、硫酸锌、醋酸锌、乙酰丙酮锌、硝酸铬、氯化铬、硫酸铬、钼酸铵、氯化铂、硝酸铂、氯铂酸、氯铂酸铵、亚硝基二铵合铂、硝酸铑、氯化铑、硫酸铑、醋酸铑、三苯基膦氯化铑、乙酰丙酮三苯基膦羰基铑、硝酸钯、氯化钯、硫酸钯、醋酸钯、四氯钯酸铵、六氯钯酸铵、三苯基膦钯、氯铱酸、氯化铱、醋酸铱、氯铱酸铵、氯化金、氯金酸、氯金酸铵、硝酸银、醋酸银、碳酸银、硝酸镁、氯化镁、醋酸镁、硝酸钙、氯化钙、醋酸钙、硝酸锶、氯化锶、醋酸锶、硝酸钠、氯化钠、醋酸钠、氢氧化钠、碳酸钠、碳酸氢钠、硝酸钾、氯化钾、氢氧化钾、碳酸钾、碳酸氢钾和醋酸钾。
7.根据权利要求4-6中任一项所述的制备方法,其特征在于:所述含碳气氛为含碳气体与惰性气体的混合气;
所述含碳气体为甲烷、乙烷、乙烯、乙炔、丙烷、丙烯、CO和/或合成气;
所述含碳气氛中,所述含碳气体的体积浓度为0.5~100%;
所述惰性气体选自氮气、氦气、氩气、氙气和氡气中至少一种。
所述碳化的温度为350~1100℃,时间为1~10小时。
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:所述惰性气氛为氮气、氦气、氩气、氙气和氡气中至少一种;
所述焙烧的温度为300~500℃,时间为1~10小时。
9.权利要求1-3中任一项所述费托合成催化剂在费托合成反应中催化合成气制备烃类化合物中的应用。
10.根据权利要求9所述的应用,其特征在于:在催化所述费托合成反应之前,在还原气氛中还原所述费托合成催化剂。
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