WO2022089072A1 - 催化剂和耐硫变换催化反应的方法 - Google Patents
催化剂和耐硫变换催化反应的方法 Download PDFInfo
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- WO2022089072A1 WO2022089072A1 PCT/CN2021/118430 CN2021118430W WO2022089072A1 WO 2022089072 A1 WO2022089072 A1 WO 2022089072A1 CN 2021118430 W CN2021118430 W CN 2021118430W WO 2022089072 A1 WO2022089072 A1 WO 2022089072A1
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- Prior art keywords
- catalyst
- mol
- cobalt
- molybdenum
- oxide
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 196
- 238000000034 method Methods 0.000 title claims abstract description 22
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 9
- 239000002131 composite material Substances 0.000 claims abstract description 45
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 44
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 35
- 239000010941 cobalt Substances 0.000 claims abstract description 35
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000011733 molybdenum Substances 0.000 claims abstract description 30
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000007789 gas Substances 0.000 claims abstract description 21
- 229910000428 cobalt oxide Inorganic materials 0.000 claims abstract description 16
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims abstract description 16
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 13
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 11
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 11
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- 239000001301 oxygen Substances 0.000 claims abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 58
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 44
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 14
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 13
- 238000012360 testing method Methods 0.000 claims description 13
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 11
- 238000002441 X-ray diffraction Methods 0.000 claims description 11
- 238000001179 sorption measurement Methods 0.000 claims description 10
- 238000001228 spectrum Methods 0.000 claims description 10
- 238000003795 desorption Methods 0.000 claims description 9
- 229910052746 lanthanum Inorganic materials 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 8
- 230000009467 reduction Effects 0.000 claims description 8
- 229910052684 Cerium Inorganic materials 0.000 claims description 7
- 229910052791 calcium Inorganic materials 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 6
- 229910052779 Neodymium Inorganic materials 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000000395 magnesium oxide Substances 0.000 claims description 6
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 6
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 229910052712 strontium Inorganic materials 0.000 claims description 6
- 238000005486 sulfidation Methods 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 23
- 238000002360 preparation method Methods 0.000 abstract description 12
- 150000001342 alkaline earth metals Chemical class 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 101
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 72
- 239000002243 precursor Substances 0.000 description 65
- 239000007864 aqueous solution Substances 0.000 description 52
- 239000000203 mixture Substances 0.000 description 47
- 150000001875 compounds Chemical class 0.000 description 32
- 230000000052 comparative effect Effects 0.000 description 31
- 238000001035 drying Methods 0.000 description 27
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 26
- 239000011609 ammonium molybdate Substances 0.000 description 26
- 235000018660 ammonium molybdate Nutrition 0.000 description 26
- 229940010552 ammonium molybdate Drugs 0.000 description 26
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 26
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 26
- 239000008367 deionised water Substances 0.000 description 26
- 229910021641 deionized water Inorganic materials 0.000 description 26
- 238000009681 x-ray fluorescence measurement Methods 0.000 description 25
- 239000007787 solid Substances 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 19
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 19
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 15
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 13
- 239000011575 calcium Substances 0.000 description 12
- 230000003993 interaction Effects 0.000 description 9
- 239000011777 magnesium Substances 0.000 description 9
- 239000011593 sulfur Substances 0.000 description 9
- 229910052717 sulfur Inorganic materials 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 8
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 8
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 8
- 239000008139 complexing agent Substances 0.000 description 7
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 5
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000001069 Raman spectroscopy Methods 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- -1 oxygen ion Chemical class 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 2
- SJZRECIVHVDYJC-UHFFFAOYSA-N 4-hydroxybutyric acid Chemical compound OCCCC(O)=O SJZRECIVHVDYJC-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 102100029203 F-box only protein 8 Human genes 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- 101100334493 Homo sapiens FBXO8 gene Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910015234 MoCo Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229940009827 aluminum acetate Drugs 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- MWFSXYMZCVAQCC-UHFFFAOYSA-N gadolinium(iii) nitrate Chemical compound [Gd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O MWFSXYMZCVAQCC-UHFFFAOYSA-N 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000002751 molybdenum Chemical class 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 0.000 description 1
- WFLYOQCSIHENTM-UHFFFAOYSA-N molybdenum(4+) tetranitrate Chemical compound [N+](=O)([O-])[O-].[Mo+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] WFLYOQCSIHENTM-UHFFFAOYSA-N 0.000 description 1
- TXCOQXKFOPSCPZ-UHFFFAOYSA-J molybdenum(4+);tetraacetate Chemical compound [Mo+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O TXCOQXKFOPSCPZ-UHFFFAOYSA-J 0.000 description 1
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical compound [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 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
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000005616 pyroelectricity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
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- 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
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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- 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
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- 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
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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- 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
- B01J23/85—Chromium, molybdenum or tungsten
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- 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
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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- C10K3/02—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
- C10K3/04—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment reducing the carbon monoxide content, e.g. water-gas shift [WGS]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Definitions
- the invention relates to the field of sulfur-tolerant catalysts, in particular to a catalyst and a method for a sulfur-tolerant shift catalytic reaction using the catalyst.
- Sulfur-tolerant shift is an important way for efficient utilization of coal, and it is also the main way to produce hydrogen at present, and catalyst is the core of the sulfur-tolerant shift process.
- cobalt-molybdenum-based catalysts have the advantages of sulfur resistance, wide reaction temperature range, low cost, and simple preparation process, and are most widely used in domestic and foreign devices.
- Cobalt-molybdenum-based sulfur-tolerant shift catalysts need to have high activity and high stability.
- MoS 2 is considered as the main active component in the process of sulfur-tolerant shift reaction, but when the content of H 2 S in the feed gas is low, cobalt The catalytic activity of molybdenum-based sulfur-tolerant shift catalysts was significantly reduced.
- Perovskite has excellent electrical conductivity, magnetism, pyroelectricity, piezoelectricity and many other properties, and has low preparation cost, thermodynamic and mechanical stability at high temperature, and is an excellent oxygen ion and electron conductor under high temperature conditions.
- the specific surface area of the currently prepared perovskite-type sulfur-tolerant shift catalysts is relatively low, which severely limits the improvement of the catalytic activity of such catalysts.
- the purpose of the present invention is to overcome the low catalytic activity of the sulfur-resistant catalytic reaction existing in the prior art, especially for the low H 2 S content raw gas in the sulfur-resistant catalytic reaction.
- a method for sulfur-resistant shift catalytic reaction of a catalyst the catalyst has high catalytic activity and high stability.
- one aspect of the present invention provides a catalyst comprising a carrier and molybdenum oxide, cobalt oxide and cobalt-molybdenum-based perovskite composite oxide supported on the carrier, the cobalt-molybdenum-based perovskite
- the mineral composite oxide contains molybdenum element, cobalt element, A element and oxygen element; wherein, A element is one or more of rare earth metal elements, alkali metal elements and alkaline earth metal elements.
- the A element is one or more of La, Ce, Nd, Gd, Na, K, Mg, Ca, and Sr.
- the A element includes A 1 element and A 2 element, the A 1 element is one or more of rare earth metal elements, and the A 2 element is one or more of alkali metal elements and alkaline earth metal elements kind; preferably, the A 1 element is one or more of La, Ce, Nd, Gd, and the A 2 element is one or more of Na, K, Mg, Ca, Sr; preferably Typically, the molar ratio of the A 1 element to the A 2 element is 1-99:99-1, preferably 1-9:9-1.
- the catalyst exhibits characteristic peaks at 27.9 ⁇ 0.2°, preferably at 24.9 ⁇ 0.2°, 27.9 ⁇ 0.2° and 36.2 ⁇ 0.2°.
- the temperature of the main reduction peak of the catalyst in the H 2 -TPR spectrum is above 600°C, preferably at 600-850°C;
- the temperature-programmed sulfidation test of the catalyst there are more than 2 adsorption and desorption peaks above 200° C., preferably more than 3 peaks.
- the content of element A is 0.4 mol or more and less than 1 mol, preferably 0.4-0.9 mol, more preferably 0.5-0.9 mol, relative to 1 mol of the total content of molybdenum and cobalt elements.
- the content of molybdenum element is greater than 0.4 mol and less than 1 mol, preferably greater than 0.4 mol and less than 0.8 mol, more preferably 0.5-0.6 mol, more preferably 0.5-0.6 mol, relative to the total content of 1 mol of molybdenum element and cobalt element, and further It is preferably 0.55-0.6 mol.
- the support is alumina, silica, titania, zirconia, magnesia, nickel oxide and carbon-based support or a composite support formed by two or more of them, more preferably alumina or alumina and alumina A composite support formed by one or more selected from the group consisting of silica, titania, zirconia, magnesia, nickel oxide and carbon-based supports.
- the carrier in the catalyst accounts for 30-90% by mass, preferably 30-80% by mass.
- the specific surface area of the catalyst is 40 m 2 ⁇ g -1 or more, preferably 50 m 2 ⁇ g -1 or more, and more preferably 60 m 2 ⁇ g -1 or more.
- a second aspect of the present invention provides a method for a sulfur-tolerant shift catalytic reaction, the method comprising: in the presence of the catalyst of the present invention, contacting CO in a feed gas with water vapor, wherein the feed gas contains H 2 S, the content of the H 2 S is 100 ppm or more, preferably 100-1500 ppm.
- the inventors of the present invention have found through in-depth research that the catalyst with a perovskite structure can provide better catalytic performance than traditional catalysts when it has an appropriate composition, and at the same time, it can still be used under harsh conditions such as low sulfur and low water-to-gas ratio. It has high catalytic performance and strong stability.
- the present invention adds excess cobalt and molybdenum in the process of loading the cobalt-molybdenum-based perovskite composite oxide on the surface of the carrier, so that a part of cobalt and molybdenum and element A form a perovskite composite oxide, and the remaining cobalt and molybdenum form a perovskite composite oxide.
- a part of molybdenum is attached to the surface of the perovskite composite oxide, and the other part of cobalt and molybdenum interacts strongly with the carrier, so that there is a strong synergy between the perovskite structure and the carrier, as well as cobalt and molybdenum, so that after the catalyst is vulcanized, Sulfide exists stably.
- the catalyst can have high stability without deactivation.
- Al 2 O 3 is a traditional carrier with a high specific surface area, and there are abundant organic groups on its surface.
- the cobalt-molybdenum-based perovskite composite oxide is loaded on its surface, which can not only exert the advantages of perovskite-type catalysts, but also make full use of the interaction between Al 2 O 3 and active components.
- the strong feature significantly improves the synergistic effect of the carrier and the perovskite composite oxide, thereby significantly improving the stability of the sulfide of the sulfur-tolerant catalyst during the reaction process.
- the catalyst of the present invention not only has the high specific surface area of the perovskite catalyst, but also has high sulfur-resistant catalytic activity, and at the same time, the cobalt and molybdenum in the catalyst can produce a relatively high performance with the perovskite composite oxide and the carrier.
- the strong interaction, and the synergistic effect between the support-perovskite structure-cobalt and molybdenum, enable the catalyst to have high stability and catalyst life under harsh conditions of low sulfur content, while maintaining a high catalytic performance. active.
- the catalyst has a high specific surface area, the exposure of active sites increases, and the catalytic activity increases significantly.
- the catalyst of the present invention can be used as a solid-sulfur type sulfur-tolerant shift catalyst, and also has high stability and catalyst life under severe working conditions with low sulfur content.
- the catalyst preparation process of the present invention is relatively simple, has low cost, is suitable for easy operation, and is suitable for large-scale industrial application.
- FIG. 1 is the XRD patterns of the catalysts prepared in Example 1 of the present invention and Comparative Examples 3-4.
- Figure 3 is the TPS spectrum of the catalysts prepared in Example 1 and Comparative Examples 3-4 of the present invention.
- Example 4 shows the XPS spectra of Mo species in the catalysts of perovskite in Example 1, Example 13 and Comparative Example 3 of the present invention.
- Example 5 shows the Raman spectra of Mo species in the catalysts of perovskite in Example 1 and Comparative Example 3 of the present invention.
- One aspect of the present invention provides a catalyst comprising a carrier and molybdenum oxide, cobalt oxide and cobalt-molybdenum-based perovskite composite oxide supported on the carrier, wherein the cobalt-molybdenum-based perovskite composite oxide contains Molybdenum element, cobalt element, A element and oxygen element; wherein, A element is one or more of rare earth metal elements, alkali metal elements and alkaline earth metal elements.
- the molybdenum oxide can be any molybdenum oxide, preferably an oxide obtained by roasting a molybdenum salt, such as MoO 3 , MoO 2 or MoO, etc.; the cobalt oxide can be any The cobalt oxide is preferably an oxide obtained by roasting a cobalt salt, such as Co 3 O 4 , CoO and the like. According to a preferred embodiment of the present invention, the molybdenum oxide is MoO 3 and the cobalt oxide is Co 3 O 4 .
- the A element is used as a structural aid, and any existing perovskite composite oxide (represented by the general formula ABO 3 ) can be used as a cobalt-molybdenum-based perovskite composite oxide, and the B element is Co and
- the A element component in Mo) can be, for example, one or more of rare earth metal elements, alkali metal elements and alkaline earth metal elements.
- rare earth metal elements include La, Ce, Nd, and Gd
- examples of alkali metal elements include Na, K, and the like
- examples of alkaline earth metal elements include Mg, Ca, Sr, and the like.
- the A element is preferably a rare earth metal element and/or an alkaline earth metal element, more preferably La, Ce, Mg, Ca, Sr, or the like.
- the A element includes A 1 element and A 2 element
- the A 1 element is one or more of rare earth metal elements
- the A 2 element is an alkali metal element and One or more of alkaline earth metal elements, preferably alkaline earth metal elements.
- the cobalt-molybdenum-based perovskite composite oxide can be represented by the general formula (A 1 ) x (A 2 ) 1-x BO 3 , the B elements are Co and Mo, and x can be 0.1 or more, 0.15 or more, 0.2 0.25 or more, 0.3 or more, 0.35 or more, 0.4 or more, or 0.45 or more, and x may be 0.95 or less, 0.9 or less, 0.85 or less, 0.8 or less, 0.75 or less, 0.7 or less, 0.65 or less, 0.6 or less, or 0.55 or less.
- the A 1 element is one or more of La, Ce, Nd, and Gd
- the A 2 element is one or more of Na, K, Mg, Ca, and Sr.
- the catalytic activity and stability of the catalyst can be further improved by coordinating the above-mentioned A 1 element with the A 2 element.
- the molar ratio of element A 1 to element A 2 is 1-99:99-1, preferably 1-9:9-1, more preferably 1-2:2-1.
- the catalyst of the present invention can further improve the catalytic activity stability of the catalyst.
- the cobalt-molybdenum-based perovskite composite oxide is not particularly limited as long as it has a perovskite structure.
- the content of molybdenum element is greater than 0.4mol and less than 1mol, more preferably greater than 0.4mol and less than 0.8mol, further preferably 0.5-0.6mol, still more preferably 0.55- 0.6mol.
- the above-mentioned cobalt-molybdenum-based perovskite composite oxide can be represented by, for example, AMo z Co 1-z O 3 , wherein z is greater than 0.4 and less than 1, preferably greater than 0.4 and less than 0.8, more preferably 0.5-0.6, further preferably 0.55 -0.6.
- the molar ratio of molybdenum element and cobalt element may be 0.5-0.6:0.4-0.5, preferably 0.52-0.56:0.44-0.48 .
- the catalyst contains an appropriate amount of molybdenum oxide, cobalt oxide and cobalt-molybdenum-based perovskite composite oxide at the same time, thereby improving its catalytic activity and stability, preferably, in the catalyst, relative to molybdenum and cobalt
- the total content of elements is 1 mol
- the content of element A is 0.4 mol or more and less than 1 mol, preferably 0.4-0.9 mol, more preferably 0.5-0.9 mol.
- the molybdenum and cobalt elements and the A element form a perovskite composite oxide in a total amount of 1:1 (molar ratio), and the remaining molybdenum and cobalt elements are in the form of their respective oxides or the composite oxides of the two. form exists.
- the current detection means and the actual use effect of the present invention it is not limited by theory.
- the present invention can ensure that The catalyst contains an oxide of molybdenum (molybdenum oxide), an oxide of cobalt (cobalt oxide), and a perovskite composite oxide, and it is not necessary that the perovskite composite oxide be formed in theoretical amounts.
- molybdenum oxide, cobalt oxide and perovskite composite oxide do not affect the implementation of the present invention, and are all within the scope of the present invention.
- the carrier may be alumina, silica, titania, zirconia, magnesia, nickel oxide and carbon-based carrier or a composite carrier formed by two or more of them.
- the carrier is alumina, silica, titania and zirconia or a composite carrier formed by two or more of them.
- the support preferably contains an alumina support, more preferably the support is alumina, silica, titania, Zirconium dioxide, magnesium oxide, nickel oxide and carbon-based support or a composite support formed by two or more of them.
- the existence form of the alumina carrier is not particularly limited, and may be one of ⁇ -Al 2 O 3 , ⁇ -Al 2 O 3 , ⁇ -Al 2 O 3 or amorphous alumina One or more kinds, as long as they can provide the desired catalytic activity.
- the alumina carrier includes at least part of ⁇ -Al 2 O 3 .
- the alumina carrier in the catalyst of the present invention can be formed by an in-situ preparation method, and in addition, the catalyst of the present invention can also be obtained by supporting the alumina carrier.
- the carrier accounts for 30-90% by mass, preferably 30-80% by mass, more preferably 50-80% by mass.
- the specific surface area of the catalyst may be 40m 2 ⁇ g -1 or more, preferably 50m 2 ⁇ g -1 or more or 60m 2 ⁇ g -1 or more, more preferably 70m 2 ⁇ g -1 or more or 80m 2 ⁇ g -1 or more, more preferably 90 m 2 ⁇ g -1 or more or 100 m 2 ⁇ g -1 or more, for example, 40 to 180 m 2 ⁇ g -1 .
- the specific surface area of the catalyst can be increased, so the catalyst preferably contains a carrier.
- the perovskite composite oxide, molybdenum oxide, cobalt oxide, cobalt-molybdenum-based perovskite composite oxide and carrier contained in the catalyst can be characterized by methods such as X-ray diffraction (XRD).
- XRD X-ray diffraction
- the characteristic peak at 25.5 ⁇ 0.2° shows MoO 3
- the characteristic peak at 36.2 ⁇ 0.2° shows Co 3 O 4
- the characteristic peak at shows the cobalt-molybdenum-based perovskite composite oxide.
- the carrier taking the use of alumina carrier as an example, according to the existence of the alumina carrier, the range of There are characteristic peaks at one or more of °.
- the TPR spectrum of the catalyst shows that the main reduction peak temperature of the catalyst is above 600°C, preferably 600-850°C, more preferably 700-800°C. This shows that the reduction temperature of the reducible species inside the catalyst is mostly above 600 °C, and it can be seen that there is a strong interaction between the molybdenum oxide and cobalt oxide inside the catalyst, the support and the perovskite composite oxide.
- main reduction peak temperature refers to the peak temperature corresponding to the reduction peak with the largest peak area in the TPR spectrum of the catalyst.
- the temperature-programmed sulfidation (TPS) spectrum of the catalyst shows that in the temperature-programmed sulfidation test of the catalyst, there are more than 2 adsorption and desorption peaks above 200° C., preferably more than 3 adsorption and desorption peaks , more preferably 2 or more adsorption and desorption peaks (eg, 3 to 5) in the range of 200°C to 600°C (preferably 200 to 500°C).
- the decomposition temperature of the sulfide inside the catalyst is higher than 200°C, and multiple adsorption and desorption peaks appear between 200°C and 600°C, which indicates that the catalyst forms after sulfidation.
- the sulfide active component has strong stability. According to a preferred embodiment of the present invention, in the temperature-programmed sulfidation test of the catalyst, there are adsorption and desorption peaks in the range of 250-270° C., the range of 330-350° C., and the range of 410-430° C. respectively.
- the method for preparing the catalyst of the present invention may include, for example, forming a gel from a precursor solution including a carrier or a carrier precursor, a molybdenum-containing compound, a cobalt-containing compound, a compound containing an element A, and a complexing agent, and then gelling the The gel is dried and calcined in sequence, wherein the A element is one or more of rare earth metal elements, alkali metal elements and alkaline earth metal elements.
- the carrier or the carrier precursor can be directly used as the carrier or used to form the carrier, and the molybdenum-containing compound, the cobalt-containing compound and the A-element-containing compound are jointly used to form the molybdenum oxide and cobalt oxide supported on the carrier.
- cobalt-molybdenum-based perovskite composite oxide active components are simultaneously completed by a one-step method (that is, the carrier is synthesized by an in-situ preparation method), thereby obtaining molybdenum oxide, cobalt oxide and cobalt-molybdenum-based perovskite composite oxide at the same time Structure loaded on a carrier.
- the molybdenum-containing compound, cobalt-containing compound and compound containing element A are preferably soluble salts of corresponding elements (eg nitrate, chloride, sulfate, acetate, etc.).
- the molybdenum-containing compound can be one or more of ammonium molybdate, molybdenum nitrate and molybdenum acetate;
- the cobalt-containing compound can be one or more of cobalt nitrate, cobalt chloride, cobalt acetate and cobalt carbonate
- the compound containing element A can be one or more of lanthanum nitrate, cerium nitrate, neodymium nitrate, gadolinium nitrate, sodium nitrate, potassium nitrate, magnesium nitrate, calcium nitrate, and strontium nitrate.
- the carrier or the carrier precursor can be an alumina carrier
- the specific aluminum-containing compound can be one of aluminum isopropoxide, aluminum nitrate, aluminum acetate, pseudoboehmite, and aluminum oxide. or more.
- the precursor solution can be prepared by dissolving its constituent compounds in water.
- the above compounds can be directly dissolved in water in sequence, or the aqueous solutions of each compound can be directly mixed.
- the carrier or carrier precursor, the molybdenum-containing compound, the cobalt-containing compound, the A element-containing compound or their aqueous solutions can be mixed in sequence, wherein the molybdenum-containing compound and the cobalt-containing compound can also be dissolved simultaneously to form molybdenum-containing cobalt the aqueous solution before mixing.
- step (2) Add the aqueous solution of the compound containing element A to the mixture obtained in step (1), and mix uniformly.
- the precursor solution further contains a complexing agent.
- the complexing agent can be one or more of citric acid, EDTA, glycine, acrylamide, lactic acid, tartaric acid and hydroxybutyric acid.
- the amount of the complexing agent used is 1-4 mol, preferably 1-3 mol, more preferably 1-2 mol, relative to 1 mol of the total amount of metal ions contained in the precursor solution.
- the complexing agent is preferably added sequentially or simultaneously with the carrier or the carrier precursor, for example, in the above specific example of preparing the precursor solution, citric acid is added in step (1).
- the molybdenum-containing compound in terms of molybdenum and the cobalt-containing compound in terms of cobalt are used in the total amount of 1 mol of the molybdenum-containing compound.
- the calculated amount of the molybdenum-containing compound is preferably more than 0.4 mol and less than 1 mol, more preferably more than 0.4 mol and less than 0.8 mol, still more preferably 0.5-0.6 mol, still more preferably 0.55-0.6 mol.
- the molar ratio of the molybdenum-containing compound in terms of molybdenum and the cobalt-containing compound in terms of cobalt is 0.5-0.6:0.4-0.5, preferably 0.52-0.56:0.44-0.48.
- the prepared catalyst simultaneously contains an appropriate amount of molybdenum oxide, cobalt oxide and cobalt-molybdenum-based perovskite composite oxide, preferably, relative to the ratio of the molybdenum-containing compound calculated as molybdenum and the cobalt-containing compound calculated as cobalt
- the total amount used is 1 mol
- the amount of the A element-containing compound calculated as element A is 0.4 mol or more and less than 1 mol, preferably 0.4-0.9 mol, preferably 0.5-0.9 mol.
- the manner of forming the precursor solution into a gel is not particularly limited, for example, the gel can be obtained by removing at least part of the water in the precursor solution.
- the temperature is 40-90°C, preferably 60-80°C, more preferably 70-80°C
- the time is 4-24h, preferably 5-10h, more preferably 6- 8h.
- the drying and calcination methods are not particularly limited, and any equipment and conditions in catalyst preparation can be used.
- the drying conditions may include: the temperature is 60-200°C, preferably 80-150°C, more preferably 80-120°C, further preferably 80-110°C, The time is 4-15h, preferably 5-15h, more preferably 6-12h.
- the roasting conditions may include: the temperature is 400-1300°C, preferably 500-900°C, more preferably 600-900°C, and the time is 4-48h, preferably 6-12h, more preferably 8-12h .
- the catalytic activity and stability of the prepared catalyst can be further improved.
- the calcination temperature is preferably 600-700°C.
- a second aspect of the present invention provides a method for a sulfur-tolerant shift catalytic reaction, the method comprising: in the presence of the catalyst of the present invention, contacting CO in a feed gas with water vapor; wherein the feed gas contains H 2 S, the content of the H 2 S is 100 ppm or more, preferably 100-1500 ppm.
- the catalyst of the present invention is preferably used as a sulfur-tolerant shift catalyst.
- a good catalytic effect can be achieved when the H 2 S content of the feed gas is more than 100 ppm (for example, 100-2000 ppm or 300-2000 ppm).
- good CO conversion can be obtained even if the H2S content in the feed gas is low (eg, 1500 ppm or less, 1000 ppm or less, 800 ppm or less, 600 ppm or less, or 500 ppm or less).
- the solid obtained by drying was calcined at 600 °C for 8 h to obtain catalyst C13.
- the final alumina carrier accounts for 70% of the total mass of the catalyst, the molar ratio of the sum of La elements and Mg elements to the sum of Mo elements and Co elements is 1:2, and the molar ratio of La elements to Mg elements is 1 : 1, and the molar ratio of Mo element to Co element is 0.55:0.45.
- the final alumina carrier accounts for 70% of the total mass of the catalyst, the molar ratio of the sum of La elements and Ca elements to the sum of Mo and Co elements is 1:2, and the molar ratio of La elements to Ca elements is 1. : 1, and the molar ratio of Mo element to Co element is 0.55:0.45.
- the solid obtained by drying was calcined at 600 °C for 8 h to obtain catalyst C15.
- the final alumina carrier accounts for 70% of the total mass of the catalyst, the molar ratio of the sum of La elements and Ca elements to the sum of Mo and Co elements is 1:2, and the molar ratio of La elements to Ca elements is 4. : 1, and the molar ratio of Mo element to Co element is 0.55:0.45.
- the final alumina carrier accounts for 70% of the total mass of the catalyst, the molar ratio of the sum of La elements and Ca elements to the sum of Mo and Co elements is 1:2, and the molar ratio of La elements to Ca elements is 1. : 1, and the molar ratio of Mo element to Co element is 0.55:0.45.
- the solid obtained by drying was calcined at 600 °C for 8 h to obtain the catalyst DC10.
- the final alumina carrier accounts for 70% of the total mass of the catalyst, the molar ratio of La and Mg to Mo and Co is 1:2, and the molar ratio of Mo to Co is 0.55:0.45.
- the catalyst C1 obtained in Example 1 shows features at 24.9°, 25.5°, 27.9°, 30.6°, 35.2°, 36.2°, 43.3°, 52.5°, 57.5° in the XRD pattern, respectively. peak.
- the catalyst DC4 obtained by the comparative example 4 showed characteristic peaks at 21.6°, 24.9°, 27.9°, 30.6°, 43.3°, and 47.5°, respectively.
- the catalyst DC3 obtained in Comparative Example 3 has no obvious characteristic peaks in the XRD pattern.
- the characteristic peak at 25.5° shows MoO 3
- the characteristic peak at 36.2° shows Co 3 O 4
- the characteristic peak at 27.9° shows cobalt-molybdenum-based perovskite composite oxide
- Characteristic peaks at 21.6°, 24.9°, 30.6°, 35.2°, 43.3°, 47.5°, 52.5° and 57.5° etc. show Al 2 O 3 support.
- the catalysts prepared in Examples 2-16 and Comparative Examples 2, 5-9 were characterized by XRD using the above method. It can be seen from the measurement results that the XRD patterns of the catalysts prepared in Examples 2-16 of the present invention are similar to those of the catalyst in Example 1, which all show that Co 3 O 4 , MoO 3 , cobalt-molybdenum-based perovskite composite Characteristic peaks for oxide and alumina supports. Whereas the catalysts of Comparative Examples 1, 3 and 7-9 did not have a perovskite structure.
- the temperature-programmed vulcanization was carried out using Tianjin Xianquan TPS-5096 temperature-programmed vulcanizer to measure the vulcanization ability of the catalysts of Example 1 and Comparative Examples 3-4.
- the results are shown in Figure 3.
- the specific measurement method is as follows. First, 0.3 g of 20-mesh catalyst particles were weighed, put into a reaction tube with a funnel, heated to 40 °C at a rate of 10 °C/min in a N2 atmosphere, kept for 30 min, and cooled to room temperature. The gas was switched to a 2.0 vol% H 2 S-98 vol % H 2 atmosphere, and the temperature was increased to 900° C. at a heating rate of 10/min. The exhaust gas was detected by TCD.
- the catalyst C1 of Example 1 has adsorption and desorption peaks at around 261°C, around 340°C, around 418°C, around 647°C, and around 672°C.
- the catalyst C1 of Example 1 also has obvious H 2 S adsorption in the high temperature region, while the catalyst of Comparative Example 3 has H 2 S catalyzed in the high temperature region. desorption, which shows that the sulfide intermediate of catalyst C1 of Example 1 is relatively stable.
- the catalysts prepared in Examples 1, 13 and Comparative Example 3 were characterized by XPS.
- the XPS characterization was carried out using an AXIS-ULTRADLD ray photoelectron spectrometer with a monochromatic Al-K ⁇ target source. The samples were pressed into thin sheets and evacuated at 1 ⁇ 10 -8 Pa before the test. To deduct the charging effect, the C1s (binding energy of 284.6 eV) peak of contaminated carbon was used as the calibration standard.
- Raman spectroscopy was performed on the catalysts prepared in Example 1 and Comparative Example 3. Raman spectroscopy was performed using a HORIBA LabRAM HR Evolution confocal Raman spectrometer with a 35mV air-cooled He-Ne laser with an excitation wavelength of 532nm. Raman characterization Using a 0.1 g powder sample (less than 100 mesh), spectra were recorded in the range of 400-3000 cm -1 .
- the reaction tube was a stainless steel tube of ⁇ 45 ⁇ 5 mm, and a thermocouple tube of ⁇ 8 ⁇ 2 mm was placed in the center.
- the catalyst prepared in the embodiment of the present invention has a higher CO conversion rate in the sulfur-tolerant shift reaction, especially when the H 2 S content in the feed gas is low It also has a good CO conversion rate under low temperature, and it can be seen that the catalyst of the present invention has a good catalytic activity in the sulfur-tolerant shift reaction.
- the catalyst of the present invention is able to maintain high CO conversion and stability even when the H2S content in the reaction gas fluctuates.
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Abstract
Description
Claims (12)
- 一种催化剂,其特征在于,该催化剂含有载体以及负载在该载体上的钼氧化物、钴氧化物以及钴钼基钙钛矿复合氧化物,所述钴钼基钙钛矿复合氧化物含有钼元素、钴元素、A元素和氧元素;其中,A元素为稀土金属元素、碱金属元素和碱土金属元素中的一种或多种。
- 根据权利要求1所述的催化剂,其中,A元素为La、Ce、Nd、Gd、Na、K、Mg、Ca、Sr中的一种或多种。
- 根据权利要求1或2所述的催化剂,其中,A元素包括A 1元素和A 2元素,所述A 1元素为稀土金属元素中的一种或多种,所述A 2元素为碱金属元素和碱土金属元素中的一种或多种;优选地,所述A 1元素为La、Ce、Nd、Gd中的一种或多种,所述A 2元素为Na、K、Mg、Ca、Sr中的一种或多种;优选地,A 1元素与A 2元素的摩尔比为1-99:99-1,优选为1-9:9-1。
- 根据权利要求1-3中任意一项所述的催化剂,其中,所述催化剂在XRD图谱中,在27.9±0.2°处显示出特征峰,优选在24.9±0.2°、27.9±0.2°和36.2±0.2°处显示出特征峰。
- 根据权利要求1-4中任意一项所述的催化剂,其中,所述催化剂在H 2-TPR图谱中的主还原峰温度位于600℃以上,优选位于600-850℃。
- 根据权利要求1-5中任意一项所述的催化剂,其中,在所述催化剂的程序升温硫化测试中,在200℃以上具有2个以上吸脱附峰,优选3个以上。
- 根据权利要求1-6中任意一项所述的催化剂,其中,在所述催化剂中,相对于钼元素和钴元素的总含量1mol,A元素的含量为0.4mol以上且小于1mol,优选为0.4-0.9mol,更优选为0.5-0.9mol。
- 根据权利要求1-7中任意一项所述的催化剂,其中,在所述催化剂中,相对于钼元素和钴元素的总含量1mol,钼元素的含量大于0.4mol且小于1mol,优选大于0.4mol且小于0.8mol,更优选为0.5-0.6mol,进一步优选为0.55-0.6mol。
- 根据权利要求1-8中任意一项所述的催化剂,其中,所述载体为氧化铝、二氧化硅、二氧化钛、二氧化锆、氧化镁、氧化镍和碳基载体或者它们中的两种以上形成的复合载体,优选为氧化铝或者氧化铝与选自二氧化硅、二氧化钛、二氧化锆、氧化镁、氧化镍和碳基载体中的一种以上形成的复合载体。
- 根据权利要求1-9中任意一项所述的催化剂,其中,在所述催化剂中载体占30-90质量%,优选30-80质量%。
- 根据权利要求1-10中任意一项所述的催化剂,其中,所述催化剂的比表面积为40m 2·g -1以上,优选为50m 2·g -1以上,更优选为60m 2·g -1以上。
- 一种耐硫变换催化反应的方法,其特征在于,该方法包括:在权利要求1-11中任意一项所述的催化剂的存在下,使原料气中的CO与水蒸气接触;其中,所述原料气含有H 2S,所述H 2S的含量为100ppm以上,优选100-1500ppm。
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CN116116424A (zh) * | 2023-04-13 | 2023-05-16 | 淄博鲁源工业催化剂有限公司 | 一种双功能耐硫变换催化剂及其制备方法 |
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