CN108654630B - Sulfur-tolerant shift catalyst and preparation method thereof - Google Patents
Sulfur-tolerant shift catalyst and preparation method thereof Download PDFInfo
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- CN108654630B CN108654630B CN201710202348.2A CN201710202348A CN108654630B CN 108654630 B CN108654630 B CN 108654630B CN 201710202348 A CN201710202348 A CN 201710202348A CN 108654630 B CN108654630 B CN 108654630B
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- molybdate
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- 239000003054 catalyst Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- KYYSIVCCYWZZLR-UHFFFAOYSA-N cobalt(2+);dioxido(dioxo)molybdenum Chemical compound [Co+2].[O-][Mo]([O-])(=O)=O KYYSIVCCYWZZLR-UHFFFAOYSA-N 0.000 claims abstract description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000004898 kneading Methods 0.000 claims abstract description 32
- 239000002994 raw material Substances 0.000 claims abstract description 25
- 229910001868 water Inorganic materials 0.000 claims abstract description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 12
- 239000011593 sulfur Substances 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 34
- 150000002751 molybdenum Chemical class 0.000 claims description 32
- 150000001868 cobalt Chemical class 0.000 claims description 29
- 150000001875 compounds Chemical class 0.000 claims description 24
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 22
- 239000000395 magnesium oxide Substances 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000011777 magnesium Substances 0.000 claims description 15
- 229910052749 magnesium Inorganic materials 0.000 claims description 15
- 239000008139 complexing agent Substances 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 14
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 13
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 12
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 11
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 10
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 10
- 229910052596 spinel Inorganic materials 0.000 claims description 10
- 239000011029 spinel Substances 0.000 claims description 10
- 239000003431 cross linking reagent Substances 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 229940011182 cobalt acetate Drugs 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 4
- 239000012716 precipitator Substances 0.000 claims description 4
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical group [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 3
- 239000011609 ammonium molybdate Substances 0.000 claims description 3
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 3
- 229940010552 ammonium molybdate Drugs 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- 150000007522 mineralic acids Chemical class 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- 239000004471 Glycine Substances 0.000 claims description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- 239000011684 sodium molybdate Substances 0.000 claims description 2
- 235000015393 sodium molybdate Nutrition 0.000 claims description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 2
- 239000012752 auxiliary agent Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 16
- 229910002651 NO3 Inorganic materials 0.000 abstract description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 230000009466 transformation Effects 0.000 abstract description 5
- 238000000354 decomposition reaction Methods 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 26
- 239000012266 salt solution Substances 0.000 description 25
- 239000008367 deionised water Substances 0.000 description 24
- 229910021641 deionized water Inorganic materials 0.000 description 24
- 229910052750 molybdenum Inorganic materials 0.000 description 19
- 239000000203 mixture Substances 0.000 description 17
- 229910017052 cobalt Inorganic materials 0.000 description 15
- 239000010941 cobalt Substances 0.000 description 15
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 15
- 238000002156 mixing Methods 0.000 description 13
- 229960004106 citric acid Drugs 0.000 description 12
- 239000011733 molybdenum Substances 0.000 description 11
- 235000011054 acetic acid Nutrition 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 241000219782 Sesbania Species 0.000 description 7
- 238000001125 extrusion Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 description 6
- 229960002303 citric acid monohydrate Drugs 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 5
- -1 magnesium aluminate Chemical class 0.000 description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 229910001928 zirconium oxide Inorganic materials 0.000 description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 4
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000012265 solid product Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000009849 deactivation Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000011964 heteropoly acid Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- 239000004971 Cross linker Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910017518 Cu Zn Inorganic materials 0.000 description 1
- 229910017752 Cu-Zn Inorganic materials 0.000 description 1
- 229910017943 Cu—Zn Inorganic materials 0.000 description 1
- 229910017060 Fe Cr Inorganic materials 0.000 description 1
- 229910002544 Fe-Cr Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000012072 active phase Substances 0.000 description 1
- GSWGDDYIUCWADU-UHFFFAOYSA-N aluminum magnesium oxygen(2-) Chemical compound [O--].[Mg++].[Al+3] GSWGDDYIUCWADU-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical group [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 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
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 description 1
- QUEGLSKBMHQYJU-UHFFFAOYSA-N cobalt;oxomolybdenum Chemical compound [Mo].[Co]=O QUEGLSKBMHQYJU-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
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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
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/882—Molybdenum and cobalt
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/005—Spinels
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/20—Sulfiding
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the field of water-vapor transformation reaction, and discloses a sulfur-tolerant transformation catalyst and a preparation method thereof, wherein the preparation method comprises the following steps: kneading cobalt molybdate, a carrier raw material and water; and extruding and forming a product obtained by kneading, and then drying and roasting to obtain the sulfur-resistant shift catalyst. The preparation method provided by the invention has the advantages of high metal utilization rate, good stability and high activity, and can eliminate the problem of environmental pollution caused by nitrate decomposition.
Description
Technical Field
The invention relates to the field of water-vapor shift reaction, in particular to a preparation method of a sulfur-tolerant shift catalyst and the sulfur-tolerant shift catalyst prepared by the method.
Background
CO reacts with water vapor under the action of a catalyst to generate CO2And H2Is called Water Gas Shift (WGS) reaction. The water-vapor transformation plays an important role in the chemical industry, and is widely applied to the production processes of hydrogen production, the ammonia synthesis industry, chemical production by taking synthesis gas as a raw material, adjustment of the hydrogen-carbon ratio and the like.
The water-vapor transformation process can be divided into (1) High temperature transformation (HTS) according to the production characteristics, wherein the common catalyst is Fe-Cr catalyst, and the operation temperature is between 300 ℃ and 500 ℃; (2) low Temperature Shift (LTS), generally using Cu-Zn material as catalyst, with an operating Temperature between 200-; (3) sulfur-tolerant Shift (S-tolerant Shift) uses coal-made synthesis gas containing hydrogen sulfide as raw material, and generally adopts Co-Mo catalyst. With the development of residual oil and heavy oil hydrogenation and coal-to-hydrogen technologies in China, especially the rapid progress of coal chemical technologies in China in recent years, the demand of sulfur-tolerant shift catalysts is over 2500 tons every year.
The sulfur-tolerant shift catalyst may be prepared through kneading or soaking. Mixing Co and Mo precursors, a carrier precursor and a cross-linking agent in a solid state by a kneading method, and extruding and forming; the impregnation method comprises the steps of firstly preparing a formed catalyst carrier, then preparing Co and Mo into impregnation liquids with required concentrations respectively, and loading the Co and the Mo on the surface of the carrier in a Co-impregnation or step-by-step impregnation mode. In the above method, the active ingredient is usually added in the form of soluble salts of Co and Mo, such as nitrate, acetate, ammonium salt, etc., for example, Co adopts cobalt nitrate, cobalt acetate, etc., and Mo adopts ammonium tetramolybdate, ammonium heptamolybdate, etc. However, these soluble salts will decompose during the subsequent calcination process in the catalyst preparation to yield, for example, NOX、COXAnd acidic waste gases such as ammonia gas and the like seriously pollute the environment. The prior art generally arranges absorption treatment on the exhaust gas in the preparation process, but increases the preparation cost.
The existing preparation process of the sulfur-tolerant shift catalyst can not ensure that cobalt is fully contacted with molybdenum, the probability that cobalt and molybdenum independently exist on the surface of a carrier to form a cobalt-rich or molybdenum-rich project area is very high, the modification effect of cobalt can not be well exerted, and the activity and the stability of the sulfur-tolerant shift catalyst are further influenced.
CN1219500A discloses a CO sulfur-tolerant shift catalyst and a preparation method thereof, the catalyst adopts a kneading method, and active components are soluble salts of Co, Ni, Mo and W, such as nitrate, acetate, ammonium salt and the like. The components of the catalyst carrier are mixed evenly, then the solution of soluble salt of the active component is added, kneaded evenly and formed, dried and roasted. Then the catalyst is treated by water vapor with the temperature of 0-200 ℃. The method uses soluble salt as raw material, and can decompose and release NO during roasting processXDirect emission affects the environment if NO is addedXThe absorption device is used for absorbing the water in the water tank,the catalyst preparation cost is increased and, in addition, a shelf area which is partially rich in cobalt or molybdenum is inevitably formed by the method, and the modification effect of cobalt is not well exerted.
Disclosure of Invention
The invention aims to solve the problems that acidic or alkaline waste gas generated in the preparation process of the existing sulfur-tolerant shift catalyst pollutes the environment and the sulfur-tolerant shift catalyst is low in activity and stability, and provides a preparation method of the sulfur-tolerant shift catalyst and the sulfur-tolerant shift catalyst prepared by the method.
In order to achieve the above object, the present invention provides a method for preparing a sulfur tolerant shift catalyst, comprising: kneading cobalt molybdate, a carrier raw material and water; and extruding and forming a product obtained by kneading, and then drying and roasting to obtain the sulfur-resistant shift catalyst.
The invention also provides a sulfur-tolerant shift catalyst prepared by the method.
According to the invention, cobalt molybdate is directly used as a common active source of cobalt and molybdenum of the sulfur-tolerant shift catalyst, so that the defect that active metals Co and Mo form part of cobalt-rich or molybdenum-rich areas in the prior art is overcome, the metal utilization rate is improved, more Co-Mo-S active phases are formed, and better stability and higher activity are achieved; in addition, the direct preparation of sulfur-tolerant shift catalyst by cobalt molybdate can eliminate the problem of environmental pollution caused by nitrate decomposition.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
fig. 1 is an XRD diffraction pattern of hydrated cobalt molybdate and cobalt molybdate prepared in example 1 of the present invention.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a preparation method of a sulfur-tolerant shift catalyst, which comprises the following steps: kneading cobalt molybdate, a carrier raw material and water; and extruding and forming a product obtained by kneading, and then drying and roasting to obtain the sulfur-resistant shift catalyst.
Cobalt molybdate may also be referred to as cobalt molybdenum oxide (CoMoO)4) The cobalt molybdate is directly used as a common active source of the cobalt and the molybdenum of the sulfur-tolerant shift catalyst to replace the existing kneading method and impregnation method for preparing the sulfur-tolerant shift catalyst, so that the defect that active metals Co and Mo form part of cobalt-rich or molybdenum-rich areas in the prior art is overcome, and the metal utilization rate is improved.
It should be noted that the cobalt molybdate of the present invention is completely different from cobalt molybdic heteropoly acid, and the ratio of Co: the Mo atomic ratio is 1:1, and the ratio of Co: the Mo atomic ratio is more than 0.1-0.2, and the inventor of the invention finds that the cobalt molybdate is more favorable for improving the activity and the stability of the sulfur-tolerant shift catalyst by using the cobalt molybdate as a common active source of cobalt and molybdenum.
In the present invention, the cobalt molybdate may be anhydrous cobalt molybdate or hydrated cobalt molybdate, and the present invention is not particularly limited thereto.
According to the present invention, it is preferable that the cobalt molybdate, the support raw material and water are ball-milled before kneading. In the present invention, the conditions for the ball milling are not particularly limited as long as the cobalt molybdate and the support raw material are sufficiently contacted, and the ball milling may be performed in a ball mill.
In the present invention, the kneading is not particularly limited, and the kneading may be performed in a kneader, and in the present invention, it is preferable to limit the conditions under which the kneading is performed to acidic conditions.
According to a preferred embodiment of the invention, a cross-linking agent is introduced during said kneading, for example cobalt molybdate, a support, a cross-linking agent and water are subjected to said kneading.
The crosslinking agent is not particularly limited in the present invention, and may be various crosslinking agents conventionally used in the art, and preferably the acidity in kneading is provided by the crosslinking agent, for example, the crosslinking agent is selected from organic acids and/or inorganic acids. The organic acid may be at least one selected from formic acid, acetic acid and propionic acid; the inorganic acid may be at least one selected from nitric acid, hydrochloric acid, and sulfuric acid. To avoid the environmental pollution problem associated with nitrate decomposition, it is preferred that the crosslinker does not contain nitrate, and most preferably the crosslinker is acetic acid.
In the present invention, the carrier raw material is not particularly limited as long as it can provide a carrier composition conventionally used in the art, and the carrier raw material may include a finished carrier, and may also include a carrier precursor, and the carrier precursor may be converted into a finished carrier during a calcination process in a catalyst preparation process.
According to the present invention, it is preferred that the support raw material comprises a magnesium aluminate spinel and/or a magnesium aluminate spinel support precursor comprising a magnesium-containing compound and an aluminum-containing compound.
The magnesium-containing compound and the aluminum-containing compound are not particularly limited in the present invention as long as magnesium aluminate spinel can be produced under the firing conditions. Preferably, the magnesium-containing compound is selected from at least one of magnesium oxide, magnesium nitrate and magnesium hydroxide, the aluminum-containing compound is pseudoboehmite and/or magnesium aluminum oxide spinel, preferably, the magnesium-containing compound is selected from at least one of magnesium oxide, magnesium nitrate and magnesium hydroxide, the aluminum-containing compound is pseudoboehmite and/or aluminum oxide, most preferably, the magnesium-containing compound is magnesium oxide, and the aluminum-containing compound is pseudoboehmite.
According to the invention, the raw material of the carrier is preferably a magnesium aluminate spinel carrier precursor, and the adoption of the preferred embodiment is more beneficial to improving the activity and stability of the catalyst.
The selection range of the weight ratio of the magnesium-containing compound to the aluminum-containing compound in the carrier raw material is wide, and the weight ratio of the magnesium-containing compound to the aluminum-containing compound is preferably 0.1-1: 1, more preferably 0.2 to 0.4: 1.
in order to further improve the stability and activity of the sulfur-tolerant shift catalyst, it is preferable that the raw support material further contains a support aid selected from at least one of zirconia, ceria, lanthana and manganese oxide.
The stability and activity of the sulfur-tolerant shift catalyst can be improved by only adding the carrier aid, the selection range of the using amount of the carrier aid is wide, and the weight ratio of the carrier aid to the aluminum-containing compound is preferably 0.01-0.5: 1, more preferably 0.07 to 0.35: 1.
when the carrier raw material further contains a carrier aid, the introduction timing of the carrier aid is not particularly limited, and cobalt molybdate, a magnesium-containing compound, an aluminum-containing compound, a carrier aid and water may be kneaded together, or cobalt molybdate and the carrier aid may be mixed, then calcined, ground and kneaded together with the magnesium-containing compound, the aluminum-containing compound and water.
The selection range of the dosage of the cobalt molybdate and the carrier raw material is wide, and the dosage can be determined according to the content requirement of the metal active component, and the weight ratio of the cobalt molybdate to the carrier raw material is preferably 0.05-0.5: 1; further preferably 0.1 to 0.3: 1, more preferably 0.1 to 0.2: 1.
in order to further facilitate the subsequent extrusion forming operation according to the present invention, it is preferred that the method further comprises introducing an extrusion aid during kneading. The extrusion aid is not particularly limited in the present invention, and sesbania powder is preferable.
The invention has wide selection range of the addition amount of the extrusion aid, and the addition amount of the extrusion aid is preferably 1-3% of the total weight of the cobalt molybdate and the carrier raw material.
According to the present invention, extrusion molding is used to further shape the kneaded product into a catalyst. The product obtained by kneading may be formed into a bar-shaped agent on an extruder by an extrusion molding method, and the diameter of the cross section may be 1 to 5 mm. The formed strands are further dried and calcined.
In the present invention, the drying conditions are not particularly limited, but the drying temperature is preferably from room temperature to 100 ℃ and the drying time is preferably from 3 to 24 hours.
According to the present invention, during the firing, a carrier precursor (e.g., magnesia alumina spinel carrier precursor) is converted into a corresponding carrier (e.g., magnesia alumina spinel carrier), and metal active components Co and Mo are combined with the carrier. Preferably, the roasting temperature is 400-700 ℃, and the time is 3-8 h; further preferably, the temperature is 500-.
In the present invention, the cobalt molybdate may be any of the existing cobalt molybdates of various specifications, and may be obtained commercially or by any of the existing methods. Preferably, the method further comprises preparing cobalt molybdate by the following process of step (1) or steps (1) and (2):
(1) contacting water-soluble cobalt salt and water-soluble molybdenum salt with a precipitator, and then filtering to obtain hydrated cobalt molybdate; and
(2) roasting the hydrated cobalt molybdate obtained in the step (1).
In the preparation process of cobalt molybdate, roasting or not roasting can be carried out after filtering, and cobalt molybdate hydrate is obtained when roasting is not carried out; when in roasting, the roasting temperature can be 400-700 ℃, and the time can be 3-8 h; preferably, the temperature is 500-600 ℃, and the time is 4-6 h.
According to the present invention, it is preferable that the solid product obtained by the filtration is washed and dried. The washing and drying may be carried out according to conventional techniques in the art. For example, the drying is carried out at room temperature for 3 to 24 hours.
According to a preferred embodiment of the invention, a complexing agent is also added during the contacting. The addition of the complexing agent can more effectively control the grain size of the cobalt molybdate, thereby being more beneficial to improving the activity and stability of the sulfur-tolerant shift catalyst.
The adding time of the complexing agent is not particularly limited, and the complexing agent can be added after the water-soluble cobalt salt and the water-soluble molybdenum salt are mixed, and finally the precipitator is added; or mixing the complexing agent and one of the water-soluble cobalt salt and the water-soluble molybdenum salt, then adding the rest of the water-soluble cobalt salt and the water-soluble molybdenum salt, and finally adding the precipitator; or mixing part of complexing agent with water-soluble cobalt salt, mixing part of complexing agent with water-soluble molybdenum salt, mixing the water-soluble cobalt salt containing complexing agent with water-soluble molybdenum salt solution, and finally adding precipitant.
According to the present invention, preferably, the complexing agent is selected from at least one of citric acid, ethylenediaminetetraacetic acid, ammonia water and glycine, most preferably citric acid.
According to the invention, the molar ratio of the added amount of the complexing agent to the added amount of the water-soluble molybdenum salt calculated by molybdenum element is preferably 0.1-1: 1, more preferably 0.2 to 0.8: 1, most preferably 0.2-0.35: 1.
according to the present invention, it is preferable that the conditions of the contacting include: under the condition of stirring, the temperature is 50-80 ℃, the time is 0.1-2h, and the pH is 5-7; further preferably, the temperature is 55-70 ℃, the time is 0.25-1h, and the pH is 6-7; more preferably for a time of 0.5-1h and a pH of 6.2-6.5.
In the present invention, the kind and the addition amount of the precipitant are not particularly limited as long as the water-soluble cobalt salt and the water-soluble molybdenum salt can sufficiently perform the coprecipitation reaction, and the precipitant is preferably an alkaline precipitant, and more preferably at least one precipitant selected from the group consisting of ammonia water, sodium carbonate, and sodium hydroxide.
In the present invention, the amount of the precipitant added is preferably such that the contact is performed at a pH of 5 to 7, more preferably at a pH of 6 to 7, and still more preferably at a pH of 6.2 to 6.5.
The relative amounts of the water-soluble cobalt salt and the water-soluble molybdenum salt are selected in a wide range, and the molar ratio of the water-soluble cobalt salt to the water-soluble molybdenum salt is preferably 1-3:1, more preferably 1-1.5:1, and most preferably 1:1 in terms of metal elements. By adopting the preferred embodiment, the smooth proceeding of the cobalt molybdate reaction can be ensured, and the effective utilization of raw materials is more facilitated.
In the method provided by the invention, the water-soluble cobalt salt can be selected from cobalt compounds conventional in the field, and preferably, the water-soluble cobalt salt is selected from at least one of cobalt nitrate, cobalt acetate, cobalt sulfate, cobalt chloride and cobalt carbonate; most preferably, the water-soluble cobalt salt is cobalt nitrate and/or cobalt acetate, such as cobalt nitrate hexahydrate and/or cobalt acetate tetrahydrate.
In the method provided by the invention, the water-soluble molybdenum salt can be selected from molybdenum compounds conventional in the field, and preferably, the water-soluble molybdenum salt is selected from ammonium molybdate and/or sodium molybdate; further preferably, the water soluble molybdenum salt is ammonium molybdate, most preferably, the water soluble molybdenum salt is ammonium heptamolybdate, such as ammonium heptamolybdate tetrahydrate.
The invention also provides a sulfur-tolerant shift catalyst prepared by the method. The sulfur-tolerant shift catalyst has the advantages of good stability, long service life and good activity. And the problem of environmental pollution caused by nitrate decomposition can be solved by directly preparing the sulfur-tolerant shift catalyst by using cobalt molybdate.
The present invention is described in further detail below by way of examples and comparative examples.
Example 1
(1) Preparation of cobalt molybdate
35.6g Co (NO) are weighed3)2·6H2Dissolving O in 20mL of deionized water, and then adding 6g of citric acid monohydrate to obtain a cobalt salt solution containing citric acid; 21.8g (NH) are weighed4)6Mo7O24·4H2Dissolving O in 30mL of deionized water to obtain a molybdenum salt solution; in a water bath at 55 ℃ under stirringDropwise adding a cobalt salt solution containing citric acid into a molybdenum salt solution, simultaneously dropwise adding ammonia water (the concentration is 25 weight percent) to keep the pH value of a system at 6.2-6.5, reacting for 0.5h, filtering to obtain a solid product, washing with deionized water to obtain hydrated cobalt molybdate, roasting at 500 ℃ for 3h to obtain cobalt molybdate, and carrying out XRD analysis on the cobalt molybdate and the hydrated cobalt molybdate before roasting at 500 ℃, wherein an XRD diffraction pattern is shown in figure 1, and the prepared cobalt molybdate is consistent with an ICSD-23808 standard crystal structure and has a monoclinic phase;
(2) preparation of sulfur tolerant shift catalyst
Mixing 27g of cobalt molybdate, 140g of pseudo-boehmite, 50g of magnesium oxide, 30g of zirconium oxide and 3g of sesbania powder obtained in the step (1) in a kneading machine, adding 50g of deionized water and 5g of acetic acid, and kneading to form a uniform mixture; the mixture was shaped on a plodder (bar with a diameter of 3 mm), dried at room temperature for 3h, and then calcined at 500 ℃ for 5h to obtain the sulfur-tolerant shift catalyst C-1.
Example 2
(1) Preparation of cobalt molybdate
35.6g Co (NO) are weighed3)2·6H2Dissolving O in 20mL of deionized water, and then adding 10.5g of citric acid monohydrate to obtain a cobalt salt solution containing citric acid; 21.8g (NH) are weighed4)6Mo7O24·4H2Dissolving O in 30mL of deionized water, and then adding 10.5g of citric acid monohydrate to obtain a molybdenum salt solution containing citric acid; in a water bath at 60 ℃, dropwise adding a cobalt salt solution containing citric acid into a molybdenum salt solution containing citric acid under the stirring condition, dropwise adding a sodium hydroxide solution (with the concentration of 25 weight percent) to keep the pH value of the system at 6.2-6.5, reacting for 1h, filtering to obtain a solid product, washing with deionized water, and roasting at 500 ℃ for 3h to obtain cobalt molybdate;
(2) preparation of sulfur tolerant shift catalyst
Mixing 27g of cobalt molybdate, 140g of pseudo-boehmite, 28g of magnesium oxide and 10g of zirconium oxide obtained in the step (1) in a kneader, adding 50g of deionized water, 5g of acetic acid and 3g of sesbania powder, and kneading to form a uniform mixture; the mixture was shaped on a plodder (bar with a diameter of 3 mm), dried at room temperature for 5h, and then calcined at 600 ℃ for 4h to obtain the sulfur-tolerant shift catalyst C-2.
Example 3
(1) Preparation of cobalt molybdate
32.8g of Co (CH) are weighed out3COO)2·4H2Dissolving O in 20mL of deionized water to obtain a cobalt salt solution; 21.8g (NH) are weighed4)6Mo7O24·4H2Dissolving O in 30mL of deionized water, and then adding 10.5g of citric acid monohydrate to obtain a molybdenum salt solution containing citric acid; in a 70 ℃ water bath, under the stirring condition, dropwise adding a cobalt salt solution into a molybdenum salt solution containing citric acid, simultaneously dropwise adding a 1mol/L sodium carbonate solution to keep the pH value of the system at 6.2-6.5, reacting for 0.5h, filtering to obtain a solid product, and then washing with deionized water;
(2) preparation of sulfur tolerant shift catalyst
Mixing 27g of cobalt molybdate hydrate obtained in the step (1) with 50g of zirconia, drying at room temperature for 3h, then roasting at 500 ℃ for 3h, grinding to below 200 meshes, kneading with 140g of pseudo-boehmite, 56g of magnesia, 40g of deionized water, 5g of acetic acid and 3g of sesbania powder to form a uniform mixture; the mixture was shaped on a plodder (bar with a diameter of 3 mm), dried at room temperature for 5h, and then calcined at 550 ℃ for 6h to obtain the sulfur-tolerant shift catalyst C-3.
Example 4
The procedure of example 1 was followed except that citric acid monohydrate was not added during the preparation of cobalt molybdate. To obtain the sulfur-tolerant shift catalyst C-4.
Example 5
The procedure of example 2 was followed except that during the preparation of cobalt molybdate, sodium hydroxide solution was added dropwise so that the pH of the system was maintained at 6.6 to 7. To obtain the sulfur-tolerant shift catalyst C-5.
Example 6
The procedure of example 2 was followed except that during the preparation of cobalt molybdate, sodium hydroxide solution was added dropwise so that the pH of the system was maintained at 5.8 to 6. To obtain the sulfur-tolerant shift catalyst C-6.
Example 7
The procedure of example 1 was followed except that in the preparation of the sulfur tolerant shift catalyst, zirconia was not used and the same quality of pseudoboehmite was used in place of the zirconia. To obtain the sulfur-tolerant shift catalyst C-7.
Example 8
The procedure of example 1 was followed except that the preparation of cobalt molybdate in step (1) was excluded and that cobalt molybdate in step (2) was a commercially available product from Annai Gi chemical company. To obtain the sulfur-tolerant shift catalyst C-8.
Comparative example 1
35.6g Co (NO) are weighed3)2·6H2Dissolving O in 20mL of deionized water to obtain a cobalt salt solution; 21.8g (NH) are weighed4)6Mo7O24·4H2Dissolving O in 30mL of deionized water to obtain a molybdenum salt solution; mixing a cobalt salt solution, a molybdenum salt solution, 140g of pseudo-boehmite and 50g of magnesium oxide in a kneader, adding 50g of deionized water and 5g of acetic acid, and kneading to form a uniform mixture; the mixture was formed on a plodder (bar with a diameter of 3 mm), dried at room temperature for 3h, and then calcined at 500 ℃ for 5h to obtain the sulfur-tolerant shift catalyst D-1.
Comparative example 2
35.6g Co (NO) are weighed3)2·6H2Dissolving O in 20mL of deionized water to obtain a cobalt salt solution; 21.8g (NH) are weighed4)6Mo7O24·4H2Dissolving O in 30mL of deionized water to obtain a molybdenum salt solution; mixing a cobalt salt solution, a molybdenum salt solution, 140g of pseudo-boehmite, 50g of magnesium oxide, 30g of zirconium oxide and 3g of sesbania powder in a kneading machine, adding 50g of deionized water and 5g of acetic acid, and kneading to form a uniform mixture; the mixture was formed on a plodder (bar with a diameter of 3 mm), dried at room temperature for 3h, and then calcined at 500 ℃ for 5h to obtain the sulfur-tolerant shift catalyst D-2.
Comparative example 3
35.6g Co (NO) are weighed3)2·6H2Dissolving O in 20mL of deionized water, and adding 6g of citric acid monohydrate to obtain a cobalt salt solution containing citric acid; 21.8g (NH) are weighed4)6Mo7O24·4H2O dissolved in 30mL to removeAdding water to obtain molybdenum salt solution; mixing a cobalt salt solution containing citric acid, a molybdenum salt solution, 140g of pseudo-boehmite, 50g of magnesium oxide, 30g of zirconium oxide and 3g of sesbania powder in a kneader, adding 50g of deionized water and 5g of acetic acid, and kneading to form a uniform mixture; the mixture was shaped on a plodder (bar with a diameter of 3 mm), dried at room temperature for 3h, and then calcined at 500 ℃ for 5h to obtain the sulfur-tolerant shift catalyst D-3.
Comparative example 4
Weighing 28.92g (NH)4)6Mo7O24·4H2O was dissolved in 260mL of deionized water, heated to 150 ℃ and 5.8g of Co (NO) was added3)2·6H2Dissolving O in 30mL of deionized water and 3mL of hydrogen peroxide (volume fraction is 30%); mixing the two solutions, reacting in a solution at 150 ℃ for 1h, filtering, evaporating and concentrating, filtering for multiple times, and crystallizing to obtain a primary product. Dissolving the primary product in deionized water, heating to dissolve, evaporating to concentrate, heat filtering, standing, crystallizing, filtering, drying at 80 deg.C for 2 hr, and separating to obtain dark green crystal and blue green crystal10A heteropoly acid;
taking the CoMo obtained in the step (1)10Mixing 13.5g of heteropoly acid, 70g of pseudo-boehmite, 25g of magnesium oxide, 15g of zirconium oxide and 1.5g of sesbania powder in a kneading machine, adding 25g of deionized water and 2.5g of acetic acid, and kneading to form a uniform mixture; the mixture was shaped on a plodder (bar with a diameter of 3 mm), dried at room temperature for 3h, and then calcined at 500 ℃ for 5h to obtain the sulfur-tolerant shift catalyst D-4.
Test example 1
Evaluation of the activity and stability of the sulfur tolerant shift catalyst:
the reaction was carried out on a microreaction evaluating apparatus. The filling amount of the catalyst is 0.5g and 20-40 meshes.
The catalyst was used with 3% (v/v) H2S/H2(H2S and H2Mixed gas of (2), H2The volume content of S is 3 percent) is vulcanized at the vulcanization temperature of 250 ℃ for 5 hours.
Catalyst evaluation conditions: 400 ℃ and 0.1MPa, the raw material gas composition (v/v) is H2O/CO/N2/H2/H2S＝49.89％/40.76％/4.33％/4.86％/0.15％。
The accelerated deactivation conditions were: the temperature is 500 ℃, the pressure is 3.0MPa, the composition of the raw material gas is unchanged, and the temperature is kept for 5 hours.
The vulcanized catalyst was used as a fresh agent to conduct evaluation tests under the above evaluation conditions, and the results of the tests are shown in table 1. Then, accelerated deactivation was carried out under the above-mentioned accelerated deactivation conditions to obtain a deactivator, and evaluation tests were carried out under the above-mentioned evaluation conditions. The results of the experiment are shown in table 2.
TABLE 1
TABLE 2
As can be seen from the data in the above examples, comparative examples, tables 1 and 2, the sulfur-tolerant shift catalyst provided by the present invention directly uses cobalt molybdate as a common active source of cobalt and molybdenum of the sulfur-tolerant shift catalyst, so that the defect that active metals Co and Mo form part of cobalt-rich or molybdenum-rich areas in the prior art is overcome, the metal utilization rate is improved, and the catalyst has better activity and stability.
In particular, as can be seen from the comparison between example 1 and example 4, the addition of the complexing agent during the preparation of cobalt molybdate is more beneficial to improve the activity and stability of the catalyst; from the comparison results of example 1 and example 6, it can be seen that the preferred water-soluble cobalt salt and water-soluble molybdenum salt contact conditions of the present invention are more favorable for improving the activity and stability of the catalyst during the preparation of cobalt molybdate.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (20)
1. A method of making a sulfur tolerant shift catalyst comprising: kneading cobalt molybdate, a carrier raw material and water; extruding and forming a product obtained by kneading, and then drying and roasting to obtain a sulfur-resistant shift catalyst; the weight ratio of the cobalt molybdate to the carrier raw material is 0.05-0.5: 1.
2. the production method according to claim 1, wherein a crosslinking agent is introduced during the kneading.
3. The production method according to claim 2, wherein the crosslinking agent is selected from an organic acid and/or an inorganic acid.
4. The preparation method according to claim 1, wherein the carrier raw material comprises a magnesia alumina spinel and/or a magnesia alumina spinel carrier precursor, the magnesia alumina spinel carrier precursor comprises a magnesium-containing compound selected from at least one of magnesium oxide, magnesium nitrate and magnesium hydroxide and an aluminum-containing compound which is pseudoboehmite and/or alumina.
5. The production method according to claim 4, wherein the weight ratio of the magnesium-containing compound to the aluminum-containing compound is from 0.1 to 1: 1.
6. the production method according to claim 4, wherein the support raw material further contains a support auxiliary agent selected from at least one of zirconia, ceria, lanthana, and manganese oxide.
7. The production method according to claim 6, wherein the weight ratio of the carrier aid to the aluminum-containing compound is 0.01 to 0.5: 1.
8. the method of claim 1, wherein the weight ratio of cobalt molybdate to support raw material is 0.1-0.3: 1.
9. the preparation method as claimed in claim 1, wherein the calcination temperature is 400-700 ℃ and the calcination time is 3-8 h.
10. The method according to any one of claims 1 to 9, wherein the method further comprises preparing cobalt molybdate by the following procedure of step (1) or steps (1) and (2):
(1) contacting water-soluble cobalt salt and water-soluble molybdenum salt with a precipitator, and then filtering to obtain hydrated cobalt molybdate; and
(2) roasting the hydrated cobalt molybdate obtained in the step (1).
11. The method according to claim 10, wherein a complexing agent is further added during the contacting.
12. The production method according to claim 11, wherein the complexing agent is selected from at least one of citric acid, ethylenediaminetetraacetic acid, aqueous ammonia, and glycine.
13. The preparation method according to claim 11, wherein the molar ratio of the added amount of the complexing agent to the added amount of the water-soluble molybdenum salt calculated by molybdenum element is 0.1-1: 1.
14. the production method according to claim 10, wherein the precipitant is at least one selected from the group consisting of aqueous ammonia, sodium carbonate, and sodium hydroxide.
15. The production method according to claim 10, wherein the conditions of the contacting include: under the condition of stirring, the temperature is 50-80 ℃, the time is 0.1-2h, and the pH value is 5-7.
16. The method of claim 15, wherein the contacting conditions comprise: under the condition of stirring, the temperature is 55-70 ℃, the time is 0.25-1h, and the pH value is 6-7.
17. The production method according to claim 10, wherein the molar ratio of the water-soluble cobalt salt to the water-soluble molybdenum salt is 1-3:1 in terms of the metal element.
18. The method according to claim 17, wherein the molar ratio of the water-soluble cobalt salt to the water-soluble molybdenum salt is 1-1.5:1 in terms of the metal element.
19. The production method according to claim 10, wherein the water-soluble cobalt salt is selected from at least one of cobalt nitrate, cobalt acetate, cobalt sulfate, and cobalt chloride; the water-soluble molybdenum salt is selected from ammonium molybdate and/or sodium molybdate.
20. A sulfur tolerant shift catalyst prepared by the process of any one of claims 1-19.
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| CN101214442A (en) * | 2007-12-26 | 2008-07-09 | 厦门大学 | Sulphur resistant carbon monoxide transfer catalyst and preparation thereof |
| CN101439289A (en) * | 2008-12-17 | 2009-05-27 | 中国石油天然气集团公司 | Preparation of hydrogenation catalyst |
| CN102049261B (en) * | 2010-11-18 | 2013-03-27 | 中国海洋石油总公司 | Method for preparing catalyst of acrolein by propylene oxidization |
| CN103611544A (en) * | 2013-12-05 | 2014-03-05 | 湖北双雄催化剂有限公司 | Preparation method capable of improving low-temperature activity of low-pressure cobalt-molybdenum sulfur-tolerant shift catalyst |
| CN105579556A (en) * | 2013-09-18 | 2016-05-11 | 国际壳牌研究有限公司 | Methods and systems for supplying hydrogen to a hydrocatalytic reaction |
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| FR3012449B1 (en) * | 2013-10-24 | 2015-10-30 | Arkema France | PROCESS FOR SYNTHESIZING A MERCAPTAN BY ADDING HYDROGEN SULFIDE TO OLEFIN |
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| CN101214442A (en) * | 2007-12-26 | 2008-07-09 | 厦门大学 | Sulphur resistant carbon monoxide transfer catalyst and preparation thereof |
| CN101439289A (en) * | 2008-12-17 | 2009-05-27 | 中国石油天然气集团公司 | Preparation of hydrogenation catalyst |
| CN102049261B (en) * | 2010-11-18 | 2013-03-27 | 中国海洋石油总公司 | Method for preparing catalyst of acrolein by propylene oxidization |
| CN105579556A (en) * | 2013-09-18 | 2016-05-11 | 国际壳牌研究有限公司 | Methods and systems for supplying hydrogen to a hydrocatalytic reaction |
| CN103611544A (en) * | 2013-12-05 | 2014-03-05 | 湖北双雄催化剂有限公司 | Preparation method capable of improving low-temperature activity of low-pressure cobalt-molybdenum sulfur-tolerant shift catalyst |
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