CN112090435B - Cobalt-molybdenum-based sulfur-tolerant shift catalyst and preparation method and application thereof - Google Patents
Cobalt-molybdenum-based sulfur-tolerant shift catalyst and preparation method and application thereof Download PDFInfo
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- CN112090435B CN112090435B CN201910527894.2A CN201910527894A CN112090435B CN 112090435 B CN112090435 B CN 112090435B CN 201910527894 A CN201910527894 A CN 201910527894A CN 112090435 B CN112090435 B CN 112090435B
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- cobalt
- molybdenum
- catalyst
- carrier
- oxide
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- 239000003054 catalyst Substances 0.000 title claims abstract description 143
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 42
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 37
- 239000010941 cobalt Substances 0.000 claims abstract description 37
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 37
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000007788 liquid Substances 0.000 claims abstract description 25
- 238000007654 immersion Methods 0.000 claims abstract description 23
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 23
- 239000011733 molybdenum Substances 0.000 claims abstract description 23
- 230000002378 acidificating effect Effects 0.000 claims abstract description 22
- -1 molybdenum phosphorus compound Chemical class 0.000 claims abstract description 21
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000011574 phosphorus Substances 0.000 claims abstract description 17
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 13
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical group O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000002791 soaking Methods 0.000 claims abstract description 10
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 33
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical group [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 33
- 239000011148 porous material Substances 0.000 claims description 27
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 22
- 238000009826 distribution Methods 0.000 claims description 21
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 15
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 229910052717 sulfur Inorganic materials 0.000 claims description 12
- 239000011593 sulfur Substances 0.000 claims description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 9
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical group [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- 239000000395 magnesium oxide Substances 0.000 claims description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 7
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical group [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 7
- 102000002322 Egg Proteins Human genes 0.000 claims description 5
- 108010000912 Egg Proteins Proteins 0.000 claims description 5
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 5
- 239000012752 auxiliary agent Substances 0.000 claims description 5
- 210000003278 egg shell Anatomy 0.000 claims description 5
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 5
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000292 calcium oxide Substances 0.000 claims description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 4
- 229940011182 cobalt acetate Drugs 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 2
- 238000001802 infusion Methods 0.000 claims description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 239000002671 adjuvant Substances 0.000 claims 1
- KDPJLLVSZLZTAN-UHFFFAOYSA-K cobalt(3+);carbonate;hydroxide Chemical compound [OH-].[Co+3].[O-]C([O-])=O KDPJLLVSZLZTAN-UHFFFAOYSA-K 0.000 claims 1
- 238000010304 firing Methods 0.000 claims 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 abstract description 10
- 230000003647 oxidation Effects 0.000 abstract description 9
- 238000007254 oxidation reaction Methods 0.000 abstract description 9
- 238000004073 vulcanization Methods 0.000 abstract description 7
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 abstract description 5
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 abstract description 5
- 239000006185 dispersion Substances 0.000 abstract description 5
- 230000009467 reduction Effects 0.000 abstract description 4
- 238000011946 reduction process Methods 0.000 abstract description 2
- 238000005470 impregnation Methods 0.000 description 17
- 239000000243 solution Substances 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 229910001429 cobalt ion Inorganic materials 0.000 description 10
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 238000007598 dipping method Methods 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 239000011964 heteropoly acid Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 150000001868 cobalt Chemical class 0.000 description 5
- 238000009827 uniform distribution Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 4
- 239000011609 ammonium molybdate Substances 0.000 description 4
- 235000018660 ammonium molybdate Nutrition 0.000 description 4
- 229940010552 ammonium molybdate Drugs 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000012702 metal oxide precursor Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- POTRNMJIMIESGR-UHFFFAOYSA-L cobalt(2+);diacetate;hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O POTRNMJIMIESGR-UHFFFAOYSA-L 0.000 description 3
- OBWXQDHWLMJOOD-UHFFFAOYSA-H cobalt(2+);dicarbonate;dihydroxide;hydrate Chemical group O.[OH-].[OH-].[Co+2].[Co+2].[Co+2].[O-]C([O-])=O.[O-]C([O-])=O OBWXQDHWLMJOOD-UHFFFAOYSA-H 0.000 description 3
- 230000009849 deactivation Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 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 2
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000011363 dried mixture Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000002751 molybdenum Chemical class 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 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
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- 206010037423 Pulmonary oedema Diseases 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 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
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical group 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 1
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 208000006673 asthma Diseases 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical group N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 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
- 239000008139 complexing agent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 150000004715 keto acids Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- AMWVZPDSWLOFKA-UHFFFAOYSA-N phosphanylidynemolybdenum Chemical compound [Mo]#P AMWVZPDSWLOFKA-UHFFFAOYSA-N 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 208000005333 pulmonary edema Diseases 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
- C01B2203/1241—Natural gas or methane
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- 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
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Abstract
The invention relates to the field of preparation of water gas shift catalysts, and discloses a cobalt-molybdenum-based sulfur-tolerant shift catalyst, and a preparation method and application thereof. Wherein, the method comprises the following steps: preparing an acidic co-immersion liquid containing a cobalt source and a molybdenum source; (2) soaking the acidic co-soaking solution and a carrier in equal volume; and (3) drying and roasting the product obtained in the step (2); wherein the molybdenum source is phosphomolybdic acid. According to the method, ammonia water is not used in the preparation process, a cobalt source is prevented from generating a large amount of cobalt hydroxide under an alkaline condition, the dispersion of cobalt is promoted, the preparation process is shortened, and the introduction of the phosphorus element can enable a molybdenum phosphorus compound and/or a cobalt molybdenum phosphorus compound to form partial phosphide in the reduction and vulcanization process, so that the oxidation resistance of the catalyst is enhanced, and the stability of the catalyst is improved.
Description
Technical Field
The invention relates to the field of preparation of water gas shift catalysts, in particular to a cobalt-molybdenum-based sulfur-tolerant shift catalyst and a preparation method and application thereof.
Background
The water gas shift reaction can catalytically convert CO and water vapor in the coal gasification product into H 2 And CO 2 To achieve the purpose of hydrogen production or adjusting CO/H in reaction gas 2 The proportion is high, so the method has wide application in the aspects of direct coal liquefaction, ammonia synthesis industry, methanol synthesis, methanol-to-olefin, fischer-Tropsch synthesis and the like.
At present, an iron-chromium-based catalyst, a copper-zinc-based catalyst and a cobalt-molybdenum-based shift catalyst can play a role in catalyzing shift reaction, but compared with the iron-chromium-based catalyst and the copper-zinc-based catalyst, the catalyst taking cobalt and molybdenum as active components has the advantages of sulfur resistance, wide reaction temperature range, no chromium and the like, and is widely used in shift equipment at home and abroad.
At present, the preparation method of the cobalt-molybdenum-based sulfur-tolerant shift catalyst is mainly prepared by a kneading method and an impregnation method, compared with the kneading method, the impregnation method has the advantages that active components are more dispersed, the catalyst activity is high, and the distribution of the active components in a carrier can be controlled, and the common loading of the active components cobalt and molybdenum is to prepare a precursor of the cobalt and molybdenum active components into a solution and then load the solution on the catalyst carrier by the impregnation method.
CN1089634C discloses a preparation method of a low-sulfur resistant cobalt-molybdenum sulfur-tolerant shift catalyst, which is to use carrier active gamma-Al 2 O 3 Co-dipping by using an ammonia water solution consisting of soluble cobalt salt, ammonium molybdate and potassium carbonate, wherein the concentration of each component of the dipping solution is 4% of soluble cobalt salt, 10% of ammonium molybdate, 12.5% of potassium carbonate and 1% of ammonia, and drying at 50-150 ℃ after dipping, and the method is characterized in that any soluble sylvite selected from oxoacid nitric acid, nitrous acid, sulfurous acid, sulfuric acid, thiosulfuric acid, tungstic acid, acetic acid and oxalic acid is added into the dipping solution, and the adding amount is 1% -10% of the weight of the dipping solution.
CN103949285B discloses a method for preparing a wide temperature range sulfur-tolerant shift catalyst by using heteropolyacid as a precursor, wherein the catalyst uses active alumina or magnesium aluminate spinel as a carrier, heteropolyacid or heteropolyacid salt as an active component, and the catalyst is used for catalyzing water gas shift reaction. The heteropolyacid salt comprises: sodium salt, potassium salt or ammonium salt of heteropoly acid, and the element of hetero atom in heteropoly acid is the eighth group element, and the element of complex atom is the sixth subgroup element.
CN106925355A discloses an impregnation liquid, wherein the impregnation liquid comprises a mixed solution prepared from a complexing agent, a metal cobalt salt and a metal molybdenum salt, the mixed solution is adjusted in pH value by ammonia water, the metal cobalt salt is basic cobalt carbonate, and the impregnation liquid is used for preparing a cobalt-molybdenum-based sulfur-tolerant shift catalyst by an impregnation method with magnesium aluminate spinel as a carrier. Wherein the molybdenum salt is ammonium molybdate tetrahydrate.
However, ammonium molybdate and cobalt salt are not mutually soluble in water, and a large amount of concentrated ammonia water is required to be added to prepare a solution of the cobalt-molybdenum precursor to increase the solubility of ammonium molybdate. Strong irritation of strong ammonia water, and short breath, asthma, pulmonary edema and the like can be caused by long-time contact of strong ammonia water.
Therefore, the research on the environment-friendly cobalt-molybdenum-based sulfur-tolerant shift catalyst and the preparation method thereof have important significance.
Disclosure of Invention
The invention aims to solve the problem that a large amount of strong ammonia water is needed to pollute the environment in the process of preparing a cobalt-molybdenum-based sulfur-tolerant shift catalyst in the prior art, and provides the cobalt-molybdenum-based sulfur-tolerant shift catalyst and a preparation method and application thereof. The method avoids using ammonia water in the preparation process, prevents a cobalt source from generating a large amount of cobalt hydroxide under an alkaline condition, promotes the dispersion of cobalt, shortens the preparation process, and can lead the molybdenum-phosphorus compound and/or the cobalt-molybdenum-phosphorus compound to form partial phosphide in the reduction and vulcanization process by introducing phosphorus, thereby enhancing the oxidation resistance of the catalyst and improving the stability of the catalyst.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing a cobalt-molybdenum-based sulfur-tolerant shift catalyst, wherein the method comprises:
(1) Preparing an acidic co-immersion liquid containing a cobalt source and a molybdenum source;
(2) Soaking the acidic co-soaking solution and the carrier in equal volume; and
(3) Drying and roasting the product obtained in the step (2);
wherein the molybdenum source is phosphomolybdic acid.
In a second aspect, the present invention provides a cobalt-molybdenum-based sulfur-tolerant shift catalyst, wherein the catalyst comprises a carrier and an active component loaded on the carrier, wherein the active component is cobalt oxide, molybdenum oxide and phosphide, and preferably, the phosphide comprises a cobalt-molybdenum-phosphorus compound and/or a molybdenum-phosphorus compound.
In a third aspect, the invention provides the cobalt-molybdenum-based sulfur-tolerant shift catalyst prepared by the method or the application of the cobalt-molybdenum-based sulfur-tolerant shift catalyst in water-gas shift reaction.
By adopting the technical scheme, ammonia water is avoided in the preparation process, the preparation flow is shortened, and the introduction of phosphorus can enable the molybdenum phosphorus compound and/or the cobalt molybdenum phosphorus compound to form partial phosphide in the reduction vulcanization process, so that the oxidation resistance of the catalyst is enhanced, and the stability of the catalyst is improved.
Drawings
FIG. 1 is an XRD pattern of a catalyst prepared according to example 2 of the present invention;
FIG. 2 is a schematic representation of the radial distribution test points of cobalt oxide in the catalyst from the center of the sphere to the surface layer;
FIG. 3 is a radial distribution, eggshell distribution, of cobalt oxide in the catalyst prepared in accordance with example 1 of the present invention;
FIG. 4 is a radial distribution of cobalt oxide in the catalyst prepared in example 2 of the present invention, in a uniform distribution;
FIG. 5 is a schematic representation of a catalyst prepared in example 2 of the present invention after drying at room temperature;
fig. 6 is a view showing the appearance of the catalyst prepared in comparative example 3 after drying at room temperature.
Detailed Description
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 numerical ranges, each range between its endpoints and individual point values, and each individual point value can be combined with each other to give one or more new numerical ranges, and such numerical ranges should be construed as specifically disclosed herein.
The first aspect of the present invention provides a preparation method of the cobalt-molybdenum-based sulfur-tolerant shift catalyst, wherein the method comprises:
(1) Preparing an acidic co-immersion liquid containing a cobalt source and a molybdenum source;
(2) Soaking the acidic co-soaking solution and the carrier in equal volume; and
(3) Drying and roasting the product obtained in the step (2);
wherein the molybdenum source is phosphomolybdic acid.
According to the method, when the acid co-immersion liquid and the carrier are co-immersed, the surface of the carrier is positively charged, the diffusion speed and the adsorption speed of cobalt ions with positive charges in the solution can be influenced, the adsorption speed of the cobalt ions with positive charges on the surface of the carrier can be reduced, the cobalt ions with positive charges can be favorably diffused in the pore channels of the carrier, and the cobalt ions with positive charges can be diffused more uniformly.
According to the present invention, the phosphomolybdic acid may be commercially available, or may be prepared by using molybdenum oxide and phosphoric acid, and in the present invention, the molybdenum source may be commercially available, for example, from Zhengzhou Dongda chemical products Co., ltd.
According to the invention, the cobalt source can be one or more of cobalt nitrate, basic cobalt carbonate and cobalt acetate, wherein the cobalt nitrate can be cobalt nitrate hexahydrate, and the cobalt acetate can be cobalt acetate hexahydrate. In addition, in the present invention, the cobalt source may be commercially available, for example, from Guangzhou Delhi Chemicals, inc.
According to the invention, in the preparation of an acidic co-infusion, the cobalt source and the molybdenum source may be dissolved in water or ethanol; among them, water is not particularly limited, and deionized water is preferable. In the present invention, when the cobalt source and the molybdenum source are dissolved in water, the pH of the acidic co-immersion liquid is 7 or less, preferably 1 to 6, more preferably 3 to 5; in the present invention, when the cobalt source and the molybdenum source are dissolved in ethanol, the pH of the acidic co-immersion liquid is 0.1 to 2, preferably 0.5 to 1. In the present invention, when the cobalt source and the molybdenum source are dissolved in water, the pH is 7 or less, whereas when the cobalt source and the molybdenum source are dissolved in ethanol, the pH is relatively low because the hydrogen ions are not hydrated and exhibit strong acid properties when the acid is in an organic solvent, for example, ethanol.
In the present invention, the advantages of impregnating the co-immersion liquid of the cobalt source and the molybdenum source with the same volume of the carrier under acidic conditions are: because molybdenum ions mainly exist in a hexacoordinate form in the acid impregnation liquid, the prepared cobalt-molybdenum-based sulfur-tolerant shift catalyst is easier to form molybdenum octahedron species after roasting, presents an octahedron structure and is easier to sulfide and reduce, partial phosphide formed after introducing phosphorus element has better oxidation resistance, ammonia water is avoided in the technical process, a cobalt source is prevented from generating a large amount of cobalt hydroxide under an alkaline condition, the dispersion of cobalt is promoted, the preparation process is shortened, and the preparation method is more environment-friendly.
According to the invention, the conditions of drying include: the temperature is 80-150 ℃, and the time is 2-24h; preferably, the temperature is 100-120 ℃ and the time is 8-12h.
According to the invention, the conditions of the calcination include: the temperature is 300-600 ℃, and the time is 2-10h; preferably, the temperature is 400-500 ℃ and the time is 2-8h, more preferably 3-5h.
According to the invention, the method also comprises the addition of an auxiliary agent to the acidic co-immersion liquid; wherein, the auxiliary agent can be one or more of citric acid, phosphoric acid and tartaric acid, and citric acid and/or phosphoric acid are preferred. In the present invention, the addition of the auxiliary agent serves to promote dissolution and dispersion of cobalt ions and to increase a certain acidity, and further, when phosphoric acid is used, a certain amount of phosphorus element can be added.
Citric acid is commercially available, for example, from Renjin Chemicals, inc., tianjin, and phosphoric acid is commercially available, for example, from Aladdin reagent, inc.
According to the present invention, the carrier may be one or more of a spherical shape, a strip shape, a clover shape and a dentate sphere shape; in addition, in the present invention, the support may be one or more of alumina, alkaline earth metal oxide-modified alumina, and rare earth metal oxide-modified alumina; wherein, the alkaline earth metal oxide can be magnesium oxide and/or calcium oxide; the rare earth metal oxide may be lanthanum oxide and/or cerium oxide. In the present invention, alumina, an alkaline earth metal oxide precursor and a rare earth metal oxide precursor are commercially available, for example, alumina is available from Shandong division, aluminum industries, inc. of China, and an alkaline earth metal oxide precursor and a rare earth metal oxide precursor are available from Shandong desheng New materials, inc.
According to the invention, the average of the supportThe particle diameter can be 1-6mm, and the specific surface area can be 150-300m 2 The pore volume can be 0.4-0.8mL/g, and the most probable pore diameter can be 4-12nm; preferably, the carrier has an average particle diameter of 2 to 5mm and a specific surface area of 180 to 250m 2 Pore volume of 0.5-0.7mL/g, and most probable pore diameter of 6-10nm. In the present invention, the structural parameters of the carrier are controlled within the aforementioned ranges, and the active ingredient can be more preferably supported on the carrier.
According to the invention, the cobalt source, the molybdenum source, the support and optionally the promoter are used in amounts such that in the cobalt-molybdenum based sulfur-tolerant shift catalyst prepared: based on the total weight of the cobalt-molybdenum-based sulfur-tolerant shift catalyst, the content of the carrier is 70-95 wt%, the content of cobalt element is 0.8-4.8 wt%, the content of molybdenum element is 2-10 wt%, and the content of phosphorus element is 0.05-0.3 wt%; preferably, the content of the carrier is 70-94 wt%, the content of cobalt element is 1.3-4.0 wt%, the content of molybdenum element is 4-7 wt%, and the content of phosphorus element is 0.1-0.2 wt%, based on the total weight of the cobalt-molybdenum-based sulfur-tolerant shift catalyst.
In a second aspect, the present invention provides a cobalt-molybdenum-based sulfur-tolerant shift catalyst, wherein the catalyst comprises a carrier and an active component loaded on the carrier, wherein the active component is cobalt oxide, molybdenum oxide and phosphide.
According to the invention, the cobalt-molybdenum-based sulfur-tolerant shift catalyst contains an active component cobalt-molybdenum-phosphorus compound and/or molybdenum-phosphorus compound, preferably, the cobalt-molybdenum-based sulfur-tolerant shift catalyst contains an active component cobalt-molybdenum-phosphorus compound and molybdenum-phosphorus compound, and because a phosphorus element is introduced in the preparation method process, the molybdenum-phosphorus compound and/or cobalt-molybdenum-phosphorus compound in the catalyst forms a partial phosphide in the reduction vulcanization process, and the phosphide has higher water vapor oxidation resistance than sulfide, so that the oxidation resistance of the catalyst is enhanced, and the activity and stability of the catalyst can be improved.
According to the invention, the cobalt-molybdenum-based sulfur-tolerant shift catalyst is prepared by adopting an impregnation method, wherein the impregnation method for preparing the catalyst comprises isometric impregnation (dry impregnation) and over-volume impregnation (wet impregnation), and preferably isometric impregnation is adopted; compared with a kneading method (the kneading method can be used for directly forming a precursor of an active component while mixing and crosslinking carrier raw materials, and has a simple process) the impregnation method has the advantages that the distribution of the active component in the carrier can be controlled, a catalyst with enriched surface or uniformly dispersed active component can be obtained, the utilization rate of the active component is improved, the dispersion degree of the active component is higher, and the activity of the catalyst is improved. For example, fig. 2 is a schematic diagram of the radial distribution test points of cobalt oxide in the catalyst from the center of the sphere to the surface layer, and it can be seen from fig. 2 that the active component can be dispersed in the interior and/or on the surface of the catalyst.
According to the invention, based on the total weight of the cobalt-molybdenum-based sulfur-tolerant shift catalyst, the content of the carrier is 70-95 wt%, the content of cobalt element is 0.8-4.8 wt%, the content of molybdenum element is 2-10 wt%, and the content of phosphorus element is 0.05-0.3 wt%; preferably, the content of the carrier is 70-94 wt%, the content of cobalt element is 1.3-4.0 wt%, the content of molybdenum element is 4-7 wt%, and the content of phosphorus element is 0.1-0.2 wt%, based on the total weight of the cobalt-molybdenum-based sulfur-tolerant shift catalyst. In the present invention, controlling the content of each active component within the aforementioned range can improve the stability of the catalyst.
According to the invention, the molybdenum oxide may have a tetrahedral structure and/or an octahedral structure.
According to the invention, the active components are dispersed in the form of ions or complexes in the solution, enter the pores of the carrier or are attached to the surface of the carrier through capillary action in the impregnation process, and are subjected to chemical adsorption and physical adsorption in the pores or on the surface of the carrier, when the catalyst is dried, the solvent is evaporated to separate out the active components, so that solid substances are formed, and then the solid substances are decomposed at a higher roasting temperature to form metal oxides with certain dispersity, and the metal oxides are loaded in the pores of the carrier or are attached to the surface of the carrier, wherein the radial distribution of the cobalt oxide comprises two types: an eggshell-type radial distribution predominantly attached to the exterior of the carrier and/or a uniform type radial distribution predominantly distributed to the interior and exterior of the carrier. The method comprises the steps of preparing an ethanol solvent, preparing a carrier, preparing an acidic immersion liquid, and carrying out cobalt ion deposition on the carrier, wherein the ethanol solvent has a high volatilization speed and a high deposition speed of active component cobalt ions, so that the radial distribution of cobalt oxide is in an eggshell shape mainly attached to the outside of the carrier, and the surface of the carrier is positively charged in the acidic immersion liquid, so that the diffusion speed and the adsorption speed of the positively charged cobalt ions in the solution are influenced, the adsorption speed of the positively charged cobalt ions on the surface of the carrier is reduced, and the uniform diffusion of the positively charged cobalt ions in a carrier pore channel is facilitated, so that the radial distribution of cobalt oxide is in uniform radial distribution mainly distributed inside and outside the carrier.
According to the invention, the catalyst has an average particle diameter of 1 to 6mm and a specific surface area of 70 to 200m 2 The pore volume is 0.1-0.8mL/g, and the most probable pore diameter is 4-50nm; preferably, the catalyst has an average particle diameter of 2 to 5mm and a specific surface area of 80 to 150m 2 Pore volume of 0.2-0.5mL/g, and most probable pore diameter of 8-25nm.
According to the present invention, the specific surface area, pore volume and most probable pore diameter were measured according to the nitrogen adsorption method.
According to the invention, by controlling the amount of each reaction raw material and the reaction conditions, the cobalt source, the molybdenum source and the carrier defined by the invention can be used to prepare the catalyst with high oxidation resistance and stability under simple operation conditions, and the structural parameters of the catalyst are controlled within the range, so that the catalyst in an oxidation state can be obtained, and the activity and the stability of the catalyst can be improved.
In a third aspect, the invention provides a use of the cobalt-molybdenum-based sulfur-tolerant shift catalyst prepared by the cobalt-molybdenum-based sulfur-tolerant shift catalyst or the method in water-gas shift reaction.
According to the invention, the cobalt-molybdenum-based sulfur-tolerant shift catalyst or the cobalt-molybdenum-based sulfur-tolerant shift catalyst prepared by the method can catalyze the water-gas shift reaction after being sulfurized.
According to the invention, the vulcanization treatment can be carried out at a temperature of 250 to 450 ℃ with H 2 S/H 2 Vulcanizing; the cobalt molybdenum in a sulfided state is an active phase of the sulfur-tolerant shift catalyst, is easily oxidized to an oxide under high water-gas ratio and high temperature conditions, and the cobalt and/or molybdenum phosphide has unique catalytic properties and higher oxidation resistance compared to the metal and metal sulfide in a reduced state.
The present invention will be described in detail below by way of examples.
Example 1
This example illustrates a cobalt molybdenum based sulfur tolerant shift catalyst prepared by the process of the present invention.
Dissolving 3.7g of cobalt nitrate hexahydrate and 2.25g of phosphomolybdic acid in ethanol, and adjusting the volume of the solution to be 12mL, wherein the pH value of the acidic co-immersion liquid is 0.53; soaking the alumina carrier in an equal volume soaking mode on 21.5g of the alumina carrier, airing the alumina carrier at room temperature, drying the alumina carrier at 120 ℃ for 5 hours, and roasting the alumina carrier at 500 ℃ for 5 hours; wherein the alumina carrier is spherical, has an average particle diameter of 4mm and a specific surface area of 200m 2 Pore volume of 0.64mL/g, and most probable pore diameter of 8.6nm.
As a result, a catalyst S1 was prepared, of which cobalt oxide (cobalt oxide) was attached to the outside of the carrier, i.e., an eggshell type distribution; the molybdenum oxide is in an octahedral structure; the catalyst had a carrier content of 81.5 wt%, a cobalt element content of 3.1 wt%, a molybdenum element content of 5.2 wt%, and a phosphorus element content of 0.13 wt%, based on the total weight of the catalyst, and the structural parameters of the catalyst are shown in table 1.
In addition, FIG. 3 is a radial distribution diagram of cobalt oxide in the catalyst prepared in example 1 of the present invention, in an eggshell type distribution; wherein, the abscissa is the distance from the center of the catalyst sphere to the test point, and the ordinate is the percentage content of cobalt oxide, and can be seen as follows: the percentage of cobalt oxide increased gradually with increasing distance tested from inside to outside, indicating that cobalt oxide was attached to the outside of the support. The characterization shows that the XRD pattern of the catalyst does not observe the crystalline phase peaks of cobalt oxide, molybdenum oxide and phosphide, and the judgment of professional knowledge of the catalyst shows that the active phase of the catalyst is relatively dispersed, which shows that the catalyst prepared in example 1 has good effect.
Example 2
This example illustrates a cobalt molybdenum based sulfur tolerant shift catalyst prepared by the process of the present invention.
Dissolving 2.25g of cobalt acetate tetrahydrate and 2.4g of phosphomolybdic acid in water, and adjusting the volume of the solution to be 12mL, wherein the pH value of the acidic co-immersion liquid is 4.37; dipping the mixture on 23g of alumina carrier modified by magnesium oxide and calcium oxide in an equal-volume dipping mode, drying the mixture at room temperature, drying the dried mixture for 12 hours at 120 ℃, and roasting the dried mixture for 3 hours at 550 ℃; wherein the alumina carrier is spherical, has an average particle diameter of 4mm and a specific surface area of 200m 2 Pore volume 0.64mL/g, and best mode pore diameter 8.6nm.
As a result, a catalyst S2 having a cobalt oxide (cobalt oxide) distributed inside and outside the carrier, i.e., a uniform distribution, was prepared; the molybdenum oxide has a tetrahedral and octahedral structure; based on the total weight of the catalyst, the content of the carrier was 87.5 wt%, the content of cobalt element was 3.1 wt%, the content of molybdenum element was 5.7 wt%, and the content of phosphorus element was 0.14 wt%.
The structural parameters of the catalyst are shown in table 1.
In addition, FIG. 4 is a radial distribution diagram of cobalt oxide in the catalyst prepared in example 2 of the present invention, in a uniform distribution; wherein, the abscissa is the distance from the center of the catalyst sphere to the test point, and the ordinate is the percentage content of cobalt oxide, and can be seen as follows: the percent content of the cobalt oxide does not greatly fluctuate with the increase of the testing distance from inside to outside, and the cobalt oxide is in a uniform distribution state, which shows that the cobalt oxide is distributed in the inside and the outside of the carrier.
In addition, fig. 1 is an XRD chart of the catalyst prepared in example 2 of the present invention, from which it can be seen that no crystalline phase peaks of cobalt oxide, molybdenum oxide and phosphide are observed, and it can be concluded from catalyst expertise that such a catalyst active phase is relatively dispersed, and if crystalline phase peaks of cobalt oxide, molybdenum oxide and phosphide are observed, the effect is not good, and thus, the XRD chart shows that the catalyst prepared in example 2 is good.
Example 3
This example illustrates a cobalt molybdenum based sulfur tolerant shift catalyst prepared by the process of the present invention.
1.66g of basic cobalt carbonate, 2.4g of phosphomolybdic acid and 2.49g of citric acid are dissolved in water, and the volume of the solution is adjusted to be 14mL; wherein the pH value of the acidic co-immersion liquid is 3.5, the acidic co-immersion liquid is immersed on 23g of magnesium oxide modified alumina carrier in an immersion mode, and is dried at room temperature, dried for 5 hours at 150 ℃, and roasted for 3 hours at 550 ℃; wherein, the shape of the alumina carrier modified by the magnesium oxide is spherical, the average grain diameter is 3mm, and the specific surface area is 180m 2 Pore volume of 0.5mL/g, and most probable pore diameter of 8nm.
As a result, a catalyst S3 having a cobalt oxide (cobalt oxide) distributed inside and outside the carrier, i.e., a uniform type distribution, was prepared; the molybdenum oxide has a tetrahedral and octahedral structure; based on the total weight of the catalyst, the content of the carrier was 87.5 wt%, the content of cobalt element was 3.1 wt%, the content of molybdenum element was 5.5 wt%, and the content of phosphorus element was 0.14 wt%. The characterization shows that the XRD pattern of the catalyst does not observe crystalline phase peaks of cobalt oxide, molybdenum oxide and phosphide, and the judgment of professional knowledge of the catalyst shows that the active phase of the catalyst is relatively dispersed, which indicates that the catalyst prepared in example 3 has good effect.
The structural parameters of the catalyst are shown in table 1.
Example 4
This example illustrates a cobalt molybdenum based sulfur tolerant shift catalyst prepared by the method of the present invention.
Dissolving 2.25g of cobalt acetate hexahydrate and 2.4g of phosphomolybdic acid in water, adding 0.1mL85% phosphoric acid, and adjusting the volume of the solution to be 13.5mL; the pH value of the acid co-immersion liquid is 4.02, the acid co-immersion liquid is immersed on 23g of alumina carrier modified by magnesium oxide and lanthanum oxide auxiliary agent in an immersion mode, after being dried in the air at room temperature, the acid co-immersion liquid is dried for 10 hours at 120 ℃, and is roasted for 5 hours at 400 ℃; wherein the lanthanum oxide modified alumina carrier is spherical, the average particle diameter is 5mm, and the specific surface area is195m 2 Pore volume 0.53mL/g, and best mode pore diameter 8.2nm.
As a result, a catalyst S4 having a cobalt oxide (cobalt oxide) distributed inside and outside the carrier, i.e., a uniform distribution, was prepared; the molybdenum oxide has a tetrahedral and octahedral structure; based on the total weight of the catalyst, the content of the carrier was 87.1 wt%, the content of cobalt element was 3.1 wt%, the content of molybdenum element was 5.5 wt%, and the content of phosphorus element was 0.16 wt%. The characterization shows that the XRD pattern of the catalyst does not observe crystalline phase peaks of cobalt oxide, molybdenum oxide and phosphide, and the judgment of professional knowledge of the catalyst shows that the active phase of the catalyst is relatively dispersed, which shows that the catalyst prepared in example 4 has good effect.
The structural parameters of the catalyst are shown in table 1.
In addition, FIG. 5 is a schematic view of the catalyst prepared in example 4 of the present invention after drying at room temperature, from which it can be seen that the catalyst surface is substantially free of black cobalt hydroxide.
Comparative example 1
A cobalt molybdenum based sulfur tolerant shift catalyst was prepared in the same manner as in example 2, except that: the amount of cobalt acetate hexahydrate and phosphomolybdic acid and the amount of magnesium oxide and calcium oxide modified alumina support were such that the resulting catalyst DS1 was prepared, and based on the total weight of the catalyst, the support was 97 wt%, the cobalt element was 0.5 wt%, the molybdenum element was 1.5 wt%, and the phosphorus element was 0.04 wt%.
The structural parameters of the catalyst are shown in table 1.
Comparative example 2
A cobalt-molybdenum-based sulfur-tolerant shift catalyst was prepared in the same manner as in example 3, except that: the phosphomolybdic acid was replaced with ammonium heptamolybdate and dissolved using 17% ammonia, the pH of the alkaline co-immersion liquid was 10.
As a result, a catalyst DS2 was prepared, and the content of the carrier was 87.6 wt%, the content of cobalt element was 3.1 wt%, the content of molybdenum element was 5.5 wt%, and the content of phosphorus element was 0 wt%, based on the total weight of the catalyst. And the structural parameters of the catalyst are shown in table 1.
Wherein fig. 6 is a view showing the appearance of the catalyst of comparative example 2 after drying at room temperature, and it can be seen from fig. 6 that the catalyst surface had a distinct black cobalt hydroxide.
TABLE 1
Test example 1
The sulfur tolerant shift catalysts of examples 1-4 and comparative examples 1-2 provided by the present invention were evaluated.
The reaction was carried out on a microreaction evaluating apparatus. The amount of the catalyst of 20 to 40 mesh packed was 0.5g, and the result of dilution with 1g of quartz sand is shown in Table 2.
1. Catalyst sulfidation
The catalyst is mixed with a sulfurated gas (H) 2 S and H 2 In which H is 2 The volume content of S is 3 percent) is contacted for 5 hours at the vulcanization temperature of 450 ℃ for vulcanization. Obtaining the sulfuration catalyst.
2. Catalyst evaluation
And contacting the sulfurized catalyst serving as a fresh agent with feed gas to evaluate the catalyst.
The conditions are as follows: reacting for 4H at 450 deg.C, heating to 550 deg.C for 4H, cooling to 450 deg.C for 4H, and reacting at 0.1MPa with feed gas composition (v/v) of H 2 O/CO/N 2 /H 2 /H 2 S＝49.89％/40.76％/4.33％/4.86％/0.15％。
TABLE 2
| CO conversion (%) | Accelerated deactivation Retention (%) | |
| Example 1 | 52.1 | 52.8 |
| Example 2 | 48.8 | 54.6 |
| Example 3 | 53.8 | 51.2 |
| Example 4 | 49.1 | 54.1 |
| Comparative example 1 | 18.9 | 49.8 |
| Comparative example 3 | 41.9 | 50.0 |
As can be seen from the results in Table 2, the catalysts prepared in examples 1-4 of the present invention have higher CO conversion and accelerated deactivation retention than those of comparative examples 1-2, which shows that the catalysts prepared in the present invention have not only higher activity but also better accelerated deactivation stability.
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, simple modifications can be made to the technical solution of the invention, including combinations of the 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 (15)
1. A preparation method of a cobalt-molybdenum-based sulfur-tolerant shift catalyst is characterized by comprising the following steps:
(1) Preparing an acidic co-immersion liquid containing a cobalt source and a molybdenum source, wherein the molybdenum source is phosphomolybdic acid;
(2) Soaking the acidic co-soaking solution and the carrier in equal volume; the carrier is one or more of alumina, alumina modified by alkaline earth metal oxide and alumina modified by rare earth metal oxide; the average particle diameter of the carrier is 1-6mm, and the specific surface area is 150-300m 2 The pore volume is 0.4-0.8mL/g, and the most probable pore diameter is 4-12nm;
(3) Drying and roasting the product obtained in the step (2);
the cobalt source, the molybdenum source and the carrier are used in such amounts that the content of the carrier is 70-95 wt%, the content of cobalt element is 0.8-4.8 wt%, the content of molybdenum element is 2-10 wt% and the content of phosphorus element is 0.05-0.3 wt% in the prepared cobalt-molybdenum-based sulfur-tolerant shift catalyst based on the total weight of the cobalt-molybdenum-based sulfur-tolerant shift catalyst.
2. The method of claim 1, wherein the cobalt source is one or more of cobalt nitrate, cobalt carbonate hydroxide, and cobalt acetate.
3. The method according to claim 1, wherein the acidic co-immersion liquid has a pH of less than 7.
4. A method according to claim 3, wherein the acidic co-immersion liquid has a pH of 1-6.
5. The method of claim 1, wherein the firing conditions comprise: the temperature is 300-600 ℃, and the time is 2-10h.
6. A method according to any one of claims 1 to 5, further comprising adding an auxiliary agent to the acidic co-infusion.
7. The method of claim 6, wherein the adjuvant is one or more of citric acid, phosphoric acid, and tartaric acid.
8. The method of claim 1, wherein the carrier is one or more of spherical, strip-shaped, clover-shaped, and dentate spherical.
9. The method of claim 1, wherein the alkaline earth metal oxide is magnesium oxide and/or calcium oxide; the rare earth metal oxide is lanthanum oxide and/or cerium oxide.
10. A cobalt molybdenum based sulfur tolerant shift catalyst prepared by the process of any one of claims 1 to 9, comprising a support and an active component supported on the support, wherein the active component is cobalt oxide, molybdenum oxide and phosphide.
11. The catalyst of claim 10, wherein the phosphide comprises a cobalt molybdenum phosphorus compound and/or a molybdenum phosphorus compound.
12. The catalyst of claim 10, wherein the type of radial distribution of cobalt oxide comprises: an eggshell distribution attached to the exterior of the carrier and/or a homogeneous type distribution distributed both internally and externally of the carrier.
13. The catalyst of claim 10, wherein the molybdenum oxide is of a tetrahedral structure and/or an octahedral structure.
14. According to any one of claims 10-13The catalyst, wherein the average particle diameter of the catalyst is 1-6mm, and the specific surface area is 70-200m 2 Pore volume of 0.1-0.8mL/g, and most probable pore diameter of 4-50nm.
15. Use of a cobalt molybdenum based sulfur tolerant shift catalyst prepared by the process of any one of claims 1 to 9 or the cobalt molybdenum based sulfur tolerant shift catalyst of any one of claims 10 to 14 in a water gas shift reaction.
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