CN109201071B - Sulfur-tolerant shift catalyst and preparation method thereof - Google Patents
Sulfur-tolerant shift catalyst and preparation method thereof Download PDFInfo
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- CN109201071B CN109201071B CN201710536442.1A CN201710536442A CN109201071B CN 109201071 B CN109201071 B CN 109201071B CN 201710536442 A CN201710536442 A CN 201710536442A CN 109201071 B CN109201071 B CN 109201071B
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- sulfur
- containing compound
- shift catalyst
- oxide
- cobalt
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- 239000003054 catalyst Substances 0.000 title claims abstract description 154
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000001035 drying Methods 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 32
- 229910001868 water Inorganic materials 0.000 claims abstract description 32
- 238000004898 kneading Methods 0.000 claims abstract description 27
- 239000002243 precursor Substances 0.000 claims abstract description 27
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 25
- 239000011593 sulfur Substances 0.000 claims abstract description 25
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 22
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 19
- 239000010941 cobalt Substances 0.000 claims abstract description 19
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000011733 molybdenum Substances 0.000 claims abstract description 18
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000010955 niobium Substances 0.000 claims abstract description 14
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 13
- 238000001125 extrusion Methods 0.000 claims abstract description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 51
- 239000000395 magnesium oxide Substances 0.000 claims description 33
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 29
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 27
- 229910052593 corundum Inorganic materials 0.000 claims description 21
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 21
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 17
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical group O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 17
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical group [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 16
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 12
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 12
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical group [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 12
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 12
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 12
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 12
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 11
- 239000010936 titanium Substances 0.000 claims description 11
- 229910052719 titanium Inorganic materials 0.000 claims description 11
- UPWOEMHINGJHOB-UHFFFAOYSA-N cobalt(III) oxide Inorganic materials O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 claims description 10
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 9
- 239000004408 titanium dioxide Substances 0.000 claims description 8
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 7
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 6
- 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 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims description 2
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims description 2
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 239000004480 active ingredient Substances 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 13
- 239000000243 solution Substances 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 239000007789 gas Substances 0.000 description 11
- 229910052749 magnesium Inorganic materials 0.000 description 11
- 239000011777 magnesium Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 238000004073 vulcanization Methods 0.000 description 9
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 8
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical group [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- -1 magnesium aluminate Chemical class 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229910052596 spinel Inorganic materials 0.000 description 4
- 239000011029 spinel Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 3
- 239000004568 cement Substances 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000005987 sulfurization reaction Methods 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical group O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 239000011265 semifinished product Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910017318 Mo—Ni Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical group [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8877—Vanadium, tantalum, niobium or polonium
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the field of catalysts used in water gas shift reaction, and discloses a sulfur-tolerant shift catalyst and a preparation method thereof. The method comprises the following steps: (1) kneading a cobalt-containing compound, a molybdenum-containing compound, a niobium-containing compound, a carrier precursor and water; (2) carrying out extrusion molding on the product obtained by kneading, and carrying out first drying and first roasting; (3) and (3) carrying out water treatment on the product obtained in the step (2) at the temperature of 20-150 ℃ for 0.5-10h, and then carrying out second drying and second roasting to obtain the sulfur-resistant shift catalyst. The catalyst provided by the invention has the advantages of simple preparation method, high activity and good strength.
Description
Technical Field
The invention relates to the field of catalysts used in water gas shift reaction, in particular to a sulfur-tolerant shift catalyst and a preparation method thereof.
Background
The sulfur-tolerant shift reaction is a reaction process which is necessary to be undergone in the fields of ammonia synthesis, methanol synthesis, hydrogen production and the like, and the sulfur-tolerant shift catalyst is an essential important role in the fields. 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 has Co, Mo, K, Mg, Al, RE and other metals as main components. The catalyst is classified into a high-temperature sulfur-tolerant shift catalyst and a low-temperature sulfur-tolerant shift catalyst according to the use temperature. The high-temperature sulfur-tolerant shift catalyst adopts magnesium aluminate spinel as a carrier, and Co and Mo are active components. The low-temperature sulfur-tolerant shift catalyst adopts part of active alumina of magnesium aluminate spinel as a carrier, active components of Co and Mo and an auxiliary agent of K.
The shift reaction is carried out under the condition of high-temperature water vapor, the temperature can reach 470 ℃, and the ratio of the water vapor to the dry gas can reach 2:1 at most. Under the working condition of high-temperature high-water vapor-dry gas ratio, the carrier can be hydrated, and structural phase change can occur, so that the catalyst is inactivated. Thus, in addition to catalytic activity, stability is also an important factor that should be considered during the development of a shift catalyst.
CN105562022A discloses a high space velocity sulfur-tolerant pre-shift catalyst and a preparation method thereof, the catalyst takes magnesium, aluminum and titanium as composite carriers, molybdenum, cobalt and nickel as active components, and auxiliary active components are added, the auxiliary active components are one or more of tungsten oxide, iron oxide, manganese oxide, copper oxide or magnesium oxide. The preparation method of the catalyst comprises the following steps: (1) preparing an active component solution: dissolving ammonium molybdate with deionized water, and adjusting the pH value to 7.1-8.0 with organic amine to obtain a solution A; dissolving nickel nitrate and cobalt nitrate in deionized water, and stirring and dissolving to obtain a solution B; dissolving the binder and the auxiliary agent in deionized water to obtain a solution C; (2) and (3) carrier molding: uniformly mixing an aluminum-containing compound, a magnesium-containing compound, a titanium-containing compound and a pore-expanding agent, adding the solution C, kneading uniformly, extruding into a honeycomb-like shape by using a porous die, and drying and roasting to obtain a catalyst carrier; (3) pretreatment of a carrier: soaking the roasted catalyst carrier in a weak acid solution with the pH value of 5.5-6.8, and drying to obtain a pretreated carrier; (4) impregnating the active components of the catalyst: and (3) putting the pretreated catalyst carrier into the solution B for isovolumetric impregnation, then drying, putting the dried semi-finished catalyst into the solution A for isovolumetric impregnation, drying, and roasting to obtain the finished sulfur-resistant pre-conversion catalyst. The catalyst has higher compressive strength, good structure and activity stability, and strong adsorption and removal capacity on poisons, but the preparation process of the catalyst is complex.
CN102151574A discloses a novel CO sulfur-tolerant shift catalyst and a preparation method thereof, wherein the catalyst comprises a carrier and an active component, the carrier is titanium dioxide, and the active component is composed of molybdenum and cobalt or/and nickel; the titanium dioxide in the carrier is TiO2The calculated mass is 75-92% of the total mass of the catalyst; the molybdenum in the active component is MoO3The calculated mass is 5-15% of the total mass of the catalyst; the mass of cobalt in the active component, calculated as CoO, is 0.5-5% of the total mass of the catalyst; the mass of nickel in the active component, calculated as NiO, is 0.5-5% of the total mass of the catalyst. The preparation method of the catalyst comprises the following steps: (1) preparing a titanium dioxide carrier: adding water with a wetting amount or an aqueous solution of at least one soluble salt of magnesium, calcium, zinc, zirconium, cerium and lanthanum into metatitanic acid, fully soaking and kneading, then adding a peptizing agent, a pore-forming agent and a lubricant, continuously kneading, extruding and molding after the materials become plastic material masses, drying at 90-120 ℃ for 4-10 hours, and roasting at 400-550 ℃ for 2-4 hours to obtain a titanium dioxide carrier; (2) preparing an active component solution: weighing soluble salts of Mo, Co or Ni, adding the soluble salts into industrial ammonia water, and preparing an impregnation liquid; (3) preparing a catalyst: soaking the titanium dioxide carrier in the soaking solution for 0.5-1 hour, drying the soaked carrier at 90-120 ℃ for 4-10 hours, and roasting at 400-550 ℃ for 2-4 hours to obtain the finished catalyst. The catalyst has the characteristics of high conversion activity, particularly high low-sulfur activity and stable structure.
CN102151574A discloses a sulfur-tolerant carbon monoxide pre-shift catalyst suitable for low water-gas ratio conditions and a preparation method thereof, wherein the catalyst takes magnesium oxide, aluminum oxide and titanium dioxide as a composite carrier, takes Co-Mo-Ni as an active component, calcium aluminate cement is added as an auxiliary agent, the mass percentages of the active components cobalt, molybdenum and nickel in the catalyst are that, calculated by oxide, molybdenum oxide is 1.5-5.0%, cobalt oxide is 0.5-3.0%, nickel oxide is 0.5-2%, the content of aluminum oxide in the carrier is 20-60% of the mass of the catalyst, the content of magnesium oxide is 5-20%, the content of titanium oxide is 1-15%, and the content of calcium aluminate cement is 1-15%. The preparation method of the catalyst comprises the following steps: (1) preparing an active component solution: dissolving ammonium molybdate with deionized water to obtain a solution A with the mass concentration of 10-25%; dissolving nickel nitrate and cobalt nitrate in deionized water, adding a binder into the solution, stirring and dissolving to obtain a solution B with the mass concentration of 25-45%; (2) and (3) catalyst molding: uniformly mixing a powdery aluminum-containing compound, a magnesium-containing compound, a titanium-containing compound, a pore-expanding agent and calcium aluminate cement, adding the solution A, and uniformly kneading; adding the solution B, kneading uniformly, and preparing a catalyst semi-finished product after molding, drying and roasting; (3) treating the strength of the catalyst: and (3) placing the calcined catalyst semi-finished product into deionized water, soaking for 2-8h at the temperature of 10-80 ℃, taking out, naturally airing, and calcining to obtain the finished product.
The prior method improves the catalytic activity and the strength of the sulfur-tolerant shift catalyst to a certain extent, but still needs to be further improved.
Disclosure of Invention
The invention aims to simultaneously improve the catalytic activity and the strength of the existing sulfur-tolerant shift catalyst and provides a sulfur-tolerant shift catalyst and a preparation method thereof.
In order to achieve the above object, according to a first aspect of the present invention, there is provided a sulfur-tolerant shift catalyst comprising a carrier, metal active components of cobalt oxide and molybdenum oxide, and a co-agent of niobium oxide.
Preferably, the carrier is present in an amount of 79 to 92 wt%, the cobalt oxide is present in an amount of 2 to 6 wt%, the molybdenum oxide is present in an amount of 5 to 10 wt%, and the coagent is present in an amount of 1 to 5 wt%, based on the total weight of the sulfur-tolerant shift catalyst.
In a second aspect of the present invention, there is provided a process for preparing the sulfur tolerant shift catalyst of the present invention, the process comprising the steps of:
(1) kneading a cobalt-containing compound, a molybdenum-containing compound, a niobium-containing compound, a carrier precursor and water;
(2) carrying out extrusion molding on the product obtained by kneading, and carrying out first drying and first roasting;
(3) and (3) carrying out water treatment on the product obtained in the step (2) at the temperature of 20-150 ℃ for 0.5-10h, and then carrying out second drying and second roasting to obtain the sulfur-resistant shift catalyst.
The catalyst provided by the invention adopts Co and Mo as active components and Nb as an active auxiliary agent, so that the catalytic activity and strength of the catalyst are effectively improved. Preferably, TiO is used2MgO and Al2O3The composite carrier further improves the catalytic activity and strength of the catalyst.
The sulfur-tolerant shift catalyst provided by the invention is simple in preparation method, and the prepared sulfur-tolerant shift catalyst is high in strength and good in activity. For example, the catalyst of example 1 of the present invention has an activity (CO conversion) of 65.3% and a strength of 365N/cm, while the catalyst of comparative example 1 has an activity (CO conversion) of 57.9% and a strength of 278N/cm.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
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.
In a first aspect of the present invention, there is provided a sulfur tolerant shift catalyst comprising a support, a metal active component and a co-agent, wherein the metal active component is a cobalt oxide and a molybdenum oxide, and the co-agent is a niobium oxide.
In the sulfur tolerant shift catalyst provided by the present invention, preferably, the carrier is contained in an amount of 65 to 96 wt%, preferably 79 to 92 wt%, based on the total weight of the sulfur tolerant shift catalyst; the content of cobalt oxide is 0.5 to 10% by weight, preferably 2 to 6% by weight; the content of molybdenum oxide is 3 to 15% by weight, preferably 5 to 10% by weight; the content of niobium oxide is 0.5 to 10% by weight, preferably 1 to 5% by weight.
The selection range of the carrier is wide, various carriers which are conventionally used in the field can be used in the invention, and in order to further improve the strength and activity of the catalyst, the carrier is preferably TiO-containing carrier2MgO and Al2O3The composite carrier of (1).
According to a preferred embodiment of the present invention, the sulfur tolerant shift catalyst comprises magnesium titanate and magnesium aluminate spinel phases.
According to the present invention, preferably, TiO is based on the total weight of the sulfur-tolerant shift catalyst21-20 wt%, MgO 2-35 wt%, Al2O3In an amount of 30-85% by weight; further preferably, TiO is based on the total weight of the sulfur-tolerant shift catalyst25-15 wt%, MgO 5-30 wt%, Al2O3The content of (B) is 40-70 wt%.
The method for producing the sulfur-tolerant shift catalyst of the present invention is not particularly limited, and any method can be used as long as the catalyst can be obtained.
In a second aspect of the present invention, there is provided a process for preparing the sulfur tolerant shift catalyst of the present invention, the process comprising the steps of:
(1) kneading a cobalt-containing compound, a molybdenum-containing compound, a niobium-containing compound, a carrier precursor and water;
(2) carrying out extrusion molding on the product obtained by kneading, and carrying out first drying and first roasting;
(3) and (3) carrying out water treatment on the product obtained in the step (2) at the temperature of 20-150 ℃ for 0.5-10h, and then carrying out second drying and second roasting to obtain the sulfur-resistant shift catalyst.
The method provided by the invention does not need to prepare the carrier firstly, can mix and knead the carrier precursor, the active component precursor and water together, is simple and convenient to operate, has few working procedures, and is more beneficial to industrial production. The product obtained in the step (2) is subjected to water treatment, so that the strength and the activity of the catalyst are improved.
According to the present invention, the cobalt-containing compound, the molybdenum-containing compound, the niobium-containing compound and the carrier precursor are preferably used in such amounts that the sulfur-tolerant shift catalyst is obtained in which the carrier is contained in an amount of 65 to 96% by weight, preferably 79 to 92% by weight, based on the total weight of the sulfur-tolerant shift catalyst; the content of cobalt oxide is 0.5 to 10% by weight, preferably 2 to 6% by weight; the content of molybdenum oxide is 3 to 15% by weight, preferably 5 to 10% by weight; the content of niobium oxide is 0.5 to 10% by weight, preferably 1 to 5% by weight.
According to the present invention, it is preferable that in the step (1), the cobalt element-containing compound is at least one selected from the group consisting of cobalt nitrate, cobalt acetate, cobalt carbonate and cobalt hydroxide.
According to the invention, it is preferred that in step (1) the compound containing molybdenum is selected from ammonium tetramolybdate and/or ammonium heptamolybdate.
According to the present invention, preferably, in the step (1), the niobium element-containing compound is at least one selected from the group consisting of ni pentoxide, niobic acid and niobium oxalate, and more preferably ni pentoxide.
The carrier precursor is a substance capable of forming a carrier after subsequent treatment, the selection range of the carrier precursor is wide, and preferably, the carrier precursor comprises a titanium-containing compound, magnesium oxide and an aluminum oxide precursor. The strength and activity of the catalyst can be further improved by this preferred embodiment.
According to the present invention, preferably, the alumina precursor is selected from at least one of alumina, pseudo-boehmite, and amorphous aluminum hydroxide. Preferably pseudoboehmite.
According to the present invention, preferably, the titanium element-containing compound is at least one selected from the group consisting of titanium dioxide, metatitanic acid, titanium isopropoxide and tetrabutyl titanate. Metatitanic acid is preferred.
According to the present invention, preferably, the magnesium oxide is light magnesium oxide. The light magnesium oxide can be prepared or obtained commercially.
The amount of the titanium-containing compound, the magnesium oxide and the aluminum oxide precursor is selected from a wide range, and preferably, the amount of the titanium-containing compound, the magnesium oxide and the aluminum oxide precursor is such that the sulfur-tolerant shift catalyst is prepared by using TiO based on the total weight of the sulfur-tolerant shift catalyst21-20 wt%, MgO 2-35 wt%, Al2O3In an amount of 30-85% by weight; further preferably, TiO is based on the total weight of the sulfur-tolerant shift catalyst25-15 wt%, MgO 5-30 wt%, Al2O3The content of (B) is 40-70 wt%.
According to the present invention, there is provided a method wherein the step (1) is for mixing the respective raw materials constituting the sulfur-tolerant shift catalyst by kneading. The raw materials are the above raw materials, and water is added during the kneading to form a dough-shaped blank with elasticity. Preferably, the amount of water is 20 to 60 wt% based on the total weight of the cobalt-containing compound, the molybdenum-containing compound, the niobium-containing compound, and the carrier precursor.
According to a preferred embodiment of the invention, the method further comprises: introducing a peptizing agent in the kneading process of the step (1). The selection range of the kind of the peptizing agent is wide, and for example, the peptizing agent may be at least one of calcium nitrate, nitric acid, sulfuric acid, oxalic acid, citric acid and acetic acid, and calcium nitrate is preferable.
It should be noted that the peptizing agent may partially remain in the catalyst after the subsequent treatment, and therefore, the catalyst provided by the present invention may contain a small amount of the peptizing agent existing in the form of oxide.
According to the present invention, preferably, the peptizing agent is used in an amount of 1 to 10 wt% based on the total weight of the cobalt-containing compound, the molybdenum-containing compound, the niobium-containing compound and the carrier precursor.
The present invention is not particularly limited as long as the cobalt-containing compound, the molybdenum-containing compound, the niobium-containing compound, the carrier precursor, water and the peptizing agent are mixed, and according to one embodiment of the present invention, the cobalt-containing compound, the molybdenum-containing compound, the niobium-containing compound, the carrier precursor and water may be mixed first, and then the peptizing agent (preferably calcium nitrate) may be added in the form of a solution. Then kneading is performed. The concentration of the peptizer solution of the present invention is not particularly limited, and may be, for example, 0.005 to 0.3 g/mL.
The kneading in the step (1) is not particularly limited in the present invention, and may be, for example, 0.5 to 3 hours.
According to the invention, step (2) is used for subjecting the kneaded product to catalyst molding.
According to the present invention, in the step (2), the first drying and first baking steps are performed, and the components in the shaped product can be converted into oxide forms. Preferably, the first drying is carried out at 100-200 ℃ for 5-20 h; the first roasting is carried out at the temperature of 400-600 ℃ for 3-8h, and the first drying is further preferably carried out at the temperature of 100-150 ℃ for 8-12 h; the first calcination is carried out at 400-600 ℃ for 4-6 h.
According to the invention, in step (3), a water treatment is provided to optimize the product obtained in step (2), mainly to reduce the free MgO in the catalyst and to form magnesium titanate and magnesium aluminate spinel phases. The water treatment can be that the product obtained in the step (2) is put into a closed container and is immersed in water, and the container is heated, so that the materials in the container are subjected to water treatment under the autogenous pressure.
In the present invention, it is preferable that, in the step (3), the water treatment is performed at 20 to 100 ℃ for 3 to 8 hours.
In the invention, the second drying and the second roasting in the step (3) are used for removing moisture in the water-treated material and converting various components in the material into oxide forms to obtain the sulfur-tolerant shift catalyst. Preferably, in the step (3), the second drying is carried out at 100-120 ℃ for 10-20 h; the second calcination is carried out at 500-800 ℃ for 1-8 h.
According to the present invention, in the step (3), preferably, the product obtained by the water treatment is filtered before the second drying, and then the second drying and the second baking are performed. The filtration can be carried out according to the conventional technical means in the field.
The catalyst provided by the invention can be subjected to sulfurization treatment by the conventional means in the field before use. For example: under the condition of vulcanization, the sulfur-tolerant shift catalyst provided by the invention is contacted with a vulcanization gas phase to carry out vulcanization reaction, so as to obtain the vulcanization catalyst.
The sulfuration gas may be H2S and H2The invention is to the H2S and H2The concentration of hydrogen sulfide in the mixed gas of (2) is not particularly limited, and the sulfidized gas may contain 0.3 to 5 vol% of H2S, e.g. containing 3% by volume of H2S。
The vulcanization condition is not particularly limited in the invention, for example, the vulcanization temperature can be 230-460 ℃, and the vulcanization time can be 4-6 h.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples, the composition of the sulfur-resistant shift catalyst was measured by a ZSX Primus II X-ray fluorescence spectrometer from Rigaku corporation;
the catalyst strength was measured using a particle strength tester from the company VINCI.
Example 1
65g of pseudo-boehmite, 23g of light magnesium oxide, 10g of ammonium heptamolybdate, 15g of cobalt nitrate, 2.5g of niobium pentoxide, 20g of metatitanic acid and 20g of water are weighed and kneaded in a kneader for 30 min. Then 10mL of calcium nitrate solution (concentration of 0.3g/mL) was added and kneading was continued for 1 hour to form a kneadable material having plasticity.
And extruding the mixed material on a strip extruding machine for strip forming to prepare a strip sample with the diameter of 2.5 mm. Then drying the mixture in a drying oven at 120 ℃ for 12 hours, and roasting the mixture at 500 ℃ for 3 hours to obtain a sample;
putting the sample into a beaker, and carrying out water treatment for 5 hours at the temperature of 25 ℃; and taking out the catalyst to perform second drying at 120 ℃ for 12h, and performing second roasting at 700 ℃ for 3h to obtain the sulfur-resistant shift catalyst.
The catalyst comprises the following components: 4.8 wt.% Co2O39.2% by weight of MoO32.7% by weight of Nb2O58% by weight of TiO247.3% by weight of Al2O3And 28 wt.% MgO.
The catalyst strengths are listed in table 1.
Comparative example 1
A sulfur tolerant shift catalyst was prepared by the method of example 1 except that, during kneading, niobium pentoxide was replaced with pseudo-boehmite of the same quality without adding niobium pentoxide.
The catalyst comprises the following components: 4.8 wt.% Co2O39.2% by weight of MoO38% by weight of TiO250% by weight of Al2O3And 28 wt.% MgO.
The catalyst strengths are listed in table 1.
Comparative example 2
A sulfur-tolerant shift catalyst was obtained by following the procedure of example 1, except that, during the kneading, niobium pentoxide was replaced with tin dioxide of equal mass.
The catalyst comprises the following components: 4.8 wt.% Co2O39.2% by weight of MoO32.7% by weight of SnO28% by weight of TiO247.3% by weight of Al2O3And 28 wt.% MgO.
The catalyst strengths are listed in table 1.
Comparative example 3
A sulfur tolerant shift catalyst was prepared by the method of example 1 except that niobium pentoxide was replaced with zinc oxide of equal mass during the kneading.
The catalyst comprises the following components: 4.8 wt.% Co2O39.2% by weight of MoO32.7% by weight of ZnO, 8% by weight of TiO247.3% by weight of Al2O3And 28 wt.% MgO.
The catalyst strengths are listed in table 1.
Comparative example 4
A sulfur tolerant shift catalyst was prepared by the method of example 1 except that niobium pentoxide was replaced with tantalum pentoxide of equal mass during the kneading.
The catalyst comprises the following components: 4.8 wt.% Co2O39.2% by weight of MoO32.7% by weight of Ta2O58% by weight of TiO247.3% by weight of Al2O3And 28 wt.% MgO.
The catalyst strengths are listed in table 1.
Example 2
109g of pseudo-boehmite, 4g of light magnesium oxide, 7.6g of ammonium heptamolybdate, 6.2g of cobalt nitrate, 1.4g of niobium pentoxide, 12.5g of metatitanic acid and 20g of water were weighed and kneaded in a kneader for 30 min. Then 10mL of nitric acid solution (concentration of 0.02g/mL) was added and kneading was continued for 1 hour to form a kneaded material having plasticity.
And extruding the mixed material on a strip extruding machine for strip forming to prepare a strip sample with the diameter of 2.5 mm. Then drying the mixture in a drying oven at 120 ℃ for 12 hours, and roasting the mixture at 500 ℃ for 3 hours to obtain a sample;
putting the sample into a hydrothermal reaction kettle, and carrying out water treatment for 8 hours at 50 ℃; and taking out the catalyst to perform second drying at 120 ℃ for 12h, and performing second roasting at 600 ℃ for 3h to obtain the sulfur-resistant shift catalyst.
The catalyst comprises the following components: 2 wt.% Co2O37% by weight of MoO31.5% by weight of Nb2O55% by weight of TiO279.5% by weight of Al2O3And 5 wt% MgO.
The catalyst strengths are listed in table 1.
Example 3
73g of pseudo-boehmite, 16g of light magnesium oxide, 12.3 g of ammonium heptamolybdate, 17.7g of cobalt nitrate, 5g of niobium pentoxide, 29g of metatitanic acid and 20g of water are weighed and kneaded in a kneader for 30 min. Then 15mL of nitric acid aqueous solution (concentration: 0.07g/mL) was added and kneading was continued for 1 hour to form a kneaded material having plasticity.
And extruding the mixed material on a strip extruding machine for strip forming to prepare a strip sample with the diameter of 2.5 mm. Then drying the mixture in a drying oven at 120 ℃ for 12 hours, and roasting the mixture at 500 ℃ for 3 hours to obtain a sample;
putting the sample into a hydrothermal reaction kettle, and carrying out water treatment for 3h at 100 ℃; and taking out the catalyst to perform second drying at 120 ℃ for 12h, and performing second roasting at 700 ℃ for 3h to obtain the sulfur-resistant shift catalyst.
The catalyst comprises the following components: 5 wt% Co2O310% by weight of MoO35% by weight of Nb2O515% by weight of TiO249% by weight of Al2O3And 16 wt.% MgO.
The catalyst strengths are listed in table 1.
Example 4
A sulfur-tolerant shift catalyst was obtained by following the procedure of example 1 except that niobium pentoxide was used in an amount of 1.2 g.
The catalyst comprises the following components: 4.8 wt.% Co2O39.2% by weight of MoO31.3% by weight of Nb2O58% by weight of TiO248.7% by weight of Al2O3And 28 wt.% MgO.
The catalyst strengths are listed in table 1.
Example 5
A sulfur tolerant shift catalyst was prepared by the method of example 1 except that 20g of metatitanic acid was replaced with 14.9g of pseudo-boehmite.
The catalyst comprises the following components: 4.8 wt.% Co2O39.2% by weight of MoO32.7% by weight of Nb2O555.3% by weight of Al2O3And 28 wt.% MgO.
The catalyst strengths are listed in table 1.
Test example 1
The sulfur tolerant shift catalysts of examples 1-5 and comparative examples 1-4 provided by the present invention were evaluated and tested for accelerated deactivation.
The reaction was carried out on a microreaction evaluating apparatus. The packing amount of the 20-40 mesh catalyst is 1 g.
1. Catalyst sulfidation
The catalyst is mixed with a sulfiding gas (H)2S and H2In which H is2The volume content of S is 3 percent) is contacted for 5 hours at the vulcanization temperature of 350 ℃ 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: 450 ℃, 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 results are shown in Table 1.
TABLE 1
| Catalyst and process for preparing same | Activity (CO conversion,%) | Strength (N/cm) |
| Example 1 | 65.3 | 365 |
| Comparative example 1 | 57.9 | 278 |
| Comparative example 2 | 48.2 | 322 |
| Comparative example 3 | 56.1 | 256 |
| Comparative example 4 | 58.9 | 270 |
| Example 2 | 60.5 | 310 |
| Example 3 | 65.7 | 350 |
| Example 4 | 62.9 | 328 |
| Example 5 | 57.2 | 310 |
As can be seen from the examples and the results in table 1, the catalyst provided by the present invention has significantly higher activity and strength. As can be seen from the comparison of example 1 with comparative examples 1-4, the performance of the catalyst can be significantly improved by using niobium as a co-promoter in combination with cobalt and molybdenum. From the comparison of example 1 with example 5, it can be seen that the preferred TiO according to the invention is used2MgO and Al2O3The performance of the catalyst is improved to a certain extent by the composite carrier. The catalyst prepared by the method for preparing the sulfur-tolerant shift catalyst provided by the invention not only has obviously higher catalyst activity and strength, but also can be added into a reaction material for kneading at one time, has simple preparation process and is very suitable for industrial production.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (17)
1. A sulfur tolerant shift catalyst, the sulfur tolerant shift catalyst is made up of carrier, metal active ingredient and coagent, the said metal active ingredient is cobalt oxide and molybdenum oxide, characterized by, the said coagent is niobium oxide; the cobalt oxide is Co2O3The molybdenum oxide is MoO3The niobium oxide is Nb2O5；
Based on the total weight of the sulfur-tolerant shift catalyst, the content of the carrier is 65-96 wt%, the content of the cobalt oxide is 0.5-10 wt%, the content of the molybdenum oxide is 3-15 wt%, and the content of the active assistant is 0.5-10 wt%;
the carrier is TiO-containing2MgO and Al2O3Based on the total weight of the sulfur-tolerant shift catalyst, TiO21-20 wt%, MgO 2-35 wt%, Al2O3Is contained in an amount of 30 to 85% by weight.
2. The sulfur-tolerant shift catalyst of claim 1, wherein the support is present in an amount of 79 to 92 wt.%, based on the total weight of the sulfur-tolerant shift catalyst; the content of the cobalt oxide is 2-6 wt%; the content of the molybdenum oxide is 5-10 wt%; the content of the active auxiliary agent is 1-5 wt%.
3. The sulfur-tolerant shift catalyst of claim 1 or 2, wherein TiO is based on the total weight of the sulfur-tolerant shift catalyst25-15 wt%, MgO 5-30 wt%, Al2O3The content of (B) is 40-70 wt%.
4. A method of making the sulfur tolerant shift catalyst of claim 1, comprising the steps of:
(1) kneading a cobalt-containing compound, a molybdenum-containing compound, a niobium-containing compound, a carrier precursor and water;
(2) carrying out extrusion molding on the product obtained by kneading, and carrying out first drying and first roasting;
(3) and (3) carrying out water treatment on the product obtained in the step (2) at the temperature of 20-150 ℃ for 0.5-10h, and then carrying out second drying and second roasting to obtain the sulfur-resistant shift catalyst.
5. The method according to claim 4, wherein the cobalt-containing compound, the molybdenum-containing compound, the niobium-containing compound, and the support precursor are used in amounts such that the sulfur-tolerant shift catalyst is obtained in which the support is contained in an amount of 65 to 96 wt%, the cobalt oxide is contained in an amount of 0.5 to 10 wt%, the molybdenum oxide is contained in an amount of 3 to 15 wt%, and the coagent is contained in an amount of 0.5 to 10 wt%, based on the total weight of the sulfur-tolerant shift catalyst.
6. The method according to claim 4, wherein the cobalt-containing compound, the molybdenum-containing compound, the niobium-containing compound, and the carrier precursor are used in amounts such that the sulfur-tolerant shift catalyst is obtained in which the carrier is contained in an amount of 79 to 92% by weight, based on the total weight of the sulfur-tolerant shift catalyst; the content of the cobalt oxide is 2-6 wt%; the content of the molybdenum oxide is 5-10 wt%; the content of the active auxiliary agent is 1-5 wt%.
7. The method according to any one of claims 4 to 6, wherein the cobalt-containing compound is at least one selected from the group consisting of cobalt nitrate, cobalt acetate, cobalt carbonate, and cobalt hydroxide; the molybdenum element-containing compound is selected from ammonium tetramolybdate and/or ammonium heptamolybdate; the niobium element-containing compound is at least one selected from niobium pentoxide, niobic acid and niobium oxalate.
8. The method of any of claims 4-6, wherein the support precursor comprises an elemental titanium-containing compound, magnesium oxide, and an aluminum oxide precursor.
9. The method of claim 8, wherein the elemental titanium-containing compound is selected from at least one of titanium dioxide, metatitanic acid, titanium isopropoxide, and tetrabutyl titanate; the magnesium oxide is light magnesium oxide; the alumina precursor is selected from at least one of alumina, pseudoboehmite, and amorphous aluminum hydroxide.
10. The method of claim 8, wherein the alumina precursor is pseudoboehmite; the titanium-containing compound is metatitanic acid.
11. The method of claim 8, wherein,
the titanium-containing compound, the magnesium oxide and the alumina precursor are used in such amounts that the sulfur-tolerant shift catalyst is obtained in which the TiO is present in an amount corresponding to the total weight of the sulfur-tolerant shift catalyst21-20 wt%, MgO 2-35 wt%, Al2O3Is contained in an amount of 30 to 85% by weight.
12. The method of claim 8, wherein,
the titanium-containing compound, the magnesium oxide and the alumina precursor are used in such amounts that the sulfur-tolerant shift catalyst is obtained in which the TiO is present in an amount corresponding to the total weight of the sulfur-tolerant shift catalyst2The content of (A) is 5-15 wt%, and the content of MgO is 5-30% by weight of Al2O3The content of (B) is 40-70 wt%.
13. The method of any of claims 4-6, wherein the method further comprises: introducing a peptizing agent in the kneading process of the step (1).
14. The method of claim 13, wherein the peptizing agent is selected from at least one of nitric acid, sulfuric acid, oxalic acid, citric acid, and acetic acid.
15. The method of claim 13, wherein the peptizing agent is used in an amount of 1 to 10 wt% based on the total weight of the cobalt-containing compound, the molybdenum-containing compound, the niobium-containing compound, and the carrier precursor.
16. The method of claim 4, wherein,
in the step (2), the first drying is carried out for 5-20h at the temperature of 100-200 ℃; the first calcination is carried out at 400-600 ℃ for 3-8 h.
17. The method of claim 4, wherein,
in the step (3), the second drying is carried out at the temperature of 100-120 ℃ for 10-20 h; the second calcination is carried out at 500-800 ℃ for 1-8 h.
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