CN110314675B - TiO 2 Modified alumina-based magnesium aluminate spinel, preparation method thereof and sulfur-tolerant shift catalyst - Google Patents
TiO 2 Modified alumina-based magnesium aluminate spinel, preparation method thereof and sulfur-tolerant shift catalyst Download PDFInfo
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- CN110314675B CN110314675B CN201810264420.9A CN201810264420A CN110314675B CN 110314675 B CN110314675 B CN 110314675B CN 201810264420 A CN201810264420 A CN 201810264420A CN 110314675 B CN110314675 B CN 110314675B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 75
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 40
- 239000011029 spinel Substances 0.000 title claims abstract description 40
- 239000011777 magnesium Substances 0.000 title claims abstract description 33
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 33
- -1 magnesium aluminate Chemical class 0.000 title claims abstract description 30
- 229910010413 TiO 2 Inorganic materials 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 41
- 239000011593 sulfur Substances 0.000 claims abstract description 17
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 17
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims description 26
- 238000005470 impregnation Methods 0.000 claims description 22
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 18
- 239000010936 titanium Substances 0.000 claims description 18
- 229910052719 titanium Inorganic materials 0.000 claims description 17
- 229910052700 potassium Inorganic materials 0.000 claims description 13
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 12
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 12
- 239000011591 potassium Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- 150000002681 magnesium compounds Chemical class 0.000 claims description 9
- 229910017052 cobalt Inorganic materials 0.000 claims description 8
- 239000010941 cobalt Substances 0.000 claims description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 8
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims description 8
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 238000011068 loading method Methods 0.000 claims description 7
- 239000011733 molybdenum Substances 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- 239000011159 matrix material Substances 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 229940043430 calcium compound Drugs 0.000 claims description 4
- 150000001674 calcium compounds Chemical class 0.000 claims description 4
- 150000001785 cerium compounds Chemical class 0.000 claims description 4
- 150000002604 lanthanum compounds Chemical class 0.000 claims description 4
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 4
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 4
- 150000003755 zirconium compounds Chemical class 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- 235000011147 magnesium chloride Nutrition 0.000 claims description 3
- 229910052566 spinel group Inorganic materials 0.000 claims description 3
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 2
- 239000011654 magnesium acetate Substances 0.000 claims description 2
- 229940069446 magnesium acetate Drugs 0.000 claims description 2
- 235000011285 magnesium acetate Nutrition 0.000 claims description 2
- QWDJLDTYWNBUKE-UHFFFAOYSA-L magnesium bicarbonate Chemical compound [Mg+2].OC([O-])=O.OC([O-])=O QWDJLDTYWNBUKE-UHFFFAOYSA-L 0.000 claims description 2
- 235000014824 magnesium bicarbonate Nutrition 0.000 claims description 2
- 239000002370 magnesium bicarbonate Substances 0.000 claims description 2
- 229910000022 magnesium bicarbonate Inorganic materials 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 22
- 238000006703 hydration reaction Methods 0.000 abstract description 9
- 230000036571 hydration Effects 0.000 abstract description 7
- 239000003960 organic solvent Substances 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 27
- 229940091250 magnesium supplement Drugs 0.000 description 26
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 19
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 14
- 238000010521 absorption reaction Methods 0.000 description 13
- 239000000395 magnesium oxide Substances 0.000 description 10
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 238000010335 hydrothermal treatment Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 229910010415 TiO(OH) Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-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
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 150000001869 cobalt compounds Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000011363 dried mixture Substances 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 229960002337 magnesium chloride Drugs 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000005078 molybdenum compound Substances 0.000 description 2
- 150000002752 molybdenum compounds Chemical class 0.000 description 2
- 235000011118 potassium hydroxide Nutrition 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011684 sodium molybdate Substances 0.000 description 2
- 235000015393 sodium molybdate Nutrition 0.000 description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910004664 Cerium(III) chloride Inorganic materials 0.000 description 1
- 229910017518 Cu Zn Inorganic materials 0.000 description 1
- 229910017752 Cu-Zn Inorganic materials 0.000 description 1
- 229910017943 Cu—Zn Inorganic materials 0.000 description 1
- 229910017060 Fe Cr Inorganic materials 0.000 description 1
- 229910002544 Fe-Cr Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 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 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- NKCVNYJQLIWBHK-UHFFFAOYSA-N carbonodiperoxoic acid Chemical compound OOC(=O)OO NKCVNYJQLIWBHK-UHFFFAOYSA-N 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- OBWXQDHWLMJOOD-UHFFFAOYSA-H cobalt(2+);dicarbonate;dihydroxide;hydrate Chemical compound O.[OH-].[OH-].[Co+2].[Co+2].[Co+2].[O-]C([O-])=O.[O-]C([O-])=O OBWXQDHWLMJOOD-UHFFFAOYSA-H 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- VQEHIYWBGOJJDM-UHFFFAOYSA-H lanthanum(3+);trisulfate Chemical compound [La+3].[La+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VQEHIYWBGOJJDM-UHFFFAOYSA-H 0.000 description 1
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 1
- 229940050906 magnesium chloride hexahydrate Drugs 0.000 description 1
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 150000002751 molybdenum Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound 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 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 235000007686 potassium Nutrition 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
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 150000003112 potassium compounds Chemical class 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
Images
Classifications
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/005—Spinels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/10—Magnesium; Oxides or hydroxides thereof
-
- 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
- B01J23/8872—Alkali or alkaline earth metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/024—Multiple impregnation or coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- 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
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
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Abstract
The invention relates to the field of sulfur-resistant shift catalysts and discloses TiO 2 Modified alumina-based magnesium aluminate spinel, a preparation method thereof and a sulfur-tolerant shift catalyst. TiO prepared by the method of the invention 2 The modified alumina-based magnesium aluminate spinel avoids the use of organic solvents and reduces the preparation cost. Using the TiO 2 The modified alumina-based magnesia-alumina spinel is used as a carrier, the prepared catalyst overcomes the defect of easy hydration, widens the application range of the catalyst, and has better activity and stability within the temperature range of 200-500 ℃.
Description
Technical Field
The invention relates to the field of sulfur-resistant shift catalysts, in particular to TiO 2 Modified alumina-based magnesium aluminate spinel, a preparation method thereof and a sulfur-tolerant shift catalyst.
Background
The CO shift reaction is widely applied to industries of methanol preparation from coal, ammonia synthesis, hydrogen production and the like, and is used for modulating CO and H in synthesis gas 2 To meet the requirements of different chemical processes. Compared with the traditional Fe-Cr based high-temperature transformation catalyst and Cu-Zn based low-temperature transformation catalyst, the cobalt-molybdenum based sulfur-tolerant transformation catalyst has high transformation activity, wide use temperature range and no influence of sulfur poisoning, thereby being widely applied. The existing Co-Mo based sulfur-tolerant shift catalyst is mainly divided into two main categories, one is a cobalt-molybdenum shift catalyst without alkali metal auxiliary agent. The catalysts mostly adopt magnesium aluminate spinel as a carrier, such as K8-11 catalyst widely used by BASF company in Germany. The catalyst has higher strength, is suitable for reaction under the conditions of high temperature, high pressure (3-8Mpa) and high water-gas ratio, but has poorer low-temperature activity, and requires higher sulfur content in the shift gas, otherwise, the activity is seriously degraded. Another class is Co-Mo based shift catalysts containing an alkali metal promoter (mainly potassium), such as those disclosed in US3850840A and CN87107892A, among others. The catalyst has better activity under the conditions of low temperature and low sulfur, but the existence of potassium can promote the hydration reaction of carrier alumina at high temperature, and the structural stability of the catalyst is influenced, so that the activity of the catalyst is seriously degraded.
By mixing TiO with 2 The introduction of the modified Co-Mo catalyst into the carrier is an effective method for solving the problems of poor low-temperature activity, water resistance and performance of the existing Co-Mo catalyst. CN1429763A prepared by using a catalyst prepared from TiO 2 、MgO、 Al 2 O 3 The cobalt-molybdenum shift catalyst is prepared by a composite carrier consisting of four components of cement, and the catalyst does not contain alkali metal but has better low temperature (250 ℃ C.) -300 ℃ C.) and low sulfur (C.), (>0.01v/v) activity. CN103447049B discloses a potassium-free cobalt-molybdenum shift catalyst using aluminum-titanium-based magnesium aluminate spinel as a carrier, compared with a titanium-free catalyst, the titanium-containing catalyst has better activity stability and is suitable for shift of synthesis gas with high CO content (more than or equal to 60%). CN1096494A discloses a wide-temperature and wide-sulfur type sulfur-tolerant carbon monoxide shift catalyst without alkali metal promoter, wherein the carrier is composed of magnesium oxide, aluminum oxide and titanium dioxide, and is prepared by a suspension precipitation method. TiO is directly used for CN1087192C and CN102151574B 2 As carrier for preparing sulfur-resistant shift catalyst with excellent hydration resistanceEnergy, low temperature activity and structural stability.
However, in the method provided by the invention, most of the titanium-containing substance is added into the carrier in a solid mode and is prepared by a kneading method, so that the titanium raw material cannot be well combined with other elements, the utilization efficiency is low, and the exertion of the effect is limited. CN103447049B although the titanium element was introduced by impregnation method, since it uses organic titanium or TiCl 4 Is a titanium source, needs volatile organic matters as a solvent, has high preparation cost and is not beneficial to industrial production.
Disclosure of Invention
The invention aims to overcome the problems of poor bonding and low utilization rate when Ti is introduced into a carrier in a solid mode in the prior art and to overcome the defects of poor bonding and low utilization rate when organic titanium or TiCl is used 4 Provides TiO for the problems of organic solvent requirement and high cost in titanium source 2 Modified alumina-based magnesium aluminate spinel, a preparation method thereof and a sulfur-tolerant shift catalyst.
In order to achieve the above object, the present invention provides, in a first aspect, a TiO 2 A process for the preparation of a modified alumina-based magnesium aluminate spinel, the process comprising the steps of:
(1) loading magnesium compound on gamma-Al by dipping method 2 O 3 Drying and roasting the substrate;
(2) impregnating TiOSO 4 Loading the substrate prepared in the step (1) and then drying; and
(3) and (3) placing the matrix prepared in the step (2) in an ammonia water solution for heat treatment, and then drying and roasting.
In a second aspect, the present invention provides TiO prepared by the process of the first aspect 2 Modified alumina-based magnesium aluminate spinels.
In a third aspect, the invention provides a sulfur tolerant shift catalyst comprising a carrier and an active component supported on the carrier, wherein the carrier is the TiO described in the second aspect of the invention 2 The modified alumina-based magnesium aluminate spinel comprises cobalt, molybdenum and potassium as active components.
The invention uses water-soluble TiOSO 4 Preparation of TiO as a starting Material 2 The modified alumina-based magnesium aluminate spinel avoids the use of organic solvents, reduces the preparation cost, has good titanium dispersibility, and can cover the alumina-based magnesium aluminate spinel to the maximum extent.
The catalyst of the present invention uses the above TiO 2 The modified alumina-based magnesia-alumina spinel is used as a carrier, overcomes the defect that a potassium-containing catalyst is easy to hydrate under severe conditions, widens the application range of the catalyst, and ensures that the catalyst has better activity and stability within a wider temperature range of 200-500 ℃.
Drawings
Figure 1 is an XRD pattern after hydrothermal treatment of the catalyst of the present invention.
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 invention provides a TiO compound 2 A process for the preparation of a modified alumina-based magnesium aluminate spinel, the process comprising the steps of:
(1) loading magnesium compound on gamma-Al by dipping method 2 O 3 Drying and roasting the substrate;
(2) impregnating TiOSO 4 Loading the substrate prepared in the step (1) and then drying; and
(3) and (3) placing the matrix prepared in the step (2) into an ammonia water solution for heat treatment, and then drying and roasting.
In the present invention, the gamma-Al 2 O 3 Matrix, magnesium compound, TiOSO 4 Respectively with Al 2 O 3 、MgO、 TiO 2 The mass ratio is 100: 1-20: 1-15, preferably 100: 1-15: 1-8.
In the present invention, the gamma-Al 2 O 3 The substrate may be in various shapes commonly used in the art, such as a ball shape, a teethed ball shape, or a bar shape, preferably a ball shape.
In the present invention, in step (1), the impregnation method is preferably an equal-volume impregnation method.
In the present invention, the impregnation liquid used in the impregnation process contains a magnesium compound and optionally one or more selected from a lanthanum compound, a calcium compound, a zirconium compound, and a cerium compound;
preferably, the magnesium compound may be a water-soluble salt, for example, may be selected from one or more of, but not limited to, magnesium nitrate, magnesium chloride, magnesium acetate, and magnesium bicarbonate. The lanthanum compound, the calcium compound, the zirconium compound and the cerium compound may be water-soluble salts of the corresponding elements, and the lanthanum compound may be, for example, one or more selected from lanthanum chloride, lanthanum nitrate, lanthanum acetate and lanthanum sulfate; the calcium compound may be selected, for example, from one or more of calcium chloride and calcium nitrate, and the zirconium compound may be selected, for example, from one or more of zirconium chloride and zirconium nitrate; the cerium compound may be selected, for example, from one or more of cerium trichloride and cerium nitrate.
In the present invention, the drying conditions in step (1) include: the temperature is 100-150 ℃, and the time is 6-18 h; the roasting conditions comprise: the temperature is 400 ℃ and 1000 ℃, and the time is 1-5 h. In the present invention, alumina-based magnesium aluminate spinel particles are obtained after the drying and firing step in step (1).
In the present invention, in the step (2), TiOSO is used 4 And (2) carrying out solution impregnation on the alumina-based magnesium aluminate spinel particles obtained in the step (1), wherein the impregnation method is preferably an equal-volume impregnation method.
In the present invention, in the step (2), the drying conditions include: the temperature is 80-150 ℃ and the time is 3-12 h.
In the present invention, TiOSO is added 4 After being dipped on alumina-based magnesium aluminate spinel, the aluminum aluminate spinel needs to be thermally treated in dilute ammonia water. Preferably, in the step (3), the heat treatment conditions include: heat treating at 50-100 deg.C for 1-5 hrThe pH of the aqueous ammonia solution in the process is maintained at greater than 11.
During the treatment, the following reactions occur:
TiOSO 4 +2NH 3 ·H 2 O=TiO(OH) 2 ↓+(NH 4 ) 2 SO 4
TiO(OH) 2 =TiO 2 +H 2 O
3(NH 4 ) 2 SO 4 =4NH 3 ↑+3SO 2 ↑+N 2 ↑+6H 2 O
in the present invention, the aqueous ammonia solution used in step (3) may be an aqueous ammonia solution having any suitable concentration range as long as it is ensured that the pH of the aqueous ammonia solution is maintained at a value of more than 11 during the heat treatment, and may be, for example, 0.1 to 0.5 mol/L.
Compared with the conventional kneading method which uses titanium-containing solid such as metatitanic acid as a starting material, the method has better titanium dispersibility, can cover the alumina-based magnesia-alumina spinel to the maximum extent, and enhances the hydration resistance of the catalyst carrier; with the use of TiCl 4 Or an organic titanium such as tetrabutyl titanate, using a water-soluble TiOSO 4 The raw materials are adopted, the use of organic solvents is avoided, and the preparation cost is reduced. Furthermore, the sulfate ion introduced into the carrier of the present invention can be formed by (NH) 4 ) 2 SO 4 And then the catalyst is removed in a roasting mode, does not need a large amount of water washing, and is simple and easy to implement.
In the present invention, the drying conditions in step (3) include: the temperature is 100-150 ℃, and the time is 6-18 h; the roasting conditions comprise: the temperature is 500-600 ℃, and the time is 1-5 h.
The invention also provides TiO prepared by the method 2 Modified alumina-based magnesium aluminate spinels.
With the above TiO 2 The modified alumina-based magnesia-alumina spinel is used as a carrier, and active components Co, Mo and K can be loaded on the carrier by an impregnation method to prepare the sulfur-resistant shift catalyst, wherein the impregnation liquid contains a cobalt compound, a molybdenum compound and a potassium compoundThe compound (I) is prepared. The cobalt compound may be a soluble cobalt salt, for example, may be one or more of cobalt nitrate, cobalt acetate, cobalt chloride, cobalt sulfate, and cobalt hydroxycarbonate; the molybdenum compound may be a soluble molybdenum salt, and may be, for example, one or more of ammonium molybdate, sodium molybdate, potassium molybdate, and phosphomolybdic acid, preferably ammonium molybdate; the potassium compound may be a soluble potassium salt, and may be one or more of potassium carbonate, potassium chloride, potassium hydroxide, and potassium nitrate, for example, with potassium carbonate being preferred.
The components in the catalyst are preferably introduced by an isometric impregnation method, so that the catalyst has the advantages of high utilization efficiency of the components, uniform dispersion and simple and convenient operation.
In the present invention, an impregnation method is used to load an active component to TiO 2 Drying and roasting the modified alumina-based magnesia-alumina spinel carrier to obtain the sulfur-resistant shift catalyst. The drying conditions may be those commonly used in the art, and preferably include: the temperature is 100-; the time is 8-18h, more preferably 12 h. The firing conditions may be firing conditions commonly used in the art, and preferably include: the temperature is 450-600 ℃, more preferably 550-600 ℃; the time is 2-5 h.
The invention provides a sulfur-tolerant shift catalyst comprising the above TiO 2 The modified alumina-based magnesium aluminate spinel carrier comprises a modified alumina-based magnesium aluminate spinel carrier and active components loaded on the carrier, wherein the active components are cobalt, molybdenum and potassium.
Preferably, the carrier is contained in an amount of 60 to 95 wt%, the cobalt component is contained in an amount of 1 to 10 wt% in terms of oxide, the molybdenum component is contained in an amount of 2 to 20 wt% in terms of molybdenum trioxide, and the potassium component is contained in an amount of 1 to 15 wt% in terms of potassium oxide, based on the total weight of the catalyst.
Preferably, the carrier has a magnesium content, expressed as MgO, of from 1 to 15 wt.%, based on the total weight of the carrier, for example, from 2, 5, 7, 10, 12, 15 wt.%, and any value within the compositional range of any two of the above, preferably, from 1 to 10 wt.%, expressed as MgO; with TiO 2 The titanium content is 1-10% by weight, for example, 2, 3, 4, 5, 6, 7, 8, 9, 10% by weight and any value within the range of any two of the foregoing, preferably TiO 2 The titanium content is 1-8 wt%; with Al 2 O 3 The aluminum content is 80 to 95 wt.%, and may be, for example, 85, 87, 89, 92 wt.%, or any value within the range defined by any two of the foregoing.
The catalyst provided by the invention has better strength, water resistance and performance, is free from water and phase change when used at high temperature (250-500 ℃), has excellent low-temperature activity (200-250 ℃), is wide in use temperature range, and has better activity and stability within a wider temperature range of 200-500 ℃.
The present invention will be described in detail below by way of examples.
The raw materials used in the following examples are as follows:
spherical gamma-Al 2 O 3 : a product purchased from Ziboruifeng chemical company and having a specific surface area of 200m 2 The water absorption rate is 63 percent, wherein the water absorption rate is 110N per particle and the water absorption rate is 7 nm.
Technical grade magnesium nitrate hexahydrate: a product available from star chemical ltd, shanxi, handed over from city.
Titanyl sulfate: a product purchased from Shanghai Yi Huai chemical Co., Ltd.
The water absorption test described in the examples was carried out by a method commonly used in the art.
Example 1
740g of spherical gamma-Al is weighed 2 O 3 Carrier, water absorption 63%. 364g of industrial-grade magnesium nitrate hexahydrate is taken, dissolved by water and then is added to 466 ml. The magnesium nitrate solution was immersed in 740g of gamma-Al in equal volume 2 O 3 Drying the carrier at 120 ℃ for 12h, and roasting the carrier at 800 ℃ for 3h to obtain 813g of alumina-based magnesia-alumina spinel carrier, wherein the water absorption rate is measured to be 56%. 61g of titanyl sulfate is dissolved in water to reach the constant volume of 455ml, and the solution is dipped on the alumina-based magnesium aluminate spinel carrier in the same volume and dried for 12 hours at the temperature of 120 ℃. The dried carrier is cooled to room temperature and then is placed at 70 ℃ for heat treatment for 3h in 0.5mol/L ammonia solution. After thatDrying at 120 deg.C for 12 hr, and calcining at 550 deg.C for 3 hr to obtain TiO 2 828g of modified alumina-based magnesia alumina spinel carrier, based on the total weight of the carrier, has a magnesium content of 6.9 wt.% in terms of MgO, calculated as TiO 2 The titanium content was 3.7 wt%, the balance being γ -Al 2 O 3 Water absorption: 50 percent.
Preparing 64.34g of basic cobalt carbonate, 106.55g of ammonium heptamolybdate and 97.47g of potassium carbonate into co-impregnation liquid by a conventional method, and impregnating the co-impregnation liquid into the TiO in equal volume 2 Drying the modified alumina-based magnesia-alumina spinel on a carrier at 120 ℃ for 12h, and roasting the carrier at 600 ℃ for 3h to obtain a catalyst finished product A1. Based on the total weight of the catalyst, the cobalt component was present in an amount of 4 wt.% as an oxide, the molybdenum component was present in an amount of 8.5 wt.% as molybdenum trioxide, and the potassium component was present in an amount of 6.5 wt.% as potassium oxide.
Example 2
A sulfur tolerant shift catalyst A2 was prepared in a similar manner to example 1, except that TiO was prepared in accordance with the following procedure 2 Modified alumina-based magnesium aluminate spinel support:
679g of spherical gamma-Al are weighed 2 O 3 Carrier, water absorption 63%. 527g of industrial grade magnesium nitrate hexahydrate is taken, dissolved by water and then fixed to 428 ml. Magnesium nitrate solution was immersed in 679g of gamma-Al in equal volume 2 O 3 Drying the carrier for 15h at 110 ℃, and roasting the carrier for 3h at 900 ℃ to obtain 762g of alumina-based magnesia-alumina spinel carrier, wherein the water absorption rate is measured to be 52%. 132g of titanyl sulfate is dissolved in water to reach the constant volume of 396ml, and the solution is dipped on the alumina-based magnesium aluminate spinel carrier in the same volume and dried for 12 hours at the temperature of 120 ℃. The dried carrier is cooled to room temperature and then placed at 60 ℃ for heat treatment for 4h in 0.3mol/L ammonia solution. Then drying the mixture at 120 ℃ for 12h, and roasting the dried mixture at 500 ℃ for 5h to obtain TiO 2 The modified alumina-based magnesia-alumina spinel carrier has a magnesium content of 10 wt% calculated by MgO and TiO content based on the total weight of the carrier 2 The titanium content was 8 wt%, the balance being γ -Al 2 O 3 Water absorption: and 48 percent.
Example 3
In accordance with and implementExample 1A sulfur tolerant shift catalyst A3 was prepared in a similar manner except that TiO was prepared according to the following procedure 2 Modified alumina-based magnesium aluminate spinel support:
687g of spherical gamma-Al are weighed 2 O 3 Carrier, water absorption 63%. 500g of magnesium chloride hexahydrate is taken, dissolved by water and then the volume is adjusted to 433 ml. Soaking magnesium chloride solution in 687g of gamma-Al in the same volume 2 O 3 Drying the carrier at 100 ℃ for 12h, and roasting the carrier at 500 ℃ for 3h to obtain 787g of alumina-based magnesia-alumina spinel carrier, wherein the water absorption rate is measured to be 50%. 82g of titanyl sulfate is dissolved in water to achieve a constant volume of 394ml, dipped on the alumina-based magnesium aluminate spinel carrier in an equal volume, and dried for 12 hours at 120 ℃. The dried carrier is cooled to room temperature and then is placed at 80 ℃ for heat treatment for 3h in 0.3mol/L ammonia solution. Then drying the mixture at 120 ℃ for 12h, and roasting the dried mixture at 500 ℃ for 5h to obtain TiO 2 The modified alumina-based magnesia-alumina spinel carrier comprises the following components by taking the total weight of the carrier as a reference: the magnesium content, calculated as MgO, is 12% by weight, calculated as TiO 2 The titanium content was 5 wt%, the remainder being γ -Al 2 O 3 Water absorption: 50 percent.
Example 4
A sulfur tolerant shift catalyst a4 was prepared in a similar manner to example 1, except that the active component was supported according to the following procedure:
taking 287g of cobalt nitrate hexahydrate, 206g of sodium molybdate and 110g of potassium hydroxide, preparing a co-impregnation liquid according to a conventional method, and impregnating the co-impregnation liquid into the TiO in equal volume 2 Drying the modified alumina-based magnesia-alumina spinel on a carrier at 120 ℃ for 12h, and roasting the carrier at 550 ℃ for 3h to obtain a catalyst finished product A4. Based on the total weight of the catalyst, the cobalt component was present in an amount of 8 wt.% as an oxide, the molybdenum component was present in an amount of 12 wt.% as molybdenum trioxide, and the potassium component was present in an amount of 9 wt.% as potassium oxide.
Comparative example 1
A sulfur tolerant shift catalyst was prepared in a similar manner to example 1, except that there was no Ti-supporting step in comparative example 1. Finally obtaining the finished catalyst D1.
Comparative example 2
A sulfur tolerant shift catalyst was prepared in a similar manner to example 1 except that TiO was used in comparative example 2 2 、Al 2 O 3 Mixing with MgO to obtain TiO 2 A modified magnesium aluminate spinel carrier. Finally obtaining the finished catalyst D2.
Test example
1. Atmospheric activity of the catalyst
The evaluation conditions of the normal pressure activity of the catalyst are as follows: the loading of the catalyst is 0.5g, the granularity is 20-40 meshes, the reaction pressure is 0.1Mpa, and the gas airspeed is 6000h -1 The reaction temperature is 200-500 ℃, and the feed gas composition is as follows: CO 81.45%, H 2 9.92%,N 2 8.55%,H 2 S0.08%, water to gas ratio 1.0, characterizing catalyst activity with CO conversion.
In-situ vulcanization is required before catalyst activity evaluation, wherein the vulcanization conditions are as follows: h 2 /H 2 S (99.2%/0.8% (v/v)), 50ml/min, pressure 0.1MPa, temperature 450 deg.C, and vulcanization time 5 h.
The CO conversion rate is calculated by the formula X CO =[(C 1 -C 2 )/C 1 ]*100%,C 1 CO concentration (v/v, dry basis (water vapor removal)) at the reactor inlet C 2 CO concentration (v/v, dry basis (water vapor removed)) at the reactor outlet.
The catalysts A1-A4 and D1-D2 were each tested for their normal pressure activity at different temperatures (200 ℃, 300 ℃, 400 ℃, 500 ℃) in accordance with the above-mentioned methods, and the results are shown in Table 1.
TABLE 1
2. Evaluation of hydration resistance of catalyst
Putting the catalysts A1, D1 and D2 into a hydrothermal kettle, adding a certain amount of deionized water, sealing, heating to 200 ℃ for hydrothermal treatment for 15 hours, drying, detecting the phase change by XRD, and expressing the strength of the hydration resistance of the catalysts by the amplitude of the phase change.
As shown in Table 1, catalysts A1-A4 all had higher activity at 200 ℃ and 500 ℃ and D1 catalyst was severely deactivated at a high temperature of 500 ℃ as compared with comparative catalysts D1 and D2, while the catalyst of the present invention had substantially no change in activity and the activity at 500 ℃ was maintained at 65% or more.
As shown in fig. 1, after hydrothermal treatment, the catalysts a1 and D1 both undergo significant hydration reaction of the supported alumina, but the hydration peak of the a1 catalyst alumina is smaller, indicating that it has better hydration resistance.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (11)
1. TiO 2 2 A process for the preparation of a modified alumina-based magnesium aluminate spinel, the process comprising the steps of:
(1) loading magnesium compound on gamma-Al by dipping method 2 O 3 Drying and roasting the substrate;
(2) impregnating TiOSO 4 Loading the substrate prepared in the step (1) and then drying; and
(3) and (3) placing the matrix prepared in the step (2) into an ammonia water solution for heat treatment, and then drying and roasting.
2. The method of claim 1, wherein the γ -Al is 2 O 3 Matrix, magnesium compound, TiOSO 4 Respectively with Al 2 O 3 、MgO、TiO 2 The mass ratio is 100: 1-20: 1-15.
3. The method according to claim 1, wherein, in step (1), the impregnation method is an equal-volume impregnation method,
and/or the impregnation liquid used in the impregnation process contains a magnesium compound and optionally one or more selected from a lanthanum compound, a calcium compound, a zirconium compound and a cerium compound;
and/or, the magnesium compound is selected from one or more of magnesium nitrate, magnesium chloride, magnesium acetate and magnesium bicarbonate.
4. The method according to claim 1 or 3, wherein in step (1), the drying conditions comprise: the temperature is 100-150 ℃, and the time is 6-18 h; the roasting conditions comprise: the temperature is 400 ℃ and 1000 ℃, and the time is 1-5 h.
5. The method according to claim 1, wherein, in the step (2), the impregnation method is an equal-volume impregnation method.
6. The method of claim 1 or 5, wherein in step (2), the drying conditions comprise: the temperature is 80-150 ℃ and the time is 3-12 h.
7. The method according to claim 1, wherein, in step (3), the conditions of the heat treatment include: the temperature is 50-100 deg.C, the time is 1-5h, and the pH value of ammonia water solution is kept above 11 during heat treatment.
8. The method of claim 1, wherein, in step (3), the drying conditions comprise: the temperature is 100-150 ℃, and the time is 6-18 h; the roasting conditions comprise: the temperature is 500-600 ℃, and the time is 1-5 h.
9. TiO prepared by the process of any one of claims 1 to 8 2 Modified alumina-based magnesium aluminate spinels.
10. A sulfur tolerant shift catalyst comprising a carrier and an active component supported on the carrier, wherein the carrier is the TiO according to claim 9 2 Modified alumina-based magnesiumThe aluminum spinel comprises cobalt, molybdenum and potassium as active components.
11. The catalyst of claim 10, wherein the support is present in an amount of 60 to 95 wt%, the cobalt component is present in an amount of 1 to 10 wt% as an oxide, the molybdenum component is present in an amount of 2 to 20 wt% as molybdenum trioxide, and the potassium component is present in an amount of 1 to 15 wt% as potassium oxide, based on the total weight of the catalyst;
and/or in the carrier, the magnesium content calculated by MgO is 1-15 wt% based on the total weight of the carrier, and the magnesium content is TiO 2 The titanium content is 1-10 wt.% calculated as Al 2 O 3 The calculated aluminum content is 80-95 wt.%.
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