CN109433222B - 一种耐硫甲烷化催化剂及其制备方法 - Google Patents
一种耐硫甲烷化催化剂及其制备方法 Download PDFInfo
- Publication number
- CN109433222B CN109433222B CN201811542631.0A CN201811542631A CN109433222B CN 109433222 B CN109433222 B CN 109433222B CN 201811542631 A CN201811542631 A CN 201811542631A CN 109433222 B CN109433222 B CN 109433222B
- Authority
- CN
- China
- Prior art keywords
- oxide
- metal
- mass
- catalyst
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 88
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- 239000007921 spray Substances 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims description 55
- 239000002184 metal Substances 0.000 claims description 48
- 229910052751 metal Inorganic materials 0.000 claims description 47
- 239000000243 solution Substances 0.000 claims description 43
- 238000001694 spray drying Methods 0.000 claims description 37
- 239000002244 precipitate Substances 0.000 claims description 34
- 238000001556 precipitation Methods 0.000 claims description 32
- 239000002002 slurry Substances 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 239000000843 powder Substances 0.000 claims description 26
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 24
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 23
- 238000004537 pulping Methods 0.000 claims description 21
- 150000003839 salts Chemical class 0.000 claims description 21
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 20
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 17
- 239000011609 ammonium molybdate Substances 0.000 claims description 17
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 17
- 229940010552 ammonium molybdate Drugs 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 17
- 239000011593 sulfur Substances 0.000 claims description 17
- 229910052717 sulfur Inorganic materials 0.000 claims description 17
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 238000000975 co-precipitation Methods 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 229910021645 metal ion Inorganic materials 0.000 claims description 11
- 239000002243 precursor Substances 0.000 claims description 11
- 239000002270 dispersing agent Substances 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 238000000465 moulding Methods 0.000 claims description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 10
- 230000032683 aging Effects 0.000 claims description 9
- 238000005469 granulation Methods 0.000 claims description 9
- 230000003179 granulation Effects 0.000 claims description 9
- 239000012018 catalyst precursor Substances 0.000 claims description 6
- 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 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 5
- 239000001099 ammonium carbonate Substances 0.000 claims description 5
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 3
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 238000000498 ball milling Methods 0.000 claims description 2
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 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 claims 2
- 239000007789 gas Substances 0.000 abstract description 13
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 12
- 238000005516 engineering process Methods 0.000 abstract description 10
- 230000008901 benefit Effects 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 6
- 239000003345 natural gas Substances 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 230000008569 process Effects 0.000 description 14
- 239000012752 auxiliary agent Substances 0.000 description 13
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 9
- 239000003245 coal Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 229910052593 corundum Inorganic materials 0.000 description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000000969 carrier Substances 0.000 description 6
- 235000019359 magnesium stearate Nutrition 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 239000012798 spherical particle Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 5
- 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 4
- 238000002309 gasification Methods 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000006477 desulfuration reaction Methods 0.000 description 3
- 230000023556 desulfurization Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- WXKDNDQLOWPOBY-UHFFFAOYSA-N zirconium(4+);tetranitrate;pentahydrate Chemical compound O.O.O.O.O.[Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O WXKDNDQLOWPOBY-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 238000005261 decarburization Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 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 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 2
- -1 polyoxyethylene Polymers 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 238000013341 scale-up Methods 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910003296 Ni-Mo Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920002535 Polyethylene Glycol 1500 Polymers 0.000 description 1
- 229920002538 Polyethylene Glycol 20000 Polymers 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000011038 discontinuous diafiltration by volume reduction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
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
- B01J23/70—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
- B01J23/8871—Rare earth metals or actinides
-
- 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
- B01J23/883—Molybdenum and nickel
-
- 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
- B01J23/888—Tungsten
- B01J23/8885—Tungsten containing also molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0045—Drying a slurry, e.g. spray drying
-
- 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
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0425—Catalysts; their physical properties
- C07C1/043—Catalysts; their physical properties characterised by the composition
- C07C1/0435—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/85—Chromium, molybdenum or tungsten
- C07C2523/88—Molybdenum
- C07C2523/883—Molybdenum and nickel
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/85—Chromium, molybdenum or tungsten
- C07C2523/88—Molybdenum
- C07C2523/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/85—Chromium, molybdenum or tungsten
- C07C2523/888—Tungsten
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
本发明涉及一种耐硫甲烷化催化剂及制备方法,具体的采用一种沉淀‑负载‑喷雾干燥‑锻烧制备技术的制备方法,该催化剂可应用于合成气耐硫甲烷化生产天然气。本发明公开的制备方法组分机动可调、原料简便易得、制备工艺简单、成本低廉。
Description
技术领域
本发明属于催化剂领域,具体涉及一种耐硫甲烷化催化剂及制备方法。
背景技术
“富煤、贫油、少气”是我国的资源禀赋,发展煤制天然气是煤基气态能源产业的一个重要方向,能够有效促进煤的清洁利用,缓解天然气的供需矛盾,同时煤基合成气制SNG也是我国“十三五规划”的重点发展项目之一。目前煤基合成气制天然气工艺有两大类,一是间接甲烷化技术,主要包括煤气化、变换、脱硫、脱碳、甲烷化等一些列步骤,也是目前工业上广泛采用的技术,甲烷化一般采用镍基催化剂,该催化剂对硫十分敏感,极易中毒失活,需要将原料气中的硫控制在0.1ppm以下,并且需要通过变换将原料气H/C调节到3以上,这在很大程度上限制了镍基催化剂的应用;二是直接耐硫甲烷化技术,主要包括煤气化、直接耐硫甲烷化、脱酸气、补充甲烷化等步骤,直接甲烷化技术将甲烷化工段置于气体净化之前,由于甲烷化是缩体积反应,耐硫甲烷化减少了低温甲醇洗的工艺负荷,避免了低温甲醇洗处理前后原料先降温后升温而造成的能量浪费,同时降低了脱硫工艺负荷及难度,有利于降低操作成本。目前气化、变换、脱硫、脱碳等技术都比较成熟,甲烷化已成为煤制天然气技术的关键技术,而甲烷合成催化剂又是甲烷化技术的关键。
MoS2由于具有优秀的水汽变换活性同时具有甲烷化活性而成为耐硫甲烷化催化剂的重点研发方向。耐硫甲烷化催化剂的研发一般分为两种,一种是针对间接甲烷化工艺,提高镍基催化剂的耐硫性能,一般是对镍基催化剂进行钼改性,制成Ni、Mo双金属催化剂,该类型催化剂甲烷化活性好但仅适合在低硫含量原料气下使用,CN102389808B公开了一种共沉淀法制备的耐硫甲烷化催化剂,该催化剂有较高的镍含量,甲烷化活性很高,但仅耐1-3ppm的硫,远低于气化气中的硫含量,不能直接用做直接耐硫甲烷化催化剂。另一种即是针对直接耐硫甲烷化工艺开发的钼基耐硫甲烷化催化剂,目前公开的耐硫甲烷化催化剂的制备方法主要有负载型催化剂制备法(浸渍法、沉淀沉积法、溶液蒸法等,均是先获得符合要求的多孔载体,然后通过不同的手段将活性组分及助剂负载到载体表面)、共沉淀法、溶胶凝胶法、水热合成法等。负载型催化剂制备方法是目前应用较多的方法,不可否认其具有工艺成熟、便于实施等有点,但由于耐硫甲烷化催化剂可能涉及包括活性组分、活性助剂、载体改性剂、载体在内的多种组分,载体经多次负载各类组分后容易造成载体表面孔道堵塞、活性组分聚集长大等一系列问题,这些均是制备催化剂时需要着重注意的且是影响催化剂性能的主要因素;对于沉淀法制备催化剂,由于活性组分及助剂分散均匀有利于提高催化剂的活性、稳定性及温度适用范围,但由于活性组分钼跟其他助剂如镧、铈、镍等助剂的盐沉淀所需PH值相差太大,且共混体系不稳定需要加入大量的螯合剂及表面活性剂等(如专利CN105597802A所公开的制备方法),成本高,原子利用率低,不利于催化剂的工业化生产;而溶胶凝胶及水热合成法生产工艺复杂,耗水、耗能均较高,不利于催化剂的工业放大生产。
专利CN102416329公开了一种高温甲烷化催化剂的制备方法,其中涉及到使用喷雾干燥法对浆料进行干燥及造粒。专利CN105417570A公开了一种尖晶石复合氧化物的制备方法,同样使用了喷雾干燥的手段,并认为喷雾干燥在极短时间内使其同时完成脱水、造粒过程,缩短了生产周期且前驱体组分不会偏析,两篇专利所使用的喷雾干燥手段都只是着眼于干燥上。
发明内容
基于以上耐硫甲烷化催化剂制备方法中所呈现的问题,本发明人有机的结合了沉淀型及负载型催化剂的制备方法的优势并巧妙地利用了喷雾干燥这一制备手段,发明一种组分机动可调、原料简便易得、制备工艺简单的、成本低廉易于工业化生产的耐硫甲烷化催化剂及其制备方法。
本发明的第一个方面提供一种耐硫甲烷化催化剂的制备方法,该方法包括:
(1)将金属M4的可溶性金属盐、氢氧化物和氧化物中的一种或多种以及金属M2、M3的可溶性金属盐中的一种或两种(即M2的可溶性金属盐和M3的可溶性金属盐二者中存在至少一种)的溶液在碳酸盐沉淀剂的存在下进行沉淀,获得作为沉淀物的金属M2、M3、M4的碳酸盐或碱式碳酸盐前驱体,
(2)将步骤(1)中获得的沉淀物与金属M1的水溶性盐溶液共同制浆,然后将所制备浆液进行喷雾干燥,得到催化剂前驱体造粒粉,
(3)步骤2所得的催化剂前驱体造粒粉预煅烧(例如煅烧温度为300-450℃),然后将预煅烧所得物料成型,制得耐硫甲烷化催化剂。
进一步地,金属M1、M2、M3的水溶性盐、M4的可溶性金属盐、氢氧化物和氧化物中的一种或多种的用量使得预煅烧后的催化剂中包括:
其中,M1为Mo和/或W;M2为Ni和/或Co;M3为La、Ce中的一种或两种;M4为Zr和/或Al,其中,M2的氧化物和M3的氧化物中至少一种不为0。
优选包括:
其中,按金属离子功能进行简单分类:M1On为活性金属组分,M1为Mo和/或W;M2On为活性金属助剂,M2为Ni和/或Co;M3On为载体改性剂,M3为La和/或Ce;M4On为载体,M4为Zr和/或Al。以上分类只是对各金属粒子作用的归纳及说明并非对其作用的限制。
进一步地,步骤(1)中金属M2、M3、M4的可溶性金属盐的溶液中金属离子浓度为0.8-2.5mol/L,优选各金属的硝酸盐溶液,金属M4的氢氧化物和氧化物可以选自氢氧化锆、氧化锆或氢氧化铝、一水软石中的任意一种或几种。一般,M1的氧化物为MoO3、WO3的一种或两种,M2的氧化物为NiO、Co3O4的一种或两种,M3的氧化物为La2O3、CeO2中的一种或两种,M4的氧化物为Al2O3与ZrO2中的一种或两种。
优选地,M1氧化物为MoO3或重量比为2-5:1的MoO3与WO3混合物,优选2.5-4:1;M2氧化物为NiO或重量比为1-3:1的NiO与Co3O4混合物,优选1.5-2.5:1;M3氧化物为CeO2或重量比为1-2:1的CeO2与La2O3的混合物,M4氧化物中Al2O3与ZrO2的重量比为0.1-8:1,优选0.5-4:1。
优选地,碳酸盐沉淀剂为0.8-2.5mlo/L的碳酸盐溶液,选自碳酸钠水溶液、碳酸氢钠水溶液、碳酸钾水溶液、碳酸铵水溶液、碳酸氢铵水溶液中的任意一种或几种,优选碳酸钠水溶液。相对于金属M4的可溶性金属盐、氢氧化物和氧化物中的一种或多种以及任选的金属M2、M3的可溶性金属盐的金属总摩尔量,碳酸盐沉淀剂按碳酸盐计的用量一般是1.3-2.5:1,优选1.5-2:1。
优选地,步骤(2)中所述M1的水溶性盐为钼酸铵或/和偏钨酸铵。M1的水溶性盐溶液的浓度可以为0.3-1.2mol/L,优选0.5-0.9mol/L。
进一步地,步骤(1)中采用并流共沉法得到沉淀,沉淀温度为40-80℃、pH值为7.5-9.5、沉淀时间20-120min,优选30-80min,经0-3h老化、过滤、洗涤得沉淀,制得的沉淀为各金属组分的碳酸盐或碱式碳酸盐前驱体。
进一步地,步骤(2)中制浆方法选用机械搅拌破碎制浆或球磨制浆,浆液中固含量按氧化物计为8-25wt%,优选10-20wt%。
进一步地,步骤(2)中所述喷雾干燥方式为压力式喷雾干燥、气流式喷雾干燥、离心式喷雾干燥、喷雾流化干燥中的任意一种,优选压力式喷雾干燥,喷雾干燥的操作压力0-5Mpa,优选0.5-3Mpa,进口温度200-400℃,优选250-350℃,出口温度80-170℃,优选90-150℃。
进一步地,步骤(2)中喷雾干燥的生产方式为浆液中加入分散剂的连续喷雾干燥生产或不加分散剂的半连续生产,喷雾干燥所得到的催化剂前驱体造粒粉颗粒呈球形及类球形,颗粒大小为50-350μm,流动角≤30°,300-450℃预烧后形状完整且仍能保持较好的流动性,便于催化剂的打片成型。
所述连续喷雾干燥生产是指在分散剂的作用下将所需制浆组分全部制成稳定的悬浊液体系浆液,然后统一进行喷雾干燥,所述半连续型生产是指所需制浆组分不添加分散剂仅通过机械破碎的方法制浆,制浆后直接进行喷雾干燥,此方法对浆料的稳定性要求降低。
分散剂可以是无机类的如聚磷酸盐、硅酸盐,也可是有机类的如烷基酚聚乙烯醚、聚氧乙烯烷基酚基醚、三甲基硬脂酰铵氯化物等,也可以是高分子聚合物如聚乙二醇(PEG1500、PEG20000)等,优选PVP(聚乙烯吡咯烷酮)、CTNC(十六烷基三甲基氯化铵)、聚乙二醇中的一种或几种。分散剂的用量为浆液中固体物质含量的1-15wt%,优选2-8wt%。
进一步地,成型通过将预煅烧所得物料与脱模剂(例如为石墨或硬脂酸镁,使用量可以为预煅烧所得物料总量的1-3wt%)混合后打片来进行。
根据本发明的一个优选实施方案,本发明的制备方法包括:
(1)分别称取一定量的硝酸镍、硝酸铈、硝酸铝、硝酸镁溶解于去离子水中配置金属离子浓度为0.8-2.5mol/L的溶液A,配置溶度为0.8-2.5mlo/L的碳酸钠溶液B,将A、B两种溶液均水浴加热到50-80℃,然后在相同的温度下并流共沉,沉淀pH值为7.5-9.5,沉淀用时20-120min,沉淀结束后在60-90℃老化0-3h,过滤、洗涤所得沉淀;
(2)配置钼酸铵水溶液,将其与步骤(1)所得沉淀共同搅拌制成均匀浆料,然后将所制得浆料用压力式喷雾干燥机进行干燥、造粒,优选喷雾干燥条件为,压力0.5-3Mpa,进口温度200-400℃,出口温度80-170℃;
(3)将步骤(2)所得喷雾干燥颗粒在300-450℃条件下进行预煅烧,然后与基于预煅烧物的1-3wt%的脱模剂例如石墨混合打片成型。
优选地,金属M1、M2、M3的水溶性盐、M4的可溶性金属盐、氢氧化物和氧化物中的一种或多种的用量使得预煅烧后的催化剂中包括:
优选包括:
本发明进一步涉及通过上述方法制备的耐硫甲烷化催化剂。
本发明制备的耐硫甲烷化催化剂的比表面积为100-300m2/g,不要求合成气的H/C比,经在线或离线预硫化后,适用于含硫量为0.1-1vol%的合成气的耐硫甲烷合成反应,反应温度为260-600℃,体积空速1000-50000h-1,优选5000-50000h-1,压力0.5-5MPa。
本发明还进一步提供了上述耐硫甲烷化催化剂用于CO甲烷化的用途。与现有技术相比本发明的优点:
1、本发明采用并流共沉淀法实现助剂及载体的均质共沉,有效提高助剂及载体之间的相互作用。通过制浆的方法将活性组分与载体及助剂组分混合,因在制浆之前各组分均未经过高温焙烧,各组分仍能在浆液中以离子态相互作用、相互取代,与现有的先制备载体再进行活性组分负载的制备方法相比,有效提高了活性组分与助剂及载体间的相互作用,提高了催化剂的活性及稳定性。同时制备过程中巧妙的规避了活性组分Mo、W不能与其他助剂及载体组分共沉的问题,利用共沉与负载相结合的制备方法达到了全组份共沉的均质效果。特别是不加分散剂的制浆工艺与现有共沉淀法相比完全杜绝了非必要组分的加入对催化剂的影响,有利于实现催化剂的清洁生产,环境友好。
2、本发明采用喷雾干燥技术实现催化剂的干燥及造粒,简化工艺流程,而且喷雾干燥法在非常短时间内实现热量和质量的快速转移,在制备各种复合组分,特别是组分要求精确的粉体材料上有其突出的优点,因此用喷雾干燥法处理本发明所给出的金属可溶性盐与固相沉淀共混的浆料体系,能够精确控制活性金属与其他组分的配比,不会造成组分偏析,催化剂中各组分的均匀分布。
3、本发明原料易得、工艺流程简单,成本低廉,是一种特别适合工业放大生产的催化剂及制备方法。
附图说明
图1为本发明的一种耐硫甲烷化催化剂的制备工艺流程图。
具体实施方式
实施例中催化剂的分析表征方法有:
1、采用美国麦克公司ASAP2460装置测定催化剂的孔大小及孔结构;
2、采用大连智能试验机厂的ZQJ-Ⅱ智能颗粒强度试验机测定单颗载体压裂强度;
3、采用美国安捷伦公司7890N气相色谱分析产物组成。
实施例1
按下表所示的氧化物质量百分含量进行投料。
MoO<sub>3</sub> | NiO | Co<sub>3</sub>O<sub>4</sub> | CeO<sub>2</sub> | ZrO2 | Al<sub>2</sub>O<sub>3</sub> |
15% | 5% | 5% | 5% | 21% | 49% |
如图1所示的工艺流程:
1、沉淀法制备助剂及载体前驱体:分别称取38.9g的六水硝酸镍、25.2g的六水硝酸铈、36.2g的六水硝酸钴、146.3g五水硝酸锆、721.12g九水硝酸铝溶解于去离子水中配置金属离子浓度为1.5mol/L的溶液A,称取720g无水碳酸钠,配置溶度为1.5mol/L的碳酸钠溶液B,将A、B两种溶液均水浴加热到75℃,然后并流共沉,A、B两溶液流量分别为51.1ml/min及100.7ml/min,沉淀PH值为7.5-7.8,沉淀用时45min,沉淀结束后在75℃老化2h,过滤、洗涤所得沉淀。
2、制浆:称取36.8g钼酸铵(NH4)6Mo7O24■4H2O溶解于400ml去离子水中,并加入6g的聚乙二醇作为分散剂,用搅拌的方式将步骤1所得沉淀分散于上述钼酸铵溶液中,充分搅拌制得均匀浆液,此时所得浆料中固含量按氧化物计为13%,然后将所制得浆料用小型压力式喷雾干燥机进行干燥、造粒,喷雾干燥条件为,进料压力0.8-1.0MPa,进口温度290-300℃,出口温度110-115℃。所得造粒粉颗粒呈球状或类球状,大小为20-200目。
3、将步骤2所得造粒粉在350℃、4h条件下进行预煅烧,所得预煅烧粉料约190g,加入4g石墨,混合均匀后压片成型,制得所需耐硫甲烷化催化剂,该催化剂比表面积为230.62m2/g,催化剂颗粒平均强度343N/cm。
实施例2
按下表所示的氧化物质量百分含量进行投料。
MoO<sub>3</sub> | NiO | Co<sub>3</sub>O<sub>4</sub> | CeO<sub>2</sub> | ZrO<sub>2</sub> | Al<sub>2</sub>O<sub>3</sub> |
25% | 3% | 2% | 3% | 30% | 37% |
1、沉淀法制备助剂及载体前驱体:分别称取23.4g的六水硝酸镍、15.1g的六水硝酸铈、14.5g的六水硝酸钴、209.1g-、544.5g九水硝酸铝溶解于去离子水中配置金属离子浓度为1.5mol/L的溶液A,称取605g无水碳酸钠,配置溶度为1.5mol/L的碳酸钠溶液B,将A、B两种溶液均水浴加热到65℃,然后并流共沉,A、B两溶液流量分别为49.7ml/min及108.7ml/min,沉淀PH值为8.0-8.3,沉淀用时35min,沉淀结束后在65℃老化2h,过滤、洗涤所得沉淀。
2、制浆:称取61.33g钼酸铵(NH4)6Mo7O24·4H2O溶解于350ml去离子水中,用搅拌的方式将步骤1所得沉淀分散于上述钼酸铵溶液中,充分搅拌制得均匀浆液,此时所得浆料中固含量按氧化物计为16%,然后将所制得浆料用小型压力式喷雾干燥机进行干燥、造粒,喷雾干燥条件为,进料压力1.5-1.8MPa,进口温度320-340℃,出口温度110-115℃。所得造粒粉颗粒呈球状或类球状,大小为20-200目。
3、成型:将步骤2所得造粒粉在400℃、4h条件下进行预煅烧,所得预煅烧粉料约195g,加入4g硬脂酸镁,混合均匀后压片成型,制得所需耐硫甲烷化催化剂,该催化剂比表面积为210.53m2/g,催化剂颗粒平均强度382N/cm。
实施例3
按下表所示的氧化物质量百分含量进行投料。
MoO<sub>3</sub> | WO<sub>3</sub> | NiO | Co<sub>3</sub>O<sub>4</sub> | ZrO<sub>2</sub> | Al<sub>2</sub>O<sub>3</sub> |
15% | 8% | 3% | 2% | 20% | 52% |
1、沉淀法制备助剂及载体前驱体:分别称取23.4g的六水硝酸镍、139.4g的五水硝酸锆、14.5g的六水硝酸钴、765g九水硝酸铝溶解于去离子水中配置金属离子浓度为1.5mol/L的溶液A,称取737g无水碳酸钠,配置溶度为1.5mol/L的碳酸钠溶液B,将A、B两种溶液均水浴加热到65℃,然后并流共沉,A、B两溶液流量分别为51.5ml/min及92.76ml/min,沉淀PH值为8.5-8.7,沉淀用时50min,沉淀结束后在80℃老化2h,过滤、洗涤所得沉淀。
2、制浆:称取36.8g钼酸铵(NH4)6Mo7O24■4H2O及18.3g的偏钨酸铵(NH4)6H2W12O40■nH2O共同溶解于450ml去离子水中,用搅拌的方式将步骤1所得沉淀分散于上述钼酸铵溶液中,充分搅拌制得均匀浆液,此时所得浆料中固含量按氧化物计为11%,然后将所制得浆料用小型压力式喷雾干燥机进行干燥、造粒,喷雾干燥条件为,进料压力1.5-1.8MPa,进口温度320-340℃,出口温度95-100℃。所得造粒粉颗粒呈球状或类球状,大小为20-200目。
3、成型:将步骤2所得造粒粉在450℃、4h条件下进行预煅烧,所得预煅烧粉料约195g,加入4g硬脂酸镁,混合均匀后压片成型,制得所需耐硫甲烷化催化剂,该催化剂比表面积为230.84m2/g,催化剂颗粒平均强度266N/cm。
实施例4
按下表所示的氧化物质量百分含量进行投料。
MoO<sub>3</sub> | WO<sub>3</sub> | NiO | Co<sub>3</sub>O<sub>4</sub> | ZrO<sub>2</sub> | Al<sub>2</sub>O<sub>3</sub> |
20% | 6% | 5% | 2% | 13% | 54% |
1、沉淀法制备助剂及载体前驱体:分别称取38.9g的六水硝酸镍、90.6g的五水硝酸锆、14.5g的六水硝酸钴、794.7g九水硝酸铝溶解于去离子水中配置金属离子浓度为1.5mol/L的溶液A,称取727g无水碳酸钠,配置溶度为1.5mol/L的碳酸钠溶液B,将A、B两种溶液均水浴加热到70℃,然后并流共沉,A、B两溶液流量分别为49ml/min及87.9ml/min,沉淀PH值为8.5-8.7,沉淀用时52min,沉淀结束后在70℃老化2h,过滤、洗涤所得沉淀。
2、制浆:称取49.1g钼酸铵(NH4)6Mo7O24■4H2O及13.7g的偏钨酸铵(NH4)6H2W12O40■nH2O共同溶解于500ml去离子水中,加入聚乙烯吡咯烷酮5.5g作为分散剂,用搅拌的方式将步骤1所得沉淀分散于上述钼酸铵溶液中,充分搅拌制得均匀浆液,此时所得浆料中固含量按氧化物计为8%,然后将所制得浆料用小型压力式喷雾干燥机进行干燥、造粒,喷雾干燥条件为,进料压力2.5-2.8MPa,进口温度350-360℃,出口温度95-100℃。所得造粒粉颗粒呈球状或类球状,大小为20-200目。
3、成型:将步骤2所得造粒粉在450℃、4h条件下进行预煅烧,所得预煅烧粉料约195g,加入4g硬脂酸镁,混合均匀后压片成型,制得所需耐硫甲烷化催化剂,该催化剂比表面积为198.62m2/g,催化剂颗粒平均强度352N/cm。
实施例5
按下表所示的氧化物质量百分含量进行投料。
MoO<sub>3</sub> | NiO | ZrO<sub>2</sub> | Al<sub>2</sub>O<sub>3</sub> |
20% | 6% | 32% | 42% |
1、沉淀法制备助剂及载体前驱体:分别称取46.7g的六水硝酸镍、92.5g的氧氯化锆、617.9g九水硝酸铝溶解于去离子水中配置金属离子浓度为1.5mol/L的溶液A,称取810g碳酸铵,配置溶度为1.5mol/L的碳酸铵溶液B将A、B两种溶液均水浴加热到55℃,然后并流共沉,A、B两溶液流量分别为87ml/min及188ml/min,沉淀PH值为9.0-9.2,沉淀用时30min,沉淀结束后在70℃老化2h,过滤、洗涤所得沉淀。
2、制浆:称取49.1g钼酸铵(NH4)6Mo7O24■4H2O溶解于450ml去离子水中,将钼酸铵溶液与步骤1所得沉淀共同加入小型湿式球磨机,以氧化铝瓷球为研磨介质,充分研磨制浆,此时所得浆料中固含量按氧化物计为11%,然后将所制得浆料用小型压力式喷雾干燥机进行干燥、造粒,喷雾干燥条件为,进料压力2.5-2.8MPa,进口温度350-360℃,出口温度95-100℃。所得造粒粉颗粒呈球状或类球状,大小为20-200目。
3、成型:将步骤2所得造粒粉在400℃、4h条件下进行预煅烧,所得预煅烧粉料约195g,加入4g硬脂酸镁,混合均匀后压片成型,制得所需耐硫甲烷化催化剂,该催化剂比表面积为226.2m2/g,催化剂颗粒平均强度298N/cm。
实施例6
按下表所示的氧化物质量百分含量进行投料。
MoO<sub>3</sub> | WO<sub>3</sub> | NiO | La<sub>2</sub>O<sub>3</sub> | ZrO<sub>2</sub> | Al<sub>2</sub>O<sub>3</sub> |
15% | 5% | 5% | 3% | 32% | 40% |
1、沉淀法制备助剂及载体前驱体:分别称取38.9g的六水硝酸镍、15.9g的六水硝酸镧、92.5g的氧氯化锆、588g九水硝酸铝溶解于去离子水中配置金属离子浓度为1.5mol/L的溶液A,称取610g碳酸钠,配置溶度为1.5mol/L的碳酸钠溶液B,将A、B两种溶液均水浴加热到65℃,然后并流共沉,A、B两溶液流量分别为57ml/min及91ml/min,沉淀PH值为8.5-8.7,沉淀用时42min,沉淀结束后在65℃老化2h,过滤、洗涤所得沉淀。
2、制浆:称取36.8g钼酸铵(NH4)6Mo7O24■4H2O及11.4g的偏钨酸铵(NH4)6H2W12O40■nH2O共同溶解于450ml去离子水中,将上述溶液与步骤1所得沉淀共同加入小型湿式球磨机,以氧化铝瓷球为研磨介质,充分研磨制浆,此时所得浆料中固含量按氧化物计为11%,然后将所制得浆料用小型压力式喷雾干燥机进行干燥、造粒,喷雾干燥条件为,进料压力1.5-1.8MPa,进口温度320-340℃,出口温度95-100℃。所得造粒粉颗粒呈球状或类球状,大小为20-200目。
3、成型:将步骤2所得造粒粉在450℃、4h条件下进行预煅烧,所得预煅烧粉料约195g,加入4g硬脂酸镁,混合均匀后压片成型,制得所需耐硫甲烷化催化剂,该催化剂比表面积为256.84m2/g,催化剂颗粒平均强度328N/cm。
对比例1
按照专利CN103191720B中公开的方法,共沉淀法制备镁铝尖晶石载体:将311.4g九水硝酸铝和128.4g六水硝酸镁共同溶解于500ml去离子水中形成混合溶液,将该混合液与浓度为3mol/L的氨水在70℃剧烈搅拌下并流加入烧杯中,保持PH值在11左右,反应至沉淀完全后静置陈化2h,过滤、去离子水洗三次,将滤饼放入120℃烘箱中干燥12h,然后在700℃马弗炉中焙烧2h,得到71Al2O3/29MgO载体。
浸渍法制备催化剂:将5.58g(NH4)6Mo7O24■4H2O溶解于50ml去离子水中,称取30g的71Al2O3/29MgO载体粉末加入到上述溶液中剧烈搅拌,蒸干水分,再放入120℃烘箱中干燥12h,然后在750℃马弗炉中焙烧2h,得到催化剂。
测试例1
催化剂的测试在微型固定床反应器上进行,反应器内径12mm,催化剂研磨过筛至40-60目,装填量5ml,催化剂活性测试前先在3vol%H2S含量的H2/H2S混合气中,0.1Mpa、550℃、2h条件下进行硫化,硫化结束后降温、置换系统进行催化剂活性测试实验,测试条件为:H2:CO:N2:H2S=40:40:19.7:0.3,水气比为0.25:1,体积空速8000h-1,压力2.5MPa,分别在300、580℃条件下进行活性测试,然后在580℃进行48h稳定性测试。测试结果如下表所示:
从上述评价结果可以看出,用沉淀-负载-喷雾干燥法制备的耐硫甲烷化催化剂,均具有较好的CO甲烷化活性及选择性,并且具有很好的耐高温稳定性,在活性测试过程中发现,该一系列的催化剂均在240-280℃起活(即CO转化率为10%的反应温度点),起活温度低,温度适用范围宽。
Claims (23)
1.一种耐硫甲烷化催化剂的制备方法,其特征在于,该制备方法包括:
(1)将金属M4的可溶性金属盐以及金属M2、M3的可溶性金属盐中的一种或两种的溶液在碳酸盐沉淀剂的存在下采用并流共沉法进行沉淀,获得作为沉淀物的金属M2、M3、M4的碳酸盐或碱式碳酸盐前驱体,
(2)将步骤(1)中获得的沉淀物与金属M1的水溶性盐溶液共同制浆,然后将所制备浆液进行喷雾干燥,得到催化剂前驱体造粒粉,
(3)步骤(2)所得的催化剂前驱体造粒粉预煅烧,然后将预煅烧所得物料成型,制得耐硫甲烷化催化剂;
其中,M1为Mo和/或W;M2为Ni和/或Co;M3为La、Ce中的一种或两种;M4为Zr和/或Al;
金属M1、M2、M3的水溶性盐、M4的可溶性金属盐的用量使得预煅烧后的催化剂中包括:
M1的氧化物5-30质量份,
M2的氧化物0-10质量份,
M3的氧化物0-10质量份,
M4的氧化物30-75质量份,
其中,M2的氧化物和M3的氧化物中至少一种不为0。
2.根据权利要求1所述的制备方法,其特征在于,金属M1、M2、M3的水溶性盐、M4的可溶性金属盐的用量使得预煅烧后的催化剂中包括:
M1的氧化物10-25质量份,
M2的氧化物3-7质量份,
M3的氧化物2-7质量份,
M4的氧化物40-70质量份。
3.根据权利要求1所述的制备方法,其特征在于,步骤(1)中金属M2、M3、M4的可溶性金属盐为金属M2、M3、M4的硝酸盐溶液。
4.根据权利要求1-3中任一项所述的制备方法,其特征在于,金属M2、M3、M4的可溶性金属盐溶液中金属离子浓度为0.8-2.5mol/L。
5.根据权利要求1-3中任一项所述的制备方法,其特征在于,M1氧化物为MoO3或重量比为2-5:1 的MoO3与WO3混合物;M2氧化物为NiO或重量比为1-3:1的 NiO与Co3O4混合物;M3氧化物为CeO2或重量比为1-2:1的CeO2与La2O3的混合物,M4氧化物中Al2O3与ZrO2的重量比为0.1-8:1。
6.根据权利要求1-3中任一项所述的制备方法,其特征在于,M1氧化物为MoO3或重量比为2.5-4:1 的MoO3与WO3混合物;M2氧化物为NiO或重量比为1.5-2.5:1的 NiO与Co3O4混合物;M4氧化物中Al2O3与ZrO2的重量比为0.5-4:1。
7.根据权利要求1-3中任一项所述的制备方法,其特征在于,碳酸盐沉淀剂为0.8-2.5mol/L的碳酸盐溶液,选自碳酸钠水溶液、碳酸氢钠水溶液、碳酸钾水溶液、碳酸铵水溶液、碳酸氢铵水溶液中的任意一种或几种;
相对于金属M4的可溶性金属盐以及任选的金属M2、M3的可溶性金属盐的金属总摩尔量,碳酸盐沉淀剂按碳酸盐计的用量是1.3-2.5:1。
8.根据权利要求7所述的制备方法,其特征在于,相对于金属M4的可溶性金属盐以及任选的金属M2、M3的可溶性金属盐的金属总摩尔量,碳酸盐沉淀剂按碳酸盐计的用量是1.5-2:1。
9.根据权利要求1或2所述的制备方法,其特征在于,步骤(2)中所述M1的水溶性盐为钼酸铵或/和偏钨酸铵。
10.根据权利要求9所述的制备方法,其特征在于,M1的水溶性盐溶液的浓度为0.3-1.2mol/L。
11.根据权利要求9所述的制备方法,其特征在于,M1的水溶性盐溶液的浓度为0.5-0.9mol/L。
12.根据权利要求1-3中任一项所述的制备方法,其特征在于,步骤(1)中沉淀温度为40-80℃、pH值为7.5-9.5、沉淀时间30-120min,经0-3h老化、过滤、洗涤得沉淀,制得的沉淀为各金属组分的碳酸盐或碱式碳酸盐前驱体。
13.根据权利要求1-3中任一项所述的制备方法,其特征在于,步骤(2)中制浆方法选用机械搅拌破碎制浆或球磨制浆,浆液中固含量按氧化物计为8-25wt%。
14.根据权利要求13所述的制备方法,其特征在于,浆液中固含量按氧化物计为10-20wt%。
15.根据权利要求1-3中任一项所述的制备方法,其特征在于,步骤(2)中所述喷雾干燥方式为压力式喷雾干燥、气流式喷雾干燥、离心式喷雾干燥、喷雾流化干燥中的任意一种,喷雾干燥的操作压力0-5MPa,进口温度200-400℃,出口温度80-170℃。
16.根据权利要求15所述的制备方法,其特征在于,喷雾干燥的操作压力0.5-3MPa,进口温度250-350℃,出口温度90-150℃。
17.根据权利要求1-3中任一项所述的制备方法,其特征在于,步骤(2)中喷雾干燥的生产方式为浆液中加入分散剂的连续喷雾干燥生产或不加分散剂的半连续生产,喷雾干燥所得到的催化剂前驱体造粒粉颗粒呈球形及类球形,颗粒大小为50-350μm,流动角≤30°,300-450℃预烧后形状完整且仍能保持较好的流动性,便于催化剂的打片成型。
18.一种耐硫甲烷化催化剂的制备方法,其特征在于,制备方法包括:
(1)分别称取一定量的硝酸镍、硝酸铈、硝酸铝、硝酸锆溶解于去离子水中配置金属离子浓度为0.8-2.5mol/L的溶液A,配置溶度为0.8-2.5mol/L的碳酸钠溶液B,将A、B两种溶液均水浴加热到50-80℃,然后在相同的温度下并流共沉淀pH值为7.5-9.5,沉淀时间20-120min,沉淀结束后在60-90℃老化0-3h,过滤、洗涤所得沉淀;
(2)配置钼酸铵水溶液,将其与步骤(1)所得沉淀共同搅拌制成均匀浆料,然后将所制得浆料用压力式喷雾干燥机进行干燥、造粒;
(3)将步骤(2)所得喷雾干燥颗粒在300-450℃条件下进行预煅烧,然后与基于预煅烧物的1-3wt%的脱模剂混合打片成型;
金属M1、M2、M3的水溶性盐、M4的可溶性金属盐的用量使得预煅烧后的催化剂中包括:
M1的氧化物5-30质量份,
M2的氧化物0-10质量份,
M3的氧化物0-10质量份,
M4的氧化物30-75质量份,
其中,M2的氧化物和M3的氧化物中至少一种不为0,
其中,M1 为 Mo 和/或 W;M2 为 Ni 和/或 Co;M3 为 La、Ce 中的一种或两种;M4 为Zr 和/或 Al。
19.根据权利要求18所述的制备方法,其特征在于,喷雾干燥条件为,压力0.5-3MPa,进口温度200-400℃,出口温度80-170℃。
20.根据权利要求18所述的制备方法,其特征在于,脱模剂为石墨。
21.根据权利要求18所述的制备方法,其特征在于,金属M1、M2、M3的水溶性盐、M4的可溶性金属盐的用量使得预煅烧后的催化剂中包括:
M1的氧化物10-25质量份,
M2的氧化物3-7质量份,
M3的氧化物2-7质量份,
M4的氧化物40-70质量份。
22.通过权利要求1-21中任一项所述的制备方法获得的耐硫甲烷化催化剂。
23.权利要求22所述的耐硫甲烷化催化剂用于CO甲烷化的用途。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811542631.0A CN109433222B (zh) | 2018-12-17 | 2018-12-17 | 一种耐硫甲烷化催化剂及其制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811542631.0A CN109433222B (zh) | 2018-12-17 | 2018-12-17 | 一种耐硫甲烷化催化剂及其制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN109433222A CN109433222A (zh) | 2019-03-08 |
CN109433222B true CN109433222B (zh) | 2022-02-08 |
Family
ID=65559044
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201811542631.0A Active CN109433222B (zh) | 2018-12-17 | 2018-12-17 | 一种耐硫甲烷化催化剂及其制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN109433222B (zh) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115672331A (zh) * | 2021-07-23 | 2023-02-03 | 国家能源投资集团有限责任公司 | 甲烷化催化剂及其制备方法和应用 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102416329A (zh) * | 2011-10-11 | 2012-04-18 | 新地能源工程技术有限公司 | 一种高温甲烷合成催化剂及其生产方法 |
CN103801287A (zh) * | 2012-11-05 | 2014-05-21 | 北京低碳清洁能源研究所 | 一种负载型耐硫甲烷化催化剂的制备方法 |
CN105381803A (zh) * | 2015-12-08 | 2016-03-09 | 大唐国际化工技术研究院有限公司 | 一种合成气甲烷化的流化床催化剂及其制备方法和应用 |
CN106807392A (zh) * | 2017-03-07 | 2017-06-09 | 北京工业大学 | 一种用于低温CO催化的MoCeCoOX催化剂的制备及应用 |
-
2018
- 2018-12-17 CN CN201811542631.0A patent/CN109433222B/zh active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102416329A (zh) * | 2011-10-11 | 2012-04-18 | 新地能源工程技术有限公司 | 一种高温甲烷合成催化剂及其生产方法 |
CN103801287A (zh) * | 2012-11-05 | 2014-05-21 | 北京低碳清洁能源研究所 | 一种负载型耐硫甲烷化催化剂的制备方法 |
CN105381803A (zh) * | 2015-12-08 | 2016-03-09 | 大唐国际化工技术研究院有限公司 | 一种合成气甲烷化的流化床催化剂及其制备方法和应用 |
CN106807392A (zh) * | 2017-03-07 | 2017-06-09 | 北京工业大学 | 一种用于低温CO催化的MoCeCoOX催化剂的制备及应用 |
Non-Patent Citations (1)
Title |
---|
共沉淀法制备氧化铝负载 Co-Mo 双金属氮化物催化剂;张新波;《催化学报》;20090731;第30卷(第7期);第613-618页 * |
Also Published As
Publication number | Publication date |
---|---|
CN109433222A (zh) | 2019-03-08 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN106391028B (zh) | 一种用于流化床的甲烷化催化剂及其制备方法 | |
CA1233810A (en) | Catalyst composition suitable for synthesis of methanol | |
JP2015527190A (ja) | 流動層反応器に使用されるブテンの酸化脱水素によるブタジエン製造用触媒およびその製造方法と用途 | |
CN105381803A (zh) | 一种合成气甲烷化的流化床催化剂及其制备方法和应用 | |
CN104174420A (zh) | 一种用于合成气甲烷化的碳化硅基整体催化剂及制备方法 | |
CN105668647A (zh) | 一种高比表面积钙钛矿型纳米LaCoO3多孔空心球材料及其制备方法 | |
CN109433222B (zh) | 一种耐硫甲烷化催化剂及其制备方法 | |
CN102189003B (zh) | 一种甲烷化催化剂载体的制备方法 | |
CN103071807A (zh) | 一种超细球形钴粉的制备方法 | |
CN108339548A (zh) | 一种镍/氧化铝催化剂微球及其制备方法 | |
CN103495421A (zh) | 一种耐硫甲烷化催化剂及其制备方法 | |
CN109675543A (zh) | 一种海泡石-氧化铝复合载体及使用其的抗高温烧结型甲烷化催化剂 | |
CN100491260C (zh) | 一种块状α-氧化铁纳米结构的合成方法 | |
CN103801304A (zh) | 一种免还原的浆态床甲烷化催化剂及制法和应用 | |
CN110327989A (zh) | 一种催化剂载体的制备方法及其应用 | |
CN106622276B (zh) | 一种用于沸腾床反应器的甲烷低温燃烧催化剂及其制备方法与应用 | |
CN104058737A (zh) | 一种镍钨铁氧体的制备方法 | |
CN107913714B (zh) | 费托合成铁基催化剂及其制备方法和费托合成方法 | |
CN113600207B (zh) | 一种适用于高co的宽温变换催化剂及其制备和应用 | |
CN109718843A (zh) | 一种新型二氧化碳甲烷化催化剂的制备和应用 | |
CN115254124B (zh) | 一种预还原型加氢催化剂的制备方法 | |
CN114073954B (zh) | 一种应用于流化床反应器的镍/氧化铝催化剂微球及其制备方法和用途 | |
KR20180013283A (ko) | 산소전달입자, 이의 제조방법 및 상기 산소전달입자를 이용한 케미컬루핑연소 방법 | |
CN109926077B (zh) | 一种劣质原料加氢转化催化剂及其制备方法 | |
CN101774024A (zh) | 钨钴复合氧化物粉末的制备方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |