CN117732462A - Carrier for preparing silver catalyst, preparation method of carrier, silver catalyst, preparation method of silver catalyst and application of silver catalyst - Google Patents
Carrier for preparing silver catalyst, preparation method of carrier, silver catalyst, preparation method of silver catalyst and application of silver catalyst Download PDFInfo
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- CN117732462A CN117732462A CN202211122838.9A CN202211122838A CN117732462A CN 117732462 A CN117732462 A CN 117732462A CN 202211122838 A CN202211122838 A CN 202211122838A CN 117732462 A CN117732462 A CN 117732462A
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- silver
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- silver catalyst
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- 229910052709 silver Inorganic materials 0.000 title claims abstract description 148
- 239000004332 silver Substances 0.000 title claims abstract description 148
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 136
- 239000003054 catalyst Substances 0.000 title claims abstract description 134
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 22
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 21
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910001930 tungsten oxide Inorganic materials 0.000 claims abstract description 21
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000005977 Ethylene Substances 0.000 claims abstract description 17
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 10
- 230000003647 oxidation Effects 0.000 claims abstract description 9
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 110
- 229910052702 rhenium Inorganic materials 0.000 claims description 61
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 52
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 50
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 33
- 238000001035 drying Methods 0.000 claims description 30
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 28
- 229910052792 caesium Inorganic materials 0.000 claims description 28
- 239000011259 mixed solution Substances 0.000 claims description 27
- XNGYKPINNDWGGF-UHFFFAOYSA-L silver oxalate Chemical compound [Ag+].[Ag+].[O-]C(=O)C([O-])=O XNGYKPINNDWGGF-UHFFFAOYSA-L 0.000 claims description 26
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 23
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 22
- 238000005470 impregnation Methods 0.000 claims description 22
- -1 amine compounds Chemical class 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 20
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical group [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 20
- 229920001661 Chitosan Polymers 0.000 claims description 19
- 239000012752 auxiliary agent Substances 0.000 claims description 17
- 229910052783 alkali metal Inorganic materials 0.000 claims description 16
- 150000001340 alkali metals Chemical class 0.000 claims description 16
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 14
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 14
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims description 14
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 238000002791 soaking Methods 0.000 claims description 11
- 150000003754 zirconium Chemical class 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 10
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 4
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 claims description 4
- 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 description 4
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- MSWZFWKMSRAUBD-IVMDWMLBSA-N 2-amino-2-deoxy-D-glucopyranose Chemical compound N[C@H]1C(O)O[C@H](CO)[C@@H](O)[C@@H]1O MSWZFWKMSRAUBD-IVMDWMLBSA-N 0.000 claims description 2
- QSHYGLAZPRJAEZ-UHFFFAOYSA-N 4-(chloromethyl)-2-(2-methylphenyl)-1,3-thiazole Chemical compound CC1=CC=CC=C1C1=NC(CCl)=CS1 QSHYGLAZPRJAEZ-UHFFFAOYSA-N 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- MSWZFWKMSRAUBD-UHFFFAOYSA-N beta-D-galactosamine Natural products NC1C(O)OC(CO)C(O)C1O MSWZFWKMSRAUBD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- AAQNGTNRWPXMPB-UHFFFAOYSA-N dipotassium;dioxido(dioxo)tungsten Chemical compound [K+].[K+].[O-][W]([O-])(=O)=O AAQNGTNRWPXMPB-UHFFFAOYSA-N 0.000 claims description 2
- 229960002442 glucosamine Drugs 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- DYIZHKNUQPHNJY-UHFFFAOYSA-N oxorhenium Chemical compound [Re]=O DYIZHKNUQPHNJY-UHFFFAOYSA-N 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 2
- 229910003449 rhenium oxide Inorganic materials 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 2
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 2
- 229940071536 silver acetate Drugs 0.000 claims description 2
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- VZSXFJPZOCRDPW-UHFFFAOYSA-N carbanide;trioxorhenium Chemical compound [CH3-].O=[Re](=O)=O VZSXFJPZOCRDPW-UHFFFAOYSA-N 0.000 claims 2
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 238000011068 loading method Methods 0.000 abstract description 13
- 230000009257 reactivity Effects 0.000 abstract description 5
- 238000005530 etching Methods 0.000 abstract description 2
- 239000011521 glass Substances 0.000 description 60
- 239000007864 aqueous solution Substances 0.000 description 36
- 238000003756 stirring Methods 0.000 description 33
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 31
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 16
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 239000003513 alkali Substances 0.000 description 11
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 229910052726 zirconium Inorganic materials 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 238000007654 immersion Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 238000002386 leaching Methods 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000006735 epoxidation reaction Methods 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 150000003755 zirconium compounds Chemical class 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 159000000009 barium salts Chemical class 0.000 description 1
- 229910052916 barium silicate Inorganic materials 0.000 description 1
- HMOQPOVBDRFNIU-UHFFFAOYSA-N barium(2+);dioxido(oxo)silane Chemical compound [Ba+2].[O-][Si]([O-])=O HMOQPOVBDRFNIU-UHFFFAOYSA-N 0.000 description 1
- QKYBEKAEVQPNIN-UHFFFAOYSA-N barium(2+);oxido(oxo)alumane Chemical compound [Ba+2].[O-][Al]=O.[O-][Al]=O QKYBEKAEVQPNIN-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000002459 porosimetry Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000003375 selectivity assay Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229940100890 silver compound Drugs 0.000 description 1
- 150000003379 silver compounds Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 150000004684 trihydrates Chemical class 0.000 description 1
- 150000003658 tungsten compounds Chemical class 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 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 1
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- Catalysts (AREA)
Abstract
The invention belongs to the field of silver catalysts, and particularly relates to a carrier for preparing a silver catalyst, a preparation method of the carrier, the silver catalyst, a preparation method of the silver catalyst and application of the silver catalyst. The carrier comprises: alpha-Al 2 O 3 Carrier, supported on alpha-Al 2 O 3 Zirconium oxide and tungsten oxide with hollow configuration on the surface of the carrier; relative to the alpha-Al 2 O 3 The carrier comprises the following components in percentage by weight: 0.02 to 4.00 weight percent of zirconia with hollow structure and 0.002 to 0.500 weight percent of tungsten oxide. The invention is realized by the method that the catalyst is prepared by the following steps of 2 O 3 The surface of the carrier is subjected to acid etching to enable the surface to be roughened, and orderly loading of hollow zirconium oxide and tungsten oxide is sequentially carried outAnd then roasting and solidifying at high temperature, the silver catalyst prepared from the silver catalyst has higher selectivity and reactivity, and is particularly suitable for the reaction of ethylene oxidation to produce ethylene oxide.
Description
Technical Field
The invention belongs to the field of silver catalysts, and particularly relates to a carrier for preparing a silver catalyst, a preparation method of the carrier, the silver catalyst, a preparation method of the silver catalyst and application of the silver catalyst.
Background
Ethylene is oxidized to mainly generate ethylene oxide under the action of a silver catalyst, and side reactions simultaneously occur to generate carbon dioxide and water, wherein the activity, the selectivity and the stability are main performance indexes of the silver catalyst. The activity refers to the reaction temperature required for the production process of the ethylene oxide to reach a certain reaction load. The lower the reaction temperature, the higher the activity of the catalyst. By selectivity is meant the ratio of the moles of ethylene converted to ethylene oxide in the reaction to the total moles of ethylene reacted. Stability is expressed as the rate of decrease in activity and selectivity, with lower rates indicating better catalyst stability. The use of a silver catalyst with high activity, high selectivity and good stability in the process of producing ethylene oxide by ethylene oxidation can greatly improve economic benefit, so that the production of the silver catalyst with high activity, high selectivity and good stability is the main direction of silver catalyst research. The performance of the silver catalyst has important relation with the composition of the catalyst and the preparation method, and also has important relation with the performance of a carrier used by the catalyst and the preparation method.
The preparation method of the silver catalyst in the prior art comprises the preparation of a porous carrier (such as alumina) And applying an active ingredient and an adjuvant to the carrier. In the preparation of silver catalyst, for alpha-Al 2 O 3 The carrier of the main component has proper specific surface and pore structure, and has enough space for the epoxidation of ethylene to diffuse out the heat of reaction, and is favorable to desorbing the reaction product ethylene oxide in time to avoid deep oxidation to produce carbon dioxide as side product. German patent WO2021260138A1 provides a shaped catalyst body for the vapor phase oxidation of ethylene to ethylene oxide having a BET surface area of from 2 to 20m 2 And comprising silver and rhenium promoters deposited on a porous-alumina catalyst support, characterized in that the support has a calcination history of at least 1460 ℃, the catalyst support having a high surface area and a small amount of ethylene oxide isomerisation and/or decomposition activity. Chinese patent CN1009437B adopts alumina trihydrate with proper proportion to prepare the alumina powder with specific surface area of 0.2-2 m 2 And/g, the pore volume is larger than 0.5mL/g, wherein pores with the pore radius larger than 30 mu m account for less than 25 percent, and the selectivity of the catalyst can reach 83 to 84 percent when the catalyst is used for ethylene epoxidation reaction.
The addition of other components to alumina supports to improve the support and improve the performance of the silver catalyst is also an important research direction. In addition, the performance of the silver catalyst can also be improved by chemically treating the alumina carrier. German patent WO2021260185A1 provides a sheet-like catalyst support, characterized in that the alpha-alumina content is at least 85wt.%, the pore volume as determined by mercury porosimetry is at least 0.40mL/g, and the BET surface area is from 0.5 to 5.0m 2 The platelet-shaped catalyst support is an alpha-alumina catalyst support which has a high geometric accuracy and shows a high total pore volume, allowing impregnation with a large amount of silver, while showing a sufficiently large surface area to provide an optimal dispersion of the catalytically active species, in particular the metal species. European patent EP0150238B1 claims to improve the crushing strength and abrasion resistance of a support by using a small amount of barium aluminate or barium silicate binder in the manufacture of high purity, low surface alumina supports having a specific surface area of less than 0.3m 2 /g, activity and selection of the catalyst producedThe properties were low. The alumina supports used in US4740493A, US4829043a and EP0501317A1 contain some amount of Ca, al, K, na soluble salts which purportedly reduce the rate of catalyst selectivity decline during use. US5384302a states that by pretreatment of α -Al 2 O 3 Reducing the Na, K, ca, al ion content in the carrier improves the crushing strength and abrasion resistance of the carrier. Korean patent No. KR102258044B1 is a method for preparing a catalyst for producing high-yield ethylene oxide from ethylene by adjusting a metal crystal size by adding polyvinyl pyrrolidone. EP0712334B1 provides a silver catalyst having improved stability by supporting an effective amount of silver, an auxiliary amount of an alkali metal, an auxiliary amount of magnesium, and an auxiliary amount of rhenium on a carrier comprising at least 85% alumina and 0.001-2% magnesium in the form of an oxide. U.S. Pat. No. 3,979,B1, U.S. Pat. No. 3, 5801259A, US5733842A incorporates alkaline earth metals, silicon, zirconium into alpha-Al 2 O 3 The silver catalyst is prepared by impregnating a carrier with silver, an alkali metal promoter, a rhenium promoter and a promoter thereof, and the patent indicates that alkaline earth metals, preferably calcium, strontium and barium salts are used together with zirconium compounds, and the influence of the addition of the two on the catalyst performance cannot be known. US5739075A prepares a silver catalyst from a treated carrier by depositing a promoter amount of a rare earth metal and another promoter amount of a metal salt (alkaline earth metal or group VIII transition metal) on the surface of an alumina carrier in advance, and then calcining the catalyst, and the evaluation result shows that the selectivity reduction rate of the catalyst is smaller than that of a catalyst sample which is not subjected to the pre-deposition treatment. CN1511632a found that the activity and selectivity of the silver catalyst prepared by adding a heavy alkaline earth metal compound to an alumina raw material to prepare a carrier, impregnating a solution prepared from a silver compound, an organic amine and a specific auxiliary agent, and performing heat treatment in an oxygen-containing mixed gas are improved in ethylene oxidation reaction.
Although the above patent documents respectively adopt various methods to improve the alumina carrier, which brings about different improvements to the activity, stability and selectivity of the catalyst, the requirements for the catalyst performance are continuously increased along with the large-scale industrial application of the silver catalyst with high Re selectivity, and therefore, the performance of the silver catalyst is required to be continuously improved.
Disclosure of Invention
In view of the above-described state of the art, the inventors of the present invention have conducted extensive and intensive studies in the field of silver catalysts, and as a result, found that α -Al 2 O 3 The method comprises the steps of carrying out acid etching on the surface of a carrier, simultaneously impregnating zirconium salt and a template agent, drying, loading hollow zirconium oxide on the surface of alumina, then impregnating tungstic acid and/or tungstate solution, drying, roasting at high temperature, finally impregnating silver ammonia solution, and drying, so that the selectivity and the reactivity of a silver catalyst prepared from the silver ammonia solution can be obviously improved.
A first aspect of the present invention provides a carrier for preparing a silver catalyst, the carrier comprising:
α-Al 2 O 3 carrier, supported on alpha-Al 2 O 3 Zirconium oxide and tungsten oxide with hollow configuration on the surface of the carrier;
relative to the alpha-Al 2 O 3 The carrier comprises the following components in percentage by weight:
0.02 to 4.00 weight percent of zirconia with hollow structure and 0.002 to 0.500 weight percent of tungsten oxide.
In a second aspect, the present invention provides a method for preparing a carrier for preparing a silver catalyst, the method comprising:
(1) alpha-A1 2 O 3 Soaking in the first solution, then carrying out solid-liquid separation and drying;
(2) Soaking the carrier obtained in the step (1) in a second solution, and then carrying out solid-liquid separation, drying and roasting to obtain the carrier for preparing the silver catalyst;
The first solution is a mixed solution of acid, zirconium salt and a template agent;
the second solution is a tungstic acid and/or tungstate solution, and the solvent of the tungstate solution is at least one selected from water, ammonia water and amine compounds.
In a third aspect the present invention provides a carrier obtainable by the above-described preparation method.
A fourth aspect of the present invention provides a silver catalyst comprising:
a carrier, silver loaded on the surface of the carrier, an alkali metal auxiliary agent, an optional rhenium auxiliary agent and an optional co-auxiliary agent of the rhenium auxiliary agent;
the carrier is the carrier for preparing the silver catalyst or the carrier prepared by the method.
A fifth aspect of the present invention provides a method for preparing the above silver catalyst, comprising:
immersing the carrier in silver ammonia solution, separating solid from liquid, and drying to obtain the silver catalyst.
In a sixth aspect, the present invention provides the use of the silver catalyst described above in the oxidation of ethylene to ethylene oxide.
Compared with the prior art, the invention has the following advantages:
at alpha-Al 2 O 3 The carrier surface is etched by acid, zirconium salt and template agent are immersed and dried, hollow zirconium oxide is loaded on the alumina surface, then tungstic acid and/or tungstate solution is immersed and dried, and then roasting is carried out at high temperature, finally silver ammonia solution is immersed and dried, so that the selectivity and the reactivity of the silver catalyst prepared by the silver ammonia solution can be obviously improved, and the silver ammonia solution is particularly suitable for the reaction of ethylene oxidation production of ethylene oxide.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
A first aspect of the present invention provides a carrier for preparing a silver catalyst, the carrier comprising:
α-Al 2 O 3 carrier, supported on alpha-Al 2 O 3 Zirconium oxide and tungsten oxide with hollow configuration on the surface of the carrier;
relative to the alpha-Al 2 O 3 The carrier comprises the following components in percentage by weight:
0.02 to 4.00 weight percent of zirconia with hollow structure and 0.002 to 0.500 weight percent of tungsten oxide.
Preferably, relative to said alpha-Al 2 O 3 The carrier comprises the following components in percentage by weight: 0.05 to 1.00 weight percent of zirconia with hollow structure and 0.005 to 0.100 weight percent of tungsten oxide.
Preferably, the alpha-Al 2 O 3 The carrier comprises at least one of the following features:
α-A1 2 O 3 the content is more than or equal to 90 percent;
crushing strength is 20-200N/grain;
the specific surface area is 0.2-3.0 m 2 /g；
The water absorption rate is more than or equal to 30 percent;
the pore volume is 0.30-0.85 mL/g.
In a second aspect, the present invention provides a method for preparing a carrier for preparing a silver catalyst, the method comprising:
(1) alpha-A1 2 O 3 Soaking in the first solution, then carrying out solid-liquid separation and drying;
(2) Soaking the carrier obtained in the step (1) in a second solution, and then carrying out solid-liquid separation, drying and roasting to obtain the carrier for preparing the silver catalyst;
the first solution is a mixed solution of acid, zirconium salt and a template agent;
the second solution is a tungstic acid and/or tungstate solution, and the solvent of the tungstate solution is at least one selected from water, ammonia water and amine compounds.
In the present invention, the surface of the carrier formed after the carrier is etched by the acid is roughened.
In the present invention, the solid-liquid separation in the step (1) and the step (2) may be performed by leaching, and the leaching process is preferably performed while minimizing the excessive impregnation liquid adhering to the surface of the support, and the excessive dust in the alumina support may be removed.
Preferably, in the step (1), the time for the impregnation is 10 to 300 minutes, and the impregnation is performed at a pressure of 100mmHg or less.
Preferably, in the step (2), the time for the impregnation is 10 to 300 minutes, and the impregnation is performed at a pressure of 100mmHg or less.
Preferably, in step (1), the drying is performed in air or in a nitrogen-oxygen mixture having an oxygen content of not more than 21%; the drying temperature is 100-600 ℃, preferably 150-500 ℃; the drying time is 0.5 to 120 minutes, preferably 1 to 30 minutes.
Preferably, in the step (2), the drying is performed in air or in a nitrogen-oxygen mixture with an oxygen content of not more than 21%; the drying temperature is 100-600 ℃, preferably 150-500 ℃; the drying time is 0.5 to 120 minutes, preferably 1 to 30 minutes.
Preferably, in the step (2), roasting is performed in air or in a nitrogen-oxygen mixture gas with an oxygen content of not more than 21%; the roasting temperature is 500-1400 ℃, preferably 700-1200 ℃; the calcination time is 5 to 240 minutes, preferably 10 to 120 minutes.
Preferably, the acid is at least one selected from sulfuric acid, nitric acid and oxalic acid.
Preferably, the zirconium salt is at least one selected from zirconium sulfate, zirconium nitrate and zirconyl nitrate.
Preferably, the template agent is at least one selected from chitosan, polystyrene and glucosamine.
Preferably, the content of the acid is 0.2 to 20.0 weight percent, the content of the zirconium salt is 0.05 to 10.00 weight percent, and the content of the template agent is 0.02 to 6.0 weight percent based on the total weight of the first solution.
As a further preferable scheme, the content of the acid is 1.0-15.0 wt%, the content of the zirconium salt is 0.1-5.0 wt% and the content of the template agent is 0.05-3.0 wt% based on the total weight of the first solution.
Preferably, the tungstate is ammonium tungstate and/or potassium tungstate.
Preferably, the content of the tungstic acid and/or tungstate is 0.002 to 0.500wt percent based on the total weight of the second solution.
As a further preferable scheme, the content of the tungstic acid and/or tungstate is 0.01-0.20 wt percent based on the total weight of the second solution.
In a third aspect the present invention provides a carrier obtainable by the above-described preparation method.
A fourth aspect of the present invention provides a silver catalyst comprising:
a carrier, silver loaded on the surface of the carrier, an alkali metal auxiliary agent, an optional rhenium auxiliary agent and an optional co-auxiliary agent of the rhenium auxiliary agent;
the carrier is the carrier for preparing the silver catalyst or the carrier prepared by the method.
As a preferred scheme, the content of each component relative to the silver catalyst is as follows:
silver 2-39 wt% in atom, alkali metal promoter 1-2000 ppm, rhenium promoter 0-2000 ppm in atom and rhenium promoter co-promoter 0-2000 ppm in atom.
As a further preferable scheme, the content of each component relative to the silver catalyst is as follows:
10 to 35wt% of silver in atomic terms, 5 to 2000ppm of alkali metal promoter, 100 to 1000ppm of rhenium promoter in atomic terms of rhenium, and 100 to 1000ppm of co-promoter of rhenium promoter in atomic terms.
Preferably, the alkali metal auxiliary is at least one selected from the group consisting of compounds of lithium, sodium, potassium, rubidium and cesium. Preferably, the alkali metal promoter is added in an amount such that the content of the alkali metal promoter in the silver catalyst is 1 to 2000ppm.
Preferably, the rhenium promoter is selected from at least one of rhenium oxide, perrhenic acid, cesium perrhenate, rhenium (VII) methyl trioxide and ammonium perrhenate.
Preferably, the co-promoter of the rhenium promoter is selected from at least one of salts or acids containing manganese, chromium, sulfur, cobalt, molybdenum, nickel.
A fifth aspect of the present invention provides a method for preparing the above silver catalyst, comprising:
and (3) immersing the carrier in silver ammonia solution, carrying out solid-liquid separation and drying to obtain the silver catalyst.
In the preparation method of the silver catalyst, the solid-liquid separation mode can be leaching, the leaching process is suitable for reducing the excessive impregnating solution attached to the surface of the carrier as much as possible, and the excessive dust in the alumina carrier can be removed while the leaching process is carried out.
In the preparation method of the silver catalyst, the impregnation can be carried out according to the conventional method in the field, the carrier is completely impregnated in the silver ammonia solution, and the impregnation time is preferably 10-300 minutes; the temperature of the impregnating solution is preferably kept below 30 ℃ to prevent the silver-containing compound and the like from being decomposed by heat and precipitated in advance; the impregnation process can be accelerated by decompressing to below 100mmHg pressure, and the surface of the carrier is suitable for full infiltration without tiny bubbles and the inner and outer surfaces.
Preferably, the time for the impregnation is 10 to 300 minutes, and the impregnation is performed at a pressure of 100mmHg or less.
Preferably, the drying is carried out in air or in a nitrogen-oxygen mixture with an oxygen content of not more than 21%, the drying temperature being 100-600 ℃, more preferably 150-500 ℃; the drying time is 0.5 to 120 minutes, more preferably 1 to 30 minutes.
Preferably, the silver ammonia solution comprises a silver-containing compound, an amine compound, water, an alkali metal promoter, an optional rhenium promoter, and an optional rhenium promoter co-promoter; the content of the amine compound is 10-90 wt% based on the total weight of the silver-ammonia solution.
As a further preferred embodiment, the silver-containing compound is selected from at least one of silver acetate, silver nitrate and silver oxalate. Preferably, the silver-containing compound is added in such an amount that the silver content in the silver catalyst is 2 to 39wt%, preferably 10 to 35wt% in terms of atoms.
As a further preferred embodiment, the amine compound is at least one selected from the group consisting of ammonia, ethylamine, N-propylamine, ethylenediamine, 1, 3-propylenediamine, 1, 4-butylenediamine, N-dimethylformamide, ethanolamine and propanolamine.
In a sixth aspect, the present invention provides the use of the silver catalyst described above in the oxidation of ethylene to ethylene oxide.
The silver catalyst prepared by the invention has higher selectivity and reactivity, and can be used in the reaction of producing ethylene oxide by ethylene oxidation. Specifically, in the presence of the silver catalyst, a mixed gas of ethylene and a gas such as oxygen is reacted in a fixed bed micro-tubular reactor.
The present invention will be further described with reference to examples, but the scope of the present invention is not limited to these examples.
Determination of catalyst Performance:
the various silver catalysts of the present invention were tested for initial performance and stability using a laboratory reactor (hereinafter abbreviated as "micro-reverse") evaluation apparatus. The reactor used in the micro-reaction evaluation device is a stainless steel tube with an inner diameter of 4mm, and the reactor is placed in a heating sleeve. The catalyst loading volume was 1mL, and inert packing was placed in the lower portion to allow the catalyst bed to be located in the constant temperature zone of the heating mantle.
Determination of initial Activity, selectivity:
the activity and selectivity assay conditions used in the present invention are as follows:
the reaction gas composition (mol%) is shown in Table 1.
TABLE 1
| Ethylene (C) 2 H 4 ) | 28±1 |
| Oxygen (O) 2 ) | 7.4±0.2 |
| Carbon dioxide (CO) 2 ) | ＜3 |
| Gas-stabilizing (N) 2 ) | Allowance of |
| Inhibitor dichloroethane | Optimizing adjustments |
| Reaction pressure | 2.1MPa |
| Airspeed of (space velocity) | Adjustable between 3000-7000/h |
| EO concentration at reactor outlet | 1.5-2.8mol％ |
| Space time yield | 88-385gEO/mLCat./h |
When the above reaction conditions were reached, the reactor inlet and outlet gas compositions were continuously measured. After the volume shrinkage correction is carried out on the measurement result, the selectivity is calculated according to the following formula:
where Δeo is the difference in the concentration of ethylene oxide in the outlet gas and the inlet gas ring, and the average of more than 10 sets of test data was taken as the test result on the same day.
The activity of the catalyst is measured by the reaction temperature at which a certain EO concentration is reached.
The elemental content in the invention is determined using chemical analysis and XRF. The microscopic morphology of the catalyst and its carrier is characterized by SEM and TEM.
Examples 1 to 9 and comparative example 1 were usedThe alpha-alumina supports of (a) are all prepared from the same support formulation, and specific details are found in CN88100400.6, CN1634652a and US5063195, which are not described in detail herein. The alpha-alumina carrier has the following characteristics: alpha-A1 2 O 3 The content is 99.5 percent; crush strength 85N/grain; specific surface area of 1.13m 2 /g; the water absorption rate is 45%; the pore volume was 0.47mL/g.
Example 1
First, 198mL of 5wt% sulfuric acid aqueous solution was prepared in a glass beaker, then 2g of zirconium sulfate and 0.5g of chitosan were added to the sulfuric acid aqueous solution, and they were mixed and stirred uniformly. 15g of alpha-alumina carrier is taken, placed into a glass container capable of being vacuumized, and the impregnating solution is added to completely immerse the carrier. After evacuating to above 10mmHg and holding for about 15 minutes, excess solution was leached off and the impregnated support sample was placed in a stream of air at 400℃for about 3 minutes. 200mL of a 10wt% aqueous ammonia solution was prepared in a glass, and 1.3g of ammonium tungstate (H) 26 N 6 O 40 W 12 ) And mixing and stirring the materials uniformly. Putting the carrier which is immersed in the dilute sulfuric acid solution of zirconium persulfate and chitosan and heated into a glass container capable of being vacuumized, adding ammonium tungstate ammonia water immersion liquid, and completely immersing the carrier. After evacuating to above 10mmHg and maintaining for about 15 minutes, the excess solution was leached off, the impregnated support sample was placed in an air stream at 400℃for about 3 minutes and finally heated at 900℃for 1 hour to produce support example 1.
The surface loading of the carrier example 1 was as follows: 0.22wt% of zirconia with a hollow structure and 0.026wt% of tungsten oxide.
32.1g of ethylenediamine, 10.8g of ethanolamine and 179.8g of deionized water are added into a glass beaker with stirring to obtain a mixed solution; slowly adding 72.2g of silver oxalate into the mixed solution, and keeping the temperature below 40 ℃ and continuously stirring to completely dissolve the silver oxalate; then, 2.25mL of cesium nitrate aqueous solution (with a concentration of 0.03995g/mL based on the weight of cesium atoms) and 2.78mL of ammonium perrhenate aqueous solution (with a concentration of 0.0162g/mL based on the weight of rhenium atoms) were added in sequence, and mixed uniformly to prepare 300g of impregnating solution for standby.
15g of the support example 1 were taken and placed in a glass container which can be evacuated, and the above silver amine impregnation solution was added to completely immerse the support. After evacuating to above 10mmHg and holding for about 15 minutes, the excess solution was leached off. Finally, the impregnated support sample was placed in an air stream at 350 ℃ and heated for about 2 minutes to produce silver catalyst example 1.
The contents of the components relative to the silver catalyst example 1 were: 11.1wt% silver on an atomic basis, 169ppm alkali cesium promoter, 94ppm rhenium promoter on a rhenium atomic basis.
Example 2
First, 198mL of a 10wt% aqueous sulfuric acid solution was prepared in a glass beaker, then 2g of zirconium sulfate and 0.5g of chitosan were added to the aqueous sulfuric acid solution, and they were mixed and stirred uniformly. 15g of alpha-alumina carrier is taken, placed into a glass container capable of being vacuumized, and the impregnating solution is added to completely immerse the carrier. After evacuating to above 10mmHg and holding for about 15 minutes, excess solution was leached off and the impregnated support sample was placed in a stream of air at 400℃for about 3 minutes. 200mL of a 10wt% aqueous ammonia solution was prepared in a glass, and 1.3g of ammonium tungstate (H) 26 N 6 O 40 W 12 ) And mixing and stirring the materials uniformly. Putting the carrier which is immersed in the dilute sulfuric acid solution of zirconium persulfate and chitosan and heated into a glass container capable of being vacuumized, adding ammonium tungstate ammonia water immersion liquid, and completely immersing the carrier. After evacuating to above 10mmHg and maintaining for about 15 minutes, the excess solution was leached off, the impregnated support sample was placed in an air stream at 400℃for about 3 minutes and finally heated at 900℃for 1 hour to produce support example 2.
The surface loading of the components of carrier example 2 was as follows: 0.23wt% of zirconia with a hollow structure and 0.025wt% of tungsten oxide.
32.1g of ethylenediamine, 10.8g of ethanolamine and 179.8g of deionized water are added into a glass beaker with stirring to obtain a mixed solution; slowly adding 72.2g of silver oxalate into the mixed solution, and keeping the temperature below 40 ℃ and continuously stirring to completely dissolve the silver oxalate; then, 2.25mL of cesium nitrate aqueous solution (with a concentration of 0.03995g/mL based on the weight of cesium atoms) and 2.78mL of ammonium perrhenate aqueous solution (with a concentration of 0.0162g/mL based on the weight of rhenium atoms) were added in sequence, and mixed uniformly to prepare 300g of impregnating solution for standby.
15g of the support example 2 were taken and placed in a glass container which can be evacuated, and the above silver amine impregnation solution was added to completely immerse the support. After evacuating to above 10mmHg and holding for about 15 minutes, the excess solution was leached off. Finally, the impregnated support sample was placed in an air stream at 350 ℃ and heated for about 2 minutes to produce silver catalyst example 2.
The contents of the components relative to the silver catalyst example 2 were: 11.2wt% silver on an atomic basis, 172ppm alkali cesium promoter, 96ppm rhenium promoter on a rhenium atomic basis.
Example 3
First, 198mL of 5wt% aqueous nitric acid solution was prepared in a glass beaker, then 2g of zirconium sulfate and 0.5g of chitosan were added to the aqueous nitric acid solution, and they were mixed and stirred uniformly. 15g of alpha-alumina carrier is taken, placed into a glass container capable of being vacuumized, and the impregnating solution is added to completely immerse the carrier. After evacuating to above 10mmHg and holding for about 15 minutes, excess solution was leached off and the impregnated support sample was placed in a stream of air at 400℃for about 3 minutes. 200mL of a 10wt% aqueous ammonia solution was prepared in a glass, and 1.3g of ammonium tungstate (H) 26 N 6 O 40 W 12 ) And mixing and stirring the materials uniformly. Putting the carrier which is immersed in the dilute nitric acid solution of zirconium persulfate and chitosan and heated into a glass container capable of being vacuumized, adding ammonium tungstate ammonia water immersion liquid, and completely immersing the carrier. After evacuating to above 10mmHg and maintaining for about 15 minutes, the excess solution was leached off, the impregnated support sample was placed in an air stream at 400℃for about 3 minutes and finally heated at 900℃for 1 hour to produce support example 3.
The surface loading of the components of carrier example 3 was as follows: 0.21wt% of zirconia with a hollow structure and 0.027wt% of tungsten oxide.
32.1g of ethylenediamine, 10.8g of ethanolamine and 179.8g of deionized water are added into a glass beaker with stirring to obtain a mixed solution; slowly adding 72.2g of silver oxalate into the mixed solution, and keeping the temperature below 40 ℃ and continuously stirring to completely dissolve the silver oxalate; then, 2.25mL of cesium nitrate aqueous solution (with a concentration of 0.03995g/mL based on the weight of cesium atoms) and 2.78mL of ammonium perrhenate aqueous solution (with a concentration of 0.0162g/mL based on the weight of rhenium atoms) were added in sequence, and mixed uniformly to prepare 300g of impregnating solution for standby.
15g of the support example 3 were taken and placed in a glass container which can be evacuated, and the above silver amine impregnation solution was added to completely immerse the support. After evacuating to above 10mmHg and holding for about 15 minutes, the excess solution was leached off. Finally, the impregnated support sample was placed in an air stream at 350 ℃ and heated for about 2 minutes to produce silver catalyst example 3.
The contents of the components relative to the silver catalyst example 3 were: 11.1% by weight of silver in atomic terms, 171ppm of alkali metal cesium promoter and 93ppm of rhenium promoter in atomic terms of rhenium.
Example 4
First, 198mL of 5wt% sulfuric acid aqueous solution was prepared in a glass beaker, followed by adding 4g of zirconium sulfate and 0.5g of chitosan to the sulfuric acid aqueous solution, and mixing and stirring them uniformly. 15g of alpha-alumina carrier is taken, placed into a glass container capable of being vacuumized, and the impregnating solution is added to completely immerse the carrier. After evacuating to above 10mmHg and holding for about 15 minutes, excess solution was leached off and the impregnated support sample was placed in a stream of air at 400℃for about 3 minutes. 200mL of a 10wt% aqueous ammonia solution was prepared in a glass, and 1.3g of ammonium tungstate (H) 26 N 6 O 40 W 12 ) And mixing and stirring the materials uniformly. Putting the carrier which is immersed in the dilute sulfuric acid solution of zirconium persulfate and chitosan and heated into a glass container capable of being vacuumized, adding ammonium tungstate ammonia water immersion liquid, and completely immersing the carrier. Vacuumizing to above 10mmHg, maintaining for 15 min, leaching to remove excessive solution, and soakingThe impregnated carrier sample was placed in an air stream at 400 c for about 3 minutes and finally heated at 900 c for 1 hour to produce carrier example 4.
The surface loading of the components of carrier example 4 was as follows: 0.43wt% of zirconia with a hollow structure and 0.026wt% of tungsten oxide.
32.1g of ethylenediamine, 10.8g of ethanolamine and 179.8g of deionized water are added into a glass beaker with stirring to obtain a mixed solution; slowly adding 72.2g of silver oxalate into the mixed solution, and keeping the temperature below 40 ℃ and continuously stirring to completely dissolve the silver oxalate; then, 2.25mL of cesium nitrate aqueous solution (with a concentration of 0.03995g/mL based on the weight of cesium atoms) and 2.78mL of ammonium perrhenate aqueous solution (with a concentration of 0.0162g/mL based on the weight of rhenium atoms) were added in sequence, and mixed uniformly to prepare 300g of impregnating solution for standby.
15g of the support example 4 were taken and placed in a glass container which can be evacuated, and the above silver amine impregnation solution was added to completely immerse the support. After evacuating to above 10mmHg and holding for about 15 minutes, the excess solution was leached off. Finally, the impregnated support sample was placed in an air stream at 350 ℃ and heated for about 2 minutes to produce silver catalyst example 4.
The contents of the components relative to the silver catalyst example 4 were: 11.3wt% silver on an atomic basis, 167ppm alkali cesium promoter, 92ppm rhenium promoter on a rhenium atomic basis.
Example 5
First, 198mL of 5wt% sulfuric acid aqueous solution was prepared in a glass beaker, then 2g of zirconium nitrate pentahydrate and 0.5g of chitosan were added to the sulfuric acid aqueous solution, and they were mixed and stirred uniformly. 15g of alpha-alumina carrier is taken, placed into a glass container capable of being vacuumized, and the impregnating solution is added to completely immerse the carrier. After evacuating to above 10mmHg and holding for about 15 minutes, excess solution was leached off and the impregnated support sample was placed in a stream of air at 400℃for about 3 minutes. 200mL of a 10wt% aqueous ammonia solution was prepared in a glass, and 1.3g of ammonium tungstate (H) 26 N 6 O 40 W 12 ) And mixing and stirring the materials uniformly. Will be impregnated withPutting the zirconium sulfate and chitosan dilute sulfuric acid solution and the heated carrier into a glass container capable of vacuumizing, adding ammonium tungstate ammonia water impregnating solution, and completely immersing the carrier. After evacuating to above 10mmHg and maintaining for about 15 minutes, the excess solution was leached off, the impregnated support sample was placed in an air stream at 400℃for about 3 minutes and finally heated at 900℃for 1 hour to produce support example 5.
The surface loading of the components of carrier example 5 was as follows: 0.14wt% of zirconia with a hollow structure and 0.025wt% of tungsten oxide.
32.1g of ethylenediamine, 10.8g of ethanolamine and 179.8g of deionized water are added into a glass beaker with stirring to obtain a mixed solution; slowly adding 72.2g of silver oxalate into the mixed solution, and keeping the temperature below 40 ℃ and continuously stirring to completely dissolve the silver oxalate; then, 2.25mL of cesium nitrate aqueous solution (with a concentration of 0.03995g/mL based on the weight of cesium atoms) and 2.78mL of ammonium perrhenate aqueous solution (with a concentration of 0.0162g/mL based on the weight of rhenium atoms) were added in sequence, and mixed uniformly to prepare 300g of impregnating solution for standby.
15g of the support example 5 were taken and placed in a glass container which can be evacuated, and the above silver amine impregnation solution was added to completely immerse the support. After evacuating to above 10mmHg and holding for about 15 minutes, the excess solution was leached off. Finally, the impregnated support sample was placed in an air stream at 350 ℃ and heated for about 2 minutes to produce silver catalyst example 5.
The contents of the components relative to the silver catalyst example 5 were: 11.2wt% silver in atomic terms, 173ppm alkali cesium promoter, 95ppm rhenium promoter in atomic terms.
Example 6
First, 198mL of 5wt% sulfuric acid aqueous solution was prepared in a glass beaker, then 2g of zirconium sulfate and 1g of chitosan were added to the sulfuric acid aqueous solution, and they were mixed and stirred uniformly. 15g of alpha-alumina carrier is taken, placed into a glass container capable of being vacuumized, and the impregnating solution is added to completely immerse the carrier. Vacuumizing to above 10mmHg, maintaining for about 15 min, leaching to remove excessive solution, and standing the impregnated carrier sampleHeated in an air stream at 400 c for about 3 minutes. 200mL of a 10wt% aqueous ammonia solution was prepared in a glass, and 1.3g of ammonium tungstate (H) 26 N 6 O 40 W 12 ) And mixing and stirring the materials uniformly. Putting the carrier which is immersed in the dilute sulfuric acid solution of zirconium persulfate and chitosan and heated into a glass container capable of being vacuumized, adding ammonium tungstate ammonia water immersion liquid, and completely immersing the carrier. After evacuating to above 10mmHg and maintaining for about 15 minutes, the excess solution was leached off, the impregnated support sample was placed in an air stream at 400℃for about 3 minutes and finally heated at 900℃for 1 hour to produce support example 6.
The surface loading of the components of carrier example 6 was as follows: 0.22wt% of zirconia with a hollow structure and 0.027wt% of tungsten oxide.
32.1g of ethylenediamine, 10.8g of ethanolamine and 179.8g of deionized water are added into a glass beaker with stirring to obtain a mixed solution; slowly adding 72.2g of silver oxalate into the mixed solution, and keeping the temperature below 40 ℃ and continuously stirring to completely dissolve the silver oxalate; then, 2.25mL of cesium nitrate aqueous solution (with a concentration of 0.03995g/mL based on the weight of cesium atoms) and 2.78mL of ammonium perrhenate aqueous solution (with a concentration of 0.0162g/mL based on the weight of rhenium atoms) were added in sequence, and mixed uniformly to prepare 300g of impregnating solution for standby.
15g of the support example 6 were taken and placed in a glass container which can be evacuated, and the above silver amine impregnation solution was added to completely immerse the support. After evacuating to above 10mmHg and holding for about 15 minutes, the excess solution was leached off. Finally, the impregnated support sample was placed in an air stream at 350 ℃ and heated for about 2 minutes to produce silver catalyst example 6.
The contents of the components relative to the silver catalyst example 6 were: 11.0wt% silver on an atomic basis, 171ppm alkali cesium promoter, 92ppm rhenium promoter on a rhenium atomic basis.
Example 7
First, 198mL of 5wt% aqueous sulfuric acid solution was prepared in a glass beaker, then 2g of zirconium sulfate and 0.5g of polystyrene microspheres were added to the aqueous sulfuric acid solution, and they were mixed and stirred And (5) uniformity. 15g of alpha-alumina carrier is taken, placed into a glass container capable of being vacuumized, and the impregnating solution is added to completely immerse the carrier. After evacuating to above 10mmHg and holding for about 15 minutes, excess solution was leached off and the impregnated support sample was placed in a stream of air at 400℃for about 3 minutes. 200mL of a 10wt% aqueous ammonia solution was prepared in a glass, and 1.3g of ammonium tungstate (H) 26 N 6 O 40 W 12 ) And mixing and stirring the materials uniformly. Putting the carrier which is immersed in the dilute sulfuric acid solution of zirconium persulfate and chitosan and heated into a glass container capable of being vacuumized, adding ammonium tungstate ammonia water immersion liquid, and completely immersing the carrier. After evacuating to above 10mmHg and maintaining for about 15 minutes, the excess solution was leached off, the impregnated support sample was placed in an air stream at 400℃for about 3 minutes and finally heated at 900℃for 1 hour to produce support example 7.
The surface loading of the components of carrier example 7 was as follows: hollow configuration zirconia 0.23 wt% and tungsten oxide 0.026wt%.
32.1g of ethylenediamine, 10.8g of ethanolamine and 179.8g of deionized water are added into a glass beaker with stirring to obtain a mixed solution; slowly adding 72.2g of silver oxalate into the mixed solution, and keeping the temperature below 40 ℃ and continuously stirring to completely dissolve the silver oxalate; then, 2.25mL of cesium nitrate aqueous solution (with a concentration of 0.03995g/mL based on the weight of cesium atoms) and 2.78mL of ammonium perrhenate aqueous solution (with a concentration of 0.0162g/mL based on the weight of rhenium atoms) were added in sequence, and mixed uniformly to prepare 300g of impregnating solution for standby.
15g of the support example 7 were taken and placed in a glass container which can be evacuated, and the above silver amine impregnation solution was added to completely immerse the support. After evacuating to above 10mmHg and holding for about 15 minutes, the excess solution was leached off. Finally, the impregnated support sample was placed in an air stream at 350 ℃ and heated for about 2 minutes to produce silver catalyst example 7.
The contents of the components relative to the silver catalyst example 7 were: 11.3wt% silver on an atomic basis, 174ppm alkali cesium promoter, 96ppm rhenium promoter on a rhenium atomic basis.
Example 8
First, 198mL of 5wt% sulfuric acid aqueous solution was prepared in a glass beaker, then 2g of zirconium sulfate and 0.5g of chitosan were added to the sulfuric acid aqueous solution, and they were mixed and stirred uniformly. 15g of alpha-alumina carrier is taken, placed into a glass container capable of being vacuumized, and the impregnating solution is added to completely immerse the carrier. After evacuating to above 10mmHg and holding for about 15 minutes, excess solution was leached off and the impregnated support sample was placed in a stream of air at 400℃for about 3 minutes. 200mL of a 10wt% aqueous ammonia solution was prepared in a glass, and 2.6g of ammonium tungstate (H) 26 N 6 O 40 W 12 ) And mixing and stirring the materials uniformly. Putting the carrier which is immersed in the dilute sulfuric acid solution of zirconium persulfate and chitosan and heated into a glass container capable of being vacuumized, adding ammonium tungstate ammonia water immersion liquid, and completely immersing the carrier. After evacuating to above 10mmHg and maintaining for about 15 minutes, the excess solution was leached off, the impregnated support sample was placed in an air stream at 400℃for about 3 minutes and finally heated at 900℃for 1 hour to produce support example 8.
The surface loading of the components of carrier example 8 was as follows: 0.21wt% of zirconia with a hollow structure and 0.052wt% of tungsten oxide.
32.1g of ethylenediamine, 10.8g of ethanolamine and 179.8g of deionized water are added into a glass beaker with stirring to obtain a mixed solution; slowly adding 72.2g of silver oxalate into the mixed solution, and keeping the temperature below 40 ℃ and continuously stirring to completely dissolve the silver oxalate; then, 2.25mL of cesium nitrate aqueous solution (with a concentration of 0.03995g/mL based on the weight of cesium atoms) and 2.78mL of ammonium perrhenate aqueous solution (with a concentration of 0.0162g/mL based on the weight of rhenium atoms) were added in sequence, and mixed uniformly to prepare 300g of impregnating solution for standby.
15g of the support example 8 were taken and placed in a glass container which can be evacuated, and the above silver amine impregnation solution was added to completely immerse the support. After evacuating to above 10mmHg and holding for about 15 minutes, the excess solution was leached off. Finally, the impregnated support sample was placed in an air stream at 350 ℃ and heated for about 2 minutes to produce silver catalyst example 8.
The contents of the components relative to the silver catalyst example 8 were: 11.2wt% silver in atomic terms, 173ppm alkali cesium promoter, 91ppm rhenium promoter in atomic terms.
Example 9
First, 198mL of 5wt% sulfuric acid aqueous solution was prepared in a glass beaker, then 2g of zirconium sulfate and 0.5g of chitosan were added to the sulfuric acid aqueous solution, and they were mixed and stirred uniformly. 15g of alpha-alumina carrier is taken, placed into a glass container capable of being vacuumized, and the impregnating solution is added to completely immerse the carrier. After evacuating to above 10mmHg and holding for about 15 minutes, excess solution was leached off and the impregnated support sample was placed in a stream of air at 400℃for about 3 minutes. 200mL of a 10wt% aqueous ammonia solution was prepared in a glass, and then 1.3g of tungstic acid was added to the aqueous ammonia solution, and the mixture was stirred well. Putting the carrier which is immersed in the dilute sulfuric acid solution of zirconium persulfate and chitosan and heated into a glass container capable of being vacuumized, adding ammonium tungstate ammonia water immersion liquid, and completely immersing the carrier. After evacuating to above 10mmHg and maintaining for about 15 minutes, the excess solution was leached off, the impregnated support sample was placed in an air stream at 400℃for about 3 minutes and finally heated at 900℃for 1 hour to produce support example 9.
The surface loading of the components of carrier example 9 was as follows: 0.23wt% of zirconia with a hollow structure and 0.026wt% of tungsten oxide.
32.1g of ethylenediamine, 10.8g of ethanolamine and 179.8g of deionized water are added into a glass beaker with stirring to obtain a mixed solution; slowly adding 72.2g of silver oxalate into the mixed solution, and keeping the temperature below 40 ℃ and continuously stirring to completely dissolve the silver oxalate; then, 2.25mL of cesium nitrate aqueous solution (with a concentration of 0.03995g/mL based on the weight of cesium atoms) and 2.78mL of ammonium perrhenate aqueous solution (with a concentration of 0.0162g/mL based on the weight of rhenium atoms) were added in sequence, and mixed uniformly to prepare 300g of impregnating solution for standby.
15g of the support example 9 were taken and placed in a glass container which can be evacuated, and the above silver amine impregnation solution was added to completely immerse the support. After evacuating to above 10mmHg and holding for about 15 minutes, the excess solution was leached off. Finally, the impregnated support sample was placed in an air stream at 350 ℃ and heated for about 2 minutes to produce silver catalyst example 9.
The contents of the components relative to the silver catalyst example 9 were: 11.0wt% silver on an atomic basis, 172ppm alkali cesium promoter, 94ppm rhenium promoter on a rhenium atomic basis.
Comparative example 1
32.1g of ethylenediamine, 10.8g of ethanolamine and 179.8g of deionized water are added into a glass beaker with stirring to obtain a mixed solution; slowly adding 72.2g of silver oxalate into the mixed solution, and keeping the temperature below 40 ℃ and continuously stirring to completely dissolve the silver oxalate; then, 2.25mL of cesium nitrate aqueous solution (with a concentration of 0.03995g/mL based on the weight of cesium atoms) and 2.78mL of ammonium perrhenate aqueous solution (with a concentration of 0.0162g/mL based on the weight of rhenium atoms) were added in sequence, and mixed uniformly to prepare 300g of impregnating solution for standby.
15g of alpha-alumina carrier is taken, placed into a glass container capable of being vacuumized, and added with the silver amine impregnating solution, and the carrier is completely immersed. After evacuating to above 10mmHg and holding for about 15 minutes, the excess solution was leached off. Finally, the impregnated support sample was placed in an air stream at 350 ℃ and heated for about 2 minutes to produce a silver catalyst comparative example 1.
The contents of the respective components relative to the silver catalyst comparative example 1 were: 11.1wt% silver on an atomic basis, 170ppm alkali cesium promoter, 93ppm rhenium promoter on a rhenium atomic basis.
Comparative example 2
The difference from example 8 is that 2.4g of zirconium sulfate was added without adding a tungsten compound. The contents of the components carried on the surface of the carrier comparative example 2 are as follows: zirconia in hollow configuration 0.26wt%.
32.1g of ethylenediamine, 10.8g of ethanolamine and 179.8g of deionized water are added into a glass beaker with stirring to obtain a mixed solution; slowly adding 72.2g of silver oxalate into the mixed solution, and keeping the temperature below 40 ℃ and continuously stirring to completely dissolve the silver oxalate; then, 2.25mL of cesium nitrate aqueous solution (with a concentration of 0.03995g/mL based on the weight of cesium atoms) and 2.78mL of ammonium perrhenate aqueous solution (with a concentration of 0.0162g/mL based on the weight of rhenium atoms) were added in sequence, and mixed uniformly to prepare 300g of impregnating solution for standby.
15g of carrier comparative example 2 was taken and placed in a glass container which was evacuated, and the above silver amine impregnating solution was added to completely immerse the carrier. After evacuating to above 10mmHg and holding for about 15 minutes, the excess solution was leached off. Finally, the impregnated support sample was placed in an air stream at 350 ℃ and heated for about 2 minutes to produce silver catalyst comparative example 2.
The contents of the respective components relative to the silver catalyst comparative example 2 were: 11.2wt% silver on an atomic basis, 168ppm alkali cesium promoter, 96ppm rhenium promoter on a rhenium atomic basis.
Comparative example 3
The difference from example 8 is that 13.7g of ammonium tungstate was added without adding zirconium compound.
The contents of the components of the surface loading of the carrier comparative example 3 were: tungsten oxide 0.26wt%.
32.1g of ethylenediamine, 10.8g of ethanolamine and 179.8g of deionized water are added into a glass beaker with stirring to obtain a mixed solution; slowly adding 72.2g of silver oxalate into the mixed solution, and keeping the temperature below 40 ℃ and continuously stirring to completely dissolve the silver oxalate; then, 2.25mL of cesium nitrate aqueous solution (with a concentration of 0.03995g/mL based on the weight of cesium atoms) and 2.78mL of ammonium perrhenate aqueous solution (with a concentration of 0.0162g/mL based on the weight of rhenium atoms) were added in sequence, and mixed uniformly to prepare 300g of impregnating solution for standby.
15g of the carrier of comparative example 3 was taken, placed in a glass container which can be evacuated, and the above silver amine impregnating solution was added to completely immerse the carrier. After evacuating to above 10mmHg and holding for about 15 minutes, the excess solution was leached off. Finally, the impregnated support sample was placed in an air stream at 350 ℃ and heated for about 2 minutes to produce silver catalyst comparative example 3.
The contents of the respective components relative to the silver catalyst comparative example 3 were: 11.3wt% silver in atomic terms, 174ppm alkali cesium promoter, 91ppm rhenium promoter in atomic terms of rhenium.
The performance of the catalyst samples was measured under the aforementioned process conditions using a microreactor evaluation device for the silver catalysts of examples and comparative examples, and the evaluation results thereof are shown in table 2.
Table 2 silver catalysts comparative examples 1 to 3 and examples 1 to 9 were evaluated for results
As can be seen from Table 1, the selectivity and the reactivity of the silver catalyst sample prepared by adopting the alpha-alumina carrier surface composite modification technology are obviously improved.
The foregoing description of embodiments of the invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the various embodiments described.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
Claims (13)
1. A carrier for preparing a silver catalyst, characterized in that the carrier comprises:
α-Al 2 O 3 Carrier, supported on alpha-Al 2 O 3 Zirconium oxide and tungsten oxide with hollow configuration on the surface of the carrier;
relative to the alpha-Al 2 O 3 The carrier comprises the following components in percentage by weight:
0.02 to 4.00 weight percent of zirconia with hollow structure and 0.002 to 0.500 weight percent of tungsten oxide.
2. The carrier for preparing a silver catalyst according to claim 1, wherein,
relative to the alpha-Al 2 O 3 The carrier comprises the following components in percentage by weight:
0.05 to 1.00 weight percent of zirconia with hollow structure and 0.005 to 0.100 weight percent of tungsten oxide.
3. The carrier for preparing a silver catalyst according to claim 1 or 2, wherein the α -Al 2 O 3 The carrier comprises at least one of the following features:
α-A1 2 O 3 the content is more than or equal to 90 percent;
crushing strength is 20-200N/grain;
the specific surface area is 0.2-3.0 m 2 /g；
The water absorption rate is more than or equal to 30 percent;
the pore volume is 0.30-0.85 mL/g.
4. A method for preparing a carrier for preparing a silver catalyst, the method comprising:
(1) alpha-A1 2 O 3 Soaking in the first solution, then carrying out solid-liquid separation and drying;
(2) Soaking the carrier obtained in the step (1) in a second solution, and then carrying out solid-liquid separation, drying and roasting to obtain the carrier for preparing the silver catalyst;
the first solution is a mixed solution of acid, zirconium salt and a template agent;
The second solution is a tungstic acid and/or tungstate solution, and the solvent of the tungstate solution is at least one selected from water, ammonia water and amine compounds.
5. The preparation method according to claim 4, wherein,
in the step (1), the soaking time is 10-300 minutes, and the soaking is performed under the pressure of 100 mmHg;
in the step (2), the soaking time is 10-300 minutes, and the soaking is performed under the pressure of 100 mmHg;
in the step (1), drying is carried out in air or in a nitrogen-oxygen mixture with an oxygen content of not more than 21%; the drying temperature is 100-600 ℃, preferably 150-500 ℃; the drying time is 0.5 to 120 minutes, preferably 1 to 30 minutes;
in the step (2), drying is carried out in air or in a nitrogen-oxygen mixture with an oxygen content of not more than 21%; the drying temperature is 100-600 ℃, preferably 150-500 ℃; the drying time is 0.5 to 120 minutes, preferably 1 to 30 minutes;
in the step (2), roasting is carried out in air or in a nitrogen-oxygen mixture with the oxygen content not more than 21%; the roasting temperature is 500-1400 ℃, preferably 700-1200 ℃; the calcination time is 5 to 240 minutes, preferably 10 to 120 minutes.
6. The preparation method according to claim 4, wherein,
The acid is at least one selected from sulfuric acid, nitric acid and oxalic acid;
the zirconium salt is at least one selected from zirconium sulfate, zirconium nitrate and zirconyl nitrate;
the template agent is at least one of chitosan, polystyrene and glucosamine;
preferably, the content of the acid is 0.2 to 20.0wt percent, the content of the zirconium salt is 0.05 to 10.00wt percent, and the content of the template agent is 0.02 to 6.0wt percent based on the total weight of the first solution;
more preferably, the acid content is 1.0 to 15.0wt%, the zirconium salt content is 0.1 to 5.0wt%, and the templating agent content is 0.05 to 3.0wt%, based on the total weight of the first solution;
the tungstate is ammonium tungstate and/or potassium tungstate;
preferably, the content of the tungstic acid and/or tungstate is 0.002 to 0.500wt percent based on the total weight of the second solution;
more preferably, the content of tungstic acid and/or tungstate is 0.01 to 0.20wt% based on the total weight of the second solution.
7. A carrier obtainable by the process of any one of claims 4 to 6.
8. A silver catalyst, characterized in that the silver catalyst comprises:
a carrier, silver loaded on the surface of the carrier, an alkali metal auxiliary agent, an optional rhenium auxiliary agent and an optional co-auxiliary agent of the rhenium auxiliary agent;
The carrier is the carrier for preparing a silver catalyst according to claim 1 or 2 or 3, or the carrier according to claim 7.
9. The silver catalyst according to claim 8, wherein,
the content of each component relative to the silver catalyst is as follows:
silver 2-39 wt% in atom, alkali metal promoter 1-2000 ppm, rhenium promoter 0-2000 ppm in atom and rhenium promoter co-promoter 0-2000 ppm in atom;
preferably, the silver is 10-35 wt% in atomic terms, the alkali metal promoter is 5-2000 ppm, the rhenium promoter is 100-1000 ppm in atomic terms, and the co-promoter of the rhenium promoter is 100-1000 ppm in atomic terms.
10. The silver catalyst according to claim 8, wherein,
the alkali metal auxiliary agent is at least one of compounds of lithium, sodium, potassium, rubidium and cesium respectively;
the rhenium promoter is selected from at least one of rhenium oxide, perrhenic acid, cesium perrhenate, methyl rhenium trioxide (VII) and ammonium perrhenate;
the co-promoter of the rhenium promoter is selected from at least one of salts or acids containing manganese, chromium, sulfur, cobalt, molybdenum, nickel.
11. The method for producing a silver catalyst according to any one of claims 8 to 10, characterized in that the method comprises:
Soaking the carrier in silver ammonia solution, carrying out solid-liquid separation and drying to obtain the silver catalyst;
preferably, the time of the impregnation is 10 to 300 minutes, and the impregnation is performed under a pressure of 100mmHg or less;
preferably, the drying is carried out in air or in a mixture of nitrogen and oxygen having an oxygen content of not more than 21%, the drying temperature being between 100 and 600 ℃, more preferably between 150 and 500 ℃; the drying time is 0.5 to 120 minutes, more preferably 1 to 30 minutes.
12. The method for producing a silver catalyst according to claim 11, wherein,
the silver ammonia solution comprises a silver-containing compound, an amine compound, water, an alkali metal auxiliary agent, an optional rhenium auxiliary agent and an optional rhenium auxiliary agent; the content of the amine compound is 10-90 wt% based on the total weight of the silver-ammonia solution;
preferably, the silver-containing compound is selected from at least one of silver acetate, silver nitrate and silver oxalate;
preferably, the amine compound is selected from at least one of ammonia, ethylamine, N-propylamine, ethylenediamine, 1, 3-propylenediamine, 1, 4-butylenediamine, N-dimethylformamide, ethanolamine and propanolamine.
13. Use of the silver catalyst of any one of claims 8-10 in a reaction for the oxidation of ethylene to produce ethylene oxide.
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