CN86104383A - 含银催化剂的制备方法 - Google Patents
含银催化剂的制备方法 Download PDFInfo
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- CN86104383A CN86104383A CN86104383.9A CN86104383A CN86104383A CN 86104383 A CN86104383 A CN 86104383A CN 86104383 A CN86104383 A CN 86104383A CN 86104383 A CN86104383 A CN 86104383A
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- Prior art keywords
- silver
- carrier
- catalyzer
- compound
- weight
- Prior art date
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000003054 catalyst Substances 0.000 title claims abstract description 38
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 38
- 239000004332 silver Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 33
- -1 aluminum compound Chemical class 0.000 claims abstract description 21
- 229940100890 silver compound Drugs 0.000 claims abstract description 15
- 150000003379 silver compounds Chemical class 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 13
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 12
- 230000002829 reductive effect Effects 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 22
- 229910052792 caesium Inorganic materials 0.000 claims description 17
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 17
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 11
- 229910052700 potassium Inorganic materials 0.000 claims description 11
- 239000011591 potassium Substances 0.000 claims description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052728 basic metal Inorganic materials 0.000 claims description 10
- 150000003818 basic metals Chemical class 0.000 claims description 10
- 229910052701 rubidium Inorganic materials 0.000 claims description 10
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000007598 dipping method Methods 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 239000005977 Ethylene Substances 0.000 claims description 4
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 3
- 239000004480 active ingredient Substances 0.000 claims description 2
- 229910001593 boehmite Inorganic materials 0.000 claims description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 238000007493 shaping process Methods 0.000 claims 1
- 239000000243 solution Substances 0.000 description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 14
- 239000001301 oxygen Substances 0.000 description 14
- 229910052760 oxygen Inorganic materials 0.000 description 14
- 238000012360 testing method Methods 0.000 description 11
- 239000007789 gas Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- XNGYKPINNDWGGF-UHFFFAOYSA-L silver oxalate Chemical compound [Ag+].[Ag+].[O-]C(=O)C([O-])=O XNGYKPINNDWGGF-UHFFFAOYSA-L 0.000 description 8
- 229910052783 alkali metal Inorganic materials 0.000 description 7
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 3
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 229910001961 silver nitrate Inorganic materials 0.000 description 3
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 150000003378 silver Chemical class 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- KOPBYBDAPCDYFK-UHFFFAOYSA-N Cs2O Inorganic materials [O-2].[Cs+].[Cs+] KOPBYBDAPCDYFK-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- KGWDUNBJIMUFAP-KVVVOXFISA-N Ethanolamine Oleate Chemical compound NCCO.CCCCCCCC\C=C/CCCCCCCC(O)=O KGWDUNBJIMUFAP-KVVVOXFISA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- FXILXJYWVRJEIC-UHFFFAOYSA-L [Ag+].C(C(=O)[O-])(=O)[O-].[K+] Chemical compound [Ag+].C(C(=O)[O-])(=O)[O-].[K+] FXILXJYWVRJEIC-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- AOOCSKCGZYCEJX-OCNDCOMTSA-N argentamine Chemical compound C([C@H]1C[C@@H]2CN3CCC(C[C@H]31)O)N1C2=CC=CC1=O AOOCSKCGZYCEJX-OCNDCOMTSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- AKUNKIJLSDQFLS-UHFFFAOYSA-M dicesium;hydroxide Chemical compound [OH-].[Cs+].[Cs+] AKUNKIJLSDQFLS-UHFFFAOYSA-M 0.000 description 1
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical class CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 229910001512 metal fluoride Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910001952 rubidium oxide Inorganic materials 0.000 description 1
- CWBWCLMMHLCMAM-UHFFFAOYSA-M rubidium(1+);hydroxide Chemical compound [OH-].[Rb+].[Rb+] CWBWCLMMHLCMAM-UHFFFAOYSA-M 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- DTPQZKZONQKKSU-UHFFFAOYSA-N silver azanide silver Chemical compound [NH2-].[Ag].[Ag].[Ag+] DTPQZKZONQKKSU-UHFFFAOYSA-N 0.000 description 1
- 229910001958 silver carbonate Inorganic materials 0.000 description 1
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 description 1
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
-
- 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
-
- 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
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
- C07D301/08—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase
- C07D301/10—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase with catalysts containing silver or gold
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- 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
- B01J35/64—Pore diameter
- B01J35/657—Pore diameter larger than 1000 nm
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Epoxy Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
一种适用于氧化乙烯制备环氧乙烷的含银催化剂的制备方法,其特征在于向载体上施加含银化合物,然后,将这种银化合物还原成银。在这种方法中,载体是通过使铝化合物与IA族金属的盐混合,然后煅烧其混合物而制成的。
Description
本发明涉及到一种含银催化剂的制备方法,该催化剂适用于环氧乙烷的制备。还涉及一种新催化剂和该催化剂在环氧乙烷制备中的应用,以及所获得的环氧乙烷。
含银催化剂用于从乙烯制备环氧乙烷已广泛为人们所知。例如,可参见British Patent Specification No1413251,以及其中引证的文献。为了获得改进的银催化剂,多年来一直致力于用助催化剂对银催化剂进行改性的工作。例如,在上面提到的British Patent Specification No1413251中叙述了一种方法,在该方法中,将一种银化合物施加于载体上,然后将施加的银化合物还原成银,除此之外,在载体上还有以氧化钾、氧化铷或氧化铯或其混合物等形式存在的助催化剂。随着时间的推移,所有银催化剂在使用中稳定性变小,亦即其活性和选择性降低,所以用新制的催化剂来代替使用过的银催化剂就变得更经济。
申请人发现了具有改进稳定性的新型银催化剂。
本发明涉及到一种含银催化剂的制备方法,该催化剂适用于使乙烯氧化制备环氧乙烷,其特征在于在载体上施加一种银化合物,然后将这种银化合物还原成金属银。在这种方法中,其载体是通过将铝化合物与元素周期表中的1A族金属的盐混合,然后使所得到的混合物煅烧而制成的。
本发明还涉及到这样一种银催化剂,它含有作为活性组分的银和作为载体的富碱氧化铝。该催化剂适用于使乙烯氧化制备环氧乙烷。
US Patent Specification No4,379,134中公开了一种α一氧化铝的制备方法,其中将胶溶酸、水和氟阴离子与氧化铝混合。将得到的混合物挤压成成型颗粒,将这种成型颗粒在400-700℃下煅烧足够的时间,以使氧化铝转变为γ一氧化铝。然后再将这些颗粒在1200-1700℃下煅烧足够的时间,以使γ一氧化铝转变为α一氧化铝。在该说明书的叙述部分还提到氟化物作为助熔剂可使氧化铝的烧结温度低于纯氧化铝的烧结温度。根据US Patent Specification No4,379,134的所有实例,该方法中使用的是HF。这个叙述部分还进一步指出,许多金属氟化物也适于作助熔剂,但没有实验基础。它还提到用二氧化硅和作为助熔剂的碱金属氧化物但是,这种应用马上就被否定了,因为这些助熔剂会向氧化铝中引入一些不希望的杂质。
出乎意料的是,本申请人发现了元素周期表中的IA族金属,特别是钾、铷或铯,可以其盐的形式混合于载体内,从而导致生成具有更好稳定性的改性银催化剂。
这些铝化合物可以是氧化铝的各种变体(例如γ-氧化铝),它们在1200°-1700℃之间的温度下煅烧时可以产生α-氧化铝。另一种可能性是选择水合氧化铝,如勃姆石,它经γ一氧化铝生成α一氧化铝。
周期表IA族金属的盐可以是,例如氟化物、硝酸盐、氯化物或硫酸盐。金属是锂、钠、钾、铷或铯。最好使用钾、铷或铯的盐。其中氟化铯尤其适用。还发现氟化锂和硝酸锂也给出良好结果。
与铝化合物混合的碱金属盐的量被选择为IA族金属与Al的原子比在0.0001到0.1之间,最好在0.001到0.01之间。
关于富化载体的制备,最好是将一种铝化合物与水和IA族金属的盐混合,然后将得到的混合物挤压成成型颗粒,继之使其煅烧。煅烧可以一步或几步进行,视选择的原料而定。一般来说,加入足够量的水使混合物可挤压。然后在挤压机内将所获得的可挤压的糊状物挤压成片。将这些成型片加热,在加热过程中蒸去所含的水份。然后煅烧这些固体片。为了制备α一氧化铝变体,煅烧温度必须在1200-1700℃之间。适宜的原料为γ一氧化铝、一水α一氧化铝、三水α一氧化铝和一水β一氧化铝的粉末。这些氧化物粉末在煅烧期间随着粉粒熔融而被烧结。加热和煅烧使晶体结构发生变化γ一氧化铝的立方结构转变为α一氧化铝的立方结构。
有效的催化剂表面面积可以在0.2-5米2/克的之间变化。还发现对α氧化铝而言,碱金属(铯)在表面上的浓度比根据碱金属的称重所预计的高6倍左右。
为了制备催化剂,用一种银化合物的溶液浸渍富碱载体,将足够的银施加到载体上,所希望的银按催化剂的总重量计算对载体的比率为1-25%(重量)。使浸渍后的载体与溶液分离,然后将沉淀的银化合物还原成银。
最好加入助催化剂,如一种或多种碱金属:钾、铷或铯。助催化剂可以在载体用银化合物浸渍之前、期间或之后施加到载体上。助催化剂也可以在银化合物被还原成银以后施加到载体上。
一般来说,是将载体与银盐或银络合物的水溶液混合,使载体被这种溶液浸渍,然后将载体与溶液分离,继之使其干燥。之后将浸渍载体在100-400℃的温度下加热一定时间,以使银盐(或络合物)分解,并形成一层粘附于载体表面的精细分布的金属银。
可以选择性地将浸渍载体在500℃下加热一定时间,例如1小时。然后可将碱金属施加到载体上(后掺铯)。在加热期间,可以使还原性或惰性气体通过载体。
加银的各种方法已众所周知。可以用硝酸银的水溶液浸渍载体,继之使载体干燥,然后用氢气或肼还原硝酸银。载体也可以用草酸银或碳酸银的氨溶液浸渍,通过盐的热分解实现银金属的淀积。含有一定量增溶剂和还原剂的银盐的特殊溶液,如连位烷醇胺、烷基二胺和氨的混合物也是适用的。
加入的助催化剂量一般为每百万份重量的催化剂中加入20-1000份重量的碱金属,如钾、铷或铯(以金属计)。加入50-300份重量的碱金属时尤其适用。用作助催化剂原料的适宜化合物有,例如,硝酸盐、草酸盐、羧酸盐或氢氧化物。最佳的助催化剂为铯,并且最好使用氢氧化铯或硝酸铯。
加入碱金属的一些优良方法已众所周知,在这些方法中,碱金属可以和银同时施加到载体上。适用的碱金属盐一般是那些可在银淀积液相中溶解的盐类。除上述提到的盐类以外,值得提出的还有硝酸盐、氯化物、碘化物、溴化物、碳酸氢盐、乙酸盐、酒石酸盐、乳酸盐和异丙醇盐。但是,应该避免所使用的碱金属盐与溶液中的银发生反应,致使银盐过早地从浸渍溶液中沉淀出来。例如,氯化钾就不应用于使用硝酸银水溶液的浸渍技术,但硝酸钾就可以在此使用。氯化钾适用于使用银胺络合物的水溶液的方法中,并且没有氯化银沉淀产生。
另外,沉积到载体上的碱金属量可以通过冲洗掉一部分碱金属方法在一定范围内进行调节,冲洗液最好使用无水甲醇或无水乙醇。如果发现施加的碱金属的浓度太高时,就可以使用这种方法。可以调节温度,接触时间和用气体的干燥。应该注意保证在载体内不残留醇。
一种最佳的使用方法组成为,用含有碱金属盐和银盐的水溶液浸渍载体,这种浸渍液是由一种羧酸的银盐、一种有机胺、一种钾、铷或铯的盐和一种水性溶剂组成。例如,含钾的草酸银溶液可以用两种方法制备。一种方法可以是:使氧化银与乙二胺和草酸的混合物进行反应,生成一种含草酸银乙二胺络合物的溶液,然后向此溶液中加入一定量的钾,也可能加入其他胺,如乙醇胺。另一种方法是:使草酸银从草酸钾和硝酸盐的溶液中沉淀出来,然后反复洗涤所得到的草酸银沉淀,以除去附着的钾盐,直至得到所需钾含量为止。然后用氨和/或胺来溶解含钾草酸银。含有铷和铯的溶液也可以用这种方法来制备。然后将浸渍载体加热到100-400℃,最好是加热到125-325℃。
应该指出的是,不论溶液中的银在沉淀到载体上之前的性能如何,常常提到还原成金属银,同时也可能提到加热分解这一概念。由于带正电荷的银离子被转化为金属银,所以我们最好认为是还原。还原时间可以简单地与所用原料相适应。
如上所述,最好向银中加入助催化剂。与用作为助催化剂的钾或铷相比较发现,铯对环氧乙烷的选择性最高,从这一事实来看,铯是最佳助催化剂。
按照本发明方法制备的银催化剂,对于借助分子氧从乙烯制取环氧乙烷的直接催化氧化过程,似乎是特别稳定的催化剂。在本发明的银催化剂存在下,这种氧化反应的条件与先有技术中叙述的十分相似,这些条件是指,例如,适宜的温度、压力、滞留时间、稀释剂(如氮气、二氧化碳、水蒸汽、氩气、甲烷或其他饱和烃),是否存在控制催化作用的缓和剂(如1,2-二氯乙烷、氯乙烯或氯化聚苯化合物),采用循环处理或在不同反应器中连续转化,以提高环氧乙烷产率的理想性,以及环氧乙烷制备过程中可以选择的其他特殊条件。通常,使用的压力在大气压和35巴之间变化。但是,决不排除更高的压力。
作为反应物的分子氧可以从常规氧源中获得。原料氧可以基本为纯氧,也可以是由大量氧和少量的一种或多种稀释剂(如氮气、氩气等)组成的浓缩氧流,或者是其他含氧流(如空气)。
在本发明银催化剂的最佳应用中,在上述的催化剂存在下,在210-285℃的温度范围内,最好在225-270℃范围内,通过使从空气中分离出来的含氧气体与乙烯接触制备环氧乙烷,所用的含氧气体氧含量不小于95%。气体的空速可以在2800-8000小时-1之间变化。
在用氧气使乙烯氧化为环氧乙烷的反应中,乙烯与氧的分子数比至少为2,而所采用乙烯的量一般远远高于此值。因此,转化率是依反应中转化的氧的量来计算,所以我们称氧转化率。此氧转化率取决于反应温度,并且是催化剂活性的量度。T30、T40和T50是指在反应器中,氧的转化率分别为30摩尔%、40摩尔%和50摩尔%时的温度。一般温度越高,反应转化率也越高,并且温度主要取决于所用催化剂和反应条件。除这些温度值以外,还发现选择性数值,它表示环氧乙烷在得到的反应混合物中的摩尔百分数。选择性表示为S30、S40或S50,它们分别表示氧的转化率为30%、40%或50%时的选择性。
“催化剂稳定性”的概念不能直接表示。稳定性测量需要长时间的试验。为了测量稳定性,本申请人在极端条件下进行了一个试验,试验时用的空速为30000升·升催化剂-1·h-1,其中通入的气体的升被理解为STP(标准温度和标准压力下)。这个空速比工业过程中的空速高许多倍。试验进行了至少一个月。在整个试验期间测定了上述的T值和S值。试验结束后,测定了由每毫升催化剂产生的环氧乙烷的总量。计算了每毫升能生产1000克环氧乙烷的催化剂的选择性和活性之差。在每个试验期间如果新催化剂的T值和S值的差小于标准催化剂的T值和S值的差,新催化剂则被认为比已知催化剂更稳定,稳定性试验一般在氧转化率为35%的情况下进行。
实例1
通过将氟化铯溶液加到氧化铝中的方式,将溶于160毫升水的1克氟化铯与137.5克Kaiser氧化铝(26102)(Al2O3·H2O)混合,然后,将混合物在捏和机中捏和10分钟。将得到的糊状物放置3小时,然后将其挤压成片。将得到的成型片在120℃下干燥3小时,接着在逐渐升高的温度下使其煅烧。煅烧开始以200℃/小时的速度升到700℃。然后在700℃下恒温1小时,之后在两小时内使温度升到1600℃。最后在1600℃下恒温1小时。成型氧化铝片的孔容积为0.54毫升/克,平均孔径为2微米。称出的铯/铝原子比为0.003,而在孔表面上的铯/铝原子比为0.019。将得到的成型片用其中加有氢氧化的草酸银溶液浸渍在真空下进行10分钟后,将成型片与溶液分离。为了使银盐转变为银,将成型片置于250-270℃的热空气流中10分钟。草酸银水溶液为含银28%(重量)的水溶液,在其中草酸银与乙二胺络合,并向溶液中加入了氢氧化铯溶液。经热空气处理后,浸渍的成型片含有19.1%(重量)的Ag(按催化剂总量计算),并且每百万份重量的催化剂中含有100份重量的。
然后,对得到的催化剂进行了试验。将长度为15厘米,截面直径3毫米的圆筒状钢制反应器充满粒度约0.3毫米的催化剂颗粒。将反应器置于一个硅/铝颗粒在里面呈流化态存在的浴中。使具有如下组成的气体混合物通过反应器:30摩尔%的乙烯、8.5摩尔%的氧气、7摩尔%的二氧化碳和54.5摩尔%的氮气和每百万份气体中含有7份作为缓和剂的氯乙烯。空速为30000升·升-1·小时-1。压力为15巴,温度视所确定的氧转化率而定。测量设备与反应器相联,并将数值输入计算机,以使其转化率和温度能得到准确控制。用相色谱法和质谱测定法测量反应组分的浓度。稳定性试验是在氧转化率为35%的情况下进行。
在整个试验期间,测定了氧转化率为35%的反应温度。同时还测定了对环氧乙烷的选择性。试验至少进行了30之后才结束,测定了每毫升催化剂产生的环氧乙烷的总量。从所测量的反应温度,计算出在每毫升催化剂能产生1000克环氧乙烷时(T1000 35)的温度升高(℃)。从所测量的选择性,计算出了在每毫升催化剂能产生出1000克环氧乙烷时(S1000 35)的选择性降低(摩尔%)。在试验中对标准催化剂进行同样的测量和计算。
表中示出了S1000 35和T1000 35与标准催化剂的S1000 35和T1000 35比较情况。
实例2
用实例1中同样方法,制备一种催化剂,并对其进行试验。催化剂中含有17.3%(重量)的Ag和每百万份重量的催化剂中含有160份重量的铯。在这个试验中,使用5.5ppm的氯乙烯作为缓和剂。
表
Claims (18)
1、一种适用于从乙烯氧化制备环氧乙烷的含银催化剂的制备方法,其特征在于向载体上施加一种银化合物,然后,使这种银化合物还原成金属银,在该方法中的载体是通过使铝化合物与1A族金属的盐混合,煅烧其所得混合物而制成的。
2、一种如权利要求1所述的方法,其特征在于其中的铝化合物是氧化铝或氧化铝的水合物。
3、一种如权利要求1或2所述的方法,其特征在于其中的铝化合物与1A族金属的氟化物、硝酸盐、氯化物或硫酸盐混合。
4、一种如权利要求1-3中的一个或多个中所述的方法,其特征在于其中的铝化合物与氟化铯或硝酸铯混合。
5、一种如权利要求1-4中的一个或多个中所述的方法,其特征在于其中的铝化合物与一定量的盐混合,使得1A族金属A1的原子数比在0.0001到0.1之间。
6、一种如权利要求5中所述的方法,其特征在于其中的原子数比在0.001到0.01之间。
7、一种如权利要求1-6中的一个或多个中所述的方法,其特征在于其中的铝化合物为勃姆石或γ-氧化铝。
8、一种如权利要求1-7中的一个或多个中所述的方法,其特征在于将铝化合物与水和1A族金属的盐混合,然后将得到的混合物挤压成成型载体颗粒,之后使其煅烧。
9、一种如权利要求1-8中的一个或多个中所述的方法,其特征在于将载体用足够量的银化合物溶液浸渍,使1-25%(重量)的银施加到载体上(以催化剂总重量计算),然后将浸渍的载体与溶液分离,并使沉积的银化合物还原成银。
10、一种如权利要求1-9中的一个或多个中所述的方法,其特征在于向载体上施加一种助催化剂。
11、一种如权利要求9或10所述的方法,其特征在于,除向载体上施加银化合物之外,在施加银化合物的同时或者在其前后,向载体上还施加足够量的一种或多种碱金属钾、铷或铯的化合物,使每百万份重量的催化剂上沉淀出20-1000份重量的碱金属(以金属计量)。
12、一种按照权利要求1-11所述方法制备的催化剂。
13、一种适用于氧化乙烯制备环氧乙烷的银催化剂,该催化剂包括作为活性组分的银和作为载体的富碱氧化铝。
14、一种如权利要求13所述的催化剂,该催化剂包括:
a)在载体表面上,有1-25%(重量)的银,以催化剂总量计算;
b)作为载体的富碱氧化铝。
15、一种如权利要求13或14所述的催化剂,其中在载体表面上还包括助催化剂。
16、一种如权利要求15所述的催化剂,其中在每百万份重量的催化剂中包括20-1000份重量的钾、铷或铯(以金属计量)。
17、一种在含银催化剂存在下,氧化乙烯制备环氧乙烷的方法,其特征在于该方法是在按权利要求1-10中的一个或多个,或权利要求11-16中的一个或多个所述的方法制备的含银催化剂存在下进行的。
18、用权利要求17所述的方法制备的环氧乙烷。
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NL8501864 | 1985-06-28 | ||
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JP (1) | JPH0761448B2 (zh) |
KR (1) | KR940000865B1 (zh) |
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CA (1) | CA1284985C (zh) |
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DE (1) | DE3674270D1 (zh) |
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EG (1) | EG18788A (zh) |
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HU (1) | HU203289B (zh) |
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MA (1) | MA20720A1 (zh) |
MX (1) | MX166917B (zh) |
NO (1) | NO169157C (zh) |
NZ (1) | NZ216673A (zh) |
PH (1) | PH23562A (zh) |
PL (1) | PL151362B1 (zh) |
PT (1) | PT82851B (zh) |
RU (1) | RU2007214C1 (zh) |
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CN102921471A (zh) * | 2011-08-10 | 2013-02-13 | 中国石油化工股份有限公司 | 合成α-氧化铝载体的氧化铝源组合物和α-氧化铝载体及其制备方法以及银催化剂和应用 |
CN103608106A (zh) * | 2011-04-14 | 2014-02-26 | 巴斯夫欧洲公司 | 用于制备氧化乙烯的含锌催化剂 |
CN103721712B (zh) * | 2012-10-12 | 2016-03-30 | 中国石油化工股份有限公司 | 一种乙烯氧化生产环氧乙烷用银催化剂 |
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NL8502993A (nl) * | 1985-11-01 | 1987-06-01 | Dow Chemical Nederland | Zilverkatalysator, alsmede werkwijze voor de bereiding daarvan. |
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US6908879B1 (en) | 1999-09-06 | 2005-06-21 | Nippon Shokubai Co., Ltd. | Ceramic article, carrier for catalyst, methods for production thereof, catalyst for producing ethylene oxide using the carrier, and method for producing ethylene oxide |
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JP4726349B2 (ja) * | 2001-08-03 | 2011-07-20 | 株式会社日本触媒 | 酸化エチレン製造用触媒、その製造方法および当該触媒による酸化エチレンの製造方法 |
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CN102397795B (zh) | 2010-09-13 | 2014-03-19 | 中国石油化工股份有限公司 | 环氧乙烷生产用银催化剂的载体、其制备方法、由其制成的银催化剂及其应用 |
CN102441435B (zh) * | 2010-09-30 | 2014-01-01 | 中国石油化工股份有限公司 | 制备银催化剂用氧化铝载体的方法、由此得到的载体及其应用 |
CN102527430B (zh) | 2010-12-29 | 2014-04-30 | 中国石油化工股份有限公司 | 银催化剂载体的制备方法、由此制备的载体、由该载体制成的银催化剂及其应用 |
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FR2403991A1 (fr) * | 1977-09-22 | 1979-04-20 | Philagro Sa | Procede de deshalogenation d'amines aromatiques halogenees |
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- 1986-06-03 IN IN490/DEL/86A patent/IN170003B/en unknown
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- 1986-06-26 AU AU59290/86A patent/AU583394B2/en not_active Ceased
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- 1986-06-26 GR GR861669A patent/GR861669B/el unknown
- 1986-06-26 NO NO862585A patent/NO169157C/no not_active IP Right Cessation
- 1986-06-26 NZ NZ216673A patent/NZ216673A/xx unknown
- 1986-06-26 CS CS864762A patent/CS266591B2/cs not_active IP Right Cessation
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- 1986-06-26 RU SU864027721A patent/RU2007214C1/ru not_active IP Right Cessation
- 1986-06-26 PH PH33954A patent/PH23562A/en unknown
- 1986-06-26 HU HU862686A patent/HU203289B/hu not_active IP Right Cessation
- 1986-06-26 CN CN86104383A patent/CN1009827B/zh not_active Expired
- 1986-06-26 BR BR8602942A patent/BR8602942A/pt not_active IP Right Cessation
- 1986-06-26 YU YU1124/86A patent/YU45345B/xx unknown
- 1986-06-26 JP JP61148361A patent/JPH0761448B2/ja not_active Expired - Lifetime
- 1986-06-26 IL IL79246A patent/IL79246A/xx not_active IP Right Cessation
- 1986-06-26 MA MA20947A patent/MA20720A1/fr unknown
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