CN87102247A - 复合氧化物催化剂生产工艺 - Google Patents
复合氧化物催化剂生产工艺 Download PDFInfo
- Publication number
- CN87102247A CN87102247A CN87102247.8A CN87102247A CN87102247A CN 87102247 A CN87102247 A CN 87102247A CN 87102247 A CN87102247 A CN 87102247A CN 87102247 A CN87102247 A CN 87102247A
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- China
- Prior art keywords
- bismuth
- compound
- catalyst
- gram
- composite oxide
- Prior art date
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- Expired - Lifetime
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- 239000003054 catalyst Substances 0.000 title claims abstract description 64
- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims description 25
- 238000004519 manufacturing process Methods 0.000 title description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 46
- 238000010438 heat treatment Methods 0.000 claims abstract description 34
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 22
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910000416 bismuth oxide Inorganic materials 0.000 claims abstract description 9
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims abstract description 9
- GMZOPRQQINFLPQ-UHFFFAOYSA-H dibismuth;tricarbonate Chemical compound [Bi+3].[Bi+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GMZOPRQQINFLPQ-UHFFFAOYSA-H 0.000 claims abstract description 7
- 229940036348 bismuth carbonate Drugs 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims description 17
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- BYUANIDVEAKBHT-UHFFFAOYSA-N [Mo].[Bi] Chemical compound [Mo].[Bi] BYUANIDVEAKBHT-UHFFFAOYSA-N 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 229910052785 arsenic Inorganic materials 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 229910052701 rubidium Inorganic materials 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 229910052792 caesium Inorganic materials 0.000 claims description 3
- 238000009472 formulation Methods 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 27
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 19
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 15
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 14
- 239000003643 water by type Substances 0.000 description 14
- 239000002994 raw material Substances 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 9
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 229910052750 molybdenum Inorganic materials 0.000 description 8
- 239000011733 molybdenum Substances 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 6
- 239000010941 cobalt Substances 0.000 description 6
- 229910017052 cobalt Inorganic materials 0.000 description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 229910021538 borax Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 150000002823 nitrates Chemical class 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 239000004328 sodium tetraborate Substances 0.000 description 4
- 235000010339 sodium tetraborate Nutrition 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000001354 calcination Methods 0.000 description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical class [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- DKUYEPUUXLQPPX-UHFFFAOYSA-N dibismuth;molybdenum;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Mo].[Mo].[Bi+3].[Bi+3] DKUYEPUUXLQPPX-UHFFFAOYSA-N 0.000 description 3
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical class [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical class [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- CJJMLLCUQDSZIZ-UHFFFAOYSA-N oxobismuth Chemical class [Bi]=O CJJMLLCUQDSZIZ-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 235000010333 potassium nitrate Nutrition 0.000 description 3
- 239000004323 potassium nitrate Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 235000010344 sodium nitrate Nutrition 0.000 description 3
- 239000004317 sodium nitrate Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- -1 bismuth molybdate compound Chemical class 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- XOOMXAQWPPHHFX-UHFFFAOYSA-N 2-methylprop-2-enal;prop-1-ene Chemical compound CC=C.CC(=C)C=O XOOMXAQWPPHHFX-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 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
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- QVYYOKWPCQYKEY-UHFFFAOYSA-N [Fe].[Co] Chemical compound [Fe].[Co] QVYYOKWPCQYKEY-UHFFFAOYSA-N 0.000 description 1
- WUTHJWCAESRVMV-UHFFFAOYSA-N [W].[Bi] Chemical compound [W].[Bi] WUTHJWCAESRVMV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- YVBOZGOAVJZITM-UHFFFAOYSA-P ammonium phosphomolybdate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])=O.[O-][Mo]([O-])(=O)=O YVBOZGOAVJZITM-UHFFFAOYSA-P 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001622 bismuth compounds Chemical class 0.000 description 1
- YLSLSHTYFFBCKG-UHFFFAOYSA-N bismuth;oxomolybdenum Chemical compound [Mo].[Bi]=O YLSLSHTYFFBCKG-UHFFFAOYSA-N 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- NWJZFGOFYNPABH-UHFFFAOYSA-N prop-1-ene;prop-2-enenitrile Chemical compound CC=C.C=CC#N NWJZFGOFYNPABH-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002195 soluble material Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8876—Arsenic, antimony or bismuth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
- B01J27/192—Molybdenum with bismuth
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/24—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons
- C07C253/26—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons containing carbon-to-carbon multiple bonds, e.g. unsaturated aldehydes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
- C07C45/35—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in propene or isobutene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
- C07C51/252—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
在制造Mo-Bi-Na复合氧化物催化剂中,将作为各元素源的诸化合物在水体系中混合成复合物并将此复合物进行热处理,氧化铋和/或碱式碳酸铋被用作铋源化合物,并且至少有一部分热处理是在450—600℃温度范围内进行的。催化剂的活性将因铋以特定的水不溶性化合物形式引入催化剂而得到显著改进。
Description
众所周知,Mo-Bi复合氧化物催化剂对于选择反应是有用的,诸如从丙烯生产丙烯醛或从异丁烯或叔丁醇生产异丁烯醛的气相催化氧化反应;从丙烯生产丙烯腈或从异丁烯生产甲基丙烯腈的气相催化氨氧化反应和从丁烯生产丁二烯的气相催化氧化脱氢反应。大家也知道这些催化剂已广泛付诸工业范围的应用。
人们也知道发表了许多在不同反应及生产工艺中涉及钼-铋氧化物催化剂复合物的专利。这些发表的专利中的一部分如:
业经审查的日本专利说明书:3670/64,4763/73,3498/74,17253/73,1645/73,41232/80,14659/81,23969/81,52013/81和26245/82;
未经审查的日本专利说明书:503/73,514/73,52713/73,57916/73,54027/73,76541/84,47144/80,20610/80,84541/80和122041/85。
上述所有专利都与钼-铋复合氧化物催化剂有关。不过,除了未经审查的日本专利47144/80和76541/84以外(这两个专利透露,在复合氧化物催化剂生产过程中先生产钼-铋或钨-铋复合物),在实例中是使用硝酸铋作铋的原料,事实上,在其叙述中也介绍了水溶性铋化合物,即硝酸铋或其氢氧化物作铋的原料。
容易理解,当用一个含水体系作分散介质将元素作为复合氧化物催化剂的组分结合进复合物时,用水溶性化合物作为这些元素的化合物是最为普通的办法,这个在催化剂中均匀分散的方法,是熟悉该技术的人都会设想到。事实上,我们也已确证当用铁、钴、镍作复合氧化物的元素时,用这类水溶性原料的水溶液来使化合物均匀分散是有效的。
不过,在这种复合氧化物催化剂的场合,在高铋含量范围不宜使用硝酸铋。理由是,在使用硝酸铋的条件下,具有低铋含量的催化剂性能更优越。
在钼-铋复合氧化物催化剂中,从催化剂寿命的观点看,高铋含量是一个重要因素。因而上面提到的问题是重要的。
本发明旨在通过使用钼-铋复合氧化物催化剂的特定组成元素改进催化剂性能,即处于非均匀体系的铋,而不是上述的一般方法。
换言之,按照本发明,可以提供一种生产复合氧化物催化剂的工艺,钼-铋复合氧化物催化剂用下面化学式表示)用水体系的方法生产,包括将作为各元素源的化合物混合成复合物,并将此复合物进行热处理,其特点是氧化铋和/或碱式碳酸铋用作铋源,热处理在450-600℃进行:
MoaBibCocNidFeeNafXgYhSiiOj
式中:X代表K,Rb,Cs和/或Ti:Y代表B,P,As和/或W;a-j分别代表原子比率,且当a=12,b=2-7,c=0-10,d=0-10,c+d=1-10,e=0.05-3f=0-0.6,g=0.04-0.4,h=0-3,i=0-48j为满足其它元素氧化态的数值。
从组成元素均匀分散的观点看,非均匀体系中铋的使用是与那些在技术上有经验的人的一般观念相违背的。钼-铋复合氧化物催化剂的催化性能因运用这样的方法得到改进。
换言之,如上所述,高铋含量的催化剂有很长的寿命。因此,按照本发明的工艺,从具有前述性质的催化剂的反应性能这一点来说,可以说是有工业价值的,即活性和选择性得以显著改进,而没有上面提到的使用硝酸铋时所遇到的问题。另一方面,不用水溶性盐作原料的工艺对其它元素即铁钴和镍不显示任何影响,只对降低催化剂反应性能起作用。
根据本发明,这个影响取决于在热处理过程中复合氧化物固相中钼和铋进行热扩散并形成钼酸铋化合物,下面作进一步叙述。一种常规的使用铋的方法是,将硝酸铋溶于硝酸水溶液中,因此在使用大量铋的条件下,此体系必然含大量的硝酸根。当已加入的溶液蒸发至干时,就形成一种在PH值很低的强酸条件下处理过的络合物盐。可以认为,这种经过络合物盐形成过程的复合氧化物催化剂的功效是很低的。另一方面,根据本发明,钼和铋的氧化物经热扩散形成钼酸铋,而不经过络合物形成过程,从而有可能形成一种具有高功效的复合氧化物催化剂,并且据估计这样一种由热扩散技术生产的复合氧化物催化剂可能形成某种晶格缺陷。
主催化剂
除了作为铋源的化合物是特定的以外,本发明的钼-铋复合氧化物催化剂基本上与常规催化剂(例如,上面提到的已发表专利中叙述的那些催化剂)一样。
因此,本发明所述的钼-铋复合氧化物催化剂能用下面化学式表示。该化学式通常用来表示复合氧化物催化剂,但并不意味着必然存在一个用此式表示的单一化合物。
MoaBibCocNidFeeNafXgYhSiiOj
式中:X代表K,Rb,Cs和/或Ti;Y代表B,P,As和/或W;以下数值代表各元素的原子比率:
a:12,
b:2-7,
C:0-10,
d:0-10,
c+d:1-10,
e:0.05-3,
f:0-0.6,
g:0.04-0.4,
h:0-3
i:0-48,
j:其数值满足其它元素氧化度值。
催化剂的制造
除了考虑作为铋源的化合物的种类(以及具体应用)以外,这种催化剂的生产工艺基本上与常规的工艺相同。
钼-铋复合氧化物催化剂的生产工艺一般包括在一水相体系中,将作为各元素源的诸化合物混合成复合物,并将其加热。
“在一水相体系中,将作为各元素源的诸化合物混合成复合物”这句话的意思是,把各化合物的水溶液或水份分散体同时或分步地混合成复合物。“作为各元素源的诸化合物”不仅仅是含一种元素的各别化合物,而且也包括含有多种元素的化合物(例如磷钼酸铵就含钼和磷)“混合”这一词不仅指将作为各元素源的诸化合物混合成一个复合物,而且,如果必要的话,也包括混合载体物质如二氧化硅、氧化铝、二氧化硅一氧化铝、耐火氧化物或其它物质。
此外,“加热”的目的是,形成作为各元素源的单独氧化物和/或复合氧化物以及对最终生成的复合氧化物进行热处理。加热的对象主要是作为各元素源的诸化合物,但是这些化合物可以不是作为所有元素源的化合物的复合物。加热不一定限于仅仅一次。因而,用在本说明书中的“加热”这个词,也包括对作为各元素源的每个化合物进行加热这种情况,化合物的生成(如果必要的话复合氧化物的形成)是分步进行的。“包括混合和进行加热”这一用语意味着除这两种过程以外还可以进行合适的过程如干燥、研磨、成型等等。
按照本发明,作为铋源的化合物是水不溶性氧化铋和/或碱式碳酸铋。此化合物最好是粉末状的。作为生产催化剂的原料的化合物可以是比粉末大的颗粒,但是,为了在加热过程中利于热扩散,最好是较小的颗粒。因此,如果作为原料的这些化合物不是小颗粒的话,那么就应在热处理之前将其磨碎。按照本发明生产催化剂工艺的实例将在下面加以描述。上面提到的专利在技术方面现已为人所熟知,因而由特定实例推断得到的其它实例对技术上有经验的人们是容易理解的。
向钼化合物最好是钼酸铵的水溶液中加入铁、钴和镍(最好是它们的硝酸盐)的水溶液。进而,钠、钾、铷、铊、硼、磷、砷和/或钨的化合物(最好是它们的水溶性盐)以它们的水溶液形式加入。而且,必要的话,加入细粒状或胶体状二氧化硅。然后,加入粉末状氧化铋和/或碱式碳酸铋。充分搅拌由此所得的浆状物,接着进行干燥。将此粒状或块状的干燥产物在270-350℃温度范围内进行短时间热处理,以生成氧化物。
用X射线衍射方法和拉曼光谱分析发现,在经热处理所得的产物中,铁、钴和镍都已与酸性氧化物形成盐,而铋仍保留其原料的形式。由此得到的分解产物用挤出成型、压片成型、附载成型等等方法加工成所期望的形状。
接下来,将此产物在450-650℃温度条件下最后热处理1-16小时,得到催化剂。
据推测,本发明的一个重要方面是在最后的热处理过程中引起的反应。估计热处理过程,在热处理以前钴和镍已分别形成钼酸盐,其它的化合物也已形成分散的复合氧化物。然而,一部分钼(通常以形成上述化合物所需的过量钼加入)和铋还没有形成盐。而是分别形成氧化物和/或碳酸盐。可以认为,当复合氧化物在最后一步进行热处理时,钼和铋互相扩散,从而均匀地形成了钼酸铋相,它与主要含铁钴和镍的钼酸盐表面接触。在这种情况下认为铁、镍、和钴从不与钼酸铋相形成固态溶体。
最后一步中的热处理温度条件是十分重要的,因为在温度低于450℃时难以得到足够的扩散速度,而且,加热时间过长不利于均匀分散。
温度超过650℃也是不利的,一部分钼酸盐熔结,从而大幅度降低了催化剂的比表面。因此,较好的加热温度是在450-650℃之间。加热时间为1-10小时,此时的加热气氛是非还原性的,所以最好是在分子氧存在下尤其是在空气中进行热处理。
催化剂的使用
按本发明生产的复合氧化物催化剂能够用于各种在分子氧存在下进行的气相催化氧化反应。
本说明书提到的气相催化氧化反应的例子包括:从丙烯、异丁烯或叔丁醇生产丙烯醛或异丁烯醛的反应,在氨存在下从丙烯或异丁烯生产丙烯腈或甲基丙烯腈的反应,从丁烯生产丁二烯的反应,等等。
实例1
在加热的条件下,将94.1克仲钼酸铵溶入400毫升纯水中接着,在加热下,将7.18克硝酸铁和51.7克硝酸镍溶入60毫升纯水中。将这两种溶液在充分搅拌下互相缓慢地混合,然后,将0.85克硼砂溶入40毫升纯水中,并将此溶液加到上面制得的浆状物中。接下来,将33.4克粒状二氧化硅“CARPLEX”和51.7克氧化铋加入,将此混合物很好地搅拌,然后蒸发至干。将所得固体物在空气气氛下于300℃热处理一小时,形成氧化物。用小型模压机将此固体物压成直径5毫米、厚4毫米的圆片,然后在马弗炉中于500℃锻烧4小时,就得到催化剂。
由所装进的原料计算得的催化剂组成可用具有下述原子比率的复合氧化物催化剂来表示:
Mo∶Bi∶Fe∶Ni∶B∶Na∶Si=12∶5∶0.4∶4∶0.2∶0.1∶24
将40毫升这种催化剂装入内经为15毫米的不锈钢反应管中,通进由10%浓度的丙烯、17浓度的蒸汽和73%浓度的空气构成的原料气,接触时间为4.8秒,在大气压下进行丙烯氧化反应。
在反应温度290℃,在一实际的实验中得到下面的反应结果:
丙烯转化率:95.4%
丙烯醛产率:80.8%
丙烯酸产率:7.8%
总产率:88.6%
比较实例1
与实例1的组分相同的催化剂按实例1的条件制造,只不过实例1中用作铋的原料的氧化铋用一种水溶液代替,这种水溶液的配制是:将108克硝酸铋溶于已加入了12毫升硝酸的98毫升纯水中中。
使用这种催化剂在与实例1相同的反应的条件下进行丙烯的氧化反应,反应温度为290℃时所得结果如下:
丙烯转化率:82.6%
丙烯醛产率:66.2%
丙烯酸产率:6.9%
总产率:73.1%
实例2
在加热下,将94.1克仲钼酸铵溶入400毫升纯水中。接着在加热下,将7.18克硝酸铁、25.8克硝酸钴和38.7克硝酸镍溶入60毫升纯水中。在充分搅拌下将这两种溶液缓慢地混合。
在40毫升纯水中溶入0.85克硼砂、0.38克硝酸钠和0.36克硝酸钾,将此溶液加热下加入上述混合溶液(浆状物),将混合物充分搅拌。然后,将57.8克碱式碳酸铋和64克二氧化硅加到此混合物中,并搅拌混合。接着,在热干燥此浆状物后,在空气气氛下于300℃热处理1小时。用小型模压机将所得固体物压成直径5毫米、厚4毫米的片,然后在马弗炉中于480℃锻烧8小时,得到催化剂。
由所填加的原料计算得的催化剂的金属成分的组成比率,可用具有下面原子比率的复合氧化物表示:
Mo∶Bi∶Co∶Ni∶Fe∶Na∶B∶K∶Si=12∶5∶2∶3∶0.4∶0.2∶0.2∶0.08∶24
在一实际的实验中使用这种催化剂,在与实例1相同的反应器中,通进由12%浓度的丙烯、10%浓度的蒸汽和78%浓度的空气构成的原料气,在常压下进行丙烯的氧化反应,接触时间为4.2秒。
在反应温度290℃时,得到下面的反应结果:
丙烯转化率:98.5%
丙烯醛产率:89.7%
丙烯酸产率:5.1%
总产率:94.8%
比较实例2
与实例2有相同组成的催化剂按实例2的条件制造,只不过是用一种水溶液代替了实例2中用作铋的原料的氧化铋,这种水溶液的配制是:将108克硝酸铋溶于已加入了12毫升硝酸的98毫升纯水中。
使用这种催化剂,在与实例2相同条件下进行丙烯的氧化反应。反应温度为290℃时所得结果如下:
丙烯转化率:97.2%
丙烯醛产率:88.0%
丙烯酸产率:4.1%
总产率:92.1%
实例3
在加热下,将94.1克仲钼酸铵溶入400毫升纯水中。接着加入5.8克仲钨酸铵,并搅拌此混合液。
然后,将17.9克硝酸铁、51.7克硝酸钴、0.38克硝酸钠、0.85克硼砂和0.27克硝酸钾溶入100毫升纯水中。在充分搅拌下,将这两种溶液缓慢地互相混合。然后,向此混合液加入62.0克氧化铋和64.0克二氧化硅,并搅拌混合此混合物,在一实际的实施例中,催化剂按与实例1相同的操作进行制造。
由所填加的原料计算所得催化剂的组成可用具有以下原子比的金属成分的复合氧化物表示:
Mo∶Bi∶Fe∶Co∶W∶B∶Na∶K∶Si=12∶6∶1∶4∶0.5∶0.2∶0.2∶0.06∶24
使用这种催化剂,丙烯的氧化反应以与实例2同样的方法进行。
290℃反应温度下所得结果如下:
丙烯转化率:98.0%
丙烯醛产率:88.9%
丙烯酸产率:4.8%
总产率:93.7%
实例4
在加热下,将94.1克仲钼酸铵溶入400毫升纯水中。接着,在加热下,将7.18克硝酸铁、25.8克硝酸钴和38.7克硝酸镍溶入60毫升纯水中。在充分搅拌下将这两种溶液缓慢地互相混合。
在加热下,向此混合液(浆状物)加入下述溶液,此溶液是在40毫升纯水中溶入0.85克硼砂、0.38克硝酸钠和0.36克硝酸钾,并充分搅拌此混合物。然后,将51.7克氧化铋和64克二氧化硅加到混合物中,并搅拌混合。接着,在热干燥此浆状物后,在空气气氛中于300℃热处理一小时。用小型模压机将所得固体物压成直径5毫米、厚4毫米的圆片,然后在马弗炉中于500℃锻烧4小时,得到催化剂。由所填加的原料计算得的催化剂的金属成分的组成比率可用具有下述原子比率的复合氧化物表示:
Mo∶Bi∶Co∶Ni∶Fe∶Na∶B∶K∶Si=12∶5∶2∶3∶0.4∶0.2∶0.2∶0.08∶24
在一实际的实施例中使用这种催化剂,在与实例1相同的反应器中,通过由4.3%的丙烯、10.1%的氨、34.2%的蒸汽和51.9的空气构成的原料气,在大气压下,进行丙烯的氨氧化反应,接触时间为2.9秒。
在反应温度为330℃时,所得的反应结果如下:
丙烯转化率:58.3%
丙烯腈产率:48.7%
丙烯腈选择性:83.5%
比较实例3
与实例4的组分相同的催化剂按实例4的条件制造,只不过是用一种水溶液代替了实例4中用作铋的原料的氧化铋。这种水溶液的配制是:将108克硝酸铋溶于已加入了12毫升硝酸的98毫升纯水中。
使用这种催化剂,在与实例4相同的条件下进行丙烯氨氧化反应,所得结果如下:
丙烯转化率:47.7%
丙烯腈产率:40.8%
丙烯腈选择性:85.7%
Claims (5)
1、一种生产复合氧化物催化剂的方法,在该方法中,用下面化学式表示的钼-铋复合氧化物催化剂通过包括将作为各元素源的诸化合物混合成复合物并将此复合物进行热处理来生产,该方法的特征是,用氧化铋和/或碱式碳酸铋作铋源,热处理在450-600℃下进行:
MoaBibCocNidFeeNafXgYhSiiOj
式中:X代表K,Rb,Cs和/或Ti;Y代表B,P,As和/或W;a-j分别代表原子比率。且a=12,b=2-7,c=0-10,d=0-10,c+d=1-10,e=0.05-3,f=0-0.6,g=0.04-0.4,h=0-3,i=0-48和j为满足其它元素氧化态的数值。
2、根据权利要求1的方法,其中氧化铋和/或碱式碳酸铋是以粉末状使用。
3、根据权利要求1的方法,在于450-600℃温度进行热处理之前,该复合物在空气中加热,并且作为各元素源的诸化合物至少有较大的部分被分解成复合氧化物。
4、根据权利要求3的方法,在450-600℃温度范围内进行热处理的复合氧化物是处于催化剂所要求的形状。
5、根据权利要求1的方法,450-600℃温度范围内的热处理是在非还原性气氛中进行。
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JP61065279A JPS62234548A (ja) | 1986-03-24 | 1986-03-24 | 複合酸化物触媒の製造法 |
JP65279/86 | 1986-03-24 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN87102247A true CN87102247A (zh) | 1987-12-02 |
CN1009339B CN1009339B (zh) | 1990-08-29 |
Family
ID=13282328
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN87102247A Expired CN1009339B (zh) | 1986-03-24 | 1987-03-24 | 含钼-铋的复合氧化物催化剂的制备方法 |
Country Status (7)
Country | Link |
---|---|
US (1) | US4803190A (zh) |
EP (1) | EP0239070B2 (zh) |
JP (1) | JPS62234548A (zh) |
CN (1) | CN1009339B (zh) |
CS (1) | CS273633B2 (zh) |
DE (1) | DE3770668D1 (zh) |
SU (1) | SU1598858A3 (zh) |
Cited By (4)
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CN1042200C (zh) * | 1993-04-03 | 1999-02-24 | 中国石油化工总公司 | 一种用于烯烃选择氧化的钼铋催化剂 |
CN100354042C (zh) * | 2001-11-08 | 2007-12-12 | 三菱化学株式会社 | 复合氧化物催化剂及其制备方法 |
CN103157483A (zh) * | 2011-12-13 | 2013-06-19 | 上海华谊丙烯酸有限公司 | 复合氧化物催化剂及其制造方法 |
CN107405610A (zh) * | 2015-03-03 | 2017-11-28 | 日本化药株式会社 | 共轭二烯烃制造用催化剂及其制造方法 |
Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4220859A1 (de) * | 1992-06-25 | 1994-01-05 | Basf Ag | Multimetalloxidmassen |
CN1108865C (zh) * | 1997-09-03 | 2003-05-21 | 中国石油化工集团公司 | 生产丙烯腈的催化剂 |
JP4185217B2 (ja) | 1999-05-25 | 2008-11-26 | 株式会社日本触媒 | 複合酸化物触媒、並びに(メタ)アクロレインおよび(メタ)アクリル酸の製造方法 |
US7851397B2 (en) * | 2005-07-25 | 2010-12-14 | Saudi Basic Industries Corporation | Catalyst for methacrolein oxidation and method for making and using same |
US7649112B2 (en) | 2005-07-25 | 2010-01-19 | Saudi Basic Industries Corporation | Integrated plant for producing 2-ethyl-hexanol and methacrylic acid and a method based thereon |
US7732367B2 (en) * | 2005-07-25 | 2010-06-08 | Saudi Basic Industries Corporation | Catalyst for methacrolein oxidation and method for making and using same |
US7649111B2 (en) * | 2005-07-25 | 2010-01-19 | Saudi Basic Industries Corporation | Catalyst for the oxidation of a mixed aldehyde feedstock to methacrylic acid and methods for making and using same |
US7799946B2 (en) * | 2007-02-14 | 2010-09-21 | Saudi Basic Industries Corporation | Process for separating methacrolein from methacrylic acid in a gas phase product from the partial oxidation of isobutene |
JP5199044B2 (ja) * | 2008-12-01 | 2013-05-15 | 三菱レイヨン株式会社 | メタクロレイン及びメタクリル酸製造用触媒の調製方法 |
CN102560656B (zh) * | 2010-12-22 | 2015-10-28 | 中国科学院大连化学物理研究所 | 微米级花状复合金属碱式碳酸盐的制备方法 |
RU2590522C2 (ru) * | 2011-02-18 | 2016-07-10 | Асахи Касеи Кемикалз Корпорейшн | Устройство для обжига, способ изготовления оксидного катализатора и способ получения ненасыщенной кислоты или ненасыщенного нитрила |
US9433929B2 (en) * | 2011-09-21 | 2016-09-06 | Ineos Europe Ag | Mixed metal oxide catalysts |
US8921257B2 (en) | 2011-12-02 | 2014-12-30 | Saudi Basic Industries Corporation | Dual function partial oxidation catalyst for propane to acrylic acid conversion |
US8722940B2 (en) | 2012-03-01 | 2014-05-13 | Saudi Basic Industries Corporation | High molybdenum mixed metal oxide catalysts for the production of unsaturated aldehydes from olefins |
US8835666B2 (en) * | 2012-11-26 | 2014-09-16 | Ineos Usa Llc | Pre calcination additives for mixed metal oxide ammoxidation catalysts |
JP6229201B2 (ja) * | 2013-03-13 | 2017-11-15 | 三菱ケミカル株式会社 | 複合金属酸化物触媒及び共役ジエンの製造方法 |
CN117181254B (zh) * | 2022-08-30 | 2024-04-12 | 海南华盛水泥投资有限公司 | 铋基催化剂的制备方法及铋基催化剂和应用 |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3173957A (en) * | 1961-08-21 | 1965-03-16 | Eastman Kodak Co | Process for the preparation of acrolein |
US3497461A (en) * | 1968-02-02 | 1970-02-24 | Du Pont | Bismuth molybdate on silica catalysts |
US3806470A (en) * | 1970-09-24 | 1974-04-23 | Du Pont | Catalyst compositions of scheelite crystal structure containing bismuth ions and cation vacancies |
CA975382A (en) * | 1971-02-04 | 1975-09-30 | Arthur F. Miller | Process for the manufacture of acrylonitrile and methacrylonitrile |
US3951861A (en) * | 1971-06-14 | 1976-04-20 | Sumitomo Chemical Company, Limited | Catalysts for the preparation of acrolein |
JPS55113730A (en) * | 1979-02-26 | 1980-09-02 | Mitsubishi Petrochem Co Ltd | Preparation of acrolein and acrylic acid |
JPS58113163A (ja) * | 1981-12-28 | 1983-07-05 | Ube Ind Ltd | 不飽和ニトリルの製造方法 |
US4409127A (en) * | 1981-12-30 | 1983-10-11 | Monsanto Company | Attrition resistant metal/oxygen compositions and a process for their preparation |
US4537874A (en) * | 1982-10-22 | 1985-08-27 | Nippon Shokubai Kagaku Kogyo Co Ltd | Catalyst for production of unsaturated aldehydes |
-
1986
- 1986-03-24 JP JP61065279A patent/JPS62234548A/ja active Granted
-
1987
- 1987-03-23 SU SU874202240A patent/SU1598858A3/ru active
- 1987-03-24 CS CS198487A patent/CS273633B2/cs not_active IP Right Cessation
- 1987-03-24 CN CN87102247A patent/CN1009339B/zh not_active Expired
- 1987-03-24 DE DE8787104302T patent/DE3770668D1/de not_active Expired - Lifetime
- 1987-03-24 EP EP87104302A patent/EP0239070B2/en not_active Expired - Lifetime
- 1987-03-24 US US07/029,645 patent/US4803190A/en not_active Expired - Lifetime
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1042200C (zh) * | 1993-04-03 | 1999-02-24 | 中国石油化工总公司 | 一种用于烯烃选择氧化的钼铋催化剂 |
CN100354042C (zh) * | 2001-11-08 | 2007-12-12 | 三菱化学株式会社 | 复合氧化物催化剂及其制备方法 |
US7579501B2 (en) | 2001-11-08 | 2009-08-25 | Mitsubishi Chemical Corporation | Composite oxide catalyst and method of producing the same |
US7632777B2 (en) | 2001-11-08 | 2009-12-15 | Mitsubishi Chemical Corporation | Composite oxide catalyst and method for preparation thereof |
CN103157483A (zh) * | 2011-12-13 | 2013-06-19 | 上海华谊丙烯酸有限公司 | 复合氧化物催化剂及其制造方法 |
CN107405610A (zh) * | 2015-03-03 | 2017-11-28 | 日本化药株式会社 | 共轭二烯烃制造用催化剂及其制造方法 |
Also Published As
Publication number | Publication date |
---|---|
EP0239070B2 (en) | 2002-02-20 |
CS273633B2 (en) | 1991-03-12 |
EP0239070A2 (en) | 1987-09-30 |
DE3770668D1 (de) | 1991-07-18 |
EP0239070B1 (en) | 1991-06-12 |
US4803190A (en) | 1989-02-07 |
JPH0587299B2 (zh) | 1993-12-16 |
SU1598858A3 (ru) | 1990-10-07 |
JPS62234548A (ja) | 1987-10-14 |
EP0239070A3 (en) | 1987-11-19 |
CN1009339B (zh) | 1990-08-29 |
CS198487A2 (en) | 1990-08-14 |
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