WO2005053844A1 - 不飽和アルデヒド及び不飽和カルボン酸の製造用触媒の製造方法 - Google Patents
不飽和アルデヒド及び不飽和カルボン酸の製造用触媒の製造方法 Download PDFInfo
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- WO2005053844A1 WO2005053844A1 PCT/JP2004/013459 JP2004013459W WO2005053844A1 WO 2005053844 A1 WO2005053844 A1 WO 2005053844A1 JP 2004013459 W JP2004013459 W JP 2004013459W WO 2005053844 A1 WO2005053844 A1 WO 2005053844A1
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- Prior art keywords
- catalyst
- producing
- unsaturated carboxylic
- unsaturated
- carboxylic acid
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 88
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims description 23
- 150000001732 carboxylic acid derivatives Chemical class 0.000 title abstract 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title abstract 3
- 239000007789 gas Substances 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002002 slurry Substances 0.000 claims abstract description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000001336 alkenes Chemical class 0.000 claims abstract description 14
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 14
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 13
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910001882 dioxygen Inorganic materials 0.000 claims abstract description 13
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims abstract description 12
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 8
- 239000011733 molybdenum Substances 0.000 claims abstract description 8
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 7
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- 150000001299 aldehydes Chemical class 0.000 claims description 24
- 150000001735 carboxylic acids Chemical class 0.000 claims description 24
- 238000007254 oxidation reaction Methods 0.000 claims description 18
- 230000003647 oxidation Effects 0.000 claims description 15
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 15
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 15
- 230000003197 catalytic effect Effects 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 10
- 239000002131 composite material Substances 0.000 claims description 9
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- 229910052785 arsenic Inorganic materials 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910052725 zinc 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 1
- 238000001035 drying Methods 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 3
- 239000004615 ingredient Substances 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000012808 vapor phase Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 13
- 238000000465 moulding Methods 0.000 description 9
- 150000002894 organic compounds Chemical class 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 238000010304 firing Methods 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000002245 particle Substances 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
- 238000003756 stirring Methods 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 235000010980 cellulose Nutrition 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 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 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 238000004064 recycling 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
- 238000005245 sintering Methods 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—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
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0045—Drying a slurry, e.g. spray drying
-
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
-
- 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
- B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
Definitions
- the present invention relates to a method for producing a catalyst for producing unsaturated aldehydes and unsaturated carboxylic acids.
- the present invention provides a method for producing the corresponding unsaturated aldehyde and unsaturated carboxylic acid by gas-phase catalytic oxidation of olefin, tertiary butyl alcohol, or methyl tertiary butyl ether with a molecular oxygen-containing gas.
- the present invention relates to a method for producing a catalyst which has high mechanical strength, is stable over a long period of time, and can produce the corresponding unsaturated aldehyde and unsaturated carboxylic acid in high yield.
- Patent Literature 1 Patent Literature 2, Patent Literature 3, and the like are known as such examples.
- This method has the advantage that the pore size of the catalyst can be changed relatively freely by adding an organic compound having a different type or particle size during the production of the catalyst and removing the used organic compound by heat treatment.
- this method when the organic compound is removed, sintering of the catalyst by combustion of the organic compound and reduction of the catalyst by the organic compound occur, so that the activation treatment is complicated and the catalyst performance is reduced. There is a problem of lack of reproducibility of.
- Patent Document 4 discloses that activated carbon is used during the production of the catalyst. That is, a mixture of the above-mentioned catalyst components is calcined, the obtained calcined product is mixed with activated carbon having a predetermined particle size, shaped, and heat-treated. However, also in this case, there is room for further improvement in the yield of the desired unsaturated aldehyde and unsaturated carboxylic acid.
- Patent Document 1 Japanese Patent Application Laid-Open No. 58-98143
- Patent Document 2 Japanese Patent Publication No. 3-109946
- Patent Document 3 Japanese Patent No. 3278246
- Patent Document 4 Patent No. 3251641
- an object of the present invention is to respond to each of olefin, tertiary butyl alcohol, or methyl tertiary butyl ether by gas phase contact oxidation with a molecular oxygen-containing gas.
- Another object of the present invention is to provide a method for producing a catalyst which can produce unsaturated aldehydes and unsaturated carboxylic acids in a high yield with good reproducibility and has high mechanical strength and high durability.
- the present inventors have conducted intensive studies to solve the above-mentioned problems, and found that a composite oxide catalyst containing at least molybdenum, bismuth, and iron for producing unsaturated aldehydes and unsaturated carboxylic acids.
- a composite oxide catalyst containing at least molybdenum, bismuth, and iron for producing unsaturated aldehydes and unsaturated carboxylic acids.
- the amount of water contained in a mixed solution containing a catalyst component or a dried product of a slurry thereof is 0.3 to 4% by weight. %.
- the desired unsaturated aldehyde and unsaturated carboxylic acid can be produced with high yield and reproducibility, and a molded catalyst having high mechanical strength and stability can be obtained.
- the moisture content of the above dried product is less than 0.3% by weight, the molding pressure required to obtain good properties increases, and catalyst molding with stable properties is performed. I can't get my body.
- the characteristics of the catalyst are changed by the calcination step following the molding, and a molded catalyst having stable characteristics cannot be obtained.
- the present invention is characterized by the following constitution.
- a method for producing a composite oxide catalyst containing at least molybdenum, bismuth, and iron comprising drying a mixed solution or an aqueous slurry containing the above-mentioned catalyst components to obtain a dried product having a water content of 0.3-4.
- a method for producing a catalyst for producing unsaturated aldehydes and unsaturated carboxylic acids wherein the catalyst is adjusted to a weight percent and tablet-molded to form a molded product.
- the molded body has an outer diameter of 3-10 mm, an inner diameter of 0.1-0.7 times the outer diameter, a length of 0.5-12 times the outer diameter, and is open in the length direction.
- X is at least one element selected from the group consisting of Na, K, Rb, Cs, and T1
- Y is at least one element selected from the group consisting of B, P, As, and W
- Z is at least one element selected from the group consisting of Mg, Ca, Zn, Ce and Sm
- Q is halogen
- a to k represent the atomic ratio of each element.
- the mixed solution containing the catalyst component or the slurry thereof is dried and molded.
- a new idea based on a new concept of controlling the amount of moisture contained in the dried product to a specific range and compressing it into tablets has a high mechanical strength, is stable for a long time, and has a high yield.
- the present invention provides a catalyst capable of producing the corresponding unsaturated aldehyde and unsaturated carboxylic acid by gas-phase catalytic oxidation of olefin, olefin, tertiary butyl alcohol, or methyl tertiary butyl ether with a molecular oxygen-containing gas.
- the catalyst produced in the present invention is obtained by subjecting olefin, tertiary butyl alcohol, or methyl tertiary butyl ether to gas-phase catalytic oxidation with a molecular oxygen-containing gas in the gas-phase catalytic oxidation, respectively.
- a catalyst for producing an acid which is a composite oxide catalyst containing at least molybdenum, bismuth, and iron.
- the present invention can be applied to any catalyst as long as it is a composite oxide catalyst containing such three components. Among them, a catalyst represented by the following formula (1) is particularly preferable.
- Mo molybdenum
- Bi bismuth
- Co cobalt
- Ni nickel
- Fe iron
- Si silicon
- O oxygen
- X, Y, Z, Q, a—k, and k are as defined above.
- the starting compound containing each elemental component of the catalyst is appropriately dissolved or dispersed in an aqueous medium in a required amount according to the composition of the catalyst to be produced, whereby the catalyst is prepared.
- a mixed solution containing the components or an aqueous slurry thereof is produced.
- a nitrate, an ammonium salt, a hydroxide, an oxide, a sulfate, a carbonate, a halide, an acetate, or the like containing each element is used.
- molybdenum ammonium paramolybdate, molybdenum trioxide, molybdenum chloride and the like are used.
- a non-aqueous solvent such as alcohol can be added to the aqueous medium as needed to adjust the viscosity.
- the mixed solution or the aqueous slurry containing the catalyst component is preferably sufficiently stirred and mixed in order to prevent uneven distribution of each component.
- the mixed solution or the aqueous slurry containing the catalyst component is dried, and the drying can be performed by various methods.
- a powdery dried product may be obtained using a usual spray dryer, slurry dryer, drum dryer or the like, but drying with a spray dryer is particularly preferred.
- the water content of the dried product is 0%. 3-4% by weight.
- the moisture content of the dried product is defined as in equation (2).
- W1 is the weight when the dried product is evaporated to dryness at 150 ° C for 10 hours
- W2 is the weight of the dried product.
- Water content (W2-WD / W1 ⁇ 100 )
- a mixed solution or an aqueous slurry containing a catalyst component is used as a method of controlling the water content of the dried product subjected to molding to the above range.
- the drying may be performed under controlled conditions, or may be performed by subjecting the manufactured dried product to appropriate humidification by, for example, spraying moisture. It is necessary to control the moisture content of the dried product within the above range, and in the present invention, the moisture content of the dried product is preferably 0.4 to 3% by weight.
- the shape of the molded product may be any of a spherical shape, a cylindrical shape, a ring shape, and the like, and various sizes can be appropriately selected.
- the molded body is ring-shaped, the outer diameter is 3 to 10 mm, the inner diameter is 0.1 to 0.7 times the outer diameter, and the length (height) is 0.1 mm of the outer diameter. It is 5-2 times, and is open in the length (height) direction, and a round shape is preferable because of a point force such as a small pressure loss.
- inorganic fibers such as glass fibers and various whiskers may be used in order to improve the mechanical strength and the degree of powdering of the molded product.
- additives commonly known as a binder such as ammonium nitrate, cellulose, starch, polyvinyl alcohol, and stearic acid can be used.
- the dried molded article containing the catalyst component obtained as described above is subsequently calcined.
- the calcination is carried out in the presence of an oxygen-containing gas, preferably at 400 to 650 ° C, particularly preferably at 450 to 600 ° C, preferably for 1 to 15 hours, particularly preferably for 3 to 12 hours.
- an atmosphere firing furnace can be used.
- the atmosphere firing furnace for example, a method in which a fixed bed reactor is filled with a catalyst and heated externally under the flow of an atmosphere gas, a method in which the fixed bed reactor is of a heat exchange type, an atmosphere gas inside a Matsufuru furnace is used.
- a method of circulating the gas, a method of circulating the atmosphere gas inside the tunnel furnace, a method of circulating the atmosphere gas inside the kiln furnace, and the like can be used.
- a fixed bed reactor is filled with a catalyst and heated externally under the flow of atmosphere gas, and more preferably, the catalyst is placed in a heat exchange fixed bed reactor. And heating from the outside while the atmosphere gas is flowing.
- the atmospheric gas besides air, a mixed gas of air and an inert gas such as nitrogen can be used. Air can be preferably used because it is economically advantageous.
- olefin, tertiary butyl alcohol, or methyl tertiary butyl ether is subjected to gas-phase catalytic oxidation with a molecular oxygen-containing gas, and the corresponding unsaturated aldehyde and
- the method for producing an unsaturated carboxylic acid can be carried out by an existing method.
- the reaction is performed using a fixed-bed tube reactor.
- the reaction can be carried out by a simple flow method or a recycling method through the reactor. Under the conditions generally used for the reaction of
- a mixed gas such as propylene (11-15% by volume), molecular oxygen (3 to 30% by volume), steam (0 to 60% by volume), and an inert gas such as nitrogen and carbon dioxide (20 to 80% by volume) is used.
- the catalyst is introduced into the catalyst layer filled in each reaction tube having an inner diameter of preferably 15 to 50 mm at 250 to 450 ° C. under a pressure of 0.1 to 1 MPa and a space velocity (SV) of 300 to 5000 hr- 1 .
- SV space velocity
- Pure water was added to the obtained granular solid and wet-pulverized, and the obtained slurry was dried with a spray drier at an inlet temperature of 300 ° C and an outlet temperature of 125 ° C.
- the water content of the obtained dried product was measured and found to be 1.5% by weight.
- the tablet molded product was placed in a firing container, and fired at 510 ° C. for 4 hours while flowing a small amount of air to produce a composite oxide catalyst.
- the catalyst calculated from the charged raw materials is a composite oxide having the following atomic ratio.
- Mo: Bi: Co: Ni: Fe: Na: B: K: Si 12: l: 4: 2: l: 0.1: 0.2: 0.1: 15
- the drop strength of this catalyst was measured, it was 98.5%. there were.
- a catalyst was prepared in the same manner as in Example 1 except that the outlet temperature of the spray dryer was set at 160 ° C. The water content of the dried product was 0.2% by weight. The measured drop strength of the catalyst was 90.1%.
- a catalyst was prepared in the same manner as in Example 1 except that the outlet temperature of the spray dryer was set at 95 ° C.
- the water content of the obtained dried product was 5.0% by weight.
- the measured drop strength of the catalyst was 91.5%.
- the catalyst produced by the method of the present invention is obtained by subjecting olefin, tertiary butyl alcohol, or methyl tertiary butyl ether to gas-phase catalytic oxidation with a molecular oxygen-containing gas to obtain the corresponding unsaturated aldehyde and Used to produce unsaturated carboxylic acids.
- the unsaturated aldehydes and unsaturated carboxylic acids produced are widely used as raw materials for various chemicals, monomers for general-purpose resins, monomers for functional resins such as water-absorbing resins, flocculants, and thickeners. Used for applications.
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US11/033,131 US7279442B2 (en) | 2003-12-04 | 2005-01-12 | Process for producing catalyst for production of unsaturated aldehyde and unsaturated carboxylic acid |
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JPH06321536A (ja) * | 1993-03-09 | 1994-11-22 | Basf Ag | 複合金属酸化物組成物 |
JP2000169149A (ja) * | 1998-12-03 | 2000-06-20 | Basf Ag | 複合金属酸化物材料、その製造方法、それの使用方法、それを含有する触媒および触媒の使用方法 |
JP2000237592A (ja) * | 1999-02-19 | 2000-09-05 | Mitsubishi Rayon Co Ltd | メタクロレインおよびメタクリル酸合成用触媒およびメタクロレインおよびメタクリル酸の製造方法 |
JP2003251183A (ja) * | 2002-02-28 | 2003-09-09 | Nippon Shokubai Co Ltd | 不飽和アルデヒド合成用触媒とその製造方法、およびその触媒を用いた不飽和アルデヒドの製造方法 |
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JPS5898143A (ja) | 1981-12-07 | 1983-06-10 | Ube Ind Ltd | オレフイン酸化用触媒の製法 |
DE3930533C1 (ja) | 1989-09-13 | 1991-05-08 | Degussa Ag, 6000 Frankfurt, De | |
JP3251641B2 (ja) | 1992-06-19 | 2002-01-28 | 三菱レイヨン株式会社 | 不飽和アルデヒド及び不飽和カルボン酸製造用触媒の製造法 |
JP3278246B2 (ja) | 1993-06-30 | 2002-04-30 | 三菱レイヨン株式会社 | 不飽和アルデヒド及び不飽和カルボン酸合成用触媒の製造法 |
US6960684B2 (en) * | 2002-03-29 | 2005-11-01 | Nippon Shokubai Co., Ltd. | Production process for unsaturated aldehyde |
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2004
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- 2004-09-15 WO PCT/JP2004/013459 patent/WO2005053844A1/ja active Application Filing
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Publication number | Priority date | Publication date | Assignee | Title |
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JPH06321536A (ja) * | 1993-03-09 | 1994-11-22 | Basf Ag | 複合金属酸化物組成物 |
JP2000169149A (ja) * | 1998-12-03 | 2000-06-20 | Basf Ag | 複合金属酸化物材料、その製造方法、それの使用方法、それを含有する触媒および触媒の使用方法 |
JP2000237592A (ja) * | 1999-02-19 | 2000-09-05 | Mitsubishi Rayon Co Ltd | メタクロレインおよびメタクリル酸合成用触媒およびメタクロレインおよびメタクリル酸の製造方法 |
JP2003251183A (ja) * | 2002-02-28 | 2003-09-09 | Nippon Shokubai Co Ltd | 不飽和アルデヒド合成用触媒とその製造方法、およびその触媒を用いた不飽和アルデヒドの製造方法 |
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US20050165253A1 (en) | 2005-07-28 |
US7279442B2 (en) | 2007-10-09 |
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