GB2040717A - Catalyst and process for producing methacrylic acid - Google Patents
Catalyst and process for producing methacrylic acid Download PDFInfo
- Publication number
- GB2040717A GB2040717A GB7944392A GB7944392A GB2040717A GB 2040717 A GB2040717 A GB 2040717A GB 7944392 A GB7944392 A GB 7944392A GB 7944392 A GB7944392 A GB 7944392A GB 2040717 A GB2040717 A GB 2040717A
- Authority
- GB
- United Kingdom
- Prior art keywords
- catalyst
- methacrylic acid
- catalysts
- methacrolein
- phosphorus
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000003054 catalyst Substances 0.000 title claims abstract description 135
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims description 23
- 239000000203 mixture Substances 0.000 claims abstract description 44
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 26
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 19
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 15
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 15
- 230000003647 oxidation Effects 0.000 claims abstract description 14
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 12
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 12
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 12
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 9
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 7
- 229910052802 copper Inorganic materials 0.000 claims abstract description 7
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 7
- 229910052701 rubidium Inorganic materials 0.000 claims abstract description 7
- 229910052788 barium Inorganic materials 0.000 claims abstract description 6
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 6
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 6
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 6
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 6
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 6
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 6
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 6
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 6
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 6
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 6
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 6
- 239000012808 vapor phase Substances 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 5
- 229910001882 dioxygen Inorganic materials 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 25
- 239000011574 phosphorus Substances 0.000 abstract description 25
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 abstract description 14
- 239000011733 molybdenum Substances 0.000 abstract description 14
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 abstract description 10
- 239000011575 calcium Substances 0.000 abstract description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 6
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 abstract description 6
- 239000010949 copper Substances 0.000 abstract description 6
- 150000001299 aldehydes Chemical class 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 description 16
- 230000000694 effects Effects 0.000 description 16
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 238000004364 calculation method Methods 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000007429 general method Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 6
- 239000010937 tungsten Substances 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 3
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Inorganic materials [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- ZUQOBHTUMCEQBG-UHFFFAOYSA-N 4-amino-5-hydroxynaphthalene-1,7-disulfonic acid Chemical compound OS(=O)(=O)C1=CC(O)=C2C(N)=CC=C(S(O)(=O)=O)C2=C1 ZUQOBHTUMCEQBG-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000011363 dried mixture Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- -1 steam Chemical compound 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- QSHYGLAZPRJAEZ-UHFFFAOYSA-N 4-(chloromethyl)-2-(2-methylphenyl)-1,3-thiazole Chemical compound CC1=CC=CC=C1C1=NC(CCl)=CS1 QSHYGLAZPRJAEZ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 101100012019 Mus musculus Etv4 gene Proteins 0.000 description 1
- 229910017974 NH40H Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910019571 Re2O7 Inorganic materials 0.000 description 1
- ACWQBUSCFPJUPN-UHFFFAOYSA-N Tiglaldehyde Natural products CC=C(C)C=O ACWQBUSCFPJUPN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Inorganic materials [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- ACWQBUSCFPJUPN-HWKANZROSA-N trans-2-methyl-2-butenal Chemical compound C\C=C(/C)C=O ACWQBUSCFPJUPN-HWKANZROSA-N 0.000 description 1
Classifications
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- 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
- B01J23/8878—Chromium
-
- 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
- B01J23/885—Molybdenum and copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8871—Rare earth metals or actinides
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- 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
- B01J23/8872—Alkali or alkaline earth metals
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- 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
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- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8993—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with chromium, molybdenum or tungsten
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- 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
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- 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
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- 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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- 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)
Abstract
A catalyst composition useful for the oxidation of unsaturated aldehydes, particularly the oxidation of methacrolein to produce methacrylic acid, comprises the combination of oxides of molybdenum, copper, phosphorus, antimony, and cesium and/or calcium and optionally may include one or more of the elements Ni, Zn, Ru, Rh, Pd, Pt, As, K, Rb, Sr, Ba, Cr, V, Nb, W, Mn, Re, and rare earth metals including La.
Description
SPECIFICATION
Catalyst and process for producing methacrylic acid
This invention relates to a process and catalyst for the vapor-phase oxidation with molecular oxygen of methacrolein to methacrylic acid.
It is well known that unsaturated acids, such as acrylic acid and methacrylic acid, can be produced by the vapor-phase oxidation of the corresponding unsaturated aldehydes by means of molecular oxygen in the presence of a suitable oxidation catalyst. A variety of catalyst compositions have been proposed for this purpose. Many such compositions comprise the oxides of molybdenum and phosphorus in association with the oxides of various other elements, both metallic and non-metallic.
The prior art catalysts generally are found to require elements not included in the catalysts of the present invention or some of the essential elements of the present catalysts are lacking in prior art catalysts.
It has been found that catalysts for oxidation of methacrolein to methacrylic acid have the characteristic property of remaining stable for a period of time and then, without warning, of beginning a rapid decline in activity. Consequently, an increase in the useful activity of such catalysts has been sought.
Despite the many disclosures of the prior art, an improved catalyst of this type is not developed merely by randomly selecting a group of the many elements which have been disclosed. Small changes in composition may be very important in achieving improved catalyst performance and particularly in optimizing the catalyst composition to suit, not only a specific reaction, but the desired operating conditions also. The point is well illustrated by the improved catalyst formulations to be described hereinafter.
It has been discovered that when using the catalysts to be described to produce methacrylic acid by vapor phase oxidation of methacrolein, it is possible to achieve both high activity and high selectivity for extended periods of time. Broadly, the catalyst composition comprises oxides of molybdenum, copper, phosphorus, antimony, and cesium and/or calcium and the composition may include one or more elements of Ni, Zn, Ru,
Rh, Pd, Pt, As, K, Rb, Sr, Ba, Cr, V, Nb, W, Mn, Re, and rare earth metals including La.
The catalyst composition used in the process of the invention also may be expressed by the following general formula: MOl2cuaPbsbcAdBeOx wherein A is cesium and/or calcium and B is Ni, Zn, Ru, Rh, Pd, Pt, As, K, Rb, Ca, Sr, Ba, Cr, V, Nb, W, Mn, Re, and rare earth metals including La, and where a-e and x indicate the atomic ratio of each component and, when a is 0.05-3, b is 0.1-5, c is 0.01-3, d is 0.1-3, e is 0-3, and x has a value which is determined by the valence and proportions of the other elements in the catalyst. Preferably, b will be 0.5-3 and more preferably 1-2, while preferably will be 0.01-1.
Preferred embodiments of the invention include catalysts containing cesium, either alone or with rhenium, or containing calcium, either alone or with rhenium or tungsten. Where tungsten is used, optionally arsenic may be added. Particularly preferred are a catalyst where A is cesium, B is either absent or present as rhenium and b is 1.2-1.8 or a catalyst where A is calcium, B is either absent or present as rhenium or tungsten (arsenic optional) and b is 1-2.
When such a catalyst as has been described is in contact with a vapor-phase mixture of methacrolein, molecular oxygen, steam, and nitrogen at typical temperatures in the range of 250-400"C and pressures in the range of 0-5 atmospheres, excellent activity and selectivity to the production of methacrylic acid is obtained for extended periods of time.
Catalyst composition and preparation
The catalyst of the invention comprises oxides or oxygen-containing compounds of molybdenum, copper, phosphorus, antimony, and cesium and/or calcium and optionally may include members of a group of elements designated "B" below. The catalyst may be represented by the general formula: MOl2cuaPbSbcAdBeOx wherein A is cesium and/or calcium and B is Ni, Zn, Ru, Rh, Pd, Pt, As, K, Rb, Sr, Ba, Cr, V, Nb, W, Mn, Re and rare earth metals including La, and where a-e and x indicate the atomic ratio of each component relative to Mo12 and, when a is 0.05-3, b is 0.1-5, c is 0.01-3, d is 0.1-3, e is 0-3, xis a value determined by the valence and proportions of the other elements in the catalyst. Preferably, b will be 0.5-3 and more preferably 1-2, while c preferably will be 0.01-1. Preferred catalysts include those in which component B is tungsten (with arsenic optional) or rhenium. Other elements, which may be included in minor amounts in the catalyst formulation in order to promote catalyst activity or selectivity and without losing the advantages to be shown for the general formula, are considered to be within the scope of the invention. The catalyst composition may be regarded either as a mixture of oxides of the named elements or as oxygen-containing compounds of the elements or both. As prepared and/or under reaction conditions, the catalyst may contain either or both forms and both are intended to be included within the phrase "mixtures of oxides".
The catalyst composition is preferably used in unsupported form, e.g. in the form of pellets or other like compressed shapes of various sizes, although conventional supports could be employed instead. The composition may be formed in conventional manner using techniques well known to persons skilled in the art. For example, compounds of molybdenum, copper, phosphorus, antimony, cesium, and rhenium are dissolved in a small amount of water or other solvent, and the solutions are then combined and evaporated to dryness, e.g. in a rotary dryer. The several components can be introduced into solution in the form of various salts or other compounds of convenient types and no specific form for the catalyst precursors is necessary. The use of ammonium salts, halides e.g. chlorides, nitrates or acid forms of the elements, e.g.
phosphoric acid, are, however, particularly suitable. Preferably, however, aqueous solutions are employed and water-soluble forms of the elements are used. In some cases the solutions may have acids and/or bases added to them to facilitate dissolution of the catalyst precursors. For example, acids such as hydrochloric or nitric acid, or bases such as ammonium hydroxide, can be used as desired. The resulting powder from the evaporation is then thoroughly dried and preferably screened to eliminate large particles which make it difficult to produce uniform compressed shapes, such as pellets. Typically, the powder is passed through a 20-mesh screen. The powder is then mixed with an organic binder which can be of any conventional type, such as polyvinyl alcohol, and the mixture is thoroughly dried and again screened, typically to provide a 20-60 mesh size. The dried mixture is then preferably combined with a lubricant, again of any conventional type, such as stearic acid or graphite, and compressed into the desired shape, e.g. pelletized, the compressed shapes typically having heights and diameters of 1/16 inch to 3/8 inch. Finally, the thus produced catalyst composition is activated at high temperature for a prolonged period in accordance with conventional practice in this art. For example, the pellets are placed in an oven or kiln, or in a tube through which air is passed, at an elevated temperature (e.g. 300-500"C, preferably 325-450"C) for at least ten hours.
In a particularly preferred activation step, the temperature is raised at the rate of 20"C per hour to a maximum of 420"C, preferably 320-400"C, and this temperature is maintained for 8 hours.
It will be understood that the foregoing description regarding preparation of the catalyst in a form suitable for use in a vapor-phase oxidationreaction is merely illustrative of many possible preparative methods, although it is a particularly suitable method and is preferred.
Methods ofoperation The catalysts described are generally useful for the production of unsaturated acids by oxidation with molecular oxygen of unsaturated aldehydes, although the reaction of methacrolein to form methacrylic acid is of particular interest. Other possible starting materials are the monoethylenically unsaturated aliphatic monoaldehydes of from 3 to 6 carbon atoms, such as acrolein, crotonaldehyde, 2-methyl-2-butenal, and the like, or mixtures thereof.
The reaction in which the catalyst compositions of this invention are of particular utility and in which they provide high conversions and selectivities involves contacting the catalyst with methacrolein and oxygen in the vapor phase, preferably also in the presence of steam and diluents. When the catalyst of this invention is used in the vapor-phase oxidation of methacrolein to form methacrylic acid, the oxidation conditions employed are those generally associated with this reaction, although it is preferred that the molar ratio of oxygen to methacrolein should be kept at a high value near the flammable range. Once reaction is begun, it is self-sustaining because of its exothermic nature. A variety of reactor types may be employed such as fluid or fixed bed types, but reactors having the catalyst disposed inside a multiplicity of heat exchanger tubes are particularly useful and convenient.
The gaseous feed to the reactor contains appropriate concentrations of methacrolein, oxygen and steam and usually an inert gas is also present, such as nitrogen and the like. The oxygen is usually added as such or as air, which may be enriched with oxygen. As mentioned, conventional oxidation conditions can be employed but it is a feature of the catalyst of this invention that methacrolein can be present in concentrations of more than 5 up to about 20 volume percent of the total feed with a preferred range of more than 5 up to about 15 volume percent. In general at least 6 volume percent of the aldehyde is used in the feed. The corresponding ranges for oxygen are 3 to 15 volume percent, preferably 5 to 12 volume percent and for steam up to 50 volume percent, preferably 5 to 35 volume percent, the balance being the inert gas or gases.
The temperature of the reaction should, for best results, be within the range of from about 270 to 4500C, preferably 280-400"C, and the optimum temperature range is 290 to 325"C. Because the reaction is exothermic, means for conducting the heat away from the reactor are normally employed to avoid a temperature increase which favors the destruction of methacrolein by complete oxidation to carbon oxides and water. The reactor temperature may be controlled by conventional methods such as by surrounding the catalyst-containing tubes with a molten salt bath.
The reaction may be conducted at atmospheric, superatmospheric or subatmospheric pressure.
Preferably, however, pressures are employed ranging from atmospheric up to about 8 kg/cm2 absolute, preferably up to about 6.3 kg/cm2 absolute, and most preferably up to about 4.5 kg/cm2 absolute.
The unsaturated acid product may be recovered by a number of methods well known to those skilled in the art. For example, the acid may be condensed, or scrubbed with water or other suitable solvents, followed by separation of the unsaturated acid product from the scrubbing liquid. The gases remaining after the acid-removal step may be recycled to the reaction preferably after removal of CO2 by conventional means, e.g., absorption in aqueous carbonate solution.
The features of the invention will be more readily apparent from the following specific examples of typical catalyst preparation and its use in the oxidation of methacrolein. It will be understood, however, that these examples are for the purpose of illustration only and are not to be interpreted as limiting the invention.
EXAMPLE 1
Catalyst preparation
In 750 cc of water are dissolved 636 grams of (NH4)6Mo7024.4H2O. Then 21.7 grams of Cu(N03)2 . 3H2O are dissolved in 100 cc of water, 58.4 grams of CsNO3 are dissolved in 150 cc of water, 20.5 grams of SbC13 are dissolved in a mixture of 30 cc of water, and 10 cc of concentrated HCI and 34.5 grams of H3PO4 are dissolved in a mixture of 100 cc of water and 50 cc of 58% NH40H solution. These solutions are mixed with 400 cc of 58% NH4OH ae fed to a rotary dryer of 4000 cc capacity and the mixture is evaporated to dryness at a temperature reaching a maximum of 140-200"C. The resulting powder is removed from the dryer and dried in an oven at 200"C for 4 hours. The dried powder is screened through a 20-mesh screen, a 4% aqueous solution of polyvinyl alcohol is added in sufficient quantity to make a damp mixture and this mixture is dried at 75-80"C until the moisture content falls to 2-4 wt.%. The dried mixture is then screened to 20-60 mesh size particles, and about 2-6% of stearic acid powder is thoroughly mixed with it. The resulting mixture is then pelletized to form pellets of 3/16 inch height and diameter in which the catalyst components molybdenum, copper, phosphorus, antimony, cesium are present (by calculation) in the atomic ratios of 12, 0.3, 1, 0.3 and 1, respectively. The pellets are then activated in an oven by heating them to 100 C in one hour and then raising the temperature gradually at a rate of about 20"C per hour to 370"C and maintaining them at this temperature for 8 hours, The catalyst is tested according to the procedure of Example 2.
EXAMPLE 2
Catalyst testing
A 150 cc quantity of the catalyst composition of Example 1 is placed in a reactor defined by a z'' x 90" stainless steel pipe, the reactor pipe being filled with 50 cc of inert filler (silicon carbide) below the catalyst bed and 100 cc of the inert filled above the catalyst bed in conventional manner to insure uniform temperature contact with the catalyst. Nitrogen-diluted mixtures containing methacrolein, oxygen and steam are fed to the reactor at a pressure of 1.74 kg/cm2(absolute) and at a space velocity of about 1200 her~1.
The term "space velocity" is used in its conventional sense to mean liters of gas (at standard temperature and pressure) per liter of catalyst per hour. The feed composition is approximately, by volume, 6-7% methacrolein, 11-12% oxygen and 20% steam, the balance being nitrogen, determination being made on a wet basis. The reaction is run continuously and the exit gas is analyzed at intervals of several hours.
Analyses are carried out by means of gas chromatography and by infrared spectrography using conventional techniques. The average amount of methacrylic acid produced is determined periodically and the reactor temperature is adjusted as necessary to obtain the desired yield, that is, the product of the conversion and the selectivity, which for purposes of the comparisons to be made is about 0.15 gm of methacrylic acid per hour per gram of catalyst.
EXAMPLE 3
A catalyst is prepared according to the method of Example 1 except that the phosphorus content is increased to provide a catalyst having the following nominal composition (by calculation): Moi2Cuc.3Pi.sSbo.3CsiOx The catalyst is tested according to the method of Example 2.
EXAMPLE 4
A catalyst is prepared according to the method of Example 1 but having a higher phosphorus content than the catalyst of Example 3, providing a catalyst having the following nominal composition (by calculation): Mol2Cuo.3P2Sbo.3CslO.
The catalyst is tested according to the method of Example 2.
The results of the tests carried out on the catalysts of Example 1,3, and 4 are summarized in the following
Table I.
TABLE I
Cat. . Phosphorus Hours Temp. Selectivity to Activity
Content (a) "C Methacrylic Coeff. K
Acid (b) (c) 1 1 35 293 77 23
80 323 74.5 6 3 1.5 150 298 77.6 26
200 296 79.7 26 4 2 26 320 70 10
122 324 65 7 (a) relative to Mo12 (b) percent of methacrolein reacted which is converted to methacrylic acid (c) a value calculated from experimental data to provide a measure of catalyst activity and derived from the
equation:
K = F. X. S. eE/RTwhere:
F = methacrolein concentration in feed
S = space velocity of feed gas
X = conversion of methacrolein
E = activation energy,25,000 k cal/mol.
R = gas constant
T = absolute temperature
As explained in Example 2 the catalysts are operated to provide a constant predetermined yield of methacrylic acid. In order to provide a proper comparison, the performance of a catalyst is reported at the period of time where the catalyst activity has stabilized after an initial break-in period. This may mean, as in
Table I, that the time selected for comparisons is not the same if the catalyst performance differs significantly. A stable period at 150-200 hours could be established readily for the catalyst of Example 3, while the catalysts of Examples 1 and 4 had relatively poorer performance and their activities declined earlier, as indicated by the data. It is clearthatthe catalyst of Example 3 is superior to those of Examples 1 and 4, since it operated consistently at a lower temperature and with higher activity and selectivity after the other catalysts had lost significant activity. Thus, is is concluded that catalysts containing molybdenum, copper, antimony, and cesium are sensitive to the phosphorus content. An optimum level should be found between a phosphorus level of 1 and 2 (relative to Moo2). It is believed that the optimum level is located between P1,2 and Pea 8, particularly between P13 and Per 7.
EXAMPLE 5
A catalyst corresponding to that of Example 1 is prepared by the same general technique except that 5 grams of perrhenic acid dissolved in 100 cc of water are included in the initial solution to provide rhenium in a catalyst having the following nominal composition (by calculation): Mo12Cuc,3PiSbo,3Cs1REo,o7Ox EXAMPLE 6
A catalyst is prepared according to the general method of Example 5 except that the amount of phosphorus is increased to produce a catalyst having the following nominal composition (by calculation).
Mo,2CuO,3P, ,5sbo3sbo 3Csl ReO.070x The catalyst is tested according to the methods of Example 2.
EXAMPLE 7
A catalyst is prepared according to the method of Example 5 but the amount of phosphorus is doubled to provide a catalyst having the following nominal composition (by calculation): Mo12Cu0,3P2Sb0,3Cs1 ReO,07Ox The catalyst is tested according to the procedures of Example 2.
The results of testing the catalysts of Examples 5, 6, and 7 are summarized in the following Table II, to which the footnotes of Table I also apply.
TABLE II
Cat. Phosphorus Hours Temp. Selectivity to Activity
Content (a) "C Methacrylic Coeff. K
Acid (b) (c) 5 1 150 292 75 26
200 293 75.5 26 6 1.5 150 279 77 46.6
250 279 77 40 7 2 150 311 73.6 11.6
250 311 76 12
As in Table I, the catalysts are operated to provide the same yield of methacrylic acid and the performance is reported during a stable period of operation after the initial break-in of the catalyst. It will be clear that the catalysts having rhenium added have better performance than those of Table I, which contain no rhenium, since they have higher activity and suggest improved aging characteristics, especially with respect to the comparison of catalysts 5 and 7 with catalysts 1 and 4. The rhenium-containing catalysts also are sensitive to the phosphorus content and an optimum value again appears between P1 and P2 (relative to Mo12). It is believed that the optimum value is between P1,2 and P1,5, particularly between Pea 3 and P1,7.
Taking the results of Tables land II together, it may be concluded that the ratio of molybdenum to phosphorus for catalysts of this type will show an optimum performance at ratios between 12/1 to 12/2.
EXAMPLE 8
A catalyst is prepared according to the general method of Example 1 except that 79.2 gms of Ca(C2H302)2.
X H2O are substituted for cesium nitrate and no aqueous ammonia is added and a catalyst having the following nominal composition (by calculation) is produced: Moi2Cuo.3PiSbc.3Cai.5Ox This catalyst is tested according to the methods of Example 2 and the significance of the phosphorus to molybdenum ratio to catalyst performance is shown. The catalyst is operated at about 304"C for a period between about 20 to 80 hours with a selectivity of 76.3 and an activity coefficient of 18.6.
EXAMPLE 9
A catalyst is prepared according to Example 8 except that 5 grams of Re2O7 dissolved in 100 cc of water is included in the solution to provide rhenium a catalyst having the following nominal composition (by calculation): Mol2CUo.3P1Sbo.3CalSRe0.070x The catalyst is tested according to the method of Example 2. The significance of the phosphorus to molybdenum ratio to catalyst performance is shown. The catalyst is operated at about 286"C for a period between about 30 to 200 hours with a selectivity of 75.2 and an activity coefficient of 42.
EXAMPLE 10
A catalyst is prepared according to the general method of Example 9 except that instead of rhenium, tungsten is included and no aqueous ammonia is used to provide a catalyst having the following nominal composition (by calculation): Mo12Cu0,3P1Sb0,3Ca1W0,5O The catalyst is tested according to the method of Example 2 and the significance of the phosphorus to molybdenum ratio to catalyst performance is shown. For a period between about 20 to 170 hours the catalyst is operated at about 302"C, with a selectivity of about 76.5 and an activity coefficient of about 22.4.
EXAMPLE 11
A catalyst is prepared according to the general method of Example 1 except that the phosphorus level is increased and palladium is included to produce a catalyst having the following nominal composition: Moi2Cuc,3P2Sbo,3CsiPdo.o3Ox The catalyst is tested under the conditions of Example 2 and the significance of the phosphorus to molybdenum ratio with respect to catalyst performance is shown.
EXAMPLE 12
A catalyst is prepared according to the general method of Example 1 except that the phosphorus level is increased and rubidium is added to produce a catalyst having the following nominal composition:
Moa2CuO,3P1.75Sb0,3C50.5Rb0.5Ox
The catalyst is tested under the conditions of Example 2 and the significance of the phosphorus to molybdenum ratio with respect to catalyst performance is shown.
EXAMPLE 13
A catalyst is prepared according to Example 9 except that the phosphorus content is doubled and having the following nominal composition (by calculation): Mo12CuO,3P2Sbo,3Cal ,5Reoo7ox When tested under the conditions of Example 2 and at an operating temperature of 276 C, the conversion of methacrolein was about 26% and the selectivity to methacrylic acid was about 54%.
EXAMPLE 14
A catalyst is prepared according to Example 10 except that arsenic is included and having the following nominal composition (by calculation):
Mo12Cu0.3P1Sb0.3Ca1W0.5As0.5Ox
This catalyst is tested with a feed gas containing 7 vol %. methacrolein, 12 vol. % oxygen,20 vol. % steam, and the remainder nitrogen and at a pressure of 1.74 kg/cm2 (absolute). At 288 C the catalyst converted 75% of the methacrolein, with a selectivity of 76% to methacrylic acid. A similar catalyst without arsenic tested under similar conditions gave 62% conversion of methacrolein with a selectivity of 70% to methacrylic acid at a temperature of 285 C. Thus, arsenic is considered to be advantageous, since it improves the performance of catalysts containing tungsten.
EXAMPLE 15
Other suitable catalysts in accordance with the invention are prepared according to the general method of
Example 1 and have the following nominal compositions: Mol2Cuo.3P2Sbo.3Cso.3Cao.7Cro.30, Mo12Cu0,3P2Sb0,3Cs0,3K0,7V0,3Ox
Mo12Cu0,3P2Sb0.3Cs0,3Sr0,7Nb0,3Ox Mo12Cuc,3P1,75b0,3Csc,sBac,7Mnc,3Ox Mo12Cu0,3P1,25b0,3Cs1La0.7Ni0.3Ox
Mo12Cu0,3P1Sb0,3Cs0,3Ce0,7Zn0,3Ox
Mo12Cu0.3P1Sb0,3Cs1Ru0,1Ox
Mo12Cu0.3P0.5Sb0.3Cs1Rh0.03Ox
Mo12Cu0.3P1Sb0.3Cs0.3Pt0.03O, Mo12CaO,3P1 ,5Sbo,3Cs1WO,5 The catalysts are tested under the conditions of Example 2 and the significance of the phosphorus to molybdenum ratio with respect to catalyst performance is shown.
Claims (16)
1. A catalyst composition suitable for the vapor-phase oxidation of methacrolein to produce methacrylic acid consisting essentially of the oxides of Mo, Cu, P, Sb, and Cs and/or Ca and optionally one or more of the elements selected from the group consisting.of Ni, Zn, Ru, Rh, Pd, Pt, As, K, Rb, Sr, Ba, Cr, V, Nb, W, Mn, Re, and the rare earth metals including La.
2. The catalyst of claim 1 expressed bytheformula: MO12cuaPbsbcAdBeox where: a = 0.05-3; b = 0.1-5; c = 0.01-1; d = 0.1-3; e = 0-3; and x = a value determined by the valence and proportions of the other elements of the formula, where A is
Cs and/or Ca and B is one or more elements selected from the group consisting of Ni, Zn, Ru, Rh, Pd, Pt, As,
K, Rb, Sr, Ba, Cr, V, Nb, W, Mn, Re, and rare earth metals including La.
3. The catalyst of claim 2 where b = 1-2.
4. The catalyst of claim 2 or 3 where c = 0.01-1.
5. The catalyst of claim 1,2,3 or 4 where A is Cs.
6. The catalyst of claim 1,2,3 or 4 where A is Ca.
7. The catalyst of claim 1,2,3,4,5 or 6 where B is Re.
8. The catalyst of claim 6 where B is Wand optionally may contain As.
9. The catalyst of claim 2,3,4 or 5 where A is Cs, e is zero, and b is 1.2-1.8.
10. The catalyst of claim 2,3,4 or 6 where A is Ca and e is zero.
11. The catalyst of claim 2,3,4,5 or 7 where a is Cs, B is Re and b is 1.2-1.8.
12. Any one of the catalysts specifically disclosed in the Examples as an embodiment of the catalyst claimed in claim 1.
13. A catalyst as claimed in claim 1, substantially as herein before described with particular reference to the Examples.
14. A process for the preparation of methacrylic acid which comprises oxidizing methacrolein in the vapor-phase with molecular oxygen in the presence of any of the catalysts of claims 1 to 13.
15. A process as claimed in claim 14, substantially as hereinbefore described.
16. Methacrylic acid when prepared by the process claimed in claim 14 or claim 15.
Applications Claiming Priority (10)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US05/972,743 US4252681A (en) | 1978-12-26 | 1978-12-26 | Catalyst for producing methacrylic acid |
US05/972,745 US4252682A (en) | 1978-12-26 | 1978-12-26 | Catalyst for producing methacrylic acid |
US05/973,495 US4252683A (en) | 1978-12-26 | 1978-12-26 | Catalyst for producing methacrylic acid |
US05/973,354 US4374757A (en) | 1978-12-26 | 1978-12-26 | Catalyst and process for producing methacrylic acid |
US06/027,632 US4240930A (en) | 1979-04-06 | 1979-04-06 | Catalyst and process for producing methacrylic acid |
US06/027,634 US4261859A (en) | 1979-04-06 | 1979-04-06 | Catalyst for producing methacrylic acid |
US06/027,635 US4261860A (en) | 1979-04-06 | 1979-04-06 | Catalyst for producing methacrylic acid |
US06/027,633 US4261858A (en) | 1979-04-06 | 1979-04-06 | Catalyst for producing methacrylic acid |
US06/047,860 US4377501A (en) | 1978-12-26 | 1979-06-12 | Catalyst and process for producing methacrylic acid |
US06/081,406 US4271040A (en) | 1978-12-26 | 1979-10-03 | Catalyst and process for producing methacrylic acid |
Publications (2)
Publication Number | Publication Date |
---|---|
GB2040717A true GB2040717A (en) | 1980-09-03 |
GB2040717B GB2040717B (en) | 1983-09-14 |
Family
ID=27580733
Family Applications (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB7944392A Expired GB2040717B (en) | 1978-12-26 | 1979-12-24 | Catalyst and process for producing methacrylic acid |
GB08307119A Expired GB2121309B (en) | 1978-12-26 | 1983-03-15 | Catalyst and process for producing methacrylic acid |
GB08307118A Expired GB2116063B (en) | 1978-12-26 | 1983-03-15 | Catalyst and process for producing methacrylic acid |
Family Applications After (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB08307119A Expired GB2121309B (en) | 1978-12-26 | 1983-03-15 | Catalyst and process for producing methacrylic acid |
GB08307118A Expired GB2116063B (en) | 1978-12-26 | 1983-03-15 | Catalyst and process for producing methacrylic acid |
Country Status (7)
Country | Link |
---|---|
BR (1) | BR7908476A (en) |
DE (1) | DE2952455C2 (en) |
FR (1) | FR2445310A1 (en) |
GB (3) | GB2040717B (en) |
IT (1) | IT1164100B (en) |
MX (1) | MX154396A (en) |
NL (1) | NL7909142A (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4409128A (en) * | 1980-08-09 | 1983-10-11 | Basf Aktiengesellschaft | Oxidation catalyst, especially for the preparation of methacrylic acid by gas phase oxidation of methacrolein |
DE3346259A1 (en) * | 1982-12-22 | 1984-06-28 | Nippon Shokubai Kagaku Kogyo Co. Ltd., Osaka | CATALYST FOR THE PRODUCTION OF METHACRYLIC ACID |
US4489170A (en) * | 1982-03-10 | 1984-12-18 | Basf Aktiengesellschaft | Oxidation catalyst, especially for the preparation of methacrylic acid by gas phase oxidation of methacrolein |
US4511548A (en) * | 1981-12-18 | 1985-04-16 | The Standard Oil Company | Ammoxidation of methanol to produce hydrogen cyanide |
US4925823A (en) * | 1982-03-10 | 1990-05-15 | Basf Aktiengesellschaft | Process and catalyst for the preparation of methacrylic acid |
WO1998005619A1 (en) * | 1996-07-31 | 1998-02-12 | Aventis Research & Technologies Gmbh & Co.Kg | Selective preparation process of acetic acid and catalysts therefor |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL8202791A (en) * | 1981-07-17 | 1983-02-16 | Halcon Sd Group Inc | METHOD FOR PREPARING METHACRYLIC ACID. |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2460541C3 (en) * | 1973-12-29 | 1979-10-18 | Nippon Shokubai Kagaku Kogyo Co. Ltd., Osaka (Japan) | Oxide catalyst containing phosphorus, molybdenum and vanadium and optionally copper, cobalt, zirconium, bismuth, antimony and / or arsenic and its use for the production of methacrylic acid |
JPS5827255B2 (en) * | 1974-05-31 | 1983-06-08 | 三菱レイヨン株式会社 | Method for producing unsaturated fatty acids |
US4000088A (en) * | 1974-06-03 | 1976-12-28 | Nippon Kayaku Co., Ltd. | Oxidation catalyst for the manufacture of methacrylic acid |
FR2273586A1 (en) * | 1974-06-07 | 1976-01-02 | Nippon Kayaku Kk | Oxidn. catalyst for methacrolein conversion - to methacrylic acid, contg. molybdenum, phosphorus, antimony, copper and chromium |
IN145044B (en) * | 1975-01-13 | 1978-08-19 | Standard Oil Co Ohio | |
GB1489559A (en) * | 1975-03-03 | 1977-10-19 | Mitsubishi Rayon Co | Catalytic process for the preparation of acrylic acid or methacrylic acid |
JPS51115414A (en) * | 1975-04-03 | 1976-10-12 | Mitsubishi Rayon Co Ltd | Process for preparation of unsaturated fatty acids |
US4118419A (en) * | 1975-12-03 | 1978-10-03 | Mitsubishi Rayon Company, Ltd. | Catalytic process for the preparation of an unsaturated carboxylic acid |
-
1979
- 1979-12-19 NL NL7909142A patent/NL7909142A/en not_active Application Discontinuation
- 1979-12-21 IT IT51168/79A patent/IT1164100B/en active
- 1979-12-21 BR BR7908476A patent/BR7908476A/en unknown
- 1979-12-24 FR FR7931595A patent/FR2445310A1/en active Granted
- 1979-12-24 GB GB7944392A patent/GB2040717B/en not_active Expired
- 1979-12-27 DE DE2952455A patent/DE2952455C2/en not_active Expired
-
1980
- 1980-01-02 MX MX180602A patent/MX154396A/en unknown
-
1983
- 1983-03-15 GB GB08307119A patent/GB2121309B/en not_active Expired
- 1983-03-15 GB GB08307118A patent/GB2116063B/en not_active Expired
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4409128A (en) * | 1980-08-09 | 1983-10-11 | Basf Aktiengesellschaft | Oxidation catalyst, especially for the preparation of methacrylic acid by gas phase oxidation of methacrolein |
US4511548A (en) * | 1981-12-18 | 1985-04-16 | The Standard Oil Company | Ammoxidation of methanol to produce hydrogen cyanide |
US4489170A (en) * | 1982-03-10 | 1984-12-18 | Basf Aktiengesellschaft | Oxidation catalyst, especially for the preparation of methacrylic acid by gas phase oxidation of methacrolein |
US4925823A (en) * | 1982-03-10 | 1990-05-15 | Basf Aktiengesellschaft | Process and catalyst for the preparation of methacrylic acid |
DE3346259A1 (en) * | 1982-12-22 | 1984-06-28 | Nippon Shokubai Kagaku Kogyo Co. Ltd., Osaka | CATALYST FOR THE PRODUCTION OF METHACRYLIC ACID |
GB2133307A (en) * | 1982-12-22 | 1984-07-25 | Nippon Catalytic Chem Ind | Catalyst for use in producing methacrylic acid |
WO1998005619A1 (en) * | 1996-07-31 | 1998-02-12 | Aventis Research & Technologies Gmbh & Co.Kg | Selective preparation process of acetic acid and catalysts therefor |
US6194610B1 (en) | 1996-07-31 | 2001-02-27 | Aventis Research & Technologies Gmbh & Co. Kg | Process for the selective preparation of acetic acid using a molybdenum and palladium based catalytic oxide |
USRE39074E1 (en) * | 1996-07-31 | 2006-04-18 | Celanese Chemicals Europe Gmbh | Process for the selective preparation of acetic acid using a molybdenum and palladium based catalytic oxide |
Also Published As
Publication number | Publication date |
---|---|
GB2116063B (en) | 1984-02-01 |
IT7951168A0 (en) | 1979-12-21 |
DE2952455A1 (en) | 1980-07-17 |
GB2116063A (en) | 1983-09-21 |
FR2445310A1 (en) | 1980-07-25 |
IT1164100B (en) | 1987-04-08 |
BR7908476A (en) | 1980-09-23 |
MX154396A (en) | 1987-08-07 |
GB8307118D0 (en) | 1983-04-20 |
GB2121309B (en) | 1984-06-06 |
NL7909142A (en) | 1980-06-30 |
GB2121309A (en) | 1983-12-21 |
DE2952455C2 (en) | 1988-07-28 |
GB2040717B (en) | 1983-09-14 |
GB8307119D0 (en) | 1983-04-20 |
FR2445310B1 (en) | 1984-05-25 |
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PCNP | Patent ceased through non-payment of renewal fee | ||
728C | Application made for restoration (sect. 28/1977) | ||
728R | Application refused (sect. 28/1977) [restoration of lapsed patent] |