NO783837L - PROCEDURE FOR THE PREPARATION OF UNSaturated Acids - Google Patents
PROCEDURE FOR THE PREPARATION OF UNSaturated AcidsInfo
- Publication number
- NO783837L NO783837L NO783837A NO783837A NO783837L NO 783837 L NO783837 L NO 783837L NO 783837 A NO783837 A NO 783837A NO 783837 A NO783837 A NO 783837A NO 783837 L NO783837 L NO 783837L
- Authority
- NO
- Norway
- Prior art keywords
- catalyst
- catalysts
- alundum
- prepared
- carrier
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 26
- 238000002360 preparation method Methods 0.000 title description 7
- 239000002253 acid Substances 0.000 title description 4
- 150000007513 acids Chemical class 0.000 title description 2
- 239000003054 catalyst Substances 0.000 claims description 117
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 29
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims description 20
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 14
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 13
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- 229910052793 cadmium Inorganic materials 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 229910052716 thallium Inorganic materials 0.000 claims description 8
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 7
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 7
- 230000003197 catalytic effect Effects 0.000 claims description 7
- 239000010931 gold Substances 0.000 claims description 7
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910001882 dioxygen Inorganic materials 0.000 claims description 6
- 229910052737 gold Inorganic materials 0.000 claims description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims description 6
- 229910052732 germanium Inorganic materials 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000012876 carrier material Substances 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 4
- 239000012808 vapor phase Substances 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 3
- VIJYFGMFEVJQHU-UHFFFAOYSA-N aluminum oxosilicon(2+) oxygen(2-) Chemical compound [O-2].[Al+3].[Si+2]=O VIJYFGMFEVJQHU-UHFFFAOYSA-N 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 238000009736 wetting Methods 0.000 claims description 3
- 229910003204 NH2 Inorganic materials 0.000 claims 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical group [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical group [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical group [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010948 rhodium Substances 0.000 claims 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical group [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims 1
- 238000005096 rolling process Methods 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 239000000203 mixture Substances 0.000 description 15
- 235000011007 phosphoric acid Nutrition 0.000 description 14
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 13
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 13
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 13
- 229910052761 rare earth metal Inorganic materials 0.000 description 13
- XPVHUBFHKQQSDA-UHFFFAOYSA-N ammonium arsenate Chemical compound [NH4+].[NH4+].O[As]([O-])([O-])=O XPVHUBFHKQQSDA-UHFFFAOYSA-N 0.000 description 11
- 239000010949 copper Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000012153 distilled water Substances 0.000 description 8
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 6
- 229940010552 ammonium molybdate Drugs 0.000 description 6
- 235000018660 ammonium molybdate Nutrition 0.000 description 6
- 239000011609 ammonium molybdate Substances 0.000 description 6
- 238000001354 calcination Methods 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 229910052785 arsenic Inorganic materials 0.000 description 4
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 4
- -1 phosphorus halides Chemical class 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 150000002910 rare earth metals Chemical class 0.000 description 3
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 3
- 229940071536 silver acetate Drugs 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 229910052776 Thorium Inorganic materials 0.000 description 2
- 229910052770 Uranium Inorganic materials 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 description 2
- 229910052702 rhenium Inorganic materials 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 2
- CAYKLJBSARHIDI-UHFFFAOYSA-K trichloroalumane;hydrate Chemical compound O.Cl[Al](Cl)Cl CAYKLJBSARHIDI-UHFFFAOYSA-K 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 241001279686 Allium moly Species 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical group [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- COQLPRJCUIATTQ-UHFFFAOYSA-N Uranyl acetate Chemical compound O.O.O=[U]=O.CC(O)=O.CC(O)=O COQLPRJCUIATTQ-UHFFFAOYSA-N 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- YZYDPPZYDIRSJT-UHFFFAOYSA-K boron phosphate Chemical compound [B+3].[O-]P([O-])([O-])=O YZYDPPZYDIRSJT-UHFFFAOYSA-K 0.000 description 1
- 229910000149 boron phosphate Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical group [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical group [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical group [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
- 229940048102 triphosphoric acid Drugs 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
- B01J23/8873—Zinc, cadmium or mercury
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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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—Molybdenum
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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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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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
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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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Description
Fremgangsmåte ved fremstilling av umettede syrer. Procedure for the production of unsaturated acids.
Methacrylsyre eller acrylsyre fremstilles ifølge oppfinnelsen ved oxydasjon av methacrolein, hhv. acrolein, med molekylært oxygeh i dampfase i nærvær av et katalytisk oxyd av molybden, fosfor, arsen, oxygen og de følgende bestanddeler angitt i tre grupper I til III: (I) et sjeldent jordelement eller blanding derav, og eventuelt minst ett av Ag, Tl, Rh, Pd, Ru, Pt, Cd, Al, Au, Cu, jordalkalimetall, Cl og NH^; eller (II) minst ett element valgt fra gruppen bestående av U., Ti, Nb, Re, Pb, Zn og Ga, og eventuelt minst ett av Cu, et sjeldent jordelement, Ag, Ta, In, Th, Cd, Tl, jordalkalimetall, NH^, Cl, Ni, Al og Ge; eller (III) minst ett element valgt fra gruppen bestående av Ag, Rh, Ru og Au, og eventuelt minst ett av Cd, Pt, Tl, Pd, Al, Ge, Cu,. Ni, jordalkalimetall, NH^og Cl. Methacrylic acid or acrylic acid is produced according to the invention by oxidation of methacrolein, respectively. acrolein, with molecular oxygen in vapor phase in the presence of a catalytic oxide of molybdenum, phosphorus, arsenic, oxygen and the following constituents specified in three groups I to III: (I) a rare earth element or mixture thereof, and possibly at least one of Ag, Tl, Rh, Pd, Ru, Pt, Cd, Al, Au, Cu, alkaline earth metal, Cl and NH^; or (II) at least one element selected from the group consisting of U., Ti, Nb, Re, Pb, Zn and Ga, and optionally at least one of Cu, a rare earth element, Ag, Ta, In, Th, Cd, Tl, alkaline earth metal, NH^, Cl, Ni, Al and Ge; or (III) at least one element selected from the group consisting of Ag, Rh, Ru and Au, and optionally at least one of Cd, Pt, Tl, Pd, Al, Ge, Cu,. Ni, alkaline earth metal, NH^and Cl.
En rekke katalysatorer er kjent for å være effektive for oxydasjonen av acrolein eller methacrolein til acrylsyre, hhv. methacrylsyre. De erholdte utbytter under anvendelse av katalysatorene for fremstilling av methacrylsyre er imidlertid lave. DT patent 2 048 620 angår katalysatorer inneholdende oxydene av molybden, fosfor og arsen for oxydasjon av methacrolein og acrolein til methacrylsyre, hhv. acrylsyre. U.S. patent nr. A number of catalysts are known to be effective for the oxidation of acrolein or methacrolein to acrylic acid, respectively. methacrylic acid. However, the yields obtained using the catalysts for the production of methacrylic acid are low. DT patent 2 048 620 relates to catalysts containing the oxides of molybdenum, phosphorus and arsenic for the oxidation of methacrolein and acrolein to methacrylic acid, respectively. acrylic acid. U.S. patent no.
"376l 5l6 angår katalysatorer inneholdende oxyder av molybden, arsen og fosfor på en bærer, særlig Al 0„, med utvendige makro-porer og en overflate ikke større enn 2 m<2>/g. "376l 5l6 concerns catalysts containing oxides of molybdenum, arsenic and phosphorus on a support, in particular Al 0„, with external macro-pores and a surface not greater than 2 m<2>/g.
Foreliggende oppfinnelse er resultatet av en undersøkelse efter mere effektive og ønskelige katalysatorer for fremstilling av acrylsyre og methacrylsyre. Uventet høyere utbytter av og selektivitetar for acrylsyre og methacrylsyre fåes ved dampfase-oxydasjon av acrolein, hhv. methacrolein, med molekylært oxygen i nærvær av de nye og nyttige katalysatorer ifølge foreliggende oppfinnelse. The present invention is the result of an investigation into more effective and desirable catalysts for the production of acrylic acid and methacrylic acid. Unexpectedly higher yields of and selectivity for acrylic acid and methacrylic acid are obtained by vapor phase oxidation of acrolein, respectively. methacrolein, with molecular oxygen in the presence of the new and useful catalysts according to the present invention.
Det har vist seg at i henhold til foreliggende oppfinnelse ved fremgangsmåten for fremstilling av acrylsyre eller methacrylsyre ved oxydasjon av acrolein,. hhv. methacrolein, med molekylært oxygen i dampfase ved en reaksjonstemperatur på fra ca. 200°C til ca. 500°C i nærvær av en oxydkatalysator, og eventuelt i nærvær av damp, den forbedring som karakteriseres ved at der som katalysator anvendes en katalysator med formelen: It has been shown that according to the present invention in the method for the production of acrylic acid or methacrylic acid by oxidation of acrolein,. respectively methacrolein, with molecular oxygen in the vapor phase at a reaction temperature of from approx. 200°C to approx. 500°C in the presence of an oxide catalyst, and optionally in the presence of steam, the improvement characterized by the use of a catalyst with the formula:
hvor X er et sjeldent jordelement eller en blanding derav; U er minst én av Ag,.Tl, Rh, Pd, Ru, Pt, Cd, Al, Au, Cu, jordalkalimetall, Cl og NH^; hvor a er 0,001 til 10; b er 0 til 10; c er 0,01 til 5; d er 0,01 til 5; x er antallet oxygenatomer som kreves for å tilfredsstille valenstilstandene av de andre tilstedeværende elementer; eller at der anvendes en katalysator med formelen: hvor X er minst ett element valgt fra gruppen bestående av U, Ti, Nb, Re, Pb, Zn og GA; Y er Cu, et sjeldent jordelement, Ag, Ta, In, Th, Cd, Tl, et jordalkalimetall, NH^, Cl, Ni, Al og Ge; og hvor a er 0,001 til 10; b er 0 til 10; c er 0,01 til 5; d er 0,01 til 5; x er antallet oxygenatomer som kreves for å tilfredsstille valenstilstandene for de andre tilstedeværende elementer; eller der anvendes en katalysator med formelen: where X is a rare earth element or a mixture thereof; U is at least one of Ag,.Tl, Rh, Pd, Ru, Pt, Cd, Al, Au, Cu, alkaline earth metal, Cl and NH^; where a is 0.001 to 10; b is 0 to 10; c is 0.01 to 5; d is 0.01 to 5; x is the number of oxygen atoms required to satisfy the valence states of the other elements present; or that a catalyst with the formula is used: where X is at least one element selected from the group consisting of U, Ti, Nb, Re, Pb, Zn and GA; Y is Cu, a rare earth element, Ag, Ta, In, Th, Cd, Tl, an alkaline earth metal, NH^, Cl, Ni, Al and Ge; and where a is 0.001 to 10; b is 0 to 10; c is 0.01 to 5; d is 0.01 to 5; x is the number of oxygen atoms required to satisfy the valence states of the other elements present; or a catalyst with the formula is used:
hvor X er minst ett element valgt fra gruppen bestående av Ag, Rh, Ru og Au; wherein X is at least one element selected from the group consisting of Ag, Rh, Ru and Au;
Y er minst ett av Cd, Tl, Pd, Al, Ge, Cu, Pt, Ni, jordalkalimetall , NH^og Cl; Y is at least one of Cd, Tl, Pd, Al, Ge, Cu, Pt, Ni, alkaline earth metal, NH^ and Cl;
og hvor a er 0,001 til 10; and where a is 0.001 to 10;
b er O til 10; b is 0 to 10;
c er 0,01 tii 5; c is 0.01 tii 5;
d er 0,01 til 5; d is 0.01 to 5;
x er antallet av oxygenatomer som kreves for å tilfredsstille valenstilstandene av de andre tilstedeværende elementer. x is the number of oxygen atoms required to satisfy the valence states of the other elements present.
De forbausende fordelaktige katalysatorer ifølge oppfinnelsen gir forbedrede utbytter av acrylsyre og methacrylsyre fra acrolein, hhv. methacrolein, på en effektiv, bekvem og økonomisk måte ved en relativt lav temperatur. Eksotermen ved reaksjonen er lav, hvilket muliggjør lett reaksjonskontroi1. The surprisingly advantageous catalysts according to the invention provide improved yields of acrylic acid and methacrylic acid from acrolein, respectively. methacrolein, in an efficient, convenient and economical way at a relatively low temperature. The exotherm of the reaction is low, which enables easy reaction control1.
Det mest betydningsfulle trekk ved foreliggende oppfinnelse er den anvendte katalysator. Katalysatoren kan være en hvilken som helst av katalysatorene angitt ved formlene I til III. Katalysatorene kan fremstilles ved en rekke forskjellige kjente metoder, som copresipitering av oppløselige salter og calcinering av det dannede produkt. Katalysatorene ifølge oppfinnelsen har foretrukne begrensninger på sin sammensetning. The most significant feature of the present invention is the catalyst used. The catalyst may be any of the catalysts indicated by formulas I to III. The catalysts can be prepared by a number of different known methods, such as coprecipitation of soluble salts and calcination of the product formed. The catalysts according to the invention have preferred restrictions on their composition.
Når katalysatorer med formel I anvendes, er foretrukne When catalysts of formula I are used, are preferred
■katalysatorer de hvor a er 0,001 til 3>katalysatorer hvor b er 0,001 til 3j og katalysatorer hvor b er 0. Særlig foretrukket er katalysatorer hvor X er cerium, erbium eller en blanding av sjeldne jordelementer bestående i det vesentlige av Ce, La, Nd og Pr. Katalysatorer av særlig interesse er de hvor Y er sølv, thallium eller kobber. ■catalysts those where a is 0.001 to 3>catalysts where b is 0.001 to 3j and catalysts where b is 0. Particularly preferred are catalysts where X is cerium, erbium or a mixture of rare earth elements consisting essentially of Ce, La, Nd and Pr. Catalysts of particular interest are those where Y is silver, thallium or copper.
Når katalysatorer med formel II anvendes, foretrekkes katalysatorer hvor a er 0,001 til 3, katalysatorer hvor b er 0,001 When catalysts of formula II are used, catalysts where a is 0.001 to 3, catalysts where b is 0.001 are preferred
til 3; og katalysatorer hvor b er 0. Særlig foretrukket er katalysatorer hvor hvert av elementene betegnet med X inkorporeres separat i katalysatoren. Dette oppnåes bekvemt ved å sette • X uavhengig lik de forskjellige elementer. Katalysatorer av særlig interesse er de hvor Y er minst ett element valgt fra gruppen bestående av et sjeldent jordelement, Al, Ag og Cu. to 3; and catalysts where b is 0. Particularly preferred are catalysts where each of the elements denoted by X is incorporated separately into the catalyst. This is conveniently achieved by setting • X independently equal to the various elements. Catalysts of particular interest are those where Y is at least one element selected from the group consisting of a rare earth element, Al, Ag and Cu.
Når katalysatorer med formel III anvendes, er foretrukne katalysatorer de hvor a er 0,001 til 3, katalysatorer hvor b er 0,001 til 3, og katalysatorer hvor b er 0. Særlig foretrukket er katalysatorer hvor hvert av elementene angitt ved X inkorporeres separat i katalysatoren.- Dette oppnåes bekvemt ved å sette X uavhengig lik de forskjellige elementer. Også foretrukket er katalysatorer hvor Y er minst én åv Cd, Tl, Cu, NH^og Cl.. When catalysts of formula III are used, preferred catalysts are those where a is 0.001 to 3, catalysts where b is 0.001 to 3, and catalysts where b is 0. Particularly preferred are catalysts where each of the elements indicated by X is incorporated separately into the catalyst.- This is conveniently achieved by setting X independently equal to the various elements. Also preferred are catalysts where Y is at least one of Cd, Tl, Cu, NH^ and Cl.
Ved katalysatorfremstillinger kombineres de forskjellige elementer av katalysatoren, og sluttproduktet calcineres for å få katalysatoren. En rekke metoder for å kombinere elementene av katalysatoren og calcinere det dannede produkt er kjent for fag-folk. For den brede oppfinnelsesidé er den spesielle metode for fremstilling av katalysatorene ikke kritisk. In catalyst production, the different elements of the catalyst are combined, and the final product is calcined to obtain the catalyst. A number of methods for combining the elements of the catalyst and calcining the resulting product are known to those skilled in the art. For the broad idea of the invention, the particular method for producing the catalysts is not critical.
Det er imidlertid fremgangsmåter ved fremstilling av katalysatorene som har vist seg å være foretrukket. En forétrukken fremgangsmåte involverer fremstilling av katalysatorene i en vandig oppslemning eller oppløsning av molybden-, arsen- og/eller fosforholdige bestanddeler, og tilsette de gjenværende bestanddeler; inndampe denne vandige blanding og calcinere de erholdte katalysatorer. Egnede molybdenforbindelser som kan anvendes ved fremstilling av katalysatorene angitt ved de ovenstående formler^innbefatter molybdentrioxyd, fosformolybdensyre, molybdensyre, ammoniumheptamolybdat og lignende. Passende fosforforbindelser som kan anvendes ved fremstilling av katalysatorene, innbefatter orthofosforsyre, metafosforsyre, trifosfor sy re og fosforhalogen-ider eller -oxyhalogenider. De gjenværende bestanddeler av katalysatorene kan tilsettes som oxyd, acetat, f ormia.t , sulfat, There are, however, methods for producing the catalysts which have been shown to be preferred. A preferred method involves preparing the catalysts in an aqueous slurry or solution of molybdenum-, arsenic- and/or phosphorus-containing constituents, and adding the remaining constituents; evaporate this aqueous mixture and calcine the catalysts obtained. Suitable molybdenum compounds which can be used in the preparation of the catalysts indicated by the above formulas include molybdenum trioxide, phosphormolybdic acid, molybdic acid, ammonium heptamolybdate and the like. Suitable phosphorus compounds which can be used in the preparation of the catalysts include orthophosphoric acid, metaphosphoric acid, triphosphoric acid and phosphorus halides or -oxyhalides. The remaining components of the catalysts can be added as oxide, acetate, formate, sulfate,
nitrat, carbonat, oxyhalogenid eller halogenid og lignende. nitrate, carbonate, oxyhalide or halide and the like.
Utmerkede resultater fåes ved tilbakeløpskokning av fosforsyre, en arsenholdig forbindelse og molybdentrioxyd eller ammoniumheptamolybdat i vann i ca. en halv time til 3 timer, men kommersiell fosformolybdensyre kan anvendes effektivt; tilsetning av de gjenværende bestanddeler til den vandige oppslemning og innkokning til én tykk pasta; tørring ved 110 - 120°C i luft; Excellent results are obtained by refluxing phosphoric acid, an arsenic-containing compound and molybdenum trioxide or ammonium heptamolybdate in water for approx. half an hour to 3 hours, but commercial phosphormolybdic acid can be used effectively; adding the remaining ingredients to the aqueous slurry and boiling to a thick paste; drying at 110 - 120°C in air;
og calcinering av de erholdte katalysatorer.and calcination of the obtained catalysts.
Calcineringen av katalysatoren utføres vanligvis ved å opp-varme de tørre katalytiske bestanddeler ved en temperatur på ca. 200 C til ca . 700 C. Den foretrukne fremgangsmåte ifølge oppf innr-eisen er den hvor katalysatoren calcineres ved en temperatur på 325 - 425°C. The calcination of the catalyst is usually carried out by heating the dry catalytic components at a temperature of approx. 200 C to approx. 700 C. The preferred method according to the invention is that where the catalyst is calcined at a temperature of 325 - 425°C.
Reaktantene ved reaksjonen ifølge oppfinnelsen er methacrolein eller acrolein og oxygen. Molekylært oxygen til-føres vanligvis til reaksjonen i form av luft, men oxygengass kan også anvendes. Ca. 0,5 til ca.. 4 mol oxygen tilsettes vanligvis pr. mol methacrolein. The reactants in the reaction according to the invention are methacrolein or acrolein and oxygen. Molecular oxygen is usually supplied to the reaction in the form of air, but oxygen gas can also be used. About. 0.5 to approx. 4 mol of oxygen are usually added per moles of methacrolein.
Reaksjonstempératuren kan variere efter som forskjellige katalysatorer anvendes. Vanligvis anvendes en temperatur på ca. 200 til ca. 500°C idet en temperatur på 250 - 370°C foretrekkes. The reaction temperature can vary according to which different catalysts are used. A temperature of approx. 200 to approx. 500°C, with a temperature of 250 - 370°C being preferred.
Katalysatoren kan anvendes alene, eller en bærer kan anvendes. Passende bærere innbefatter siliciumoxyd, aluminiumoxyd., "Alundum", siliciumcarbid, borfosfat, zirkoniumdioxyd og titandioxyd. Katalysatorene anvendes hekvemt i en fastlagsreaktor som tabletter, pellets eller lignende, eller i en sveveskikts-reaktor under anvendelse av en katalysator med en partikkelstørr-else på under ca. 300 |im . Når en sveveskikt sreaktor anvendes, er de foretrukne katalysatorer i. form av mikrokuleformige par-tikler. Kontakttiden kan være så lav som en brøkdel av et sekund eller så høy som 20 sekunder eller mere. Reaksjonen kan utføres ved atmosf æret rykk, overtrykk eller undertrykk, idet absolutte trykk på ca. 0,5 til ca. 4 ata foretrekkes. The catalyst may be used alone, or a carrier may be used. Suitable carriers include silicon oxide, aluminum oxide, "Alundum", silicon carbide, boron phosphate, zirconium dioxide and titanium dioxide. The catalysts are usually used in a fixed-bed reactor such as tablets, pellets or the like, or in a suspended-bed reactor using a catalyst with a particle size of less than approx. 300 |im . When a fluidized bed reactor is used, the preferred catalysts are in the form of microspherical particles. The contact time can be as low as a fraction of a second or as high as 20 seconds or more. The reaction can be carried out by atmospheric thrust, overpressure or underpressure, as absolute pressures of approx. 0.5 to approx. 4 ata is preferred.
Utmerkede resultater fåes under anvendelse av en belagt katalysator bestående.i det vesentlige av et inert bærermateria le med en diameter på minst 20 (i.m og med en ytre overflate og et kontinuerlig belegg av den aktive katalysator på den inerte bærer sterkt vedheftende til den ytre overflate av bæreren. Den spesielle belagte katalysator består av et indre bærermateriale med en utvendig overflate og et belegg av aktivt katalytisk materiale, på denne utvendige overflate. Disse katalysatorer kan fremstilles ved en rekke forskjellige metoder. Excellent results are obtained using a coated catalyst consisting essentially of an inert support material with a diameter of at least 20 (in.m) and with an outer surface and a continuous coating of the active catalyst on the inert support strongly adhering to the outer surface of the support. The special coated catalyst consists of an internal support material with an external surface and a coating of active catalytic material on this external surface. These catalysts can be prepared by a number of different methods.
Bærermaterialet for katalysator danner den indre kjerne av katalysatoren. Dette er. en i det vesentlige inert bærer og kan ha praktisk talt en hvilken som helst partikkelstørrelse skjønt en diameter større enn 20 um foretrekkes. Særlig foretrukket ifølge foreliggende oppfinnelse for anvendelse i en kommersiell reaktor er de bærere som er kuleformige og som har en diameter på fra ca. 0,2 cm til ca. 2 cm. Passende eksempler på i det vesentlige inerte bærermaterialer innbefatter: "Alundum", siliciumoxyd, aluminiumoxyd, aluminiumoxyd-siliciumoxyd, siliciumcarbid, titandioxyd og zirkoniumdioxyd. Særlig foretrukket blant disse bærere er "Alundum", siliciumoxyd, aluminiumoxyd og aluminiumoxyd-siliciumoxyd. The support material for the catalyst forms the inner core of the catalyst. This is. a substantially inert carrier and may have virtually any particle size although a diameter greater than 20 µm is preferred. Particularly preferred according to the present invention for use in a commercial reactor are the carriers which are spherical and have a diameter of from approx. 0.2 cm to approx. 2 cm. Suitable examples of substantially inert carrier materials include: "Alundum", silicon oxide, aluminum oxide, aluminum oxide-silicon oxide, silicon carbide, titanium dioxide and zirconium dioxide. Particularly preferred among these carriers are "Alundum", silicon oxide, aluminum oxide and aluminum oxide-silicon oxide.
Katalysatorene kan inneholde stort sett hvilke som helst forhold av bærer og katalytisk aktivt materiale. Grensene for dette forhold settes bare av den relative evne av katalysatoren og bærermaterialet.til å tilpasse seg hverandre. Foretrukne katalysatorer inneholder ca. 10 til ca. 100 vekt% katalytisk aktivt, materiale beregnet på vekten av bæreren. The catalysts can contain virtually any ratio of carrier and catalytically active material. The limits of this relationship are set only by the relative ability of the catalyst and the support material to adapt to each other. Preferred catalysts contain approx. 10 to approx. 100% by weight catalytically active, material calculated on the weight of the carrier.
Fremstillingen av disse belagte katalysatorer kan utføres ved forskjellige metoder. Den grunnleggende metode for fremstilling av disse katalysatorer er ved delvis væting av bærer-, materialet med en væske og derpå bringe bærermaterialet i kontakt med et pulver av det katalytisk aktive materiale og forsiktig ryste blandingen inntil katalysatoren er dannet. Den forsiktige rysting utføres mest bekvemt ved å anbringe den delvis våte bærer i en roterende trommel eller krukke og tilsette det pulveriserte aktive katalytiske materiale. The production of these coated catalysts can be carried out by different methods. The basic method for producing these catalysts is by partially wetting the carrier material with a liquid and then bringing the carrier material into contact with a powder of the catalytically active material and gently shaking the mixture until the catalyst is formed. The gentle shaking is most conveniently accomplished by placing the partially wet support in a rotating drum or jar and adding the powdered active catalytic material.
Under anvendelse av katalysatorene ifølge oppfinnelsen ved. fremstilling av methacrylsyre eller acrylsyre, fåes utmerkede utbytter i en bekvem reaksjon med lave mengder av biprodukter. When using the catalysts according to the invention by. production of methacrylic acid or acrylic acid, excellent yields are obtained in a convenient reaction with low amounts of by-products.
Spesifikke utførelsesformerSpecific embodiments
Sammenligningseksempler A til D og ek sempler 1 til 80: Sammenligning av katalysatorer inneholdende promotorer ifølge oppfinnelsen med grunnkatalysator ved fremstilling av methacrylsyre. - Comparative examples A to D and examples 1 to 80: Comparison of catalysts containing promoters according to the invention with basic catalyst in the production of methacrylic acid. -
En 20 cm 3'fast lagsreaktor ble konstruert av et 1,3 cm rust-fritt stålrør. Katalysatorer fremstilt som beskrevet ovenfor, A 20 cm 3' fixed bed reactor was constructed from a 1.3 cm stainless steel tube. Catalysts prepared as described above,
ble innført i reaktoren og oppvarmet til reaksjdnstemperaturen under en luftstrøm og en påmatning av methacrolein/luft/nitro-gen/damp i forholdet 1:5,7:4,6:8,7 ble matet over katalysatoren med en tilsynelatende kontakttid på 2 - 4 sekunder. Reaktoren ble kjørt under reaksjonsbetingelsene i 1 - 6 timer, og produktet ble oppsamlet og analysert. was introduced into the reactor and heated to the reaction temperature under an air stream and a feed of methacrolein/air/nitrogen/steam in the ratio 1:5.7:4.6:8.7 was fed over the catalyst with an apparent contact time of 2 - 4 seconds. The reactor was run under the reaction conditions for 1-6 hours, and the product was collected and analyzed.
Sa mmenlignende eksempel AComparative example A
25% Mo12PiAso 5°x + 75% "Alundum" 25% Mo12PiAso 5°x + 75% "Alundum"
En oppløsning ble fremstilt bestående av 211,88 g ammonium-hept amolybdat , (NH^6Mo702Zf.4H20 , (1,2 mol Mo), 500 ml destillert vann av 6o°Cog 7,94 g. ammoniumarsenat, NH^H2AsO^(0,05 mol As) A solution was prepared consisting of 211.88 g of ammonium heptamolybdate, (NH^6Mo702Zf.4H20, (1.2 mol Mo), 500 ml of distilled water of 6o°C and 7.94 g of ammonium arsenate, NH^H2AsO^( 0.05 mol As)
som oppløsning i 25 ml destillert vann. Et hvitt bunnfall ble as a solution in 25 ml of distilled water. A white precipitate was formed
dannet som ble oppvarmet til. ca. 10Q°C i 2 timer. Til denne blanding ble tilsatt 11,53985%-ig fosforsyre (0,10 mol P). En halv time senere ble 5,0 g hydrazinhydrat tilsatt. Oppslemningen ble inndampet til en tykk pasta, tørret over natten i en ovn ved 110 - 120°C og malt og siktet til under 80 mesh. Dette pulver ble belagt på "Norton 3,2 mm SA 5223" "Alundum"-kuler ved å væte 50 g "Alundum" delvis med 1,89vann og tilsette 16,7 g aktiv katalysator fremstilt ovenfor i fem like store porsjoner. Under og efter hver tilsetning ble "Alundum"-kulene rullet i en glass-krukke. Pulveret ble jevnt belagt på overflaten av "Alundum"-kulene, og sluttproduktet ble tørret. Et hårdt, jevnt materiale ble erholdt som besto av en indre kjerne av "Alundum"-bæreren med et kontinuerlig, sterkt vedheftende belegg av pulveret på den ytre overflateav bæreren. Materialet ble så calcinert i 1 time ved 370°C i 40 ml/min luft for å danne den aktive katalysator. formed which was heated to. about. 10Q°C for 2 hours. 11.53985% phosphoric acid (0.10 mol P) was added to this mixture. Half an hour later, 5.0 g of hydrazine hydrate was added. The slurry was evaporated to a thick paste, dried overnight in an oven at 110 - 120°C and ground and screened to less than 80 mesh. This powder was coated on "Norton 3.2 mm SA 5223" "Alundum" beads by wetting 50 g of "Alundum" partially with 1.8 g of water and adding 16.7 g of active catalyst prepared above in five equal portions. During and after each addition, the "Alundum" balls were rolled in a glass jar. The powder was uniformly coated on the surface of the "Alundum" balls and the final product was dried. A hard, uniform material was obtained which consisted of an inner core of the "Alundum" carrier with a continuous, highly adherent coating of the powder on the outer surface of the carrier. The material was then calcined for 1 hour at 370°C in 40 ml/min air to form the active catalyst.
Eksempel 1 til 9Examples 1 to 9
Forskjellige katalysatorer med formel 1 ble fremstilt som følger: Various catalysts of formula 1 were prepared as follows:
Eksempel 1Example 1
25% (sjelden jordblanding) Mo P As ,-0 + 75% "Alundum" 25% (rare earth mixture) Mo P As ,-0 + 75% "Alundum"
En oppløsning ble bestemt bestående av 105,9 g ammonium-hept amolybdat , (NH^)6Mo^02^.4H20, (0,6 mol Mo), 700 ml destillert vann av 6o°Cog 4,0 g ammoniumarsenat, NH^H2AsO^, (0,025 mol As) som oppløsning i 25 ml vann. Et hvitt bunnfall ble dannet som ble oppvarmet ved I0O°C i en halv time. Til denne blanding ble tilsatt 4,4 g Moly Corp. sjelden jordkloridblanding (produkt-kode nr. 4700) bestående av 48% Ce02, 33% La2°3>13% Nd2°3'A solution was determined consisting of 105.9 g of ammonium heptamolybdate, (NH^)6Mo^O2^.4H20, (0.6 mol Mo), 700 ml of distilled water of 6o°C and 4.0 g of ammonium arsenate, NH^ H2AsO^, (0.025 mol As) as a solution in 25 ml of water. A white precipitate formed which was heated at 100°C for half an hour. To this mixture was added 4.4 g of Moly Corp. rare earth chloride mixture (product code no. 4700) consisting of 48% Ce02, 33% La2°3>13% Nd2°3'
4,5% Pi^ 01 og 1,5% andre sjeldne jordelementer beregnet som oxyder. Til denne oppløsning ble tilsatt 5,8 g 85%-ig fosforsyre, H3P°4 (0>°5 .mol P) . En halv time senere ble 2,5 g hydrazinhydrat tilsatt. Oppslemningen ble inndampet til en tykk pasta, 4.5% Pi^ 01 and 1.5% other rare earth elements calculated as oxides. 5.8 g of 85% phosphoric acid, H3P°4 (0>°5.mol P) was added to this solution. Half an hour later, 2.5 g of hydrazine hydrate was added. The slurry was evaporated to a thick paste,
tørret over natten i en ovn ved .110 - 120°C og malt og siktet til under 80 mesh størrelse. Katalysatoren ble så belagt i en aktiv tykkelse på 25% på 3,2 mm "SA 5223" "Alundum"-kuler. Calcineringen var den samme som i sammenlignende eksempel A. dried overnight in an oven at .110 - 120°C and ground and sieved to below 80 mesh size. The catalyst was then coated to an active thickness of 25% on 3.2 mm "SA 5223" "Alundum" beads. The calcination was the same as in Comparative Example A.
Eksempel 2 til 7Example 2 to 7
Fremstilling av katalysatorenePreparation of the catalysts
25% X Y,Mo10P-.AsA c0 + 75% "Alundum" 25% X Y,Mo10P-.AsA c0 + 75% "Alundum"
ab 121 0 , 5 x . ab 121 0 , 5 x .
Forskjellige katalysatorer ifølge oppfinnelsen ble fremstilt. Various catalysts according to the invention were prepared.
Katalysatorene ble fremstilt i henhold til fremgangsmåten i eksempel 1 under anvendelse av 105,99ammoniummolybdat, 700 ml 6o°C destillert vann og 4,0 g ammoniumarsenat oppløst i 25 ml vann.. De katalytiske bestanddeler angitt ved X og/eller Y ble tilsatt straks før tilsetningen av 5,8985%-ig fosforsyre og 2,59hydrazinhydrat. For å fremstille katalysatorene ble de følgende forbindelser og mengder anvendt: The catalysts were prepared according to the procedure in example 1 using 105.99 ammonium molybdate, 700 ml 6o°C distilled water and 4.0 g ammonium arsenate dissolved in 25 ml water. The catalytic components indicated by X and/or Y were added immediately before the addition of 5.8985% phosphoric acid and 2.59 hydrazine hydrate. To prepare the catalysts, the following compounds and quantities were used:
Ek sempel 8 Oak sample 8
25% sjelden jordmet a llbla nding ocO-U ~ Jo. 0P_, As„ c025% rarely earthed a llbla nding ocO-U ~ Jo. 0P_, As„ c0
U0,05 12 1 0,5 x U0.05 12 1 0.5 x
<+>75% " Alundum" <+>75% "Alundum"
Denne katalysator ble fremstilt på.samme måte som beskrevet i eksempel 1, unntatt at 34,25 g ammoniumheptamolybdat, 1,289ammoniumarsenat, 1,439sjelden jordmetallkloridblanding, This catalyst was prepared in the same manner as described in Example 1, except that 34.25 g of ammonium heptamolybdate, 1.28 g of ammonium arsenate, 1.43 g of rare earth chloride mixture,
0,l6l g kobberacétat, 1,88 g 85%-ig fosforsyre og 0,89hydrazinhydrat ble anvendt. 0.161 g of copper acetate, 1.88 g of 85% phosphoric acid and 0.89 g of hydrazine hydrate were used.
Eksempel 9Example 9
25% sjelden jordmetallblandingQ 25Ago lM°12PlAsQ 5°x<+>75% " Alundum" 25% rare earth metal mixtureQ 25Ago lM°12PlAsQ 5°x<+>75% " Alundum"
Denne katalysator ble fremstilt på samme måte som beskrevet i eksempel 8?unntatt at 0,269 g sølvacetat ble anvendt. This catalyst was prepared in the same manner as described in Example 8, except that 0.269 g of silver acetate was used.
Sammenlignende eksempler B, C og eksemple r 10 til 20 Comparative examples B, C and examples r 10 to 20
Resultatene av forsøkene under anvendelse av katalysatorer med formel I ved oxydasjonen av methacrolein. for å fremstille methacrylsyre er vist i tabell I. De følgende definisjoner er anvendt for å måle carbonatomene i påmatningen og produktene. The results of the experiments using catalysts of formula I in the oxidation of methacrolein. to prepare methacrylic acid is shown in Table I. The following definitions are used to measure the carbon atoms in the feed and products.
Eksempel 21 til 43 Examples 21 to 43
Forskjellige katalysatorer med formel II ble fremstilt som følger: Various catalysts of formula II were prepared as follows:
Eks empel 21Example 21
25% U_oCMo-, _P.As_ JD75% "Alundum"25% U_oCMo-, _P.As_ JD75% "Alundum"
0,25 12 1O,Dx 0.25 12 1O,Dx
En oppløsning ble fremstilt bestående av 105,9 g ammoniumheptamolybdat , (NH^) gMo,-P2/+.4H20 , (0,6 mol Mo), 700 ml destillert vann av 6o°C og 4,0 g ammoniumarsenat, NH^H2AsO^(0,025 mol As) oppløst i 25 ml vann. Et hvitt bunnfall ble dannet som ble oppvarmet ved 100°C i ca. en halv time. Til denne blanding ble tilsatt 5,3 g uranylacetat (0,0125 mol U), fulgt av tilsetning av 5,8 g 85%-ig fosforsyre (0,05 mol P). En halv time senere ble 2,5 g hydrazinhydrat tilsatt. Oppslemningen ble inndampet til en tykk pasta, tørret over natten i en ovn ved 110 - 120°C og malt og siktet til under 80 mesh størrelse. Katalysatoren ble så belagt til et 25% aktivitetsnivå på 3,2 mm "SA 5223" "Alundum"- A solution was prepared consisting of 105.9 g of ammonium heptamolybdate, (NH^)gMo,-P2/+.4H20, (0.6 mol Mo), 700 ml of distilled water of 6o°C and 4.0 g of ammonium arsenate, NH^ H2AsO^(0.025 mol As) dissolved in 25 ml of water. A white precipitate was formed which was heated at 100°C for approx. half hour. To this mixture was added 5.3 g uranyl acetate (0.0125 mol U), followed by the addition of 5.8 g 85% phosphoric acid (0.05 mol P). Half an hour later, 2.5 g of hydrazine hydrate was added. The slurry was evaporated to a thick paste, dried overnight in an oven at 110 - 120°C and ground and sieved to below 80 mesh size. The catalyst was then coated to a 25% activity level on 3.2 mm "SA 5223" "Alundum"-
kuler . Ca1cineringen var den samme som i sammenlignende eksem-bullets. The ca1cination was the same as in comparative exem-
pel A .pile A .
Eksempel 22 Example 22
25% TiQ 2Mol2PlAsO 5°x<+>75% "Alundum" 25% TiQ 2Mol2PlAsO 5°x<+>75% "Alundum"
Denne katalysator fremstilles på samme måte som beskrevet i eksempel 21, unntatt at 7,72 g 20%-ig titantrikloridoppløsnihg ble anvendt og hydrazinhydrat ble sløyfet ved kataly-sat orf remst i 11 - ingen. This catalyst is prepared in the same way as described in example 21, except that 7.72 g of a 20% titanium trichloride solution was used and hydrazine hydrate was looped at the catalyst or remst in 11 - none.
Eksempel 23Example 23
25% (sjelden jordmetallblanding)0Ti . Mo.. „P.. As... c025% (rare earth metal mixture)0Ti . Mo.. „P.. As... c0
+75%" Alundum" Q, 2 U, l1Z1O > - > *;Denne katalysator ble fremstilt på samme måte som beskrevet;i eksempel 21, unntatt at 3,549sjelden jordmetallkloridbland-;ing, 0,5 g. hydrazinhydrat ble anvendt, og 3,85 g 20%-ig titan-, trikloridoppløsning ble tilsatt. ;Eksempel 24 til, 39;Fremstilling av katalysatorene 25% X Y.Mo^PAs. JD + 75% "Alundum" ;au 121 0,5 ^ ;Forskjellige katalysatorer ifølge oppfinnelsen ble fremstilt . Katalysatorene ble fremstilt ved fremgangsmåten i eksempel 21, under anvendelse av 105,9 g arnmoniummolybdat , 700 ml destillert vann av 60°C og 4,0 g ammoniumarsenat oppløst i 25 ml vann. Kata-lysatorbestanddelene angitt ved X og/eller Y.ble tilsatt straks før tilsetningen av. 5,8 g 85%-ig fosforsyre. 2,5 g hydrazinhydrat ble tilsatt ved alle fremstillinger, unntatt at intet hydrazin ble tilsatt i eksempel 28, 30, 32 og 38; og 1,0 g hydrazin ble tilsatt i eksempel 14. For å fremstille katalysatorene ble følgende forbindelser og mengder anvendt: ; Eksempel 40;25% Mo^P^s. ,NbA „,Agn 0 + 75%"Alundum" ;12 1 Q , 5 Q ) 25 0, Q5 x ;Denne katalysator ble fremstilt på samme måte som beskrevet i eksempel 21, unntatt at 34,25 g ammoniummolybdat, 150 ml vann, 1,28 g ammoniumarsenat, 0,537 g niobklorid, 0,134 9 sølvacetat, 1,86 g 85%-ig fosforsyre og 0,8 g hydrazinhydrat ble anvendt. ;Eksempel 4l;25% Mo.-P.ASp. cNb^ 0CCuo -.0 + 75% "Alundum" ;12 1 O ,o0,2j? 0,1 x ;Denne katalysator ble fremstilt på samme måte som beskrevet i eksempel 24, unntatt at 0,322 g kobberacetat ble tilsatt i tillegg til niobkloridet. ;Eksempel 42;25% 2nDt2Al0t08Cu0t05Mo12P1>32ASQ>jOx+ 75% " Alundum" ;Denne katalysator ble fremstilt på samme måte som beskrevet i eksempel 37, unntatt at 0,96 g aluminiumklorid-hydrat og 7,6 g 85%-ig fosforsyre ble anvendt. ;Eksempel 43;25<%>Re0) 1AlQ>091Cu0>05Mo12P1) 32As0>50>, + 75% " Alundum" ;Denne katalysator ble fremstilt på samme måte som beskrevet i eksempel 42, unntatt at 1,1 g aluminiumklorid-hydrat og 1,21 g Re20-ble anvendt. ;Sammenli gnende eksemple r B til D og eksempler 44 til 67 ;Resultatene av forsøkene under anvendelse av katalysatorer med formel .II i oxydasjonen av methacrolein til methacrylsyre er vist i tabell II. De samme definisjoner som beskrevet ovenfor, ;er anvendt ved måling av carbonatomene i påmatningen og' produktene. ;På samme måte.som beskrevet ovenfor, kan katalysatorene ifølge oppfinnelsen effektivt anvendes ved frem<*>stilling av ac-ryl--syre fra acrolein. +75%" Alundum" Q, 2 U, l1Z1O > - > *; This catalyst was prepared in the same manner as described; in Example 21, except that 3.549 rare earth metal chloride mixture, 0.5 g. hydrazine hydrate was used, and 3.85 g of 20% titanium trichloride solution was added. ;Example 24 to, 39;Preparation of the catalysts 25% X Y.Mo^PAs. JD + 75% "Alundum" ;au 121 0.5 ^ ;Various catalysts according to the invention were prepared. The catalysts were prepared by the method in example 21, using 105.9 g of ammonium molybdate, 700 ml of distilled water at 60°C and 4.0 g of ammonium arsenate dissolved in 25 ml of water. The catalyst components indicated by X and/or Y were added immediately before the addition of. 5.8 g 85% phosphoric acid. 2.5 g of hydrazine hydrate was added in all preparations, except that no hydrazine was added in examples 28, 30, 32 and 38; and 1.0 g of hydrazine was added in example 14. To prepare the catalysts, the following compounds and amounts were used: ; Example 40; 25% Mo^P^s. ,NbA „,Agn 0 + 75% "Alundum" ;12 1 Q , 5 Q ) 25 0, Q5 x ;This catalyst was prepared in the same manner as described in Example 21, except that 34.25 g of ammonium molybdate, 150 ml of water , 1.28 g of ammonium arsenate, 0.537 g of niobium chloride, 0.134 g of silver acetate, 1.86 g of 85% phosphoric acid and 0.8 g of hydrazine hydrate were used. ;Example 4l;25% Mo.-P.ASp. cNb^ 0CCuo -.0 + 75% "Alundum" ;12 1 O ,o0,2j? 0.1 x ; This catalyst was prepared in the same manner as described in Example 24, except that 0.322 g of copper acetate was added in addition to the niobium chloride. ;Example 42;25% 2nDt2Al0t08Cu0t05Mo12P1>32ASQ>jOx+ 75% " Alundum" ;This catalyst was prepared in the same manner as described in Example 37, except that 0.96 g of aluminum chloride hydrate and 7.6 g of 85% phosphoric acid were used. ;Example 43;25<%>Re0) 1AlQ>091Cu0>05Mo12P1) 32As0>50>, + 75% "Alundum" ;This catalyst was prepared in the same manner as described in Example 42, except that 1.1 g of aluminum chloride hydrate and 1.21 g of Re 2 O was used. Comparative Examples B to D and Examples 44 to 67 The results of the experiments using catalysts of formula II in the oxidation of methacrolein to methacrylic acid are shown in Table II. The same definitions as described above are used when measuring the carbon atoms in the feed and the products. In the same way as described above, the catalysts according to the invention can be effectively used in the production of acrylic acid from acrolein.
Eksempel 68 til 73 Examples 68 to 73
Forskjellige katalysatorer med formel III ble fremstiltVarious catalysts of formula III were prepared
som følger:as follows:
Ek sempel 68Oak sample 68
2<5%>Ag_ _cMon JP.,As_ c0 + 75%"Alundum" 2<5%>Ag_ _cMon JP.,As_ c0 + 75%"Alundum"
0,25 12 10,jx 0.25 12 10.jx
En oppløsning.ble fremstilt bestående av 105,9 g ammoniumheptamolybdat , (NH^ ) 6Moy02Z+ . k^ 2° > (°>6 mo1 Mo) > 700 ml destillert vann av 6o°C og 4,0 g ammoniumarsenat, NH^I-^AsO^, (0,025 mol As), som oppløsning i 25 ml vann. Et hvitt bunnfall ble dannet som ble oppvarmet ved 100°C i ca. en halv time. Til denne blanding ble tilsatt 2,089sølvacetat (0,0125 mol Ag), fulgt, av tilsetning av 5,8985%-ig fosforsyre (0,05 mol P). En halv time senere ble 2,5 g hydrazinhydrat tilsatt. Oppslemningen ble inndampet til en tykk pasta, tørret over natten i en ovn ved 110 - 120°C, og malt og siktet til under 80 mesh størrelse. Katalysatoren ble så belagt til 25% aktivt nivå på 3,2 mm ."SA 5223" "Alundum"-kuler. Calcineringen var den samme som i sammenlignende eksempel A. A solution was prepared consisting of 105.9 g of ammonium heptamolybdate, (NH 2 ) 6 MoyO 2 Z + . k^ 2° > (°>6 mo1 Mo) > 700 ml of distilled water of 6o°C and 4.0 g of ammonium arsenate, NH^I-^AsO^, (0.025 mol As), as a solution in 25 ml of water. A white precipitate was formed which was heated at 100°C for approx. half hour. To this mixture was added 2.089 silver acetate (0.0125 mol Ag), followed by the addition of 5.8985% phosphoric acid (0.05 mol P). Half an hour later, 2.5 g of hydrazine hydrate was added. The slurry was evaporated to a thick paste, dried overnight in an oven at 110 - 120°C, and ground and sieved to below 80 mesh size. The catalyst was then coated to 25% active level on 3.2 mm "SA 5223" "Alundum" beads. The calcination was the same as in Comparative Example A.
Eksempel 69Example 69
25<%><Au>0>o5Cd0>2Mo12P1>QA<s>0>5<O>xf 75% " Alundum" 25<%><Au>0>o5Cd0>2Mo12P1>QA<s>0>5<O>xf 75% "Alundum"
Denne katalysator ble fremstilt på samme måte som beskrevet i eksempel 68,. unntatt at 150 ml vann, 34,25 g ammoniummolybdat , 1,28 g ammoniumarsenat , 0,862 g cadmiumacetat , 0,318 g gull-klorid, .1,86 g 85%-ig fosforsyre og 0,89hydrazinhydrat ble anvendt . This catalyst was prepared in the same way as described in example 68. except that 150 ml of water, 34.25 g of ammonium molybdate, 1.28 g of ammonium arsenate, 0.862 g of cadmium acetate, 0.318 g of gold chloride, .1.86 g of 85% phosphoric acid and 0.89 g of hydrazine hydrate were used.
Eksempel 70Example 70
25% Ru_ _MonoPnAs„ cO + 75% "Alundum" 25% Ru_ _MonoPnAs„ cO + 75% "Alundum"
O , 2 12 1 U , _} X O , 2 12 1 U , _} X
Denne katalysator ble fremstilt på samme måte som beskrevet i eksempel 68, unntatt at 500 ml vann, 70,6 g ammoniummolybdat, 2,64 g ammoniumarsenat, 1,749rutheniumklorid, RuCl„.3H 0, (0,006 mol Ru), 3,84 g fosforsyre og 1,6 g hydrazinhydrat ble anvendt . This catalyst was prepared in the same manner as described in Example 68, except that 500 ml water, 70.6 g ammonium molybdate, 2.64 g ammonium arsenate, 1.749 ruthenium chloride, RuCl„.3H 0, (0.006 mol Ru), 3.84 g phosphoric acid and 1.6 g of hydrazine hydrate were used.
Eksempel 71 til 73Examples 71 to 73
Fremstilling av katalysatorene 25% X YKMo-.0P,As ,-0Preparation of the catalysts 25% X YKMo-.0P,As ,-0
+ 75 % " Alundum " a b 12 1 0,5 x + 75% "Alundum" a b 12 1 0.5 x
Forskjellige katalysatorer ifølge oppfinnelsen ble frem-'stilt. Katalysatorene ble fremstilt ved fremgangsmåten i eks empel 68, under anvendelse av 105,9.9ammoniummolybdat, 700 ml destillert vann av 60°C og 4,0 g ammoniumarsenat oppløst i 25 ml vann. De katalytiske bestanddeler betegnet med X og/eller Y ble tilsatt straks før tilsetningen av 5,8985%-ig fosforsyre og 2,5 g hydrazinhydrat. For å fremstille katalysatorene ble følg-ende forbindelser og mengder anvendt: Various catalysts according to the invention were prepared. The catalysts were prepared by the method in Example 68, using 105.9.9 ammonium molybdate, 700 ml of distilled water at 60°C and 4.0 g of ammonium arsenate dissolved in 25 ml of water. The catalytic components denoted by X and/or Y were added immediately before the addition of 5.8985% phosphoric acid and 2.5 g of hydrazine hydrate. To prepare the catalysts, the following compounds and quantities were used:
Sammenlignende eksempler B til D o g eksempler 74 til 80 Comparative examples B to D and examples 74 to 80
Resultatene av forsøkene under anvendelse av katalysatorer med formel III ved oxydasjon av methacrolein til methacrylsyre er vist i tabell III. De samme definisjoner som beskrevet ovenfor, ble anvendt til å måle carbonatomene i påmatningen og i produktene. The results of the experiments using catalysts of formula III in the oxidation of methacrolein to methacrylic acid are shown in Table III. The same definitions as described above were used to measure the carbon atoms in the feed and in the products.
På samme måte som beskrevet ovenfor, kan katalysatorene ifølge oppfinnelsen effektivt anvendes ved fremstilling av acrylsyre fra acrolein. In the same way as described above, the catalysts according to the invention can be effectively used in the production of acrylic acid from acrolein.
Claims (13)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US05/733,738 US4075124A (en) | 1976-10-19 | 1976-10-19 | Process for the preparation of unsaturated acids from unsaturated aldehydes |
US05/733,737 US4075123A (en) | 1976-10-19 | 1976-10-19 | Process for the preparation of unsaturated acids from unsaturated aldehydes |
US05/733,735 US4085065A (en) | 1976-10-19 | 1976-10-19 | Process for the preparation of unsaturated acids from unsaturated aldehydes |
Publications (1)
Publication Number | Publication Date |
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NO783837L true NO783837L (en) | 1978-04-20 |
Family
ID=27419180
Family Applications (6)
Application Number | Title | Priority Date | Filing Date |
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NO773568A NO773568L (en) | 1976-10-19 | 1977-10-18 | PROCEDURE FOR THE PREPARATION OF UNSaturated Acids |
NO783837A NO783837L (en) | 1976-10-19 | 1978-11-15 | PROCEDURE FOR THE PREPARATION OF UNSaturated Acids |
NO783835A NO783835L (en) | 1976-10-19 | 1978-11-15 | PROCEDURE FOR THE PREPARATION OF UNSaturated Acids |
NO783836A NO783836L (en) | 1976-10-19 | 1978-11-15 | PROCEDURE FOR THE PREPARATION OF UNSaturated Acids |
NO783834A NO783834L (en) | 1976-10-19 | 1978-11-15 | PROCEDURE FOR THE PREPARATION OF UNSaturated Acids |
NO783833A NO783833L (en) | 1976-10-19 | 1978-11-15 | PROCEDURE FOR THE PREPARATION OF UNSaturated Acids |
Family Applications Before (1)
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NO773568A NO773568L (en) | 1976-10-19 | 1977-10-18 | PROCEDURE FOR THE PREPARATION OF UNSaturated Acids |
Family Applications After (4)
Application Number | Title | Priority Date | Filing Date |
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NO783835A NO783835L (en) | 1976-10-19 | 1978-11-15 | PROCEDURE FOR THE PREPARATION OF UNSaturated Acids |
NO783836A NO783836L (en) | 1976-10-19 | 1978-11-15 | PROCEDURE FOR THE PREPARATION OF UNSaturated Acids |
NO783834A NO783834L (en) | 1976-10-19 | 1978-11-15 | PROCEDURE FOR THE PREPARATION OF UNSaturated Acids |
NO783833A NO783833L (en) | 1976-10-19 | 1978-11-15 | PROCEDURE FOR THE PREPARATION OF UNSaturated Acids |
Country Status (15)
Country | Link |
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JP (1) | JPS5351194A (en) |
BG (2) | BG40476A3 (en) |
BR (1) | BR7706924A (en) |
CA (1) | CA1099250A (en) |
DD (1) | DD133431A5 (en) |
DE (2) | DE2746135A1 (en) |
ES (5) | ES472475A1 (en) |
FR (1) | FR2371229A1 (en) |
GB (1) | GB1575334A (en) |
IN (1) | IN147123B (en) |
IT (1) | IT1088096B (en) |
NL (1) | NL7711377A (en) |
NO (6) | NO773568L (en) |
PT (1) | PT67146B (en) |
RO (1) | RO81263B (en) |
Families Citing this family (4)
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JPS5811416B2 (en) * | 1978-12-13 | 1983-03-02 | 日本化薬株式会社 | Method for producing methacrylic acid |
FR2521565B1 (en) * | 1982-02-17 | 1985-07-05 | Dior Sa Parfums Christian | PULVERULENT MIXTURE OF LIPID COMPONENTS AND HYDROPHOBIC CONSTITUENTS, METHOD FOR PREPARING SAME, HYDRATED LIPID LAMELLAR PHASES AND MANUFACTURING METHOD, PHARMACEUTICAL OR COSMETIC COMPOSITIONS COMPRISING HYDRATED LAMID PHASES |
JPH0791212B2 (en) * | 1988-07-11 | 1995-10-04 | 三菱レイヨン株式会社 | Method for producing methacrylic acid |
US10882801B2 (en) | 2016-01-04 | 2021-01-05 | Saudi Arabian Oil Company | Methods for gas phase oxidative desulphurization of hydrocarbons using CuZnAl catalysts promoted with group VIB metal oxides |
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JPS5529061B2 (en) * | 1973-08-16 | 1980-07-31 |
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1977
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- 1977-10-10 IT IT28433/77A patent/IT1088096B/en active
- 1977-10-12 PT PT67146A patent/PT67146B/en unknown
- 1977-10-13 CA CA288,657A patent/CA1099250A/en not_active Expired
- 1977-10-13 DE DE19772746135 patent/DE2746135A1/en active Granted
- 1977-10-13 DE DE2760323A patent/DE2760323C2/de not_active Expired
- 1977-10-17 FR FR7731167A patent/FR2371229A1/en active Granted
- 1977-10-17 GB GB43047/77A patent/GB1575334A/en not_active Expired
- 1977-10-17 BR BR7706924A patent/BR7706924A/en unknown
- 1977-10-17 NL NL7711377A patent/NL7711377A/en not_active Application Discontinuation
- 1977-10-18 RO RO91875A patent/RO81263B/en unknown
- 1977-10-18 BG BG7841246A patent/BG40476A3/en unknown
- 1977-10-18 JP JP12564277A patent/JPS5351194A/en active Granted
- 1977-10-18 NO NO773568A patent/NO773568L/en unknown
- 1977-10-18 BG BG7737602A patent/BG40648A3/en unknown
- 1977-10-18 DD DD77201574A patent/DD133431A5/en unknown
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1978
- 1978-08-10 ES ES472475A patent/ES472475A1/en not_active Expired
- 1978-08-10 ES ES472476A patent/ES472476A1/en not_active Expired
- 1978-08-10 ES ES472474A patent/ES472474A1/en not_active Expired
- 1978-08-10 ES ES472473A patent/ES472473A1/en not_active Expired
- 1978-08-10 ES ES472472A patent/ES472472A1/en not_active Expired
- 1978-11-15 NO NO783837A patent/NO783837L/en unknown
- 1978-11-15 NO NO783835A patent/NO783835L/en unknown
- 1978-11-15 NO NO783836A patent/NO783836L/en unknown
- 1978-11-15 NO NO783834A patent/NO783834L/en unknown
- 1978-11-15 NO NO783833A patent/NO783833L/en unknown
Also Published As
Publication number | Publication date |
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NO783836L (en) | 1978-04-20 |
NO773568L (en) | 1978-04-20 |
FR2371229A1 (en) | 1978-06-16 |
DE2746135C2 (en) | 1987-02-26 |
BR7706924A (en) | 1978-06-27 |
GB1575334A (en) | 1980-09-17 |
BG40476A3 (en) | 1986-12-15 |
DE2760323C2 (en) | 1989-07-20 |
ES472475A1 (en) | 1979-04-01 |
NO783835L (en) | 1978-04-20 |
RO81263B (en) | 1983-02-28 |
FR2371229B1 (en) | 1984-03-09 |
IT1088096B (en) | 1985-06-04 |
BG40648A3 (en) | 1986-01-15 |
JPS5351194A (en) | 1978-05-10 |
JPS6211618B2 (en) | 1987-03-13 |
PT67146A (en) | 1977-11-01 |
CA1099250A (en) | 1981-04-14 |
DE2746135A1 (en) | 1978-04-27 |
ES472472A1 (en) | 1979-04-01 |
PT67146B (en) | 1979-03-19 |
IN147123B (en) | 1979-11-17 |
NO783833L (en) | 1978-04-20 |
ES472474A1 (en) | 1979-04-01 |
ES472473A1 (en) | 1979-04-01 |
NO783834L (en) | 1978-04-20 |
RO81263A (en) | 1983-02-15 |
ES472476A1 (en) | 1979-04-16 |
NL7711377A (en) | 1978-04-21 |
DD133431A5 (en) | 1979-01-03 |
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