JP5163273B2 - 不飽和アルデヒド及び/又は不飽和カルボン酸製造用触媒の製造方法、並びに不飽和アルデヒド及び/又は不飽和カルボン酸の製造方法 - Google Patents
不飽和アルデヒド及び/又は不飽和カルボン酸製造用触媒の製造方法、並びに不飽和アルデヒド及び/又は不飽和カルボン酸の製造方法 Download PDFInfo
- Publication number
- JP5163273B2 JP5163273B2 JP2008129200A JP2008129200A JP5163273B2 JP 5163273 B2 JP5163273 B2 JP 5163273B2 JP 2008129200 A JP2008129200 A JP 2008129200A JP 2008129200 A JP2008129200 A JP 2008129200A JP 5163273 B2 JP5163273 B2 JP 5163273B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- producing
- carboxylic acid
- unsaturated
- unsaturated carboxylic
- 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.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims description 92
- 238000004519 manufacturing process Methods 0.000 title claims description 22
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title claims 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 title claims 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 28
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 27
- 239000007789 gas Substances 0.000 claims description 27
- 239000003638 chemical reducing agent Substances 0.000 claims description 26
- 229910001882 dioxygen Inorganic materials 0.000 claims description 26
- 238000010304 firing Methods 0.000 claims description 20
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 16
- 238000007254 oxidation reaction Methods 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 13
- 229910052742 iron Inorganic materials 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 10
- 229910052797 bismuth Inorganic materials 0.000 claims description 10
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims description 10
- 239000011733 molybdenum Substances 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 9
- 239000002131 composite material Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052792 caesium Inorganic materials 0.000 claims description 4
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910052701 rubidium Inorganic materials 0.000 claims description 3
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052716 thallium Inorganic materials 0.000 claims description 3
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims description 3
- 239000012808 vapor phase Substances 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 229910052785 arsenic Inorganic materials 0.000 claims description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [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 claims description 2
- 239000011133 lead Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229910052714 tellurium Inorganic materials 0.000 claims description 2
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 2
- 239000011135 tin Substances 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 150000001299 aldehydes Chemical class 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- 150000001735 carboxylic acids Chemical class 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- -1 ethylene, propylene Chemical group 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 229910001868 water Inorganic materials 0.000 description 7
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 2
- 239000012784 inorganic fiber Substances 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 229910003208 (NH4)6Mo7O24·4H2O Inorganic materials 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical group CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- WCASXYBKJHWFMY-NSCUHMNNSA-N 2-Buten-1-ol Chemical compound C\C=C\CO WCASXYBKJHWFMY-NSCUHMNNSA-N 0.000 description 1
- BYDRTKVGBRTTIT-UHFFFAOYSA-N 2-methylprop-2-en-1-ol Chemical compound CC(=C)CO BYDRTKVGBRTTIT-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229910000608 Fe(NO3)3.9H2O Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000001622 bismuth compounds Chemical class 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 229910000380 bismuth sulfate Inorganic materials 0.000 description 1
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 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
- 238000000354 decomposition reaction Methods 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- BEQZMQXCOWIHRY-UHFFFAOYSA-H dibismuth;trisulfate Chemical compound [Bi+3].[Bi+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BEQZMQXCOWIHRY-UHFFFAOYSA-H 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- WCASXYBKJHWFMY-UHFFFAOYSA-N gamma-methylallyl alcohol Natural products CC=CCO WCASXYBKJHWFMY-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- 150000004715 keto acids Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 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
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical group C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 1
Classifications
-
- B01J35/30—
-
- 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
- B01J23/881—Molybdenum and iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8876—Arsenic, antimony or bismuth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/12—Oxidising
- B01J37/14—Oxidising with gases containing free oxygen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
- C07C45/35—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in propene or isobutene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C47/00—Compounds having —CHO groups
- C07C47/02—Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen
- C07C47/04—Formaldehyde
-
- 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
-
- 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
- C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
- C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
- C07C51/252—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- B01J35/40—
-
- B01J35/50—
Description
工程(1):触媒原料を含む水溶液又は水性スラリーを乾燥した後、分子状酸素含有ガスの雰囲気下に第一段焼成して焼成体を得る工程
工程(2):工程(1)で得られた焼成体を還元性物質の存在下に熱処理して、下記式(I)で示される質量減少率が0.05〜6%である還元体を得る工程
質量減少率(%)=(Wa−Wb)/Wa×100 (I)
(式中、Waは焼成体の質量を表し、Wbは還元体の質量を表す。)
工程(3):工程(2)で得られた還元体を分子状酸素含有ガスの雰囲気下に第二段焼成する工程
水平方向に対してほぼ垂直に設置された内径30mm、長さ5mの金属製チューブの底部に目開き4.76mmのステンレス製の網をその面がほぼ水平になるよう固定し、該金属製チューブの上部よりXgの触媒を投入して落下させた。落下後の触媒を回収し、これを目開き4.76mmの篩に乗せ、該篩を振動させた後、篩上に残った触媒の質量をYgとした。ここで、触媒の落下強度(%)は次の如く定義した。
(a)焼成体の調製〔工程(1)〕
モリブデン酸アンモニウム[(NH4)6Mo7O24・4H2O]13241gを温水15000gに溶解し、これをA液とした。一方、硝酸鉄(III)[Fe(NO3)3・9H2O]6060g、硝酸コバルト[Co(NO3)2・6H2O]13096g及び硝酸セシウム[CsNO3]585gを温水6000gに溶解し、次いで硝酸ビスマス[Bi(NO3)3・5H2O]2910gを溶解し、これをB液とした。A液を攪拌し、この中にB液を添加してスラリーを得、次いでこのスラリーを気流乾燥機により乾燥して乾燥物を得た。この乾燥物100質量部に対して9質量部のシリカアルミナファイバー(サンゴバン・ティーエム製、RFC400−SL)と2.5質量部の三酸化アンチモン(Sb2O3)とを該乾燥物に添加した後、外径6.3mm、内径2.5mm、長さ6mmのリング状に成型し、次いで、空気気流下に545℃で6時間焼成して焼成体を得た。この焼成体は、モリブデン12原子に対しビスマス0.96原子、鉄2.4原子、コバルト7.2原子、セシウム0.48原子、アンチモン0.48原子を含んでいる。
実施例1(a)で得られた焼成体75mlをガラス管に充填した後、水素/窒素=5/95(容積比)の混合ガスを300ml/minの流量で供給し、345℃にて8時間還元処理を行った。次いで水素の供給を停止し、窒素気流下に室温まで冷却して還元体を得た。還元処理よる質量減少率は1.04%であった。
実施例1(b)で得られた還元体を、空気気流下、350℃で3時間焼成し、触媒Aを得た。
実施例1(c)で得られた触媒A30gを用いて、上記落下強度試験を行ったところ、触媒Aの落下強度は91.8%であった。この結果を表1に示す。
内径18mmのガラス製反応管の原料ガス入口側に、実施例(c)で得られた触媒A14.3mlを30gのシリコンカーバイド(信濃電気精錬(株)製、シナノランダム GC F16)で希釈して充填した。ここに、イソブチレン/酸素/窒素/スチーム=1.0/2.0/10.0/2.7(モル比)の混合ガスを157.5ml/minの流量で供給し、反応温度360℃にて酸化反応を行った。イソブチレンの転化率は98.9%であり、メタクロレイン及びメタクリル酸の収率は79.6%であった。
(a)触媒の調製〔工程(1)〜(3)〕
実施例1(c)における焼成温度を350℃から370℃に変更した以外は、実施例1(a)〜(c)と同様の操作を行い、触媒Bを得た。
実施例2(a)で得られた触媒B30gを用いて、上記落下強度試験を行ったところ、触媒Bの落下強度は91.9%であった。この結果を表1に示す。
(a)焼成体の調製〔工程(1)〕
実施例1(a)におけるシリカアルミナファイバーの量を9質量部から12質量部に変更した以外は、実施例1(a)と同様の操作を行い、焼成体を得た。
実施例1(a)で得られた焼成体のかわりに実施例3(a)で得られた焼成体を用いた以外は、実施例1(b)と同様の操作で還元処理を行い、還元体を得た。還元処理よる触媒の質量減少率は1.06%であった。
実施例1(b)で得られた還元体のかわりに実施例3(b)で得られた還元体を用い、焼成温度を350℃から330℃に、焼成時間を3時間から5時間にそれぞれ変更した以外は、実施例1(c)と同様の操作で第二段焼成を行い、触媒Cを得た。
実施例3(c)で得られた触媒C30gを用いて、上記落下強度試験を行ったところ、触媒Cの落下強度は92.0%であった。この結果を表1に示す。
(a)触媒の調製〔工程(1)〜(3)〕
実施例3(c)における焼成温度を330℃から420℃に変更した以外は、実施例3(a)〜(c)と同様の操作を行い、触媒Dを得た。
実施例4(a)で得られた触媒D30gを用いて、上記落下強度試験を行ったところ、触媒Dの落下強度は93.3%であった。この結果を表1に示す。
(a)触媒の調製〔工程(1)のみ〕
実施例1(a)と同様の操作を行い、焼成体を得た。この焼成体を触媒Eとした。
比較例1(a)で得られた触媒E30gを用いて、上記落下強度試験を行ったところ、触媒Eの落下強度は86.1%であった。この結果を表1に示す。
触媒Aのかわりに比較例1(a)で得られた触媒Eを用いた以外は、実施例1(e)と同様の操作で酸化反応を行った。イソブチレンの転化率は95.1%であり、メタクロレイン及びメタクリル酸の収率は79.4%であった。
(a)触媒の調製〔工程(1)〜(2)のみ〕
実施例1(a)〜(b)と同様の操作を行い、還元体を得た。この還元体を触媒Fとした。
比較例2(a)で得られた触媒F30gを用いて、上記落下強度試験を行ったところ、触媒Fの落下強度は83.8%であった。この結果を表1に示す。
(a)触媒の調製〔工程(1)のみ〕
実施例3(a)と同様の操作を行い、焼成体を得た。この焼成体を触媒Gとした。
比較例3(a)で得られた触媒G30gを用いて、上記落下強度試験を行ったところ、触媒Gの落下強度は86.4%であった。この結果を表1に示す。
(a)触媒の調製〔工程(1)〜(2)のみ〕
実施例3(a)〜(b)と同様の操作を行い、還元体を得た。この還元体を触媒Hとした。
比較例3(a)で得られた触媒H30gを用いて、上記落下強度試験を行ったところ、触媒Hの落下強度は84.6%であった。この結果を表1に示す。
Claims (7)
- モリブデン、ビスマス及び鉄を含有する複合酸化物からなる不飽和アルデヒド及び/又は不飽和カルボン酸製造用触媒の製造方法であって、以下の工程(1)〜(3)を含むことを特徴とする不飽和アルデヒド及び/又は不飽和カルボン酸製造用触媒の製造方法。
工程(1):触媒原料を含む水溶液又は水性スラリーを乾燥した後、分子状酸素含有ガスの雰囲気下に第一段焼成して焼成体を得る工程
工程(2):工程(1)で得られた焼成体を還元性物質の存在下に熱処理して、下記式(I)で示される質量減少率が0.05〜5%である還元体を得る工程
質量減少率(%)=(Wa−Wb)/Wa×100 (I)
(式中、Waは焼成体の質量を表し、Wbは還元体の質量を表す。)
工程(3):工程(2)で得られた還元体を分子状酸素含有ガスの雰囲気下に第二段焼成する工程 - 前記複合酸化物が、下記一般式(II)
MoaBibFecAdBeCfDgOx (II)
(式中、Mo、Bi及びFeはそれぞれモリブデン、ビスマス及び鉄を表し、Aはニッケル及び/又はコバルトを表し、Bはマンガン、亜鉛、カルシウム、マグネシウム、スズ及び鉛から選ばれる元素を表し、Cはリン、ホウ素、ヒ素、テルル、タングステン、アンチモン、ケイ素、アルミニウム、チタン、ジルコニウム及びセリウムから選ばれる元素を表し、Dはカリウム、ルビジウム、セシウム及びタリウムから選ばれる元素を表し、a=12としたとき、0<b≦10、0<c≦10、1≦d≦10、0≦e≦10、0≦f≦10、0<g≦2であり、xは各元素の酸化状態により定まる値である。)
で示されるものである請求項1に記載の方法。 - 前記熱処理が、200〜600℃で行われる請求項1又は2に記載の方法。
- 第一段焼成が、300〜600℃で行われる請求項1〜3のいずれかに記載の方法。
- 第二段焼成が、200〜600℃で行われる請求項1〜4のいずれかに記載の方法。
- 還元性物質が水素、アンモニア、一酸化炭素、炭素数1〜6の炭化水素、炭素数1〜6のアルコール、炭素数1〜6のアルデヒド及び炭素数1〜6のアミンから選ばれる化合物である請求項1〜5のいずれかに記載の方法。
- 請求項1〜6のいずれかに記載の方法により触媒を製造し、この触媒の存在下に、プロピレン、イソブチレン及びターシャリーブチルアルコールから選ばれる化合物を分子状酸素により気相接触酸化する不飽和アルデヒド及び/又は不飽和カルボン酸の製造方法。
Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2008129200A JP5163273B2 (ja) | 2008-05-16 | 2008-05-16 | 不飽和アルデヒド及び/又は不飽和カルボン酸製造用触媒の製造方法、並びに不飽和アルデヒド及び/又は不飽和カルボン酸の製造方法 |
SG200903050-3A SG157292A1 (en) | 2008-05-16 | 2009-05-05 | Method for producing catalyst for use in production of unsaturated aldehyde and/or unsaturated carboxylic acid, and method for producing unsaturated aldehyde and/or unsaturated carboxylic acid |
DE102009021049A DE102009021049A1 (de) | 2008-05-16 | 2009-05-13 | Verfahren zur Herstellung eines Katalysators zur Verwendung bei der Herstellung von ungesättigten Aldehyden und/oder ungesättigten Carbonsäuren, und Verfahren zur Herstellung von ungesättigten Aldehyden und/oder ungesättigten Carbonsäuren |
KR1020090041994A KR20090119719A (ko) | 2008-05-16 | 2009-05-14 | 불포화 알데히드 및/또는 불포화 카르복실산 제조용 촉매의 제조 방법, 및 불포화 알데히드 및/또는 불포화 카르복실산의 제조 방법 |
CN200910143129.7A CN101579630B (zh) | 2008-05-16 | 2009-05-14 | 制备用于生产不饱和醛和/或不饱和羧酸的催化剂的方法以及制备不饱和醛和/或不饱和羧酸的方法 |
US12/467,079 US8252714B2 (en) | 2008-05-16 | 2009-05-15 | Method for producing catalyst for use in production of unsaturated aldehyde and/or unsaturated carboxylic acid, and method for producing unsaturated aldehyde and/or unsaturated carboxylic acid |
TW098116172A TWI454312B (zh) | 2008-05-16 | 2009-05-15 | 用於生產不飽和醛類及/或不飽和羧酸類之觸媒的製造方法,及生產不飽和醛類及/或不飽和羧酸類的方法 |
US13/555,840 US8586786B2 (en) | 2008-05-16 | 2012-07-23 | Method for producing catalyst for use in production of unsaturated aldehyde and/or unsaturated carboxylic acid, and method for producing unsaturated aldehyde and/or unsaturated carboxylic acid |
KR1020150185411A KR101821023B1 (ko) | 2008-05-16 | 2015-12-23 | 불포화 알데히드 및/또는 불포화 카르복실산 제조용 촉매의 제조 방법, 및 불포화 알데히드 및/또는 불포화 카르복실산의 제조 방법 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2008129200A JP5163273B2 (ja) | 2008-05-16 | 2008-05-16 | 不飽和アルデヒド及び/又は不飽和カルボン酸製造用触媒の製造方法、並びに不飽和アルデヒド及び/又は不飽和カルボン酸の製造方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2009274034A JP2009274034A (ja) | 2009-11-26 |
JP5163273B2 true JP5163273B2 (ja) | 2013-03-13 |
Family
ID=41316779
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2008129200A Active JP5163273B2 (ja) | 2008-05-16 | 2008-05-16 | 不飽和アルデヒド及び/又は不飽和カルボン酸製造用触媒の製造方法、並びに不飽和アルデヒド及び/又は不飽和カルボン酸の製造方法 |
Country Status (7)
Country | Link |
---|---|
US (2) | US8252714B2 (ja) |
JP (1) | JP5163273B2 (ja) |
KR (2) | KR20090119719A (ja) |
CN (1) | CN101579630B (ja) |
DE (1) | DE102009021049A1 (ja) |
SG (1) | SG157292A1 (ja) |
TW (1) | TWI454312B (ja) |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013129424A1 (ja) | 2012-02-29 | 2013-09-06 | 三菱レイヨン株式会社 | アクリロニトリルの製造方法 |
CN104203908B (zh) * | 2012-02-29 | 2016-12-07 | 三菱丽阳株式会社 | 丙烯腈的制造方法 |
JP5892826B2 (ja) | 2012-03-27 | 2016-03-23 | 住友化学株式会社 | メタクリル酸の製造方法 |
CN103721722B (zh) * | 2012-10-10 | 2017-03-08 | 上海华谊丙烯酸有限公司 | 复合氧化物催化剂及其制备方法 |
CN103739467B (zh) * | 2012-10-17 | 2016-02-10 | 中国石油化工股份有限公司 | 丙烯氧化制备丙烯醛方法 |
KR101554317B1 (ko) * | 2013-05-24 | 2015-09-18 | 주식회사 엘지화학 | 아크롤레인 및 아크릴산 제조용 링 촉매 및 이의 용도 |
CN104437533B (zh) * | 2013-09-24 | 2017-01-04 | 中国石油化工股份有限公司 | 甲基丙烯醛和甲基丙烯酸的催化剂及其制备方法 |
CN104437531A (zh) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | 甲基丙烯醛催化剂及其制备方法 |
CN104549349B (zh) * | 2013-10-28 | 2016-09-07 | 中国石油化工股份有限公司 | 甲基丙烯醛和甲基丙烯酸的催化剂 |
CN104549353B (zh) * | 2013-10-28 | 2016-09-07 | 中国石油化工股份有限公司 | 甲基丙烯醛和甲基丙烯酸的催化剂和其制备方法 |
CN103933998B (zh) * | 2014-04-21 | 2016-08-17 | 清华大学 | 用于甲醇氧化制甲醛的催化剂 |
CN105435805B (zh) * | 2014-08-18 | 2018-03-23 | 上海华谊新材料有限公司 | 催化剂、用该催化剂生产丙烯酸的方法和反应系统 |
KR20180055154A (ko) | 2016-11-16 | 2018-05-25 | 주식회사 엘지화학 | 촉매의 제조 방법 |
CN113828325A (zh) * | 2020-06-24 | 2021-12-24 | 中国石油化工股份有限公司 | 一种丙烯氧化制丙烯醛、丙烯酸催化剂及其制备方法 |
WO2022202756A1 (ja) | 2021-03-24 | 2022-09-29 | 三菱ケミカル株式会社 | 触媒、触媒の製造方法、並びにα,β-不飽和アルデヒド、α,β-不飽和カルボン酸、及びα,β-不飽和カルボン酸エステルの製造方法 |
Family Cites Families (51)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL158483B (nl) * | 1970-05-29 | 1978-11-15 | Sumitomo Chemical Co | Werkwijze voor het bereiden van acrylonitrile uit propeen. |
US4547484A (en) * | 1984-04-09 | 1985-10-15 | Monsanto Company | Method of preparing a catalyst for the oxidation and ammoxidation of olefins |
JPS6122040A (ja) * | 1984-07-10 | 1986-01-30 | Mitsubishi Rayon Co Ltd | メタクロレイン及びメタクリル酸の製造法 |
DE3740271A1 (de) * | 1987-11-27 | 1989-06-01 | Basf Ag | Verfahren zur herstellung einer fuer die gasphasenoxidation von propylen zu acrolein und acrylsaeure katalytisch aktiven masse |
JPH0813332B2 (ja) * | 1989-09-25 | 1996-02-14 | 三菱レイヨン株式会社 | メタクロレイン及びメタクリル酸の製造用触媒の調製法 |
JPH044048A (ja) * | 1990-04-19 | 1992-01-08 | Mitsubishi Rayon Co Ltd | 不飽和アルデヒド及び不飽和酸合成用触媒の製造法 |
JPH0597730A (ja) | 1991-10-08 | 1993-04-20 | Mitsubishi Rayon Co Ltd | メタクロレイン及びメタクリル酸合成用触媒の充填方法 |
JP2819078B2 (ja) | 1991-10-25 | 1998-10-30 | 三菱レイヨン株式会社 | モリブデン含有酸化物触媒の充填方法 |
JPH05317714A (ja) * | 1992-05-14 | 1993-12-03 | Mitsubishi Rayon Co Ltd | 不飽和アルデヒド及び不飽和カルボン酸合成用触媒の製造法 |
JP3276984B2 (ja) | 1992-06-19 | 2002-04-22 | 三菱レイヨン株式会社 | 不飽和アルデヒド及び不飽和カルボン酸合成用担持触媒及びその製造法 |
JP3251641B2 (ja) * | 1992-06-19 | 2002-01-28 | 三菱レイヨン株式会社 | 不飽和アルデヒド及び不飽和カルボン酸製造用触媒の製造法 |
KR100277241B1 (ko) * | 1993-06-25 | 2001-02-01 | 고오사이 아끼오 | 불포화 알데하이드 및 불포화 카복실산의 제조방법 |
JP3465350B2 (ja) * | 1994-06-22 | 2003-11-10 | 住友化学工業株式会社 | メタクリル酸製造用触媒の製造法 |
JP3826413B2 (ja) | 1995-08-17 | 2006-09-27 | 住友化学株式会社 | 不飽和アルデヒド及び不飽和カルボン酸合成用触媒成形体の製造方法 |
JP3347246B2 (ja) * | 1995-10-30 | 2002-11-20 | 三菱レイヨン株式会社 | 不飽和アルデヒド及び不飽和カルボン酸合成用触媒の製造法 |
JP3562983B2 (ja) * | 1997-11-25 | 2004-09-08 | 三菱レイヨン株式会社 | メタクロレイン及びメタクリル酸の製造方法 |
RO119228B1 (ro) * | 1998-04-23 | 2004-06-30 | Mitsubishiárayon,Áco.Áltd. | Catalizator şi procedeu pentru obţinerea nitrililor nesaturaţi |
JP3573959B2 (ja) * | 1998-05-12 | 2004-10-06 | ダイヤニトリックス株式会社 | モリブデン含有酸化物流動層触媒の再生法 |
SE520276C2 (sv) * | 1999-01-25 | 2003-06-17 | Elekta Ab | Anordning för kontrollerat förstörande av vävnad |
KR100569632B1 (ko) | 1999-05-13 | 2006-04-10 | 가부시키가이샤 닛폰 쇼쿠바이 | 불포화 알데히드 및 불포화 카르복실산을 제조하기 위한촉매 및 이 촉매를 사용하여 불포화 알데히드 및 불포화카르복실산을 제조하기 위한 방법 |
JP3943291B2 (ja) * | 1999-08-04 | 2007-07-11 | 株式会社日本触媒 | アクロレインおよびアクリル酸の製造方法 |
JP3744750B2 (ja) * | 1999-12-08 | 2006-02-15 | 株式会社日本触媒 | 複合酸化物触媒およびアクリル酸の製造方法 |
DE10101695A1 (de) * | 2001-01-15 | 2002-07-18 | Basf Ag | Verfahren zur heterogen katalysierten Gasphasenpartialoxidation von Vorläuferverbindungen der (Meth)acrylsäure |
JP3892244B2 (ja) | 2001-03-21 | 2007-03-14 | 株式会社日本触媒 | 不飽和アルデヒドおよび不飽和カルボン酸製造用触媒の製造方法 |
US7396955B2 (en) * | 2001-04-25 | 2008-07-08 | Rohm And Haas Company | Annealed and promoted catalyst |
US6740620B2 (en) * | 2001-04-25 | 2004-05-25 | Rohn And Haas Company | Single crystalline phase catalyst |
JP4030740B2 (ja) * | 2001-10-11 | 2008-01-09 | ダイヤニトリックス株式会社 | アンモ酸化用触媒の製造方法 |
ZA200208247B (en) * | 2001-10-26 | 2003-05-14 | Rohm & Haas | Treatment of mixed metal oxide catalyst. |
AU2002363405A1 (en) * | 2001-11-08 | 2003-05-19 | Mitsubishi Chemical Corporation | Composite oxide catalyst and method for preparation thereof |
DE60239222D1 (de) * | 2001-12-21 | 2011-03-31 | Asahi Kasei Chemicals Corp | Oxidkatalysatorzusammensetzung |
JP2004002208A (ja) | 2002-04-03 | 2004-01-08 | Nippon Shokubai Co Ltd | 不飽和アルデヒドの製造法 |
KR100513664B1 (ko) * | 2002-05-16 | 2005-09-07 | 주식회사 엘지화학 | 프로필렌의 부분 산화 반응용 촉매의 제조 방법 |
US6916763B2 (en) * | 2002-11-27 | 2005-07-12 | Solutia Inc. | Process for preparing a catalyst for the oxidation and ammoxidation of olefins |
US7361791B2 (en) * | 2003-03-31 | 2008-04-22 | Saudi Basic Industries Corporation | Mixed metal oxide catalysts for the production of unsaturated aldehydes from olefins |
JP4242197B2 (ja) * | 2003-04-18 | 2009-03-18 | ダイヤニトリックス株式会社 | アクリロニトリル合成用触媒 |
US7524792B2 (en) * | 2003-06-04 | 2009-04-28 | Basf Aktiengesellschaft | Preparation of catalytically active multielement oxide materials which contain at least one of the elements Nb and W and the elements Mo, V and Cu |
US7161044B2 (en) * | 2003-10-22 | 2007-01-09 | Nippon Shokubai Co., Ltd. | Catalytic gas phase oxidation reaction |
DE10353954A1 (de) * | 2003-11-18 | 2005-06-09 | Basf Ag | Verfahren zur Herstellung von Acrolein durch heterogen katalysierte partielle Gasphasenoxidation von Propen |
WO2005053839A1 (ja) * | 2003-12-03 | 2005-06-16 | Mitsubishi Chemical Corporation | 不飽和アルデヒド及び不飽和カルボン酸製造用触媒及びその製造方法 |
CN1697700A (zh) * | 2003-12-04 | 2005-11-16 | 三菱化学株式会社 | 生产用于生产不饱和醛和不饱和羧酸催化剂的方法 |
CN100448539C (zh) * | 2003-12-18 | 2009-01-07 | 三菱丽阳株式会社 | 不饱和醛和不饱和羧酸制造用催化剂及其制造方法、以及不饱和醛和不饱和羧酸的制造方法 |
TWI292755B (en) * | 2003-12-26 | 2008-01-21 | Lg Chemical Ltd | Method of producing unsaturated aldehyde and/or unsaturated fatty acid |
KR100561073B1 (ko) * | 2004-02-25 | 2006-03-17 | 주식회사 엘지화학 | 기상 부분 산화 반응용 촉매 및 그의 제조방법 |
BRPI0500615B1 (pt) * | 2004-03-10 | 2015-07-14 | Rohm & Haas | Catalisador modificado, e, sistema de catalisador modificado |
JP2005314314A (ja) * | 2004-04-30 | 2005-11-10 | Mitsubishi Chemicals Corp | (メタ)アクリル酸または(メタ)アクロレインの製造方法 |
JP4947917B2 (ja) * | 2005-04-18 | 2012-06-06 | 株式会社日本触媒 | 気相接触酸化用の固定床反応器およびアクロレインまたはアクリル酸の製造方法 |
CN1939589A (zh) * | 2005-09-30 | 2007-04-04 | 住友化学株式会社 | 制备用于制备不饱和醛和不饱和羧酸的催化剂的方法以及制备不饱和醛和不饱和羧酸的方法 |
JP4720431B2 (ja) * | 2005-09-30 | 2011-07-13 | 住友化学株式会社 | 不飽和アルデヒド及び不飽和カルボン酸製造用触媒の製造方法、並びに不飽和アルデヒド及び不飽和カルボン酸の製造方法 |
JP4265621B2 (ja) * | 2006-06-06 | 2009-05-20 | 住友化学株式会社 | 不飽和アルデヒド及び不飽和カルボン酸の製造方法 |
US7888281B2 (en) * | 2007-01-19 | 2011-02-15 | Evernu Technology, Llc | Selective oxidation of alkanes and/or alkenes to valuable oxygenates |
CN101385978B (zh) * | 2007-09-12 | 2011-04-20 | 上海华谊丙烯酸有限公司 | 一种合成甲基丙烯醛的催化剂及其制备方法 |
-
2008
- 2008-05-16 JP JP2008129200A patent/JP5163273B2/ja active Active
-
2009
- 2009-05-05 SG SG200903050-3A patent/SG157292A1/en unknown
- 2009-05-13 DE DE102009021049A patent/DE102009021049A1/de not_active Withdrawn
- 2009-05-14 CN CN200910143129.7A patent/CN101579630B/zh active Active
- 2009-05-14 KR KR1020090041994A patent/KR20090119719A/ko not_active Application Discontinuation
- 2009-05-15 TW TW098116172A patent/TWI454312B/zh active
- 2009-05-15 US US12/467,079 patent/US8252714B2/en active Active
-
2012
- 2012-07-23 US US13/555,840 patent/US8586786B2/en active Active
-
2015
- 2015-12-23 KR KR1020150185411A patent/KR101821023B1/ko active IP Right Grant
Also Published As
Publication number | Publication date |
---|---|
TWI454312B (zh) | 2014-10-01 |
US20090287018A1 (en) | 2009-11-19 |
CN101579630B (zh) | 2014-04-02 |
SG157292A1 (en) | 2009-12-29 |
US8586786B2 (en) | 2013-11-19 |
JP2009274034A (ja) | 2009-11-26 |
US20120289741A1 (en) | 2012-11-15 |
KR101821023B1 (ko) | 2018-01-22 |
DE102009021049A1 (de) | 2010-01-07 |
US8252714B2 (en) | 2012-08-28 |
TW201002420A (en) | 2010-01-16 |
KR20090119719A (ko) | 2009-11-19 |
CN101579630A (zh) | 2009-11-18 |
KR20160004252A (ko) | 2016-01-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5163273B2 (ja) | 不飽和アルデヒド及び/又は不飽和カルボン酸製造用触媒の製造方法、並びに不飽和アルデヒド及び/又は不飽和カルボン酸の製造方法 | |
JP5045175B2 (ja) | 不飽和アルデヒド及び/又は不飽和カルボン酸の製造方法 | |
JP3892244B2 (ja) | 不飽和アルデヒドおよび不飽和カルボン酸製造用触媒の製造方法 | |
JP5387297B2 (ja) | 複合酸化物触媒の製造方法 | |
JP4720431B2 (ja) | 不飽和アルデヒド及び不飽和カルボン酸製造用触媒の製造方法、並びに不飽和アルデヒド及び不飽和カルボン酸の製造方法 | |
JP4318367B2 (ja) | アクロレインおよびアクリル酸の製造方法 | |
JP4265621B2 (ja) | 不飽和アルデヒド及び不飽和カルボン酸の製造方法 | |
JP2000325795A (ja) | 複合酸化物触媒、並びに(メタ)アクロレインおよび(メタ)アクリル酸の製造方法 | |
KR20170125827A (ko) | 불포화 알데히드 및/또는 불포화 카본산 제조용 촉매 및 그의 제조 방법 그리고 불포화 알데히드 및/또는 불포화 카본산의 제조 방법 | |
KR102612311B1 (ko) | 아크롤레인, 메타크롤레인, 아크릴산, 또는 메타크릴산의 제조 방법 | |
EP1350784A1 (en) | Process for production of unsaturated aldehyde or acid using Mo-Bi-Fe catalyst | |
EP1526123A1 (en) | Catalytic gas phase oxidation reaction | |
JP3939187B2 (ja) | 不飽和アルデヒドの製造方法 | |
JP2016059898A (ja) | アクリル酸製造用の触媒および該触媒を用いたアクリル酸の製造方法 | |
TW201400450A (zh) | 甲基丙烯酸烷酯的製造方法 | |
JP2007090193A (ja) | メタクリル酸製造用触媒の製造方法及びメタクリル酸の製造方法 | |
JP4970986B2 (ja) | 複合酸化物触媒の製造方法および該触媒を用いた不飽和アルデヒドおよび/または不飽和カルボン酸の製造方法 | |
JP6487242B2 (ja) | アクリル酸製造用触媒の製造方法とその触媒、ならびに該触媒を用いたアクリル酸の製造方法 | |
JP2013188669A (ja) | 不飽和アルデヒド及び/又は不飽和カルボン酸製造用触媒の製造方法 | |
JP2011088028A (ja) | 不飽和アルデヒドおよび不飽和カルボン酸製造用触媒、並びに不飽和アルデヒドおよび不飽和カルボン酸の製造方法 | |
JP2005162744A (ja) | 不飽和アルデヒド及び不飽和カルボン酸の製造方法 | |
JP4185404B2 (ja) | 不飽和アルデヒドおよび不飽和カルボン酸製造用触媒、その製造方法、および不飽和アルデヒドおよび不飽和カルボン酸の製造方法 | |
JP2019210228A (ja) | メタクロレインの製造方法 | |
JP6540422B2 (ja) | 複合酸化物触媒 | |
JP6534328B2 (ja) | アクリル酸製造用触媒の製造方法とその触媒、ならびに該触媒を用いたアクリル酸の製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20100521 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20110930 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20120828 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20121025 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20121120 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20121203 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20151228 Year of fee payment: 3 |
|
R151 | Written notification of patent or utility model registration |
Ref document number: 5163273 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20151228 Year of fee payment: 3 |
|
S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |