JP4885221B2 - (メタ)アクリル酸の選択率が高い複合金属酸化物触媒 - Google Patents
(メタ)アクリル酸の選択率が高い複合金属酸化物触媒 Download PDFInfo
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- JP4885221B2 JP4885221B2 JP2008525941A JP2008525941A JP4885221B2 JP 4885221 B2 JP4885221 B2 JP 4885221B2 JP 2008525941 A JP2008525941 A JP 2008525941A JP 2008525941 A JP2008525941 A JP 2008525941A JP 4885221 B2 JP4885221 B2 JP 4885221B2
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- metal oxide
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- acrylic acid
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- 239000003054 catalyst Substances 0.000 title claims description 74
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 title claims description 43
- 229910044991 metal oxide Inorganic materials 0.000 title claims description 41
- 150000004706 metal oxides Chemical class 0.000 title claims description 41
- 239000002131 composite material Substances 0.000 title claims description 33
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims description 124
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 35
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 31
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 25
- 238000004519 manufacturing process Methods 0.000 claims description 22
- 238000007254 oxidation reaction Methods 0.000 claims description 21
- 239000010955 niobium Substances 0.000 claims description 20
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 17
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 239000000376 reactant Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 10
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 9
- 230000003197 catalytic effect Effects 0.000 claims description 9
- 229910052758 niobium Inorganic materials 0.000 claims description 9
- 229910052700 potassium Inorganic materials 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims description 8
- 239000011733 molybdenum Substances 0.000 claims description 8
- 229910052714 tellurium Inorganic materials 0.000 claims description 8
- 229910052797 bismuth Inorganic materials 0.000 claims description 7
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical group [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 229910052718 tin Inorganic materials 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 229910052787 antimony Inorganic materials 0.000 claims description 5
- 229910052785 arsenic Inorganic materials 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical group [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 229910052732 germanium Inorganic materials 0.000 claims description 4
- 229910052745 lead Inorganic materials 0.000 claims description 4
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- 239000000047 product Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 239000007795 chemical reaction product Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 11
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000011261 inert gas Substances 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 5
- 239000001294 propane Substances 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 229910052792 caesium Inorganic materials 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 239000007809 chemical reaction catalyst Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000011133 lead Substances 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000011135 tin Substances 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 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 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Chemical class OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229910052701 rubidium Inorganic materials 0.000 description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 2
- 229910052716 thallium Inorganic materials 0.000 description 2
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical class COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
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- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 235000010980 cellulose Nutrition 0.000 description 1
- 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 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical class OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 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
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
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- 238000001704 evaporation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
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- 239000003365 glass fiber Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
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- 239000011572 manganese Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
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- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 229910017604 nitric acid Inorganic materials 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
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- 239000011669 selenium Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
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- 239000010935 stainless steel Substances 0.000 description 1
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- 239000008117 stearic acid Substances 0.000 description 1
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- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
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Description
Moa Bib Nbc Ted Ae Bf Cg Dh Ei Fj Ok
式中、Moはモリブデン、Biはビスマス、Nbはニオブ、Teはテルルであり、
Aは、W、Sb、As、P、Sn及びPbからなる群より選ばれる1種以上の元素であり、
Bは、Fe、Zn、Cr、Mn、Cu、Ru、Pd、Ag及びRuからなる群より選ばれる1種以上の元素であり、
Cは、Co、Cd、Ta、Pt及びNiからなる群より選ばれる1種以上の元素であり、
Dは、Si、Al、Zr、V及びCeからなる群より選ばれる1種以上の元素であり、
Eは、Se、Ga、Ti、Ge、Rh及びAuからなる群より選ばれる1種以上の元素であり、
Fは、Na、K、Li、Rb、Cs、Ca、Mg、Sr、Ba及びMgOからなる群より選ばれる1種以上の元素であり、
a、b、c、d、e、f、g、h、i、j及びkは、各元素の原子比率を示し、
a=12のとき、bは0.01〜20、cは0.001〜20、dは0.001〜20、eは0〜15、fは0〜20、gは0〜20、hは0〜10、iは0〜10、jは0〜10、kは前記各成分の酸化状態により定まる値である。
<第1段階の反応触媒の製造例>
製造例1:触媒1
蒸溜水2500mlを70℃〜85℃で加熱撹はんしながら、モリブデン酸アンモニウム1000gを溶解させて、溶液(1)を製造した。蒸溜水400mlに硝酸ビスマス274g、硝酸鉄228g及び硝酸カリウム2.3gを加え、混合した後に硝酸71gを添加して溶解させて、溶液(2)を製造した。蒸溜水200mlに硝酸コバルト686gを溶解させて、溶液(3)を製造した。溶液(2)と溶液(3)とを混合した後、溶液の温度を40〜60℃に維持しながら、溶液(1)に混合して触媒懸濁液を製造した。
製造した懸濁液を乾燥して、Mo12Bi1.2Fe1.2Co5K0.05を製造した後、150μm以下に粉砕した。粉砕した触媒粉末を2時間混合した後、筒形に成形した。触媒外径を4.0〜8.0mmの大きさに成形した後、500℃で5時間、空気雰囲気下で焼成し、触媒活性を検証した。
塩化ニオブ63g、塩化テルル150gを溶液(1)に追加した以外は、製造例1と同様の方法により触媒2を製造した。生成された触媒成分のうち、酸素を除いた元素の組成比率は、次の通りである。:Mo12Nb0.5Te1Bi1.2Fe1.2Co5K0.05
塩化ニオブ127g、硝酸テルル150gを溶液(1)に追加した以外は、製造例1と同様な方法により触媒3を製造した。生成された触媒成分のうち、酸素を除いた元素の組成比率は、次の通りである。:Mo12Nb1.0Te1.0Bi1.2Fe1.2Co 5 K0.05
塩化ニオブ63g、塩化テルル75gを溶液(1)に追加した以外は、製造例1と同様の方法により触媒4を製造した。生成された触媒成分のうち、酸素を除いた元素の組成比率は、次の通りである。:Mo12Nb0.5Te 0.5 Bi1.2Fe1.2Co 5 K0.05
蒸溜水2000mlを100℃で加熱撹はんしながら、タングステン酸アンモニウム246g、モリブデン酸アンモニウム1000g、バナジウム酸アンモニウム220gを混合溶解して、溶液(1)を製造した。蒸溜水500mlに硝酸銅228g、硝酸ストロンチウム49gを加え、混合溶解して、溶液(2)を製造した。溶液(1)と溶液(2)とを混合して懸濁液を製造した。製造した懸濁液を、ホモジナイザーを用いて最短でも30分以上処理した後、スプレーノズルを用いて外径が4.0mm〜8.0mmである球形担体に各々前記懸濁液状態にある触媒有効成分を20〜30wt%コートした後、120℃で十分に乾燥させ、400℃で5時間以上焼成し、最終外径が5mm(±0.2)である球形触媒を製造した。
このとき、生成された触媒成分のうちで酸素を除いた元素の組成比率は、次の通りである。:Mo12W2.0V4.0Cu2.0Sr0.5
溶融硝酸塩で加熱した内径1インチの3mステンレススチール反応器に、反応ガスの入口から出口の方に不活性物質としてアルミナシリカを150mm充填した後、第1段階の触媒として、触媒1〜触媒4の何れか一つを2800mm充填した。
続いて、不活性物質としてアルミナシリカを150mm充填した後、第2段階の触媒である触媒5を2900mm充填した。反応器を用いてプロピレンを気相酸化反応させ、アクロレイン及びアクリル酸を製造した。第1段階の酸化反応は、反応温度320℃、反応圧力0.7気圧下で、プロピレン7体積%、酸素13体積%、水蒸気8体積%及び不活性ガス72体積%の原料ガスを、空間速度1500hr−1(STP)で触媒上に導入して行った。第2段階の酸化反応は、反応温度276℃、反応圧力0.1〜3kg/cm2Gで行った。
表1及び表2において、反応物質の転換率、選択率及び歩留まりは、次のような数式1〜数式7により計算した。
[数式1]
第1段階のプロピレン転換率(%)=[反応したプロピレンのモル数/供給したプロピレンのモル数]×100
[数式2]
アクロレイン歩留まり(%)=[生成したアクロレインのモル数/供給したプロピレンのモル数]×100
[数式3]
第1段階のアクリル酸歩留まり(%)=[生成したアクリル酸のモル数/供給したプロピレンのモル数]×100
[数式4]
第1段階のアクロレイン+アクリル酸選択率(%)=[生成したアクロレイン及びアクリル酸のモル数/反応したプロピレンのモル数]×100
[数式5]
第2段階のアクロレイン転換率(%)=[反応したアクロレインのモル数/供給したアクロレインのモル数]×100
[数式6]
第2段階のアクリル酸歩留まり(%)=[生成したアクリル酸のモル数/供給したアクロレインのモル数]×100
[数式7]
第2段階のアクリル酸選択率(%)=[生成したアクリル酸のモル数/反応したアクロレインのモル数]×100
Claims (10)
- 下記の化学式1で表されることを特徴とするMo−Bi−Nb−Te系複合金属酸化物(但し、Vを含む複合金属酸化物を除く)。
[化学式1]
MoaBibNbcTedAe Fe f Co gDhEi K jOk
式中、Moはモリブデン、Biはビスマス、Nbはニオブ、Teはテルル、Feは鉄、Coはコバルト、Kはカリウム、Oは酸素であり、
Aは、Sb、As、P、Sn及びPbからなる群より選ばれる1種以上の元素であり、
Dは、Si、Al、Zr、及びCeからなる群より選ばれる1種以上の元素であり、
Eは、Se、Ga、Ti、Ge、Rh及びAuからなる群より選ばれる1種以上の元素であり、
a、b、c、d、e、f、g、h、i、j及びkは、各元素の原子比率を示し、
a=12のとき、bは0.01〜20、cは0.001〜20、dは0.001〜20、eは0〜15、fは0〜20、gは0〜20、hは0〜10、iは0〜10、jは0〜10、kは前記各成分の酸化状態により定まる値である(但し、Mo、Bi、Nb、Te、Fe、Co、およびKの全てを含まない複合金属酸化物は除く)。 - 触媒として用いられることを特徴とする、請求項1に記載のMo−Bi−Nb−Te系複合金属酸化物。
- 接触気相部分酸化反応の触媒として用いられることを特徴とする、請求項2に記載のMo−Bi−Nb−Te系複合金属酸化物。
- プロピレン、イソブチレン、t−ブチルアルコール又はメチル−t−ブチルエーテルからなる群より選ばれた1種以上の反応物から(メタ)アクリル酸を製造する方法であって、下記の化学式1で表されることを特徴とするMo−Bi−Nb−Te系複合金属酸化物(但し、Vを含む複合金属酸化物を除く。)を触媒として使用することを特徴とする、製法。
[化学式1]
Mo a Bi b Nb c Te d A e Fe f Co g D h E i K j O k
式中、Moはモリブデン、Biはビスマス、Nbはニオブ、Teはテルル、Feは鉄、Coはコバルト、Kはカリウム、Oは酸素であり、
Aは、Sb、As、P、Sn及びPbからなる群より選ばれる1種以上の元素であり、
Dは、Si、Al、Zr、及びCeからなる群より選ばれる1種以上の元素であり、
Eは、Se、Ga、Ti、Ge、Rh及びAuからなる群より選ばれる1種以上の元素であり、
a、b、c、d、e、f、g、h、i、j及びkは、各元素の原子比率を示し、
a=12のとき、bは0.01〜20、cは0.001〜20、dは0.001〜20、eは0〜15、fは0〜20、gは0〜20、hは0〜10、iは0〜10、jは0〜10、kは前記各成分の酸化状態により定まる値である(但し、Mo、Bi、Nb、Te、Fe、Co、およびKの全てを含まない複合金属酸化物は除く)。 - Mo−Bi−Nb−Te系複合金属酸化物の触媒作用により形成された生成物のうち、(メタ)アクリル酸の歩留まりが20モル%以上であることを特徴とする、請求項4に記載の製法。
- 反応温度が250〜500℃であることを特徴とする、請求項4に記載の製法。
- プロピレン、イソブチレン、t−ブチルアルコール又はメチル−t−ブチルエーテルからなる群より選ばれた1種以上の反応物から(メタ)アクロレインを主に生産する第1段階と、前記(メタ)アクロレインから(メタ)アクリル酸を生産する第2段階とを含む(メタ)アクリル酸の製造方法であって、第1段階の触媒として下記化学式1で示されるMo−Bi−Nb−Te系複合金属酸化物(但し、Vを含む複合金属酸化物を除く。)を触媒として使用し、前記第1段階の生成物のうち、(メタ)アクリル酸の歩留まりが20モル%以上であることを特徴とする、製法。
[化学式1]
Mo a Bi b Nb c Te d A e Fe f Co g D h E i K j O k
式中、Moはモリブデン、Biはビスマス、Nbはニオブ、Teはテルル、Feは鉄、Coはコバルト、Kはカリウム、Oは酸素であり、
Aは、Sb、As、P、Sn及びPbからなる群より選ばれる1種以上の元素であり、
Dは、Si、Al、Zr、及びCeからなる群より選ばれる1種以上の元素であり、
Eは、Se、Ga、Ti、Ge、Rh及びAuからなる群より選ばれる1種以上の元素であり、
a、b、c、d、e、f、g、h、i、j及びkは、各元素の原子比率を示し、
a=12のとき、bは0.01〜20、cは0.001〜20、dは0.001〜20、eは0〜15、fは0〜20、gは0〜20、hは0〜10、iは0〜10、jは0〜10、kは前記各成分の酸化状態により定まる値である(但し、Mo、Bi、Nb、Te、Fe、Co、およびKの全てを含まない複合金属酸化物は除く)。 - 第1段階の生成物のうち、(メタ)アクロレイン:(メタ)アクリル酸の比率(モル)が8:2〜7:3であることを特徴とする、請求項7に記載の製法。
- 第2段階において(メタ)アクロレインの転換率が98%〜100%であることを特徴とする、請求項7に記載の製法。
- 第1段階に供給される反応物のうち、プロピレン、イソブチレン、t−ブチルアルコール又はメチル−t−ブチルエーテルからなる群より選ばれた1種以上の反応物の濃度が7〜10体積%であることを特徴とする、請求項7に記載の製法。
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