JP2015188801A - Oxide catalyst and production method thereof, and method for producing unsaturated aldehyde or unsaturated nitrile - Google Patents
Oxide catalyst and production method thereof, and method for producing unsaturated aldehyde or unsaturated nitrile Download PDFInfo
- Publication number
- JP2015188801A JP2015188801A JP2014066762A JP2014066762A JP2015188801A JP 2015188801 A JP2015188801 A JP 2015188801A JP 2014066762 A JP2014066762 A JP 2014066762A JP 2014066762 A JP2014066762 A JP 2014066762A JP 2015188801 A JP2015188801 A JP 2015188801A
- Authority
- JP
- Japan
- Prior art keywords
- oxide catalyst
- reaction
- iron
- unsaturated
- tetracoordinated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 183
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 43
- 150000002825 nitriles Chemical class 0.000 title claims abstract description 31
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title claims abstract 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 204
- 239000002994 raw material Substances 0.000 claims abstract description 52
- 229910052742 iron Inorganic materials 0.000 claims abstract description 42
- 229910052747 lanthanoid Inorganic materials 0.000 claims abstract description 25
- 150000002602 lanthanoids Chemical class 0.000 claims abstract description 25
- 150000001336 alkenes Chemical class 0.000 claims abstract description 21
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 21
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 21
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 19
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000011733 molybdenum Substances 0.000 claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 16
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 13
- 239000010941 cobalt Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims description 83
- 238000010304 firing Methods 0.000 claims description 60
- 239000002002 slurry Substances 0.000 claims description 44
- 238000007254 oxidation reaction Methods 0.000 claims description 38
- 239000001301 oxygen Substances 0.000 claims description 36
- 229910052760 oxygen Inorganic materials 0.000 claims description 36
- 230000003647 oxidation Effects 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 29
- 230000006641 stabilisation Effects 0.000 claims description 26
- 238000011105 stabilization Methods 0.000 claims description 26
- 239000002738 chelating agent Substances 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 19
- 239000012298 atmosphere Substances 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 14
- 125000004429 atom Chemical group 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 11
- 239000011261 inert gas Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 229910052684 Cerium Inorganic materials 0.000 claims description 7
- 229910052792 caesium Inorganic materials 0.000 claims description 6
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- 229910052701 rubidium Inorganic materials 0.000 claims description 6
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- 229910052779 Neodymium Inorganic materials 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052788 barium Inorganic materials 0.000 claims description 5
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 239000011575 calcium Substances 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims description 5
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 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 5
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052712 strontium Inorganic materials 0.000 claims description 5
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- 229910052693 Europium Inorganic materials 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000470 constituent Substances 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 10
- 239000006227 byproduct Substances 0.000 abstract description 7
- 239000001569 carbon dioxide Substances 0.000 abstract description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 45
- 238000011156 evaluation Methods 0.000 description 40
- 239000007789 gas Substances 0.000 description 33
- 150000001299 aldehydes Chemical class 0.000 description 29
- 238000010521 absorption reaction Methods 0.000 description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 18
- 229910052751 metal Inorganic materials 0.000 description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 17
- 239000002184 metal Substances 0.000 description 17
- 239000000047 product Substances 0.000 description 17
- 238000003786 synthesis reaction Methods 0.000 description 17
- 229910001868 water Inorganic materials 0.000 description 16
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 15
- 230000003197 catalytic effect Effects 0.000 description 13
- 239000002131 composite material Substances 0.000 description 13
- 238000001228 spectrum Methods 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 229910001882 dioxygen Inorganic materials 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- -1 CO and CO 2 increase Chemical compound 0.000 description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 9
- 239000013078 crystal Substances 0.000 description 9
- 229910017604 nitric acid Inorganic materials 0.000 description 9
- 230000001590 oxidative effect Effects 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 239000012071 phase Substances 0.000 description 9
- 229910002552 Fe K Inorganic materials 0.000 description 8
- 229910021529 ammonia Inorganic materials 0.000 description 8
- 238000001354 calcination Methods 0.000 description 8
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 7
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 description 6
- 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 6
- 150000001875 compounds Chemical class 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- 229910017299 Mo—O Inorganic materials 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 235000006408 oxalic acid Nutrition 0.000 description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 5
- 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 4
- 150000003863 ammonium salts Chemical class 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 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 4
- 150000002500 ions Chemical class 0.000 description 4
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 4
- 238000000691 measurement method Methods 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 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 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- FCKYPQBAHLOOJQ-UHFFFAOYSA-N Cyclohexane-1,2-diaminetetraacetic acid Chemical compound OC(=O)CN(CC(O)=O)C1CCCCC1N(CC(O)=O)CC(O)=O FCKYPQBAHLOOJQ-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000000833 X-ray absorption fine structure spectroscopy Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 150000002506 iron compounds Chemical class 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 description 1
- KWYJDIUEHHCHCZ-UHFFFAOYSA-N 3-[2-[bis(2-carboxyethyl)amino]ethyl-(2-carboxyethyl)amino]propanoic acid Chemical compound OC(=O)CCN(CCC(O)=O)CCN(CCC(O)=O)CCC(O)=O KWYJDIUEHHCHCZ-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 238000004998 X ray absorption near edge structure spectroscopy Methods 0.000 description 1
- 238000002056 X-ray absorption spectroscopy Methods 0.000 description 1
- BYUANIDVEAKBHT-UHFFFAOYSA-N [Mo].[Bi] Chemical compound [Mo].[Bi] BYUANIDVEAKBHT-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000000746 allylic group Chemical group 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000027455 binding Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000003840 hydrochlorides Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 238000010405 reoxidation reaction Methods 0.000 description 1
- RTHYXYOJKHGZJT-UHFFFAOYSA-N rubidium nitrate Inorganic materials [Rb+].[O-][N+]([O-])=O RTHYXYOJKHGZJT-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 230000005469 synchrotron radiation Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- KHAUBYTYGDOYRU-IRXASZMISA-N trospectomycin Chemical compound CN[C@H]([C@H]1O2)[C@@H](O)[C@@H](NC)[C@H](O)[C@H]1O[C@H]1[C@]2(O)C(=O)C[C@@H](CCCC)O1 KHAUBYTYGDOYRU-IRXASZMISA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
Description
本発明は、酸化物触媒及びその製造方法、並びに該酸化物触媒を用いた不飽和アルデヒド又は不飽和ニトリルの製造方法に関する。 The present invention relates to an oxide catalyst, a method for producing the same, and a method for producing an unsaturated aldehyde or an unsaturated nitrile using the oxide catalyst.
モリブデン、ビスマス、鉄等の遷移金属は、それぞれが単独で酸化することによって得られる酸化物の他に、複数種の金属が固溶体となって得られるいわゆる複合酸化物になることが知られている。複合酸化物は、単独の金属の酸化物とは異なる特性を有し、その特性が金属種の選択や組成比等によっても大きく変化することから、触媒、顔料、電池の電極材料等、様々な分野で検討が進められている。 It is known that transition metals such as molybdenum, bismuth, and iron become so-called composite oxides obtained by solid solutions of a plurality of types of metals in addition to oxides obtained by oxidizing each of them. . Composite oxides have different characteristics from single metal oxides, and the characteristics change greatly depending on the choice of metal species and composition ratio. Studies are underway in the field.
例えば、モリブデン、ビスマス、及び鉄を含む金属酸化物触媒は、オレフィンやアルコールを酸化して、不飽和アルデヒドや不飽和ニトリルを製造する触媒としてこれまでに数多く報告されている。また、必須成分としてモリブデン、ビスマス及び鉄を含み、有機化合物を添加して熱処理して得られる複合酸化物触媒も数多く報告されている。 For example, many metal oxide catalysts containing molybdenum, bismuth, and iron have been reported as catalysts for producing unsaturated aldehydes and unsaturated nitriles by oxidizing olefins and alcohols. In addition, many composite oxide catalysts containing molybdenum, bismuth and iron as essential components and obtained by heat treatment by adding an organic compound have been reported.
上述のように、組成比が異なれば酸化物触媒の特性も異なるので、触媒活性を向上させたり、目的化合物の生成率を向上させたりする目的で、様々な組成比の複合酸化物の触媒特性や調製条件が検討されている。例えば、特許文献１には、モリブデン、ビスマス及び鉄を含有する触媒前駆体を分子状酸素含有ガスの雰囲気下で焼成した後、還元性物質の存在下に熱処理する触媒の製造方法が記載されている。また、特許文献２には、高い収率で目的生成物を得るために、モリブデン、ビスマス、鉄、コバルト及びセリウムを含む酸化物触媒において、Ｍｏ１２原子に対するＦｅの原子比を０＜Ｆｅ≦２．５とすることが記載されている。 As described above, the characteristics of the oxide catalyst differ depending on the composition ratio. Therefore, in order to improve the catalytic activity and the production rate of the target compound, the catalytic characteristics of the composite oxide having various composition ratios. And preparation conditions are being studied. For example, Patent Document 1 describes a method for producing a catalyst in which a catalyst precursor containing molybdenum, bismuth and iron is calcined in an atmosphere of a molecular oxygen-containing gas and then heat-treated in the presence of a reducing substance. Yes. Further, in Patent Document 2, in order to obtain a target product with high yield, in an oxide catalyst containing molybdenum, bismuth, iron, cobalt and cerium, the atomic ratio of Fe to Mo12 atoms is 0 <Fe ≦ 2. 5 is described.
気相接触酸化反応で利用されているビスマス−モリブデン系（Ｂｉ−Ｍｏ）触媒は、鉄を含むことにより、再酸化速度が上がり、活性がより向上する傾向にある。一方で、鉄を多く含む触媒では、アルデヒド以外の酸素付加化合物（例えば、二酸化炭素）の生成量が増加し、目的生成物の選択率が低下する傾向にある。 The bismuth-molybdenum-based (Bi-Mo) catalyst used in the gas phase catalytic oxidation reaction tends to increase the reoxidation rate and improve the activity when it contains iron. On the other hand, in a catalyst containing a large amount of iron, the amount of oxygen-added compound (for example, carbon dioxide) other than aldehyde increases, and the selectivity of the target product tends to decrease.
活性向上の観点で見れば、鉄は酸化物触媒中に含まれていることが好ましいものの、鉄の含有量を調節するだけでは、高活性と高選択率の両立を達成するのは困難である。 From the viewpoint of improving the activity, it is preferable that iron is contained in the oxide catalyst, but it is difficult to achieve both high activity and high selectivity only by adjusting the iron content. .
本発明は上記問題点に鑑みてなされたものであり、オレフィン及び／又はアルコールを原料とする不飽和アルデヒドや不飽和ニトリルの製造において、二酸化炭素等の副生成物の生成を抑制して、不飽和アルデヒドや不飽和ニトリルを高収率で生成させることのできる酸化物触媒及びその製造方法、並びに該酸化物触媒を用いた不飽和アルデヒドや不飽和ニトリルの製造方法を提供することを目的とする。 The present invention has been made in view of the above problems, and in the production of unsaturated aldehydes and unsaturated nitriles using olefins and / or alcohols as raw materials, the production of by-products such as carbon dioxide is suppressed. An object of the present invention is to provide an oxide catalyst capable of producing a saturated aldehyde or an unsaturated nitrile in a high yield, a method for producing the same, and a method for producing an unsaturated aldehyde or an unsaturated nitrile using the oxide catalyst. .
本発明者らは、上記問題点を解決するために鋭意検討をした。その結果、モリブデン、ビスマス、鉄、コバルト及びランタノイド元素を含む酸化物触媒中に、６配位の鉄化合物が所定量含まれるときに、この酸化物触媒を不飽和アルデヒドや不飽和ニトリルの製造反応で用いると、望まれない燃焼反応が促進され、目的生成物の収率向上にはつながらないことを見出した。 The present inventors diligently studied to solve the above problems. As a result, when a predetermined amount of a six-coordinate iron compound is contained in an oxide catalyst containing molybdenum, bismuth, iron, cobalt, and a lanthanoid element, this oxide catalyst is used to produce an unsaturated aldehyde or an unsaturated nitrile. It was found that when used in, an undesired combustion reaction is promoted and the yield of the target product is not improved.
本発明者らは、上述の望まれない燃焼反応の原因は、所定量以上の鉄が６配位の状態であることに起因することを見出した。すなわち、金属の組成のみならず、各金属の配位数も複合酸化物の機能に影響していることを見出し、全ての鉄化合物が負の作用を示すのではなく、鉄が４配位の状態であれば、寧ろ好ましい触媒作用のみを示しうることを見出した。以上より、本発明者らは、４配位Ｆｅ／（４配位Ｆｅ＋６配位Ｆｅ）の比をコントロールした酸化物を含む触媒は上記課題を解決できることを見出して、本発明をするに至った。 The present inventors have found that the cause of the above-mentioned undesirable combustion reaction is due to the fact that a predetermined amount or more of iron is in a six-coordinate state. That is, not only the composition of the metal but also the coordination number of each metal has been found to affect the function of the composite oxide, and not all iron compounds exhibit a negative effect, but iron is 4-coordinated. In other words, it was found that only a favorable catalytic action can be exhibited. As described above, the present inventors have found that a catalyst including an oxide in which the ratio of tetracoordinated Fe / (tetracoordinated Fe + 6-coordinated Fe) is controlled can solve the above problems, and has led to the present invention. .
さらに、本発明者らは、酸化物触媒の４配位Ｆｅ／（４配位Ｆｅ＋６配位Ｆｅ）の比のコントロールを達成するための手段を鋭意検討した結果、有機酸の利用、並びに不活性ガス中での焼成、酸化安定化処理を組み合わせて利用することにより、４配位Ｆｅ／（４配位Ｆｅ＋６配位Ｆｅ）の比を自由にコントロールできる酸化物触媒を製造できることを見出し、これにより従来の酸化焼成や還元焼成のみでは取りえない触媒性能を実現し、上記課題を解決できる酸化物触媒を製造する方法を見出して、本発明に想到した。 Furthermore, the present inventors have intensively studied means for achieving control of the ratio of tetracoordinated Fe / (tetracoordinated Fe + 6-coordinated Fe) of the oxide catalyst. It has been found that an oxide catalyst capable of freely controlling the ratio of 4-coordinated Fe / (4-coordinated Fe + 6-coordinated Fe) can be produced by using a combination of calcination in gas and oxidation stabilization treatment. The present inventors have found a method for producing an oxide catalyst that realizes catalyst performance that cannot be obtained only by conventional oxidation calcination and reduction calcination, and can solve the above problems, and has arrived at the present invention.
すなわち、本発明は以下に示すとおりである。
〔１〕
モリブデン、ビスマス、鉄、コバルト、及びランタノイド元素を含有し、
４配位Ｆｅ／（４配位Ｆｅ＋６配位Ｆｅ）の比が、０．２０以上１．０以下である、
酸化物触媒。
〔２〕
前記モリブデン１２原子に対する、前記ビスマスの原子比ａが、１．５≦ａ≦６．０であり、前記鉄の原子比ｂが、１．５≦ｂ≦７．０であり、前記コバルトの原子比ｃが、２．０≦ｃ≦８．０であり、前記ランタノイド元素の原子比ｄが、０．５０≦ｄ≦６．０である、前項〔１〕に記載の酸化物触媒。
〔３〕
下記組成式（１）で表される組成を有する、前項〔１〕又は〔２〕に記載の酸化物触媒。
Ｍｏ１２ＢｉａＦｅｂＣｏｃＡｄＢｅＣｆＯｇ （１）
（式（１）中、Ｍｏは前記モリブデン、Ｂｉは前記ビスマス、Ｆｅは前記鉄、Ｃｏは前記コバルトを示し、
Ａはランタン、セリウム、プラセオジウム、ネオジム、及びユーロピウムからなる群より選ばれる少なくとも１種の前記ランタノイド元素を示し、
Ｂはニッケル、マンガン、銅、亜鉛、マグネシウム、カルシウム、ストロンチウム、バリウム、錫、及び鉛からなる群より選ばれる少なくとも１種の元素を示し、
Ｃはセシウム、ルビジウム、及びカリウムからなる群より選ばれる少なくとも１種のアルカリ元素を示し、
ａ〜ｆは、Ｍｏ１２原子に対する各元素の原子比を示し、１．５≦ａ≦６．０、１．５≦ｂ≦７．０、２．０≦ｃ≦８．０、０．５０≦ｄ≦６．０、０．０１０≦ｅ≦２．０、及び０≦ｆ＜２．０を満たし、
ｇは酸素以外の構成元素の原子価によって決まる酸素の原子数である。）
〔４〕
モリブデン、ビスマス、鉄、コバルト、及びランタノイド元素を含む原料と、キレート剤と、を混合して原料スラリーを得る混合工程と、
前記原料スラリーを乾燥して乾燥体を得る乾燥工程と、
前記乾燥体を仮焼成して仮焼成体を得る仮焼成工程と、
前記仮焼成体を不活性ガス雰囲気下で本焼成して本焼成体を得る本焼成工程と、
前記本焼成体を、酸素を含む雰囲気で酸化安定化処理して、酸化物触媒を得る酸化安定化処理工程と、
を有する、
酸化物触媒の製造方法。
〔５〕
前項〔１〕〜〔３〕のいずれか１項に記載の酸化物触媒を用いて、オレフィン及び／又はアルコールを酸化反応させて、不飽和アルデヒドを得る酸化工程を有する、不飽和アルデヒドの製造方法。
〔６〕
前項〔１〕〜〔３〕のいずれか１項に記載の酸化物触媒を用いて、オレフィン及び／又はアルコールをアンモ酸化反応さて、不飽和ニトリルを得るアンモ酸化工程を有する、不飽和ニトリルの製造方法。
That is, the present invention is as follows.
[1]
Contains molybdenum, bismuth, iron, cobalt, and lanthanoid elements;
The ratio of tetracoordinated Fe / (tetracoordinated Fe + 6-coordinated Fe) is 0.20 or more and 1.0 or less.
Oxide catalyst.
[2]
The atomic ratio a of bismuth with respect to 12 atoms of molybdenum is 1.5 ≦ a ≦ 6.0, the atomic ratio b of iron is 1.5 ≦ b ≦ 7.0, and the cobalt atoms The oxide catalyst according to [1], wherein the ratio c is 2.0 ≦ c ≦ 8.0, and the atomic ratio d of the lanthanoid element is 0.50 ≦ d ≦ 6.0.
[3]
The oxide catalyst according to [1] or [2], which has a composition represented by the following composition formula (1).
Mo 12 Bi a Fe b Co c A d B e C f O g (1)
(In the formula (1), Mo represents the molybdenum, Bi represents the bismuth, Fe represents the iron, Co represents the cobalt,
A represents at least one lanthanoid element selected from the group consisting of lanthanum, cerium, praseodymium, neodymium, and europium,
B represents at least one element selected from the group consisting of nickel, manganese, copper, zinc, magnesium, calcium, strontium, barium, tin, and lead;
C represents at least one alkali element selected from the group consisting of cesium, rubidium, and potassium;
a to f indicate the atomic ratio of each element to the Mo12 atom, 1.5 ≦ a ≦ 6.0, 1.5 ≦ b ≦ 7.0, 2.0 ≦ c ≦ 8.0, 0.50 ≦ satisfy d ≦ 6.0, 0.010 ≦ e ≦ 2.0, and 0 ≦ f <2.0,
g is the number of oxygen atoms determined by the valence of the constituent elements other than oxygen. )
[4]
A mixing step of mixing a raw material containing molybdenum, bismuth, iron, cobalt, and a lanthanoid element and a chelating agent to obtain a raw material slurry;
A drying step of drying the raw slurry to obtain a dried body;
A pre-baking step of pre-baking the dried body to obtain a pre-fired body;
A main firing step of obtaining a main fired body by subjecting the temporary fired body to a main fire in an inert gas atmosphere;
An oxidation stabilization treatment step of obtaining an oxide catalyst by subjecting the main fired body to an oxidation stabilization treatment in an atmosphere containing oxygen;
Having
A method for producing an oxide catalyst.
[5]
A method for producing an unsaturated aldehyde, comprising an oxidation step of obtaining an unsaturated aldehyde by oxidizing an olefin and / or alcohol using the oxide catalyst according to any one of [1] to [3] above .
[6]
Production of an unsaturated nitrile having an ammoxidation step of obtaining an unsaturated nitrile by ammoxidation reaction of an olefin and / or alcohol using the oxide catalyst according to any one of [1] to [3] above Method.
本発明によれば、オレフィン及び／又はアルコールを原料とする不飽和アルデヒドや不飽和ニトリルの製造において、二酸化炭素等の副生成物の生成を抑制して、不飽和アルデヒドや不飽和ニトリルを高収率で生成させることのできる酸化物触媒及びその製造方法並びに該酸化物触媒を用いた不飽和アルデヒドや不飽和ニトリルの製造方法を提供することを目的とする。 According to the present invention, in the production of unsaturated aldehydes and unsaturated nitriles using olefins and / or alcohols as raw materials, the production of by-products such as carbon dioxide is suppressed, and high yields of unsaturated aldehydes and unsaturated nitriles are obtained. It is an object of the present invention to provide an oxide catalyst that can be produced at a high rate, a method for producing the oxide catalyst, and a method for producing an unsaturated aldehyde or unsaturated nitrile using the oxide catalyst.
以下、本発明を実施するための形態（以下、単に「本実施形態」という）について詳細に説明する。以下の本実施形態は、本発明を説明するための例示であり、本発明を以下の内容に限定する趣旨ではない。本発明はその要旨の範囲内で適宜変形して実施できる。 Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail. The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be appropriately modified within the scope of the gist.
〔酸化物触媒〕
本実施形態に係る酸化物触媒は、モリブデン（以下、「Ｍｏ」ともいう。）、ビスマス（以下、「Ｂｉ」ともいう。）、鉄（以下、「Ｆｅ」ともいう。）、コバルト（以下、「Ｃｏ」ともいう。）及びランタノイド元素（以下、「Ａ」ともいう。）を含有し、４配位Ｆｅ／（４配位Ｆｅ＋６配位Ｆｅ）の比が０．２０以上１．０以下である。
[Oxide catalyst]
The oxide catalyst according to this embodiment includes molybdenum (hereinafter also referred to as “Mo”), bismuth (hereinafter also referred to as “Bi”), iron (hereinafter also referred to as “Fe”), cobalt (hereinafter referred to as “Fe”). And a lanthanoid element (hereinafter also referred to as “A”), and the ratio of tetracoordinated Fe / (tetracoordinated Fe + 6-coordinated Fe) is 0.20 or more and 1.0 or less. is there.
〔４配位Ｆｅ／（４配位Ｆｅ＋６配位Ｆｅ）の比〕
４配位Ｆｅ／（４配位Ｆｅ＋６配位Ｆｅ）の比は、０．２０以上１．０以下であり、好ましくは０．２０以上０．９０以下であり、より好ましくは０．３以上０．７以下であり、さらに好ましくは０．４以上０．５以下である。４配位Ｆｅ／（４配位Ｆｅ＋６配位Ｆｅ）の比が０．２０以上であることにより、オレフィン及び／又はアルコールを原料とする不飽和アルデヒドや不飽和ニトリルの製造において、ＣＯやＣＯ２等の副生成物の生成を抑制でき、目的生成物の選択率がより向上し、不飽和アルデヒドや不飽和ニトリルを高収率で生成させることができる。より具体的には、４配位Ｆｅ／（４配位Ｆｅ＋６配位Ｆｅ）の比が０．２０以上であることにより、オレフィン又はアルコールのアリル位水素を引き抜く機能や、格子酸素伝搬能を司る触媒活性部位に、選択制の高い配位不飽和サイトが形成されることにより、不飽和アルデヒドや不飽和ニトリルを高収率で得ることができる。また、４配位Ｆｅ／（４配位Ｆｅ＋６配位Ｆｅ）の比が０．９０以下であることにより、触媒活性がより向上する。
[Ratio of 4-coordinate Fe / (4-coordinate Fe + 6-coordinate Fe)]
The ratio of tetracoordinated Fe / (tetracoordinated Fe + 6-coordinated Fe) is 0.20 or more and 1.0 or less, preferably 0.20 or more and 0.90 or less, more preferably 0.3 or more and 0. 0.7 or less, more preferably 0.4 or more and 0.5 or less. When the ratio of tetracoordinated Fe / (tetracoordinated Fe + 6-coordinated Fe) is 0.20 or more, in the production of unsaturated aldehydes and unsaturated nitriles using olefins and / or alcohols as raw materials, CO and CO 2 The production of by-products such as these can be suppressed, the selectivity of the target product is further improved, and unsaturated aldehydes and unsaturated nitriles can be produced in high yield. More specifically, when the ratio of tetracoordinated Fe / (tetracoordinated Fe + 6-coordinated Fe) is 0.20 or more, it controls the function of extracting allylic hydrogen of olefin or alcohol and the ability to propagate lattice oxygen. By forming a highly coordinated unsaturated site at the catalytically active site, an unsaturated aldehyde or unsaturated nitrile can be obtained in high yield. Further, when the ratio of tetracoordinated Fe / (tetracoordinated Fe + 6-coordinated Fe) is 0.90 or less, the catalytic activity is further improved.
「４配位Ｆｅ／（４配位Ｆｅ＋６配位Ｆｅ）の比」は、酸化物触媒に含まれる全部のＦｅ（４配位Ｆｅ＋６配位Ｆｅ）に対する４配位のＦｅの割合で表される。酸化物触媒に含まれるＦｅは４配位か６配位の２通りに分類される。例えば、４配位Ｆｅ／（４配位Ｆｅ＋６配位Ｆｅ）の比が０．４である場合、酸化物触媒に含まれるＦｅ１００モル％のうち、４０モル％が４配位のＦｅであり、残り６０モル％が６配位のＦｅである。 The “ratio of 4-coordinated Fe / (4-coordinated Fe + 6-coordinated Fe)” is expressed by the ratio of tetracoordinated Fe to the total Fe (tetracoordinated Fe + 6-coordinated Fe) contained in the oxide catalyst. . Fe contained in the oxide catalyst is classified into two types of tetracoordinate and hexacoordinate. For example, when the ratio of tetracoordinated Fe / (tetracoordinated Fe + 6-coordinated Fe) is 0.4, 40 mol% of the Fe 100 mol% contained in the oxide catalyst is tetracoordinated Fe, The remaining 60 mol% is hexacoordinated Fe.
酸化物触媒中の４配位のＦｅの割合及び６配位のＦｅの割合は、実施例に記載のＦｅ−Ｋ吸収端Ｘ線吸収微細構造スペクトルの測定を行うことによって確認できる。Ｆｅの配位数に関する情報が得られる測定法としては、Ｘ線回折も挙げられるものの、Ｘ線回折では結晶の配位数の情報しか得られない。Ｆｅ−Ｋ吸収端Ｘ線吸収微細構造スペクトルは結晶だけでなく、アモルファスな状態でも配位数を観察することができるため、より正確な情報を得ることができる。よって、本実施形態においては、Ｆｅ−Ｋ吸収端Ｘ線吸収微細構造スペクトルを測定方法として採用する。鉄のＫ吸収端Ｘ線吸収微細構造スペクトルによるより詳細な測定方法としては、実施例に記載の方法をもちいることができる。なお、４配位Ｆｅ／（４配位Ｆｅ＋６配位Ｆｅ）の比は、例えば、後述の製造方法の製造条件を調整することにより制御することができる。 The ratio of tetracoordinated Fe and the ratio of hexacoordinated Fe in the oxide catalyst can be confirmed by measuring the Fe-K absorption edge X-ray absorption fine structure spectrum described in Examples. X-ray diffraction can be used as a measuring method for obtaining information on the coordination number of Fe, but only information on the coordination number of crystals can be obtained by X-ray diffraction. Since the Fe—K absorption edge X-ray absorption fine structure spectrum can observe the coordination number not only in the crystal but also in an amorphous state, more accurate information can be obtained. Therefore, in this embodiment, the Fe—K absorption edge X-ray absorption fine structure spectrum is adopted as a measurement method. As a more detailed measurement method based on the K absorption edge X-ray absorption fine structure spectrum of iron, the method described in Examples can be used. The ratio of tetracoordinated Fe / (tetracoordinated Fe + 6-coordinated Fe) can be controlled, for example, by adjusting the production conditions of the production method described later.
〔組成〕
本実施形態に係る酸化物触媒は、モリブデン、ビスマス、鉄、コバルト、及びランタノイド元素を含有する。このように、Ｍｏ−Ｂｉ系の金属酸化物において、Ｍｏ、Ｂｉ、Ｆｅ、Ｃｏ、及びランタノイド元素を含有することにより、各金属元素が複合酸化物を形成しうる。
〔composition〕
The oxide catalyst according to this embodiment contains molybdenum, bismuth, iron, cobalt, and a lanthanoid element. Thus, in the Mo-Bi metal oxide, each metal element can form a composite oxide by containing Mo, Bi, Fe, Co, and a lanthanoid element.
本実施形態に係る酸化物触媒において、Ｂｉ及びＭｏは複合化して、気相接触酸化、アンモ酸化反応等の活性種とされているＢｉ２Ｍｏ３Ｏ１２、Ｂｉ２ＭｏＯ６等のＢｉ−Ｍｏ−Ｏ複合酸化物を形成しうる。 In the oxide catalyst according to the present embodiment, Bi and Mo are combined to form Bi—Mo such as Bi 2 Mo 3 O 12 and Bi 2 MoO 6 which are active species such as gas phase catalytic oxidation and ammoxidation reaction. -O complex oxide can be formed.
Ｍｏ１２原子に対するＢｉの原子比ａは、上記活性種を形成させる観点から、好ましくは１．５≦ａ≦６．０であり、より好ましくは２．０≦ａ≦４．５であり、さらに好ましくは２．０≦ａ≦４．０である。原子比ａが上記範囲であることにより、目的生成物の選択率がより高くなる傾向にある。 The atomic ratio a of Bi to Mo12 atoms is preferably 1.5 ≦ a ≦ 6.0, more preferably 2.0 ≦ a ≦ 4.5, and even more preferably from the viewpoint of forming the active species. Is 2.0 ≦ a ≦ 4.0. When the atomic ratio a is in the above range, the selectivity of the target product tends to be higher.
Ｍｏ１２原子に対するＦｅの原子比ｂは、好ましくは１．５≦ｂ≦７．０であり、より好ましくは２．０≦ｂ≦６．０であり、さらに好ましくは３．０≦ｂ≦５．０である。原子比ｂが上記範囲であることにより、不飽和アルデヒドや不飽和ニトリルの選択率がより高くなる傾向にある。 The atomic ratio b of Fe to Mo12 atoms is preferably 1.5 ≦ b ≦ 7.0, more preferably 2.0 ≦ b ≦ 6.0, and further preferably 3.0 ≦ b ≦ 5. 0. When the atomic ratio b is in the above range, the selectivity of unsaturated aldehyde or unsaturated nitrile tends to be higher.
本実施形態に係る酸化物触媒はＣｏを含む。Ｃｏは、Ｍｏ、Ｂｉ、Ｆｅと同様に工業的に目的生成物を合成する上で必須元素である。本実施形態に係る酸化物触媒において、Ｃｏは、複合酸化物ＣｏＭｏＯ４を形成し、該ＣｏＭｏＯ４がＢｉ−Ａ−Ｍｏ−Ｏ等の活性種を高分散させるための担体としての役割と、気相から酸素を取り込み、Ｂｉ−Ａ−Ｍｏ−Ｏ等に供給する役割を果たしていると推定される。Ｍｏ、Ｂｉ、Ｆｅ、Ｃｏ及びランタノイド元素Ａを含む酸化物触媒で、不飽和アルデヒドを高収率で得るには、該酸化物触媒において、ＣｏはＭｏと複合化させ、複合酸化物ＣｏＭｏＯ４を形成させることが好ましい。 The oxide catalyst according to this embodiment includes Co. Co, like Mo, Bi, and Fe, is an essential element for industrially synthesizing the target product. In the oxide catalyst according to the present embodiment, Co forms a composite oxide CoMoO 4 , and the CoMoO 4 plays a role as a support for highly dispersing active species such as Bi—A—Mo—O and the like. It is presumed to play a role of taking oxygen from the phase and supplying it to Bi-A-Mo-O or the like. In order to obtain an unsaturated aldehyde in a high yield with an oxide catalyst containing Mo, Bi, Fe, Co and a lanthanoid element A, Co is compounded with Mo in the oxide catalyst, and the composite oxide CoMoO 4 is formed. It is preferable to form.
Ｍｏ１２原子に対するＣｏの原子比ｃは、好ましくは２．０≦ｃ≦８．０であり、より好ましくは２．５≦ｃ≦６．０であり、さらに好ましくは３．０≦ｃ≦５．０である。原子比ｃが上記範囲であることにより、不飽和アルデヒドや不飽和ニトリルの収率がより高くなる傾向にある。 The atomic ratio c of Co to Mo12 atoms is preferably 2.0 ≦ c ≦ 8.0, more preferably 2.5 ≦ c ≦ 6.0, and even more preferably 3.0 ≦ c ≦ 5. 0. When the atomic ratio c is in the above range, the yield of unsaturated aldehyde or unsaturated nitrile tends to be higher.
酸化物触媒がランタノイド元素Ａを含むことにより、上記Ｂｉ−Ｍｏ−Ｏ複合酸化物はランタノイド元素Ａと複合化して、Ｂｉ−Ａ−Ｍｏ−Ｏ複合酸化物を形成しうる。このような複合酸化物は、耐熱性により優れる。耐熱性に優れることにより、高温での反応により適した酸化物触媒となる。 When the oxide catalyst contains the lanthanoid element A, the Bi—Mo—O composite oxide can be combined with the lanthanoid element A to form a Bi—A—Mo—O composite oxide. Such a complex oxide is more excellent in heat resistance. By being excellent in heat resistance, it becomes an oxide catalyst more suitable for reaction at high temperature.
Ｍｏ１２原子に対するランタノイド元素Ａの原子比ｄは、好ましくは０．５０≦ｄ≦６．０であり、より好ましくは０．８０≦ｄ≦４．０であり、さらに好ましくは１．４≦ｄ≦３．０である。原子比ｄが上記範囲であることにより、不飽和アルデヒドや不飽和ニトリルの選択率がより高くなる傾向にある。 The atomic ratio d of the lanthanoid element A to Mo12 atoms is preferably 0.50 ≦ d ≦ 6.0, more preferably 0.80 ≦ d ≦ 4.0, and further preferably 1.4 ≦ d ≦ 3.0. When the atomic ratio d is in the above range, the selectivity of unsaturated aldehyde or unsaturated nitrile tends to be higher.
通常、酸化物触媒の製造において、酸素を含む酸化雰囲気下で焼成した場合、Ｆｅ含有量が多くなると格子酸素によって囲まれた６配位の鉄が生成する。６配位の鉄の割合の多い酸化物触媒を用いて、不飽和アルデヒド又は不飽和ニトリルの製造を行うとＣＯやＣＯ２等の副生成物が増加し、目的生成物の選択率が低下するという問題がある。この点に関して、本発明者らは、Ｍｏ、Ｂｉ、Ｆｅ、Ｃｏ、及びランタノイド元素を含む酸化物触媒の製造において、６配位Ｆｅの副生を抑制することを狙って不活性ガス雰囲気中で焼成し、酸化物触媒のＦｅ周りの格子酸素を取り除き、さらに酸化安定化処理をすることでＦｅを４配位に制御する方法を見出した。当該制御によって、ＣＯやＣＯ２等の副生成物が減少する傾向が現れ、目的生成物の選択率が高くなることを見出した。 In general, in the production of an oxide catalyst, when calcined in an oxidizing atmosphere containing oxygen, hexacoordinate iron surrounded by lattice oxygen is generated when the Fe content increases. When an unsaturated aldehyde or an unsaturated nitrile is produced using an oxide catalyst having a high proportion of hexacoordinate iron, byproducts such as CO and CO 2 increase, and the selectivity of the target product decreases. There is a problem. In this regard, the present inventors aim to suppress the by-production of hexacoordinated Fe in the production of oxide catalysts containing Mo, Bi, Fe, Co, and lanthanoid elements in an inert gas atmosphere. The inventors discovered a method of controlling Fe to four-coordinate by firing, removing lattice oxygen around Fe of the oxide catalyst, and further performing oxidation stabilization treatment. By this control, tends to by-products such as CO and CO 2 decreases appeared and found that the selectivity of the objective product increases.
本実施形態に係る酸化物触媒は、好ましくは、下記組成式（１）で表される組成を有する。
Ｍｏ１２ＢｉａＦｅｂＣｏｃＡｄＢｅＣｆＯｇ （１）
（式（１）中、Ｍｏはモリブデン、Ｂｉはビスマス、Ｆｅは鉄、Ｃｏはコバルトを示し、
Ａはランタン、セリウム、プラセオジウム、ネオジム、及びユーロピウムからなる群より選ばれる少なくとも１種のランタノイド元素を示し、
Ｂはニッケル、マンガン、銅、亜鉛、マグネシウム、カルシウム、ストロンチウム、バリウム、錫、及び鉛からなる群より選ばれる少なくとも１種の元素を示し、
Ｃはセシウム、ルビジウム、及びカリウムからなる群より選ばれる少なくとも１種のアルカリ元素を示し、
ａ〜ｆは、Ｍｏ１２原子に対する各元素の原子比を示し、１．５≦ａ≦６．０、１．５≦ｂ≦７．０、２．０≦ｃ≦８．０、０．５０≦ｄ≦６．０、０、０．０１０≦ｅ≦２．０、及び０≦ｆ＜２．０を満たし、
ｇは酸素以外の構成元素の原子価によって決まる酸素の原子数である。）
The oxide catalyst according to the present embodiment preferably has a composition represented by the following composition formula (1).
Mo 12 Bi a Fe b Co c A d B e C f O g (1)
(In the formula (1), Mo represents molybdenum, Bi represents bismuth, Fe represents iron, Co represents cobalt,
A represents at least one lanthanoid element selected from the group consisting of lanthanum, cerium, praseodymium, neodymium, and europium,
B represents at least one element selected from the group consisting of nickel, manganese, copper, zinc, magnesium, calcium, strontium, barium, tin, and lead;
C represents at least one alkali element selected from the group consisting of cesium, rubidium, and potassium;
a to f indicate the atomic ratio of each element to the Mo12 atom, 1.5 ≦ a ≦ 6.0, 1.5 ≦ b ≦ 7.0, 2.0 ≦ c ≦ 8.0, 0.50 ≦ satisfy d ≦ 6.0, 0, 0.010 ≦ e ≦ 2.0, and 0 ≦ f <2.0,
g is the number of oxygen atoms determined by the valence of the constituent elements other than oxygen. )
Ａはランタン、セリウム、プラセオジウム、ネオジム、及びユーロピウムからなる群より選ばれる少なくとも１種のランタノイド元素を示す。Ａが酸化物触媒に含まれることにより、Ｂｉ−Ａ−Ｍｏ−Ｏ複合酸化物を形成でき、耐熱性がより向上する傾向にある。 A represents at least one lanthanoid element selected from the group consisting of lanthanum, cerium, praseodymium, neodymium, and europium. When A is contained in the oxide catalyst, a Bi—A—Mo—O composite oxide can be formed, and the heat resistance tends to be further improved.
Ｂはニッケル、マンガン、銅、亜鉛、マグネシウム、カルシウム、ストロンチウム、バリウム、錫、及び鉛からなる群より選ばれる少なくとも１種の元素を示す。Ｂは酸化物触媒において、気相からの酸素取り込みを補助する役割を示すと考えられている。原子比ｅは、好ましくは０．０１０≦ｅ≦２．０であり、より好ましくは０．０３０≦ｅ≦１．０であり、さらに好ましくは０．０５０≦ｅ≦０．４０である。原子比ｅが上記数値範囲であることにより、組成式（１）で表される組成を有する酸化物触媒の触媒活性がより優れる傾向にある。また、原子比ｅが２．０以下であることにより、酸化物触媒が塩基性となりにくく、オレフィンやアルコールの酸化反応において、原料であるオレフィンやアルコールが触媒に吸着され易くなり、触媒活性がより優れる傾向にある。 B represents at least one element selected from the group consisting of nickel, manganese, copper, zinc, magnesium, calcium, strontium, barium, tin, and lead. B is considered to show a role of assisting oxygen uptake from the gas phase in the oxide catalyst. The atomic ratio e is preferably 0.010 ≦ e ≦ 2.0, more preferably 0.030 ≦ e ≦ 1.0, and still more preferably 0.050 ≦ e ≦ 0.40. When the atomic ratio e is in the above numerical range, the catalytic activity of the oxide catalyst having the composition represented by the composition formula (1) tends to be more excellent. In addition, when the atomic ratio e is 2.0 or less, the oxide catalyst is hardly made basic, and in the oxidation reaction of olefin or alcohol, the raw material olefin or alcohol is easily adsorbed to the catalyst, and the catalytic activity is more enhanced. It tends to be excellent.
Ｃはセシウム、ルビジウム及びカリウムからなる群より選ばれる少なくとも１種のアルカリ元素を示す。Ｃは酸化物触媒において、複合化されなかったＭｏＯ３等の酸点を中和する役割を示すと考えられている。なお、セシウム及び／又はルビジウムを含有してもしなくても、４配位のＦｅ生成には影響を与えない。組成式（１）で表される組成において、Ｍｏ１２原子に対するこれらの元素の原子比ｆは、好ましくは０≦ｆ＜２．０であり、より好ましくは０．１０≦ｆ≦１．５であり、さらに好ましくは０．２０≦ｆ≦１．０である。原子比ｆが上記数値範囲であることにより、活性がより向上する傾向にある。 C represents at least one alkali element selected from the group consisting of cesium, rubidium and potassium. C is considered to exhibit a role of neutralizing acid sites such as MoO 3 that have not been complexed in the oxide catalyst. Note that whether or not cesium and / or rubidium are contained does not affect the formation of tetracoordinate Fe. In the composition represented by the composition formula (1), the atomic ratio f of these elements to Mo12 atoms is preferably 0 ≦ f <2.0, more preferably 0.10 ≦ f ≦ 1.5. More preferably, 0.20 ≦ f ≦ 1.0. When the atomic ratio f is in the above numerical range, the activity tends to be further improved.
〔担体〕
本実施形態の酸化物触媒は、上述の酸化物触媒を担持するための担体を含有してもよい。担体を含むことにより、酸化物触媒を高分散化することができ、担持された酸化物触媒に、高い耐摩耗性を与えることができるという点で好ましい。
[Carrier]
The oxide catalyst of this embodiment may contain a carrier for supporting the above-described oxide catalyst. The inclusion of the support is preferable in that the oxide catalyst can be highly dispersed and the supported oxide catalyst can be provided with high wear resistance.
担体としては、特に限定されないが、例えば、シリカ、アルミナ、チタニア、ジルコニアが挙げられる。一般的にシリカは、それ自身不活性であり、他の担体に比べて、目的生成物に対する選択性を減ずることなく、上述の酸化物触媒に対し良好なバインド作用を有する点で好ましい担体である。さらに、シリカ担体は担持された酸化物触媒に、より高い耐摩耗性を与えることができるという点でも好ましい。 Although it does not specifically limit as a support | carrier, For example, a silica, an alumina, a titania, a zirconia is mentioned. In general, silica is an inert carrier and is a preferred carrier in that it has a good binding action on the above-mentioned oxide catalyst without reducing selectivity for the target product compared to other carriers. . Further, the silica support is also preferable in that it can give higher wear resistance to the supported oxide catalyst.
流動床反応器用の酸化物触媒である場合は、上記観点から、担体を含むことが好ましい。触媒中の担体の含有量の上限は、触媒の全質量に対して８０質量％以下が好ましく、より好ましくは７０質量％以下、さらに好ましくは６０質量％以下である。また、担体の含有量の下限は、触媒の全質量に対して２０質量％以上が好ましく、３０質量％以上がより好ましく、４０質量％以上がさらに好ましい。含有量が８０質量％以下であることにより、４配位Ｆｅの影響を与えにくく、見掛け比重を調整でき流動性がより向上する傾向にある。また、含有量が２０質量％以上であることにより、流動床反応用触媒のような強度を要する触媒として用いる場合、耐破砕性及び耐摩耗性等がより向上する傾向にある。 In the case of an oxide catalyst for a fluidized bed reactor, a support is preferably included from the above viewpoint. The upper limit of the content of the carrier in the catalyst is preferably 80% by mass or less, more preferably 70% by mass or less, and still more preferably 60% by mass or less with respect to the total mass of the catalyst. Further, the lower limit of the content of the carrier is preferably 20% by mass or more, more preferably 30% by mass or more, and further preferably 40% by mass or more with respect to the total mass of the catalyst. When the content is 80% by mass or less, the influence of tetracoordinated Fe is hardly exerted, the apparent specific gravity can be adjusted, and the fluidity tends to be further improved. Moreover, when it uses as a catalyst which requires intensity | strength like a fluid bed reaction catalyst because content is 20 mass% or more, there exists a tendency for crushing resistance, abrasion resistance, etc. to improve more.
なお、固定床反応器用の打錠成型や押し出し成型法等した酸化物触媒である場合は、本実施形態に係る酸化物触媒は、担体を含まなくてもよい。また、この場合、担体の代わりに、有機バインダーを用いることが好ましい。 In addition, in the case of an oxide catalyst such as tableting molding or extrusion molding for a fixed bed reactor, the oxide catalyst according to this embodiment may not include a support. In this case, it is preferable to use an organic binder instead of the carrier.
〔酸化物触媒の製造方法〕
本実施形態の酸化物触媒の製造方法は、モリブデン、ビスマス、鉄、コバルト及びランタノイド元素を含む原料と、キレート剤と、を混合して原料スラリーを得る混合工程と、前記原料スラリーを乾燥して乾燥体を得る乾燥工程と、前記乾燥体を仮焼成して仮焼成体を得る仮焼成工程と、前記仮焼成体を不活性ガス雰囲気下で本焼成して本焼成体を得る本焼成工程と、前記本焼成体を、酸素を含む雰囲気で酸化安定化処理して、酸化物触媒を得る酸化安定化処理工程と、を有する。
[Production method of oxide catalyst]
The manufacturing method of the oxide catalyst of the present embodiment includes a mixing step of mixing a raw material containing molybdenum, bismuth, iron, cobalt, and a lanthanoid element and a chelating agent to obtain a raw material slurry, and drying the raw material slurry. A drying step for obtaining a dried body, a preliminary firing step for pre-baking the dried body to obtain a temporary fired body, and a main firing step for obtaining a fired body by subjecting the temporary fired body to main firing in an inert gas atmosphere. And an oxidation stabilization treatment step of obtaining an oxide catalyst by subjecting the fired body to an oxidation stabilization treatment in an atmosphere containing oxygen.
上述のように、本発明者らは、６配位のＦｅではなく、４配位のＦｅを得ることに着目し、その組成比や調製方法を総合的に検討した。 As described above, the inventors focused on obtaining tetracoordinate Fe instead of hexacoordinate Fe, and comprehensively studied the composition ratio and the preparation method.
単に、Ｆｅ含有量を多くしただけでは、４配位のＦｅは生成しないが、（ａ）鉄に対してキレート効果のある化合物（キレート剤）をスラリーに添加すること、（ｂ）特定の焼成方法・処理方法を用いることを満たす新たな製造技術によって、酸化物触媒中のＦｅ周りの酸素量を制御し、４配位のＦｅを得ることができる。また、上記条件によって、６配位Ｆｅの生成が抑制される。なお、４配位のＦｅや６配位のＦｅが形成されていることは、後述する鉄のＫ吸収端Ｘ線吸収微細構造スペクトルを測定することにより確認することができる。 Simply increasing the Fe content does not produce tetracoordinated Fe, but (a) adding a compound having a chelating effect on iron (chelating agent) to the slurry, (b) specific firing By a new manufacturing technique that satisfies the use of the method and the processing method, the amount of oxygen around Fe in the oxide catalyst can be controlled, and tetracoordinated Fe can be obtained. Moreover, the production | generation of hexacoordinate Fe is suppressed by the said conditions. The formation of tetracoordinated Fe or hexacoordinated Fe can be confirmed by measuring an iron K absorption edge X-ray absorption fine structure spectrum described later.
本実施形態に係る製造方法により製造された酸化物触媒は、酸化物触媒中に４配位のＦｅが存在することによって、触媒活性点であるＢｉ−Ｏ−Ｍｏの結合距離が適切に調整され、酸素付加化合物の副生を極力抑制することができ、不飽和アルデヒドや不飽和ニトリルを高収率で得ることができる。以下、各工程について詳細に説明する。 In the oxide catalyst manufactured by the manufacturing method according to this embodiment, the bond distance of Bi—O—Mo, which is a catalytic active point, is appropriately adjusted by the presence of tetracoordinate Fe in the oxide catalyst. The by-product of the oxygen addition compound can be suppressed as much as possible, and an unsaturated aldehyde or an unsaturated nitrile can be obtained in a high yield. Hereinafter, each step will be described in detail.
〔混合工程〕
混合工程では、Ｍｏ、Ｂｉ、Ｆｅ、Ｃｏ及びランタノイド元素を含む原料と、キレート剤と、を混合して原料スラリーを得る。原料スラリーは、最終的に得られる酸化物触媒において、Ｍｏ１２原子に対する、Ｂｉの原子比ａが１．５≦ａ≦６．０、Ｆｅの原子比ｂが３．０≦ｂ≦７．０、Ｃｏの原子比ｃが２．０≦ｂ≦８．０、ランタノイド元素の原子比ｄが０．５０≦ａ≦６．０となるように各原料の混合割合を調整することが好ましい。
[Mixing process]
In the mixing step, a raw material slurry is obtained by mixing a raw material containing Mo, Bi, Fe, Co, and a lanthanoid element and a chelating agent. In the finally obtained oxide catalyst, the raw slurry has an atomic ratio a of Bi to Mo12 atoms of 1.5 ≦ a ≦ 6.0, an atomic ratio b of Fe of 3.0 ≦ b ≦ 7.0, It is preferable to adjust the mixing ratio of each raw material so that the atomic ratio c of Co is 2.0 ≦ b ≦ 8.0 and the atomic ratio d of the lanthanoid element is 0.50 ≦ a ≦ 6.0.
原料スラリーは、Ｍｏ、Ｂｉ、Ｆｅ、Ｃｏ、並びにセリウム、ランタン、セリウム、プラセオジウム、及びネオジム等のランタノイド元素Ａを含むものであれば特に限定されないが、必要に応じて、セシウム、ルビジウム、カリウム、ニッケル、マンガン、銅、亜鉛、マグネシウム、カルシウム、ストロンチウム、バリウム、錫、鉛を含んでもよい。これら金属元素の触媒原料としては、水又は硝酸に可溶な、アンモニウム塩、硝酸塩、塩酸塩、有機酸塩、酸化物、水酸化物、炭酸塩等が挙げられる。金属元素の触媒原料を酸化物として用いる場合は、当該酸化物が水又は有機溶媒に分散された分散液が好ましく、当該酸化物が水に分散された分散液がより好ましい。原料となる酸化物が水に分散されている場合、酸化物の凝集を抑制し、高分散させるために高分子等の界面活性剤が含まれていてもよい。酸化物の粒子径は好ましくは１〜５００ｎｍ、より好ましくは１０〜８０ｎｍである。担体を含有する酸化物触媒を製造する場合は、原料スラリーにシリカ原料としてシリカゾルを添加することが好ましい。 The raw material slurry is not particularly limited as long as it contains Mo, Bi, Fe, Co, and lanthanoid element A such as cerium, lanthanum, cerium, praseodymium, and neodymium, but if necessary, cesium, rubidium, potassium, Nickel, manganese, copper, zinc, magnesium, calcium, strontium, barium, tin, lead may be included. Examples of the catalyst raw materials for these metal elements include ammonium salts, nitrates, hydrochlorides, organic acid salts, oxides, hydroxides, carbonates and the like that are soluble in water or nitric acid. When the metal element catalyst raw material is used as an oxide, a dispersion in which the oxide is dispersed in water or an organic solvent is preferable, and a dispersion in which the oxide is dispersed in water is more preferable. When the raw material oxide is dispersed in water, a surfactant such as a polymer may be contained in order to suppress aggregation and highly disperse the oxide. The particle diameter of the oxide is preferably 1 to 500 nm, more preferably 10 to 80 nm. When producing an oxide catalyst containing a support, it is preferable to add silica sol as a silica raw material to the raw slurry.
Ｆｅの配位数を４配位制御するため、上記原料混合スラリーにキレート剤を添加する。キレート剤を添加することにより、キレート剤がＦｅ原料と錯体を形成し、スラリー中のＦｅ原料の溶解が促進されると考えられる。 In order to control the coordination number of Fe by four, a chelating agent is added to the raw material mixed slurry. By adding the chelating agent, it is considered that the chelating agent forms a complex with the Fe raw material and the dissolution of the Fe raw material in the slurry is promoted.
キレート剤としては、特に限定されないが、例えば、ポリエチレングリコール、ポリビニルアルコール、ポリアクリル酸、ポリカルボン酸、ポリアクリルアミド、ポリビニルピロリドン等の水溶性ポリマー；アミノカルボン酸類、マロン酸、コハク酸等の多価カルボン酸；ヒドラジン、エチレンジアミン、エチレンジアミン四酢酸等のアミン類；グリコール酸、りんご酸、しゅう酸、酒石酸、クエン酸等の有機酸、イミノジ酢酸、ニトリロトリ酢酸、ジエチレントラミンペンタ酢酸、トリエチレンテトラミンヘキサ酢酸、シクロヘキサン−１，２−ジアミンテトラ酢酸、Ｎ−ヒドロキシエチルエチレンジアミントリ酢酸、エチレングリコールジエチルエーテルジアミンテトラ酢酸、エチレンジアミンテトラプロピオン酸が挙げられる。これらキレート剤は、１種単独で用いても２種以上を併用してもよい。 Although it does not specifically limit as a chelating agent, For example, water-soluble polymers, such as polyethyleneglycol, polyvinyl alcohol, polyacrylic acid, polycarboxylic acid, polyacrylamide, and polyvinylpyrrolidone; Polyvalents, such as aminocarboxylic acids, malonic acid, and succinic acid Carboxylic acids; Amines such as hydrazine, ethylenediamine, ethylenediaminetetraacetic acid; Organic acids such as glycolic acid, malic acid, oxalic acid, tartaric acid, citric acid, iminodiacetic acid, nitrilotriacetic acid, diethylenetraminepentaacetic acid, triethylenetetraminehexaacetic acid , Cyclohexane-1,2-diaminetetraacetic acid, N-hydroxyethylethylenediaminetriacetic acid, ethylene glycol diethyl etherdiaminetetraacetic acid, and ethylenediaminetetrapropionic acid. These chelating agents may be used alone or in combination of two or more.
キレート剤の添加量は、得られる酸化物触媒１００質量％に対して、好ましくは１〜１０質量％であり、より好ましくは１〜５質量％であり、さらに好ましくは２〜４質量％である。キレート剤の添加量が上記範囲であることにより、得られる酸化物触媒の酸化及び還元度をより制御しやすい傾向にある。また、キレート剤の添加量が１０質量％以下であることにより、金属が過還元されることを抑制できる傾向にある。 The addition amount of the chelating agent is preferably 1 to 10% by mass, more preferably 1 to 5% by mass, and further preferably 2 to 4% by mass with respect to 100% by mass of the obtained oxide catalyst. . When the addition amount of the chelating agent is within the above range, the oxidation and reduction degree of the obtained oxide catalyst tends to be more easily controlled. Moreover, it exists in the tendency which can suppress that a metal is over-reduced because the addition amount of a chelating agent is 10 mass% or less.
原料スラリーの調製方法は通常用いられる方法であれば、特に限定されないが、例えば、Ｍｏのアンモニウム塩を温水に溶解させた溶液と、Ｂｉ、Ｆｅ、Ｃｏ、ランタノイド元素Ａ、及び必要に応じて用いるアルカリ金属を硝酸塩として水又は硝酸水溶液に溶解させた溶液と、を混合することにより調製することができる。混合後のスラリー中の金属元素濃度は、好ましくは１〜５０質量％であり、より好ましくは１０〜４０質量％であり、さらに好ましくは２０〜３５質量％である。金属元素濃度が上記範囲であることにより、触媒の均一性がより優れる傾向にある。 The method for preparing the raw slurry is not particularly limited as long as it is a commonly used method. For example, a solution in which an ammonium salt of Mo is dissolved in warm water, Bi, Fe, Co, lanthanoid element A, and as necessary are used. It can be prepared by mixing a solution in which an alkali metal is dissolved in water or an aqueous nitric acid solution as a nitrate. The metal element concentration in the slurry after mixing is preferably 1 to 50% by mass, more preferably 10 to 40% by mass, and still more preferably 20 to 35% by mass. When the metal element concentration is in the above range, the uniformity of the catalyst tends to be more excellent.
キレート剤をＦｅにより配位しやすくするため、原料スラリーを、ホモジナイザーを用いて混合することが好ましい。金属元素の原料成分とキレート剤が存在するスラリーを、強力な剪断力を有するホモジナイザーを用いて混合することによって、原料スラリーに含まれる固形分粒子を粉砕・微細化し、固形分粒子の表面積を大きくすることができ、これによりキレート剤をＦｅに配位させ易くすることができる。さらに、ホモジナイザーを用いることによって、広い温度範囲にわたって安定で、かつＦｅが均一に高分散したスラリーが得られる傾向にある。 In order to facilitate coordination of the chelating agent with Fe, the raw material slurry is preferably mixed using a homogenizer. By mixing the slurry containing the metal component raw material component and the chelating agent using a homogenizer having a strong shearing force, the solid particles contained in the raw material slurry are pulverized and refined to increase the surface area of the solid particles. This can facilitate the coordination of the chelating agent to Fe. Furthermore, by using a homogenizer, a slurry that is stable over a wide temperature range and in which Fe is uniformly and highly dispersed tends to be obtained.
混合工程では、固形分粒子をより微細化してＦｅにキレート剤を配位させる観点から、高圧ホモジナイザーを用いることが好ましい。高圧ホモジナイザーを用いる際の圧力は、好ましくは１００〜１５００ｂａｒであり、より好ましくは５００〜１３００ｂａｒであり、さらに好ましくは１０００〜１２００ｂａｒである。圧力が１５００ｂａｒ以下であることにより、スラリー固形分破砕されすぎることを抑制できる傾向にある。また、圧力が１００ｂａｒ以上であることにより、固形分粒子を十分に微細化することができる。 In the mixing step, it is preferable to use a high-pressure homogenizer from the viewpoint of making solid particles finer and coordinating the chelating agent to Fe. The pressure when using the high-pressure homogenizer is preferably 100 to 1500 bar, more preferably 500 to 1300 bar, and still more preferably 1000 to 1200 bar. When the pressure is 1500 bar or less, the slurry solids tend to be prevented from being crushed too much. Moreover, solid content particle | grains can fully be refined | miniaturized because a pressure is 100 bar or more.
スラリー固形分のメジアン径は、好ましくは０．０１〜１０μｍであり、より好ましくは０．５〜７μｍであり、さらに好ましくは１〜５μｍである。スラリー固形分のメジアン径が１０μｍ以下であることにより、スラリー粘度が向上し、中空粒子の多い噴霧乾燥体となる。また、スラリー固形分のメジアン径が０．１μｍ以上であることにより、スラリー粘度が低下し、スラリーから噴霧乾燥機へのラインが詰まることを抑制できる傾向にある。 The median diameter of the slurry solid content is preferably 0.01 to 10 μm, more preferably 0.5 to 7 μm, and further preferably 1 to 5 μm. When the median diameter of the solid content of the slurry is 10 μm or less, the slurry viscosity is improved and a spray-dried body with many hollow particles is obtained. Moreover, when the median diameter of the slurry solid content is 0.1 μm or more, the slurry viscosity tends to decrease, and the line from the slurry to the spray dryer tends to be blocked.
〔乾燥工程〕
乾燥工程では、混合工程で得られた原料スラリーを乾燥して乾燥体（例えば、乾燥粒子）を得る。乾燥方法は、特に制限はされず、一般に用いられている方法によって行うことができ、例えば、蒸発乾涸法、噴霧乾燥法、減圧乾燥法等の任意の方法で行なうことができる。噴霧乾燥法としては、通常工業的に実施される遠心方式、二流体ノズル方式及び高圧ノズル方式等を採用することができる。また、乾燥熱源としては、特に限定されないが、例えば、スチーム、電気ヒーター等によって加熱された空気を用いることが好ましい。この際、噴霧乾燥装置の乾燥機入口の温度は、好ましくは１５０〜４００℃、より好ましくは１８０〜４００℃、さらに好ましくは２００〜３５０℃である。上記温度範囲であることにより、複合酸化物がより形成されやすい傾向にある。
[Drying process]
In the drying step, the raw material slurry obtained in the mixing step is dried to obtain a dried body (for example, dry particles). The drying method is not particularly limited and can be performed by a generally used method. For example, the drying method can be performed by an arbitrary method such as an evaporation drying method, a spray drying method, or a reduced pressure drying method. As the spray-drying method, a centrifugal method, a two-fluid nozzle method, a high-pressure nozzle method, or the like, which are usually implemented industrially, can be employed. The drying heat source is not particularly limited, but it is preferable to use air heated by, for example, steam or an electric heater. At this time, the temperature at the inlet of the dryer of the spray dryer is preferably 150 to 400 ° C, more preferably 180 to 400 ° C, and further preferably 200 to 350 ° C. By being in the above temperature range, the composite oxide tends to be more easily formed.
〔仮焼成工程〕
仮焼成工程では、乾燥工程で得られた乾燥体を仮焼成して仮焼成体を得る。仮焼成の目的は、乾燥体中に残存している水分、硝酸等の除去、アンモニウム塩等である原料及び硝酸塩等である原料に由来して生成する硝酸アンモニウム等、及びキレート剤、水に分散された酸化物を原料にした場合の界面活性剤等の有機物をおだやかに燃焼させることにある。
[Temporary firing process]
In the temporary firing step, the dried body obtained in the drying step is temporarily fired to obtain a temporary fired body. The purpose of pre-baking is to remove water, nitric acid, etc. remaining in the dried body, ammonium nitrate, etc. produced from raw materials such as ammonium salts and nitrates, etc., chelating agents, and water. The purpose is to gently burn organic substances such as surfactants when oxides are used as raw materials.
仮焼成は、不活性ガス雰囲気で行うことが好ましい。不活性ガスとしては、特に限定されないが、例えば、ヘリウム、窒素、アルゴンなどが挙げられる。このなかでも、経済的な面から窒素が好ましい。不活性ガスが酸素を含む場合、酸素の含有量は、好ましくは０〜３．０体積％であり、より好ましくは０〜１．０体積％であり、さらに好ましくは０．５体積％である。酸素の含有量が３．０体積％以下であることにより、キレート剤が燃焼することに由来する発熱を抑制することができるため、得られる酸化物触媒への熱のダメージを軽減することができる。また、Ｆｅ周りの格子酸素を除去して４配位にするための焼成時間の正確なコントロールがより容易となる。 Pre-baking is preferably performed in an inert gas atmosphere. Although it does not specifically limit as an inert gas, For example, helium, nitrogen, argon etc. are mentioned. Among these, nitrogen is preferable from the economical aspect. When the inert gas contains oxygen, the oxygen content is preferably 0 to 3.0% by volume, more preferably 0 to 1.0% by volume, and even more preferably 0.5% by volume. . Since the oxygen content is 3.0% by volume or less, heat generation due to the burning of the chelating agent can be suppressed, and thus heat damage to the resulting oxide catalyst can be reduced. . In addition, accurate control of the firing time for removing the lattice oxygen around Fe to form four-coordination becomes easier.
上記仮焼成、及び後述する本焼成を行なう装置としては、特に限定されないが、例えば、回転炉、トンネル炉、マッフル炉等の焼成炉が挙げられる。 An apparatus for performing the above-described preliminary firing and main firing described later is not particularly limited, and examples thereof include firing furnaces such as a rotary furnace, a tunnel furnace, and a muffle furnace.
仮焼成の温度は、好ましくは１２０〜５００℃であり、より好ましくは１５０℃〜４００℃であり、さらに好ましくは２００℃〜３５０℃である。このような温度とすることにより、乾燥体中に残存している硝酸等の除去、アンモニウム塩等である原料及び硝酸塩等である原料に由来して生成する硝酸アンモニウム等、キレート剤、水に分散された酸化物を原料にした場合の界面活性剤等の有機物をよりおだやかに燃焼させることができる傾向にある。 The calcination temperature is preferably 120 to 500 ° C, more preferably 150 to 400 ° C, and further preferably 200 to 350 ° C. By adjusting to such a temperature, the nitric acid remaining in the dried body is removed, the ammonium nitrate is a raw material such as ammonium salt and the ammonium nitrate produced from the raw material is a nitrate, etc., and is dispersed in a chelating agent and water. When the oxide is used as a raw material, organic substances such as surfactants tend to be burned more gently.
仮焼成の時間は、好ましくは０．１〜２４時間であり、より好ましくは１〜１２時間であり、さらに好ましくは３〜１０時間である。具体的には、仮焼成の温度が１５０℃以下の低温の場合、長時間の仮焼成を行うこが好ましく、仮焼成の温度が３５０℃以上の高温の場合、２時間以下の短時間の仮焼成を行うことが好ましい。仮焼成の温度及び／又は時間が上記範囲内であることにより、仮焼成の段階でＣｏとＭｏとの２成分系酸化物の成長より抑制される傾向にあり、後述の本焼成において４配位のＦｅがより生成しやすくなる傾向にある。 The calcination time is preferably 0.1 to 24 hours, more preferably 1 to 12 hours, and further preferably 3 to 10 hours. Specifically, it is preferable to perform temporary baking for a long time when the temperature for preliminary baking is a low temperature of 150 ° C. or lower, and for a short time of 2 hours or shorter for a high temperature of 350 ° C. or higher. It is preferable to perform firing. When the temperature and / or time of the pre-firing is within the above range, it tends to be suppressed from the growth of the binary oxide of Co and Mo at the pre-firing stage. It tends to be easier to produce Fe.
仮焼成の昇温速度は、急激な燃焼反応を抑え、均質な組成の触媒を得る観点から、好ましくは０．０１０℃／ｍｉｎ〜５．０℃／ｍｉｎであり、より好ましくは０．１０℃／ｍｉｎ〜３．０℃／ｍｉｎであり、さらに好ましくは０．５０℃／ｍｉｎ〜２．０℃／ｍｉｎである。キレート剤の添加量が多いほど、急激な発熱が起こり、酸化物触媒の組成が不均質になりやすい傾向にある。しかし、昇温速度を上記範囲内とすることにより、硝酸や有機物等の燃焼や分解成分を十分に除去し、配位数が４配位であるＦｅの含有量を増加させ、より均質に複合化された構造を有する酸化物触媒を形成させることができる。 From the viewpoint of suppressing a rapid combustion reaction and obtaining a catalyst having a homogeneous composition, the temperature increase rate of the preliminary calcination is preferably 0.010 ° C./min to 5.0 ° C./min, more preferably 0.10 ° C. / Min to 3.0 ° C./min, more preferably 0.50 ° C./min to 2.0 ° C./min. As the amount of the chelating agent added increases, a rapid exotherm occurs and the composition of the oxide catalyst tends to become heterogeneous. However, by setting the rate of temperature rise within the above range, combustion and decomposition components such as nitric acid and organic substances are sufficiently removed, and the content of Fe having a coordination number of 4 is increased, resulting in a more homogeneous composite. An oxide catalyst having a structured structure can be formed.
〔本焼成工程〕
本焼成工程では、仮焼成工程で得られた仮焼成体を不活性ガス雰囲気下で本焼成して本焼成体を得る。本焼成の目的は、所望の結晶構造を形成し易くすることにある。本発明者らの知見によると、結晶構造は焼成温度と焼成時間との積の影響を受けるため、焼成温度と焼成時間とを適切に設定することが好ましい。
[Main firing process]
In the final firing step, the temporary fired body obtained in the temporary firing step is finally fired in an inert gas atmosphere to obtain the final fired body. The purpose of this firing is to facilitate the formation of the desired crystal structure. According to the knowledge of the present inventors, since the crystal structure is affected by the product of the firing temperature and the firing time, it is preferable to appropriately set the firing temperature and the firing time.
本焼成の温度は、４配位のＦｅを生成させる観点で仮焼成の温度より高くすることが好ましい。また、本焼成は、４配位のＦｅの生成し易さの観点から、第１本焼成及び第２本焼成の２段階焼成で行うことが好ましい。 The temperature for the main baking is preferably higher than the temperature for the temporary baking from the viewpoint of generating tetracoordinate Fe. Moreover, it is preferable to perform this baking by two-stage baking of 1st main baking and 2nd main baking from a viewpoint of the ease of producing | generating 4-coordinate Fe.
第１本焼成の焼成温度は、好ましくは４００〜４８０℃であり、より好ましくは４２０〜４７０℃であり、さらに好ましくは４３０℃〜４６０℃である。第１本焼成の焼成温度を４８０℃以下とすることにより、６配位のＦｅの生成をより抑制できる傾向がある。また、第１本焼成の焼成時間は、好ましくは２ｈ以上であり、より好ましくは３．０〜２０ｈであり、さらに好ましくは３．０〜１０ｈである。第１本焼成の焼成時間が上記範囲内であることにより、触媒活性がより向上する傾向にある。 The firing temperature of the first main firing is preferably 400 to 480 ° C, more preferably 420 to 470 ° C, and further preferably 430 ° C to 460 ° C. By setting the firing temperature of the first main firing to 480 ° C. or lower, the production of hexacoordinate Fe tends to be further suppressed. Moreover, the firing time of the first main firing is preferably 2 hours or longer, more preferably 3.0 to 20 hours, and further preferably 3.0 to 10 hours. When the firing time of the first main firing is within the above range, the catalytic activity tends to be further improved.
第２本焼成の焼成温度は、好ましくは４９０℃〜〜７００℃であり、より好ましくは５００℃〜６５０℃であり、さらに好ましくは５３０℃〜６００℃である。第２本焼成の焼成温度が上記範囲内であることにより、結晶が十分に成長する傾向にある。また、第２本焼成の焼成温度と焼成時間との積を適切にすることで４配位のＦｅの生成を促すことができる。この観点から、第２本焼成の焼成時間は、好ましくは０．１〜２４時間であり、より好ましくは２〜１２時間であり、さらに好ましくは３〜１０時間である。より具体的には、結晶構造の生成のために焼成温度及び焼成時間を適切にする観点から、第２本焼成の焼成温度が４００℃以下の低温の場合には、例えば２４〜７２時間程度の長時間の第２本焼成を行うことが好ましく、第２本焼成の焼成温度が７００℃よりの高温の場合には、得られる酸化物触媒の表面積が小さくなりすぎて触媒活性が下がってしまうのを防ぐ観点から、１時間以下の短時間の第２本焼成を行うことが好ましい。 The firing temperature in the second firing is preferably 490 ° C to 700 ° C, more preferably 500 ° C to 650 ° C, and further preferably 530 ° C to 600 ° C. When the firing temperature of the second firing is within the above range, the crystals tend to grow sufficiently. In addition, generation of tetracoordinated Fe can be promoted by making an appropriate product of the firing temperature and the firing time of the second main firing. From this viewpoint, the firing time of the second firing is preferably 0.1 to 24 hours, more preferably 2 to 12 hours, and further preferably 3 to 10 hours. More specifically, from the viewpoint of appropriately adjusting the firing temperature and firing time for generating the crystal structure, when the firing temperature of the second main firing is a low temperature of 400 ° C. or lower, for example, about 24 to 72 hours. It is preferable to carry out the second firing for a long time, and when the firing temperature of the second firing is higher than 700 ° C., the surface area of the resulting oxide catalyst becomes too small and the catalytic activity decreases. From the viewpoint of preventing this, it is preferable to perform the second firing for a short time of 1 hour or less.
〔酸化安定化処理工程〕
酸化安定化処理工程では、本焼成工程で得られた本焼成体を、酸素を含む雰囲気で酸化安定化処理して、酸化物触媒を得る。「酸化安定化処理」とは、Ｆｅを４配位に維持したまま、本焼成時に還元された表面の金属成分を徐々に酸化させる処理をいう。酸化物触媒の表面の金属成分をあらかじめ酸化しておくことにより、不飽和アルデヒド又は不飽和ニトリルの製造時に急激な酸化反応が生じることを抑制でき、不飽和アルデヒドや不飽和ニトリルの収率の低下を防ぐことができる。
[Oxidation stabilization treatment process]
In the oxidation stabilization treatment step, the fired body obtained in the firing step is subjected to oxidation stabilization treatment in an atmosphere containing oxygen to obtain an oxide catalyst. “Oxidation stabilization treatment” refers to a treatment for gradually oxidizing the metal components on the surface reduced during the main firing while maintaining the tetracoordinate Fe. By oxidizing the metal components on the surface of the oxide catalyst in advance, it is possible to suppress the rapid oxidation reaction during the production of unsaturated aldehydes or unsaturated nitriles, and the yield of unsaturated aldehydes and unsaturated nitriles is reduced. Can be prevented.
酸化安定化処理工程における酸素濃度は、酸化物触媒の表面のみを酸化させる観点から、好ましくは０．０１〜１０体積％であり、より好ましくは０．１〜８体積％であり、さらに好ましくは０．２〜５体積％である。酸素濃度が１０体積％以下であることにより、Ｆｅが６配位になることをより抑制できる傾向にある。また、酸素濃度が０．０１体積％以上であることにより、酸化物触媒の表面の金属成分を適切に酸化できる傾向にある。 The oxygen concentration in the oxidation stabilization treatment step is preferably 0.01 to 10% by volume, more preferably 0.1 to 8% by volume, and still more preferably from the viewpoint of oxidizing only the surface of the oxide catalyst. 0.2 to 5% by volume. When the oxygen concentration is 10% by volume or less, there is a tendency that Fe can be more suppressed from being 6-coordinated. Further, when the oxygen concentration is 0.01% by volume or more, the metal component on the surface of the oxide catalyst tends to be appropriately oxidized.
酸化安定化処理工程における処理温度は、酸化物触媒の表面のみを酸化させる観点から、好ましくは２００〜６００℃であり、より好ましくは２５０〜５５０℃であり、さらに好ましくは３００〜５００℃である。処理温度が６００℃以下であることにより、Ｆｅが６配位になることをより抑制できる傾向にある。また、処理温度が２００℃以上であることにより、酸化物触媒の表面の金属成分を適切に酸化できる傾向にある。 From the viewpoint of oxidizing only the surface of the oxide catalyst, the treatment temperature in the oxidation stabilization treatment step is preferably 200 to 600 ° C, more preferably 250 to 550 ° C, and further preferably 300 to 500 ° C. . When the processing temperature is 600 ° C. or lower, it tends to be possible to further suppress Fe from being 6-coordinated. Moreover, when the treatment temperature is 200 ° C. or higher, the metal component on the surface of the oxide catalyst tends to be appropriately oxidized.
酸化安定化処理の処理時間は、触媒の表面のみを酸化させる観点から、好ましくは１０分〜４ｈであり、より好ましくは３０分〜３ｈであり、さらに好ましくは１ｈ〜２ｈ℃である。処理時間が４ｈ以下であることにより、Ｆｅが６配位になることをより抑制できる傾向にある。また、処理時間が１０分以上であることにより、酸化物触媒の表面の金属成分を適切に酸化できる傾向にある。以上の酸化安定化処理を行うことで、安定に４配位のＦｅが存在する酸化物触媒となる。 The treatment time for the oxidation stabilization treatment is preferably 10 minutes to 4 hours, more preferably 30 minutes to 3 hours, and further preferably 1 hour to 2 hours, from the viewpoint of oxidizing only the surface of the catalyst. When the treatment time is 4 hours or less, it tends to be possible to further suppress Fe from being 6-coordinated. Moreover, it exists in the tendency which can oxidize appropriately the metal component on the surface of an oxide catalyst because processing time is 10 minutes or more. By performing the above oxidation stabilization treatment, an oxide catalyst in which tetracoordinate Fe is stably present is obtained.
以上の工程を全て行うことで、４配位のＦｅが形成され易くなる。 By performing all the above steps, tetracoordinate Fe is easily formed.
〔不飽和アルデヒドの製造方法〕
本実施形態に係る不飽和アルデヒドの製造方法は、上記酸化物触媒を用いて、オレフィン及び／又はアルコールを酸化反応させて、不飽和アルデヒドを得る酸化工程を有する。オレフィンとしては、特に限定されないが、例えば、プロピレン、及びイソブチレンが挙げられる。また、アルコールとしては、特に限定されないが、例えば、イソブタノール、及びｔ−ブチルアルコールが挙げられる。また、製造される不飽和アルデヒドとしては、特に限定されないが、例えば、メタクロレイン、アクロレインが挙げられる。
[Method for producing unsaturated aldehyde]
The manufacturing method of the unsaturated aldehyde which concerns on this embodiment has an oxidation process which makes an olefin and / or alcohol oxidize using the said oxide catalyst, and obtains an unsaturated aldehyde. Although it does not specifically limit as an olefin, For example, a propylene and isobutylene are mentioned. Moreover, although it does not specifically limit as alcohol, For example, isobutanol and t-butyl alcohol are mentioned. Moreover, although it does not specifically limit as unsaturated aldehyde manufactured, For example, a methacrolein and acrolein are mentioned.
酸化方法としては、特に限定されないが、例えば、気相接触酸化反応を用いることができる。気相接触酸化反応は、例えば、所定の反応温度下、固定床反応器内の触媒層に、オレフィン及び／又はアルコールと、分子状酸素含有ガスと、希釈ガスと、を含む混合ガスを導入することにより進行する。 Although it does not specifically limit as an oxidation method, For example, a vapor phase catalytic oxidation reaction can be used. In the gas phase catalytic oxidation reaction, for example, a mixed gas containing an olefin and / or alcohol, a molecular oxygen-containing gas, and a diluent gas is introduced into a catalyst layer in a fixed bed reactor at a predetermined reaction temperature. It progresses by.
反応温度は、好ましくは２５０〜４５０℃である。また、反応圧力は、好ましくは常圧〜５気圧である。さらに、原料ガスを導入する空間速度は、好ましくは４００〜４０００／ｈｒ［Ｎｏｒｍａｌ ｔｅｍｐｅｒａｔｕｒｅ ｐｒｅｓｓｕｒｅ （ＮＴＰ）条件下］である。 The reaction temperature is preferably 250 to 450 ° C. The reaction pressure is preferably normal pressure to 5 atm. Further, the space velocity for introducing the raw material gas is preferably 400 to 4000 / hr (normal temperature pressure (NTP) conditions).
酸素と、オレフィン及び／又はアルコールと、のモル比は、不飽和アルデヒドの収率を向上させるために反応器の出口酸素濃度を制御する観点から、好ましくは１．０〜２．０であり、より好ましくは１．１〜１．８であり、さらに好ましくは１．２〜１．８である。 The molar ratio of oxygen to olefin and / or alcohol is preferably 1.0 to 2.0 from the viewpoint of controlling the outlet oxygen concentration of the reactor in order to improve the yield of unsaturated aldehyde, More preferably, it is 1.1-1.8, More preferably, it is 1.2-1.8.
分子状酸素含有ガスとしては、特に限定されないが、例えば、純酸素ガス、及びＮ２Ｏ、空気等の酸素を含むガスが挙げられ、工業的観点から空気が好ましい。また、分子状酸素濃度は、混合ガス１００体積％に対して、好ましくは１〜２０体積％である。 The molecular oxygen-containing gas is not particularly limited, for example, pure oxygen gas, and N 2 O, include gas containing oxygen such as air, air from an industrial point of view are preferred. The molecular oxygen concentration is preferably 1 to 20% by volume with respect to 100% by volume of the mixed gas.
希釈ガスとしては、特に限定されないが、例えば、窒素、二酸化炭素、水蒸気及びこれらの混合ガスが挙げられる。水蒸気は、成形触媒へのコーキングを防ぐ観点からは含まれることが好ましいが、アクリル酸、メタクリル酸、酢酸等のカルボン酸の副生を抑制するために、できるだけ混合ガス中の水蒸気濃度は低いことが好ましく、混合ガス１００体積％に対して、好ましくは０〜３０体積％であり、より好ましくは２〜２０体積％であり、さらに好ましくは３〜１０体積％である。 Although it does not specifically limit as a dilution gas, For example, nitrogen, a carbon dioxide, water vapor | steam, and these mixed gas are mentioned. It is preferable that water vapor is included from the viewpoint of preventing coking to the formed catalyst, but the water vapor concentration in the mixed gas should be as low as possible in order to suppress by-production of carboxylic acids such as acrylic acid, methacrylic acid, and acetic acid. Is preferably 0 to 30% by volume, more preferably 2 to 20% by volume, and further preferably 3 to 10% by volume with respect to 100% by volume of the mixed gas.
分子状酸素含有ガスと希釈ガスとの混合比は、体積比で下記不等式の条件を満足することが好ましい。
０．０１＜分子状酸素含有ガス／（分子状酸素含有ガス＋希釈ガス）＜０．３
The mixing ratio of the molecular oxygen-containing gas and the dilution gas preferably satisfies the following inequality condition in terms of volume ratio.
0.01 <molecular oxygen-containing gas / (molecular oxygen-containing gas + dilution gas) <0.3
〔不飽和ニトリルの製造方法〕
本実施形態に係る不飽和ニトリルの製造方法は、上記酸化物触媒を用いて、オレフィン及び／又はアルコールをアンモ酸化反応さて、不飽和ニトリルを得るアンモ酸化工程を有する。アンモ酸化反応は、例えば、所定の反応温度下、流動層反応器内に、オレフィン及び／又はアルコールと、分子状酸素含有ガスと、アンモニアと、を含む混合ガスを導入することにより進行する。
[Method for producing unsaturated nitrile]
The method for producing an unsaturated nitrile according to the present embodiment includes an ammoxidation step in which an olefin and / or alcohol is ammoxidized using the oxide catalyst to obtain an unsaturated nitrile. The ammoxidation reaction proceeds, for example, by introducing a mixed gas containing an olefin and / or alcohol, a molecular oxygen-containing gas, and ammonia into a fluidized bed reactor at a predetermined reaction temperature.
オレフィン及び／又はアルコール、並びにアンモニアは、必ずしも高純度である必要はなく、工業グレードのものを使用することができる。 Olefins and / or alcohols and ammonia are not necessarily highly pure, and industrial grades can be used.
また、分子状酸素含有ガスとしては、特に限定されないが、例えば、通常空気を用いるのが好ましいが、酸素を空気と混合するなどして酸素濃度を高めたガスを用いることもできる。 Further, the molecular oxygen-containing gas is not particularly limited. For example, it is usually preferable to use air, but a gas whose oxygen concentration is increased by mixing oxygen with air can also be used.
分子状酸素含有ガスが空気である場合、オレフィン及び／又はアルコールと、アンモニアと、空気と、のモル比〔（オレフィン及び／又はアルコール）／アンモニア／空気〕は、好ましくは１／（０．８〜１．４）／（７〜１２）であり、より好ましくは１／０．９〜１．３／８〜１１である。 When the molecular oxygen-containing gas is air, the molar ratio [(olefin and / or alcohol) / ammonia / air] of olefin and / or alcohol, ammonia and air is preferably 1 / (0.8 -1.4) / (7-12), more preferably 1 / 0.9-1.3 / 8-11.
また、反応温度は、好ましくは３５０〜５５０℃であり、より好ましくは４００〜５００℃である。反応圧力は、好ましくは微減圧〜０．８ＭＰａである。さらに、原料ガスと触媒との接触時間は、好ましくは０．５〜２０（ｓｅｃ・ｇ／ｃｃ）であり、より好ましくは１〜１０（ｓｅｃ・ｇ／ｃｃ）である。 Moreover, reaction temperature becomes like this. Preferably it is 350-550 degreeC, More preferably, it is 400-500 degreeC. The reaction pressure is preferably slightly reduced pressure to 0.8 MPa. Furthermore, the contact time between the source gas and the catalyst is preferably 0.5 to 20 (sec · g / cc), and more preferably 1 to 10 (sec · g / cc).
以下に実施例を挙げて本発明をより具体的に説明するが、本発明はこれらの実施例により何ら限定されるものではない。また、各種物性の評価方法は下記に示すとおりである。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. Moreover, the evaluation method of various physical properties is as showing below.
〔酸化物触媒の反応性能評価〕
反応装置は外径２３ｍｍのパイレックス（登録商標）ガラス製流動層反応管を用いた。反応温度Ｔは４３０℃、反応圧力Ｐは０．１５ＭＰａ、充填酸化物触媒量Ｗは４０〜６０ｇ、全供給ガス量Ｆは２５０〜４５０ｍＬ／ｓｅｃ（ＮＴＰ換算）条件とした。また、供給した原料ガスの組成は、プロピレン／アンモニア／空気のモル比を１／（０．７〜１．４）／（８．０〜１１．０）とし、反応ガス中の未反応アンモニア濃度が０．５％以下、未反応酸素濃度が０．２％以下になるよう供給ガス組成を上記範囲内で適宜変更して反応を実施した。原料供給開始より２４時間後の反応ガスをガスクロマトグラフィーで分析し酸化物触媒の反応性能を求めた。
接触時間（ｓｅｃ・ｇ／ｍＬ）＝（Ｗ／Ｆ）×２７３／（２７３＋Ｔ）×Ｐ／０．１０
[Evaluation of reaction performance of oxide catalyst]
As the reaction apparatus, a Pyrex (registered trademark) glass fluidized bed reaction tube having an outer diameter of 23 mm was used. The reaction temperature T was 430 ° C., the reaction pressure P was 0.15 MPa, the packed oxide catalyst amount W was 40 to 60 g, and the total supply gas amount F was 250 to 450 mL / sec (NTP conversion). The composition of the supplied raw material gas is such that the molar ratio of propylene / ammonia / air is 1 / (0.7 to 1.4) / (8.0 to 11.0), and the unreacted ammonia concentration in the reaction gas The reaction was carried out by appropriately changing the composition of the supplied gas within the above range so that the unreacted oxygen concentration was 0.2% or less. The reaction gas 24 hours after the start of raw material supply was analyzed by gas chromatography to determine the reaction performance of the oxide catalyst.
Contact time (sec · g / mL) = (W / F) × 273 / (273 + T) × P / 0.10
実施例及び比較例において、反応成績を表すために用いた転化率、選択率、収率は次式で定義される。
転化率＝（反応した原料のモル数／供給した原料のモル数）×１００
選択率＝（生成した化合物のモル数／反応した原料のモル数）×１００
収率＝（生成した化合物のモル数／供給した原料のモル数）×１００
In Examples and Comparative Examples, the conversion rate, selectivity, and yield used to represent reaction results are defined by the following equations.
Conversion rate = (number of moles of reacted raw material / number of moles of supplied raw material) × 100
Selectivity = (number of moles of compound produced / number of moles of reacted raw material) × 100
Yield = (Mole number of produced compound / Mole number of supplied raw material) × 100
〔Ｆｅ−Ｋ吸収端Ｘ線吸収微細構造（ＸＡＦＳ）スペクトルの測定方法〕
鉄のＫ吸収端Ｘ線吸収微細構造の測定は、財団法人高輝度光科学研究センター 大型放射光施設 ＳＰｒｉｎｇ−８のビームラインＢＬ１４Ｂ２において、下記条件により行うことが可能であるが、酸化物触媒のＦｅ−Ｋ ＸＡＦＳの測定は他の方法でも可能であり測定方法を限定するものではない。
[Measuring method of Fe-K absorption edge X-ray absorption fine structure (XAFS) spectrum]
The measurement of the X-ray absorption fine structure of the K absorption edge of iron can be performed under the following conditions in the beam line BL14B2 of the SPring-8, a large synchrotron radiation research center, a high-intensity photoscience research center. The measurement of Fe-K XAFS can be performed by other methods, and the measurement method is not limited.
光学系及び検出器：Ｓｉ（１１１）二結晶分光器を用いてＸ線エネルギーを分光し透過法によるＸＡＦＳ測定を行った。検出器にはイオンチャンバーを用いた。イオンチャンバーには入射Ｘ線（Ｉ０）にＮ２１００％、サンプル透過後のイオンチャンバー（Ｉ１）にＡｒ１５％＋Ｎ２８５％のガスを流通させた。イオンチャンバーの電極長はＩ０を１７０ｍｍとし、Ｉ１を３１０ｍｍとし、印加電圧を１０００Ｖとした。電流信号の電圧変換・増幅を行うカレントアンプのゲイン設定は、Ｉ０が１Ｅ＋８Ｖ／Ａ、Ｉ１が１Ｅ＋８Ｖ／Ａまたは１Ｅ＋９Ｖ／Ａで測定を行った。 Optical system and detector: X-ray energy was dispersed using a Si (111) double crystal spectrometer, and XAFS measurement was performed by a transmission method. An ion chamber was used as a detector. In the ion chamber, a gas of N2100% was circulated through the incident X-ray (I0), and Ar15% + N285% gas was circulated through the ion chamber (I1) after passing through the sample. As for the electrode length of the ion chamber, I0 was 170 mm, I1 was 310 mm, and the applied voltage was 1000V. The gain setting of the current amplifier that performs voltage conversion / amplification of the current signal was measured with I0 being 1E + 8V / A and I1 being 1E + 8V / A or 1E + 9V / A.
エネルギー校正：吸収強度が最適になるように窒化ホウ素と混合、粉砕しペレット状にしたα−Ｆｅ２Ｏ３の測定を行い、バックグラウンド処理を行い、スペクトル強度を１に規格化後、エッジジャンプの０．５を求めてエネルギー値７１２１．５ｅＶとした。本発明で使用するＸＡＦＳ解析法では、鉄のＫ吸収端のＸ線吸収微細構造（ＸＡＦＳ：Ｘ−ｒａｙ Ａｂｓｏｒｐｔｉｏｎ Ｆｉｎｅ Ｓｔｒｕｃｔｕｒｅ）の測定を行い、このうちのＸ線吸収近傍構造（ＸＡＮＥＳ：Ｘ−ｒａｙ Ａｂｓｏｒｐｔｉｏｎ Ｎｅａｒ Ｅｄｇｅ Ｓｔｒｕｃｔｕｒｅ）部分を解析することにより、金属の電子状態（価数や結合状態）の評価を行った。このようなＸＡＦＳの測定方法は、「Ｘ線吸収分光法−ＸＡＦＳとその応用−、株式会社アイピーシー発行、８３−９９頁」などに記載されている。 Energy calibration: Measurement of α-Fe 2 O 3 mixed with pulverized boron nitride and pelletized to optimize absorption intensity, background treatment, spectral intensity normalized to 1, edge jump Of 0.5 was determined to be an energy value of 7121.5 eV. In the XAFS analysis method used in the present invention, the X-ray absorption fine structure (XAFS) of the iron K absorption edge is measured, and the X-ray absorption near structure (XANES: X-ray) is measured. The electronic state (valence and bonding state) of the metal was evaluated by analyzing the Absorption Near Edge Structure) portion. Such a measurement method of XAFS is described in “X-ray absorption spectroscopy—XAFS and its application”, published by IPC Co., Ltd., pages 83-99.
さらに具体的な測定方法を以下に示す。酸化物触媒及び標準物質３〜２０ｍｇをメノウ乳鉢を用いて充分に粉砕し、適量の窒化ホウ素を希釈材として加え、さらに混合、粉砕して試料を得た。 A more specific measuring method is shown below. An oxide catalyst and 3 to 20 mg of a standard substance were sufficiently pulverized using an agate mortar, an appropriate amount of boron nitride was added as a diluent, and further mixed and pulverized to obtain a sample.
この試料をステンレス製の鋳型で厚さ１ｍｍ、直径１０ｍｍのペレット状にし、入射ビームがペレットのほぼ中心になるように試料を配置した。鉄原子が吸収する範囲のＸ線を照射し、試料前後のＸ線強度Ｉ０及びＩ１の値を計測して、Ｘ線のエネルギーを横軸に、吸光度μ＝ｌｎ（Ｉ０／Ｉ）を縦軸にプロットしたものをＸ線吸収スペクトルとした。このＸ線吸収スペクトルを「Ｘ線吸収分光法−ＸＡＦＳとその応用−、株式会社アイピーシー発行、５５−６０頁」に記載の方法により、バックグラウンドを差し引き、スペクトル強度を１に規格化した。 This sample was formed into a pellet shape having a thickness of 1 mm and a diameter of 10 mm using a stainless steel mold, and the sample was arranged so that the incident beam was substantially at the center of the pellet. Irradiate X-rays in the range absorbed by iron atoms, measure the values of X-ray intensities I0 and I1 before and after the sample, X-ray energy on the horizontal axis, and absorbance μ = ln (I0 / I) on the vertical axis The X-ray absorption spectrum was plotted in FIG. The background of the X-ray absorption spectrum was normalized and the spectrum intensity was normalized to 1 by the method described in “X-ray absorption spectroscopy -XAFS and its application-, published by IPC Corporation, pages 55-60”.
酸化物触媒のＦｅ配位状態の分離について以下に示す。分離に用いるスペクトルとして、酸化物触媒スペクトル、Ｆｅ２Ｍｏ３Ｏ１２、ＦｅＰＯ４相それぞれを用い、上記の規格化したスペクトルから、７１００ｅＶから７１５０ｅＶの範囲を抜出し、それぞれ強度を、ＩＡ（酸化物触媒）、ＩＢ（Ｆｅ２Ｍｏ３Ｏ１２）、ＩＣ（ＦｅＰＯ４相）とした。 The separation of the Fe coordination state of the oxide catalyst is described below. As a spectrum used for separation, an oxide catalyst spectrum, Fe 2 Mo 3 O 12 , and FePO 4 phases were used, respectively, and a range of 7100 eV to 7150 eV was extracted from the above normalized spectrum. ), IB (Fe 2 Mo 3 O 12 ), and IC (FePO 4 phase).
Ｆｅ２Ｍｏ３Ｏ１２は、文献「Ｈ． Ｅｈｒｅｎｂｅｒｇ ｅｔ ａｌ．， Ｊｏｕｒｎａｌ ｏｆ Ｍａｇｎｅｔｉｓｍ ａｎｄ Ｍａｇｎｅｔｉｃ Ｍａｔｅｒｉａｌｓ ２６１ （２００３） ３５３-３５９」にあるような結晶構造であり、Ｆｅ周辺は酸素が正８面体の６配位をしている。一方ＦｅＰＯ４相は、文献「Ｈａｉｎｓ．Ｊ ｅｔ ａｌ．， Ｚｅｉｔｓｃｈｒｉｆｔ ｆuｒ Ｋｒｉｓｔａｌｌｏｇｒａｐｈｉｅ， ｖｏｌ． ２１８， ｉｓｓｕｅ ３−２００３， ｐｐ． １９３−２００」にあるような結晶構造であり、Ｆｅ周辺は酸素が正４面体の４配位をしている。分離したスペクトル強度をＩＤ＝ｍ×ＩＢ＋ｎ×ＩＣ（ｍ，ｎは任意の定数、ｍ，ｎ ≧０、）と定義し、Σ（ＩＡ（Ｅｉ）−ＩＤ（Ｅｉ））＾２が最小になる、ｍとｎを計算した（Σは相和を意味する。ＩＡ（Ｅｉ），ＩＤ（Ｅｉ）は、各エネルギーにおける規格化後のスペクトル強度）。この結果より、ｍ／（ｍ＋ｎ）を６配位成分、ｎ／（ｎ＋ｍ）を４配位成分として、４配位Ｆｅ／（４配位Ｆｅ＋６配位Ｆｅ）の比を求めた。 Fe 2 Mo 3 O 12 has a crystal structure as described in the document “H. Ehrenberg et al., Journal of Magnetism and Magnetic Materials 261 (2003) 353-359”, and the periphery of Fe is an octahedron 6 Has a coordination. On the other hand, the FePO 4 phase has a crystal structure as described in the document “Hains. J et al., Zeitschifft fur Kristalography, vol. 218, issue 3-2003, pp. 193-200”, and the periphery of Fe has positive 4 oxygen. It has a tetrahedral coordination. The separated spectral intensity is defined as ID = m × IB + n × IC (m and n are arbitrary constants, m, n ≧ 0), and Σ (IA (Ei) −ID (Ei)) ^ 2 is minimized. , M, and n were calculated (Σ means phase sum. IA (Ei) and ID (Ei) are normalized spectral intensities at each energy). From this result, the ratio of tetracoordinated Fe / (tetracoordinated Fe + 6-coordinated Fe) was determined by using m / (m + n) as a hexacoordinate component and n / (n + m) as a tetracoordinate component.
［実施例１］
約９０℃の温水１９９．５ｇにヘプタモリブデン酸アンモニウム６６．５ｇを溶解させた（Ａ液）。また、硝酸ビスマス４５．６ｇ、硝酸セリウム２３．０ｇ、硝酸鉄４５．４ｇ、硝酸セシウム０．５４ｇ、及び硝酸コバルト２７．５ｇを１８質量％の硝酸水溶液４１．１ｇに溶解させ、約９０℃の温水２０５．３ｇを添加した（Ｂ液）。
[Example 1]
66.5 g of ammonium heptamolybdate was dissolved in 199.5 g of warm water at about 90 ° C. (solution A). Also, 45.6 g of bismuth nitrate, 23.0 g of cerium nitrate, 45.4 g of iron nitrate, 0.54 g of cesium nitrate, and 27.5 g of cobalt nitrate were dissolved in 41.1 g of an 18% by mass nitric acid aqueous solution. Warm water 205.3g was added (the B liquid).
Ａ液とＢ液の両液を混合し、約５０℃で約３時間程度撹拌混合し、蓚酸を４．５ｇ添加し、１２００ｂａｒで高圧ホモジナイザーを使用して処理し、メジアン径が２．０μｍの原料スラリーを得た。この原料スラリーを噴霧乾燥器に送り、入り口温度２４０℃、出口温度約１３５℃で噴霧乾燥し、噴霧乾燥体を得た。得られた噴霧乾燥体を、窒素中で室温から３３０℃まで３ｈかけて昇温した後、３３０℃で３時間保持して仮焼成体を得た。得られた仮焼成体を第１本焼成として窒素中で４４０℃まで３ｈかけて昇温し、５ｈ保持した。その後、５４０℃で１０時間第２本焼成し、本焼成体を得た。本焼成体を酸素濃度０．５体積％の雰囲気下、４５０℃で１ｈ保持することで酸化安定化処理し、酸化物触媒を得た。得られた酸化物触媒の組成はＭｏ１２Ｂｉ３．０Ｆｅ３．６Ｃｅ１．７Ｃｏ３．０Ｃｓ０．０９であった。４配位Ｆｅ／（４配位Ｆｅ＋６配位Ｆｅ）の比の測定結果を表１に示す。 Both liquid A and liquid B were mixed, stirred and mixed at about 50 ° C. for about 3 hours, added with 4.5 g of oxalic acid, treated with a high-pressure homogenizer at 1200 bar, and the median diameter was 2.0 μm. A raw slurry was obtained. This raw material slurry was sent to a spray dryer and spray-dried at an inlet temperature of 240 ° C. and an outlet temperature of about 135 ° C. to obtain a spray-dried product. The obtained spray-dried body was heated from room temperature to 330 ° C. in nitrogen over 3 hours, and then kept at 330 ° C. for 3 hours to obtain a temporarily fired body. The obtained pre-fired body was heated to 440 ° C. over 3 hours in nitrogen as the first main fire, and held for 5 hours. Then, the second main firing was performed at 540 ° C. for 10 hours to obtain a main fired body. The fired body was subjected to oxidation stabilization treatment by holding at 450 ° C. for 1 h in an atmosphere having an oxygen concentration of 0.5 vol% to obtain an oxide catalyst. The composition of the obtained oxide catalyst was Mo 12 Bi 3.0 Fe 3.6 Ce 1.7 Co 3.0 Cs 0.09. Table 1 shows the measurement results of the ratio of tetracoordinated Fe / (tetracoordinated Fe + 6-coordinated Fe).
酸化物触媒の反応評価として、酸化物触媒４．２ｇを直径１４ｍｍのジャケット付ＳＵＳ製反応管に充填し、反応温度４３０℃でイソブチレン８体積％、酸素１２．８体積％、水蒸気３．０体積％及び窒素容量７６．２％からなる混合ガスを１２０ｍＬ／ｍｉｎ（ＮＴＰ）の流量で通気し、メタクロレイン合成反応を行った。反応評価結果を表１に示す。 As a reaction evaluation of the oxide catalyst, 4.2 g of the oxide catalyst was filled into a 14 mm diameter jacketed SUS reaction tube, and at a reaction temperature of 430 ° C., 8% by volume of isobutylene, 12.8% by volume of oxygen, and 3.0% by volume of water vapor. % And a nitrogen capacity of 76.2% were aerated at a flow rate of 120 mL / min (NTP) to perform a methacrolein synthesis reaction. The reaction evaluation results are shown in Table 1.
［実施例２］
約９０℃の温水２０８．８ｇにヘプタモリブデン酸アンモニウム６９．６ｇを溶解させた（Ａ液）。また、硝酸ビスマス３５．０ｇ、硝酸セリウム２５．５ｇ、硝酸鉄４２．３ｇ、硝酸セシウム０．５７ｇ、硝酸マグネシウム４．２ｇ、硝酸ニッケル４．８ｇ、及び硝酸コバルト２８．８ｇを１８質量％の硝酸水溶液４１．３ｇに溶解させ、約９０℃の温水１９６．０ｇを添加した（Ｂ液）。
[Example 2]
69.6 g of ammonium heptamolybdate was dissolved in 208.8 g of warm water at about 90 ° C. (solution A). Further, 35.0 g of bismuth nitrate, 25.5 g of cerium nitrate, 42.3 g of iron nitrate, 0.57 g of cesium nitrate, 4.2 g of magnesium nitrate, 4.8 g of nickel nitrate, and 28.8 g of cobalt nitrate were mixed with 18% by mass of nitric acid. It was dissolved in 41.3 g of an aqueous solution, and 196.0 g of warm water at about 90 ° C. was added (Liquid B).
Ａ液とＢ液の両液を混合し、約５０℃で約３時間程度撹拌混合し、シクロヘキサン−１，２−ジアミンテトラ酢酸を２．５ｇ添加し、１０００ｂａｒで高圧ホモジナイザーを使用して処理し、メジアン径が４．０μｍの原料スラリーを得た。この原料スラリーを噴霧乾燥器に送り、入り口温度２４０℃、出口温度約１３５℃で噴霧乾燥し、噴霧乾燥体を得た。得られた噴霧乾燥体を、窒素中で室温から３２０℃まで３ｈかけて昇温した後、３２０℃で３時間保持して仮焼成体を得た。得られた仮焼成体を第１本焼成として窒素中で４６０℃まで３ｈかけて昇温し、５ｈ保持した。その後、５５０℃で８時間第２本焼成し、本焼成体を得た。本焼成体を酸素濃度０．５体積％の雰囲気下、４２０℃で１ｈ保持することで酸化安定化処理し、酸化物触媒を得た。得られた酸化物触媒の組成はＭｏ１２Ｂｉ２．２Ｆｅ３．２Ｃｅ１．８Ｃｏ３．０Ｍｇ０．５Ｎｉ０．５Ｃｓ０．０９であった。４配位Ｆｅ／（４配位Ｆｅ＋６配位Ｆｅ）の比の測定結果を表１に示す。 Mix both solution A and solution B, stir and mix at about 50 ° C. for about 3 hours, add 2.5 g of cyclohexane-1,2-diaminetetraacetic acid, and process at 1000 bar using a high-pressure homogenizer. A raw material slurry having a median diameter of 4.0 μm was obtained. This raw material slurry was sent to a spray dryer and spray-dried at an inlet temperature of 240 ° C. and an outlet temperature of about 135 ° C. to obtain a spray-dried product. The obtained spray-dried body was heated in nitrogen from room temperature to 320 ° C. over 3 hours, and then held at 320 ° C. for 3 hours to obtain a temporarily fired body. The obtained temporary fired body was heated to 460 ° C. over 3 hours in nitrogen as the first firing, and held for 5 hours. Then, the second main firing was performed at 550 ° C. for 8 hours to obtain a main fired body. The fired body was subjected to oxidation stabilization treatment by maintaining at 420 ° C. for 1 h in an atmosphere having an oxygen concentration of 0.5 vol% to obtain an oxide catalyst. The composition of the obtained oxide catalyst was Mo 12 Bi 2.2 Fe 3.2 Ce 1.8 Co 3.0 Mg 0.5 Ni 0.5 Cs 0.09. Table 1 shows the measurement results of the ratio of tetracoordinated Fe / (tetracoordinated Fe + 6-coordinated Fe).
酸化物触媒の反応評価として、酸化物触媒４．７ｇを反応管に充填し、実施例１と同じ条件で、メタクロレイン合成反応を行った。反応評価結果を表１に示す。 As an evaluation of the reaction of the oxide catalyst, 4.7 g of the oxide catalyst was filled in a reaction tube, and methacrolein synthesis reaction was performed under the same conditions as in Example 1. The reaction evaluation results are shown in Table 1.
［実施例３］
スラリーに添加する蓚酸を６．０ｇに変更し、メジアン径が２．５μｍの原料スラリーを得た以外は実施例１と同じ条件で酸化物触媒を得た。Ｆｅ−Ｋ吸収端Ｘ線吸収微細構造スペクトルを図１に示す。酸化物触媒の反応評価として、酸化物触媒４．１ｇを反応管に充填し、実施例１と同じ条件で、メタクロレイン合成反応を行った。反応評価結果を表１に示す。
[Example 3]
An oxide catalyst was obtained under the same conditions as in Example 1 except that oxalic acid added to the slurry was changed to 6.0 g and a raw material slurry having a median diameter of 2.5 μm was obtained. The Fe-K absorption edge X-ray absorption fine structure spectrum is shown in FIG. As a reaction evaluation of the oxide catalyst, 4.1 g of the oxide catalyst was filled in a reaction tube, and methacrolein synthesis reaction was performed under the same conditions as in Example 1. The reaction evaluation results are shown in Table 1.
［実施例４］
酸化安定化処理の酸素濃度を６．５体積％に変更した以外は実施例１と同じ条件で酸化物触媒を得た。酸化物触媒の反応評価として、酸化物触媒４．９ｇを反応管に充填し、実施例１と同じ条件で、メタクロレイン合成反応を行った。反応評価結果を表１に示す。
[Example 4]
An oxide catalyst was obtained under the same conditions as in Example 1 except that the oxygen concentration in the oxidation stabilization treatment was changed to 6.5% by volume. As an evaluation of the reaction of the oxide catalyst, 4.9 g of the oxide catalyst was charged into a reaction tube, and methacrolein synthesis reaction was performed under the same conditions as in Example 1. The reaction evaluation results are shown in Table 1.
［実施例５］
酸化安定化処理の酸素濃度を９．２体積％に変更した以外は実施例１と同じ条件で酸化物触媒を得た。酸化物触媒の反応評価として、酸化物触媒５．０ｇを反応管に充填し、実施例１と同じ条件で、メタクロレイン合成反応を行った。反応評価結果を表１に示す。
[Example 5]
An oxide catalyst was obtained under the same conditions as in Example 1 except that the oxygen concentration in the oxidation stabilization treatment was changed to 9.2% by volume. As a reaction evaluation of the oxide catalyst, 5.0 g of the oxide catalyst was filled in a reaction tube, and methacrolein synthesis reaction was performed under the same conditions as in Example 1. The reaction evaluation results are shown in Table 1.
［実施例６］
酸化安定化処理の温度を５６０℃に変更した以外は実施例１と同じ条件で酸化物触媒を得た。酸化物触媒の反応評価として、酸化物触媒５．４ｇを反応管に充填し、実施例１と同じ条件で、メタクロレイン合成反応を行った。反応評価結果を表１に示す。
[Example 6]
An oxide catalyst was obtained under the same conditions as in Example 1 except that the temperature of the oxidation stabilization treatment was changed to 560 ° C. As an evaluation of the reaction of the oxide catalyst, 5.4 g of the oxide catalyst was filled in a reaction tube, and methacrolein synthesis reaction was performed under the same conditions as in Example 1. The reaction evaluation results are shown in Table 1.
［実施例７］
酸化安定化処理の温度を２３０℃に変更した以外は実施例１と同じ条件で酸化物触媒を得た。酸化物触媒の反応評価として、酸化物触媒４．３ｇを反応管に充填し、実施例１と同じ条件で、メタクロレイン合成反応を行った。反応評価結果を表１に示す。
[Example 7]
An oxide catalyst was obtained under the same conditions as in Example 1 except that the temperature of the oxidation stabilization treatment was changed to 230 ° C. As a reaction evaluation of the oxide catalyst, 4.3 g of the oxide catalyst was filled in a reaction tube, and a methacrolein synthesis reaction was performed under the same conditions as in Example 1. The reaction evaluation results are shown in Table 1.
［実施例８］
第１本焼成の温度を４００℃に変更した以外は実施例１と同じ条件で酸化物触媒を得た。酸化物触媒の反応評価として、酸化物触媒４．７ｇを反応管に充填し、実施例１と同じ条件で、メタクロレイン合成反応を行った。反応評価結果を表１に示す。
[Example 8]
An oxide catalyst was obtained under the same conditions as in Example 1 except that the temperature of the first main firing was changed to 400 ° C. As an evaluation of the reaction of the oxide catalyst, 4.7 g of the oxide catalyst was filled in a reaction tube, and methacrolein synthesis reaction was performed under the same conditions as in Example 1. The reaction evaluation results are shown in Table 1.
［実施例９］
第１本焼成の温度を４２５℃に変更した以外は実施例１と同じ条件で酸化物触媒を得た。酸化物触媒の反応評価として、酸化物触媒４．７ｇを反応管に充填し、実施例１と同じ条件で、メタクロレイン合成反応を行った。反応評価結果を表１に示す。
[Example 9]
An oxide catalyst was obtained under the same conditions as in Example 1 except that the temperature of the first main firing was changed to 425 ° C. As an evaluation of the reaction of the oxide catalyst, 4.7 g of the oxide catalyst was filled in a reaction tube, and methacrolein synthesis reaction was performed under the same conditions as in Example 1. The reaction evaluation results are shown in Table 1.
［実施例１０］
第１本焼成の温度を４８０℃に変更した以外は実施例１と同じ条件で酸化物触媒を得た。酸化物触媒の反応評価として、酸化物触媒４．８ｇを反応管に充填し、実施例１と同じ条件で、メタクロレイン合成反応を行った。反応評価結果を表１に示す。
[Example 10]
An oxide catalyst was obtained under the same conditions as in Example 1 except that the temperature of the first main firing was changed to 480 ° C. As an evaluation of the reaction of the oxide catalyst, 4.8 g of the oxide catalyst was charged into a reaction tube, and methacrolein synthesis reaction was performed under the same conditions as in Example 1. The reaction evaluation results are shown in Table 1.
［実施例１１］
スラリーの高圧ホモジナイザーの圧力を７００ｂａｒに変更し、メジアン径が７．０μｍの原料スラリーを得た以外は実施例１と同じ条件で酸化物触媒を得た。酸化物触媒の反応評価として、酸化物触媒４．７ｇを反応管に充填し、実施例１と同じ条件で、メタクロレイン合成反応を行った。反応評価結果を表１に示す。
[Example 11]
An oxide catalyst was obtained under the same conditions as in Example 1 except that the pressure of the high-pressure homogenizer of the slurry was changed to 700 bar and a raw material slurry having a median diameter of 7.0 μm was obtained. As an evaluation of the reaction of the oxide catalyst, 4.7 g of the oxide catalyst was filled in a reaction tube, and methacrolein synthesis reaction was performed under the same conditions as in Example 1. The reaction evaluation results are shown in Table 1.
［実施例１２］
スラリーの高圧ホモジナイザーの圧力を２００ｂａｒに変更し、メジアン径が９．０μｍの原料スラリーを得た以外は実施例１と同じ条件で酸化物触媒を得た。酸化物触媒の反応評価として、酸化物触媒４．７ｇを反応管に充填し、実施例１と同じ条件で、メタクロレイン合成反応を行った。反応評価結果を表１に示す。
[Example 12]
An oxide catalyst was obtained under the same conditions as in Example 1 except that the pressure of the high-pressure homogenizer of the slurry was changed to 200 bar and a raw slurry having a median diameter of 9.0 μm was obtained. As an evaluation of the reaction of the oxide catalyst, 4.7 g of the oxide catalyst was filled in a reaction tube, and methacrolein synthesis reaction was performed under the same conditions as in Example 1. The reaction evaluation results are shown in Table 1.
［実施例１３］
スラリーの高圧ホモジナイザーの圧力を１５００ｂａｒに変更し、メジアン径が０．１μｍの原料スラリーを得た以外は実施例１と同じ条件で酸化物触媒を得た。酸化物触媒の反応評価として、酸化物触媒４．７ｇを反応管に充填し、実施例１と同じ条件で、メタクロレイン合成反応を行った。反応評価結果を表１に示す。
[Example 13]
An oxide catalyst was obtained under the same conditions as in Example 1 except that the pressure of the high-pressure homogenizer of the slurry was changed to 1500 bar and a raw material slurry having a median diameter of 0.1 μm was obtained. As an evaluation of the reaction of the oxide catalyst, 4.7 g of the oxide catalyst was filled in a reaction tube, and methacrolein synthesis reaction was performed under the same conditions as in Example 1. The reaction evaluation results are shown in Table 1.
［比較例１］
スラリーに蓚酸を添加せず、メジアン径が８．０μｍの原料スラリーを得た以外は実施例１と同じ条件で酸化物触媒を得た。酸化物触媒の反応評価として、酸化物触媒５．０ｇを反応管に充填し、実施例１と同じ条件で、メタクロレイン合成反応を行った。反応評価結果を表１に示す。
[Comparative Example 1]
An oxide catalyst was obtained under the same conditions as in Example 1 except that oxalic acid was not added to the slurry and a raw material slurry having a median diameter of 8.0 μm was obtained. As a reaction evaluation of the oxide catalyst, 5.0 g of the oxide catalyst was filled in a reaction tube, and methacrolein synthesis reaction was performed under the same conditions as in Example 1. The reaction evaluation results are shown in Table 1.
［比較例２］
酸化安定化処理をしない以外は実施例１と同じ条件で酸化物触媒を得た。Ｆｅ−Ｋ吸収端Ｘ線吸収微細構造スペクトルを図１に示す。酸化物触媒の反応評価として、酸化物触媒４．７ｇを反応管に充填し、実施例１と同じ条件で、メタクロレイン合成反応を行った。反応評価結果を表１に示す。
[Comparative Example 2]
An oxide catalyst was obtained under the same conditions as in Example 1 except that the oxidation stabilization treatment was not performed. The Fe-K absorption edge X-ray absorption fine structure spectrum is shown in FIG. As an evaluation of the reaction of the oxide catalyst, 4.7 g of the oxide catalyst was filled in a reaction tube, and methacrolein synthesis reaction was performed under the same conditions as in Example 1. The reaction evaluation results are shown in Table 1.
［比較例３］
第１本焼成をしない以外は実施例１と同じ条件で酸化物触媒を得た。酸化物触媒の反応評価として、酸化物触媒４．７ｇを反応管に充填し、実施例１と同じ条件で、メタクロレイン合成反応を行った。反応評価結果を表１に示す。
[Comparative Example 3]
An oxide catalyst was obtained under the same conditions as in Example 1 except that the first main firing was not performed. As an evaluation of the reaction of the oxide catalyst, 4.7 g of the oxide catalyst was filled in a reaction tube, and methacrolein synthesis reaction was performed under the same conditions as in Example 1. The reaction evaluation results are shown in Table 1.
［比較例４］
空気雰囲気下で仮焼成と本焼成をした以外は実施例１と同じ条件で酸化物触媒を得た。酸化物触媒の反応評価として、酸化物触媒４．０ｇを反応管に充填し、実施例１と同じ条件で、メタクロレイン合成反応を行った。反応評価結果を表１に示す。
[Comparative Example 4]
An oxide catalyst was obtained under the same conditions as in Example 1 except that preliminary calcination and main calcination were performed in an air atmosphere. As a reaction evaluation of the oxide catalyst, 4.0 g of the oxide catalyst was filled in a reaction tube, and a methacrolein synthesis reaction was performed under the same conditions as in Example 1. The reaction evaluation results are shown in Table 1.
［比較例５］
約９０℃の温水１９９．５ｇにヘプタモリブデン酸アンモニウム６６．５ｇを溶解させた（Ａ液）。また、硝酸ビスマス４５．６ｇ、硝酸セリウム２３．０ｇ、硝酸鉄４５．４ｇ、硝酸セシウム０．５４ｇ、及び硝酸コバルト２７．５ｇを１８質量％の硝酸水溶液４１．１ｇに溶解させ、約９０℃の温水２０５．３ｇを添加した（Ｂ液）。
[Comparative Example 5]
66.5 g of ammonium heptamolybdate was dissolved in 199.5 g of warm water at about 90 ° C. (solution A). Also, 45.6 g of bismuth nitrate, 23.0 g of cerium nitrate, 45.4 g of iron nitrate, 0.54 g of cesium nitrate, and 27.5 g of cobalt nitrate were dissolved in 41.1 g of an 18% by mass nitric acid aqueous solution. Warm water 205.3g was added (the B liquid).
Ａ液とＢ液の両液を混合し、約５０℃で約３時間程度撹拌混合し、１２００ｂａｒで高圧ホモジナイザーを使用して処理し、メジアン径が２．０μｍの原料スラリーを得た。この原料スラリーを噴霧乾燥器に送り、入り口温度２４０℃、出口温度約１３５℃で噴霧乾燥し、噴霧乾燥体を得た。得られた噴霧乾燥体１００ｇに対し、蓚酸を４．５ｇ添加して混合し、窒素中で室温から３３０℃まで３ｈかけて昇温した後、３３０℃で３時間保持して仮焼成体を得た。得られた仮焼成体を第１本焼成として窒素中で４４０℃まで３ｈかけて昇温し、５ｈ保持した。その後、５４０℃で１０時間第２本焼成し、本焼成体を得た。本焼成体を酸素濃度０．５体積％の雰囲気下、４５０℃で１ｈ保持することで酸化安定化処理し、酸化物触媒を得た。得られた酸化物触媒の組成はＭｏ１２Ｂｉ３．０Ｆｅ３．６Ｃｅ１．７Ｃｏ３．０Ｃｓ０．０９であった。４配位Ｆｅ／（４配位Ｆｅ＋６配位Ｆｅ）の比の測定結果を表１に示す。 Both liquid A and liquid B were mixed, stirred and mixed at about 50 ° C. for about 3 hours, and processed using a high-pressure homogenizer at 1200 bar to obtain a raw material slurry having a median diameter of 2.0 μm. This raw material slurry was sent to a spray dryer and spray-dried at an inlet temperature of 240 ° C. and an outlet temperature of about 135 ° C. to obtain a spray-dried product. To 100 g of the obtained spray-dried product, 4.5 g of oxalic acid was added and mixed, and the temperature was raised from room temperature to 330 ° C. over 3 hours in nitrogen, and then maintained at 330 ° C. for 3 hours to obtain a temporarily fired product. It was. The obtained pre-fired body was heated to 440 ° C. over 3 hours in nitrogen as the first main fire, and held for 5 hours. Then, the second main firing was performed at 540 ° C. for 10 hours to obtain a main fired body. The fired body was subjected to oxidation stabilization treatment by holding at 450 ° C. for 1 h in an atmosphere having an oxygen concentration of 0.5 vol% to obtain an oxide catalyst. The composition of the obtained oxide catalyst was Mo 12 Bi 3.0 Fe 3.6 Ce 1.7 Co 3.0 Cs 0.09. Table 1 shows the measurement results of the ratio of tetracoordinated Fe / (tetracoordinated Fe + 6-coordinated Fe).
［実施例１４］
金属組成がＭｏ１２Ｂｉ１．６Ｃｅ１．０Ｆｅ２．６Ｃｏ５．０Ｒｂ０．１で表される金属酸化物を４５質量％のシリカ担体に担持した酸化物触媒を下記のようにして調製した。
[Example 14]
An oxide catalyst in which a metal oxide having a metal composition represented by Mo 12 Bi 1.6 Ce 1.0 Fe 2.6 Co 5.0 Rb 0.1 is supported on a 45% by mass silica support is as follows. Prepared.
シリカ一次粒子の平均粒子直径が１２ｎｍのＳｉＯ２を３０質量％含む水性シリカゾル７５０ｇと、シリカ一次粒子の平均粒子直径が４１ｎｍのＳｉＯ２を３０質量％含む水性シリカゾル７５０ｇとを混合してシリカゾルの混合液を得た。 Mixing silica sol by mixing 750 g of aqueous silica sol containing 30% by mass of SiO 2 having an average particle diameter of 12 nm of silica primary particles and 750 g of aqueous silica sol containing 30% by mass of SiO 2 having an average particle diameter of 41 nm of silica primary particles. A liquid was obtained.
約９０℃の温水７３５．３ｇにヘプタモリブデン酸アンモニウム４１１．９ｇを溶解させ、２８％のアンモニア水１６．６ｇを添加した（Ａ液）。また、硝酸ビスマス１４７．５ｇ、硝酸セリウム８７．０ｇ、硝酸鉄２０４．３ｇ、硝酸ルビジウム２．８５ｇ、及び硝酸コバルト２８５．０ｇを１６．６質量％の硝酸水溶液３８４．９ｇに溶解させた（Ｂ液）。 411.3 g of ammonium heptamolybdate was dissolved in 735.3 g of warm water at about 90 ° C., and 16.6 g of 28% aqueous ammonia was added (solution A). Further, 147.5 g of bismuth nitrate, 87.0 g of cerium nitrate, 204.3 g of iron nitrate, 2.85 g of rubidium nitrate, and 285.0 g of cobalt nitrate were dissolved in 384.9 g of a 16.6% by mass nitric acid aqueous solution (B liquid).
シリカゾルの混合液にＡ液を加え、混合液を得た。その混合液にＢ液を入れ、酒石酸を３７．９ｇ添加し、約５０℃で約３時間程度撹拌混合した。この混合液を１２００ｂａｒで高圧ホモジナイザーを使用して処理し、メジアン径が２．０μｍの原料スラリーを得た。この原料スラリーを噴霧乾燥器に送り、入り口温度２４０℃、出口温度約１３５℃で噴霧乾燥し、噴霧乾燥体を得た。得られた噴霧乾燥体を、窒素中で室温から３３０℃まで３ｈかけて昇温した後、３３０℃で３時間保持して仮焼成体を得た。得られた仮焼成体を第１本焼成として窒素中で４５０℃まで３ｈかけて昇温し、５ｈ保持した。その後、５８０℃で２時間第２本焼成し、本焼成体を得た。本焼成体を酸素濃度０．５体積％の雰囲気下、４５０℃で１ｈ保持することで酸化安定化処理し、酸化物触媒を得た。４配位Ｆｅ／（４配位Ｆｅ＋６配位Ｆｅ）の比の測定結果を表１に示す。 Solution A was added to the silica sol mixture to obtain a mixture. Liquid B was added to the mixed liquid, 37.9 g of tartaric acid was added, and the mixture was stirred and mixed at about 50 ° C. for about 3 hours. This mixed solution was treated at 1200 bar using a high-pressure homogenizer to obtain a raw material slurry having a median diameter of 2.0 μm. This raw material slurry was sent to a spray dryer and spray-dried at an inlet temperature of 240 ° C. and an outlet temperature of about 135 ° C. to obtain a spray-dried product. The obtained spray-dried body was heated from room temperature to 330 ° C. in nitrogen over 3 hours, and then kept at 330 ° C. for 3 hours to obtain a temporarily fired body. The obtained temporary fired body was heated to 450 ° C. over 3 hours in nitrogen as the first main firing, and held for 5 hours. Thereafter, the second main baking was performed at 580 ° C. for 2 hours to obtain a main baking body. The fired body was subjected to oxidation stabilization treatment by holding at 450 ° C. for 1 h in an atmosphere having an oxygen concentration of 0.5 vol% to obtain an oxide catalyst. Table 1 shows the measurement results of the ratio of tetracoordinated Fe / (tetracoordinated Fe + 6-coordinated Fe).
酸化物触媒の反応評価として、この酸化物触媒５０ｇを用いて、接触時間＝４．０（ｓｅｃ・ｇ／ｍＬ）でプロピレンのアンモ酸化反応を行った。原料組成（モル比）はプロピレン／アンモニア／空気＝１／１．２２／９．３９であった。反応開始から２４時間後の反応評価結果を表１に示す。 As an evaluation of the reaction of the oxide catalyst, propylene ammoxidation reaction was conducted using 50 g of the oxide catalyst at a contact time of 4.0 (sec · g / mL). The raw material composition (molar ratio) was propylene / ammonia / air = 1 / 1.22 / 9.39. The reaction evaluation results 24 hours after the start of the reaction are shown in Table 1.
［比較例６］
酸化安定化処理をしない以外は実施例１４と同じ条件で酸化物触媒を得た。酸化物触媒の反応評価として、酸化物触媒５０ｇを用いて、接触時間＝４．２（ｓｅｃ・ｇ／ｍＬ）でプロピレンのアンモ酸化反応を行った。原料組成（モル比）はプロピレン／アンモニア／空気＝１／１．１７／９．９２であった。反応開始から２４時間後の反応評価結果を表１に示す。
[Comparative Example 6]
An oxide catalyst was obtained under the same conditions as in Example 14 except that the oxidation stabilization treatment was not performed. As a reaction evaluation of the oxide catalyst, an ammoxidation reaction of propylene was performed with a contact time of 4.2 (sec · g / mL) using 50 g of the oxide catalyst. The raw material composition (molar ratio) was propylene / ammonia / air = 1 / 1.17 / 9.92. The reaction evaluation results 24 hours after the start of the reaction are shown in Table 1.
本発明の酸化物触媒は、不飽和アルデヒド又は不飽和ニトリルの製造に用いられる触媒として、産業上の利用可能性を有する。 The oxide catalyst of this invention has industrial applicability as a catalyst used for manufacture of unsaturated aldehyde or unsaturated nitrile.
Claims (6)
４配位Ｆｅ／（４配位Ｆｅ＋６配位Ｆｅ）の比が、０．２０以上１．０以下である、
酸化物触媒。 Contains molybdenum, bismuth, iron, cobalt, and lanthanoid elements;
The ratio of tetracoordinated Fe / (tetracoordinated Fe + 6-coordinated Fe) is 0.20 or more and 1.0 or less.
Oxide catalyst.
Ｍｏ１２ＢｉａＦｅｂＣｏｃＡｄＢｅＣｆＯｇ （１）
（式（１）中、Ｍｏは前記モリブデン、Ｂｉは前記ビスマス、Ｆｅは前記鉄、Ｃｏは前記コバルトを示し、
Ａはランタン、セリウム、プラセオジウム、ネオジム、及びユーロピウムからなる群より選ばれる少なくとも１種の前記ランタノイド元素を示し、
Ｂはニッケル、マンガン、銅、亜鉛、マグネシウム、カルシウム、ストロンチウム、バリウム、錫、及び鉛からなる群より選ばれる少なくとも１種の元素を示し、
Ｃはセシウム、ルビジウム、及びカリウムからなる群より選ばれる少なくとも１種のアルカリ元素を示し、
ａ〜ｆは、Ｍｏ１２原子に対する各元素の原子比を示し、１．５≦ａ≦６．０、１．５≦ｂ≦７．０、２．０≦ｃ≦８．０、０．５０≦ｄ≦６．０、０．０１０≦ｅ≦２．０、及び０≦ｆ＜２．０を満たし、
ｇは酸素以外の構成元素の原子価によって決まる酸素の原子数である。） The oxide catalyst of Claim 1 or 2 which has a composition represented by the following compositional formula (1).
Mo 12 Bi a Fe b Co c A d B e C f O g (1)
(In the formula (1), Mo represents the molybdenum, Bi represents the bismuth, Fe represents the iron, Co represents the cobalt,
A represents at least one lanthanoid element selected from the group consisting of lanthanum, cerium, praseodymium, neodymium, and europium,
B represents at least one element selected from the group consisting of nickel, manganese, copper, zinc, magnesium, calcium, strontium, barium, tin, and lead;
C represents at least one alkali element selected from the group consisting of cesium, rubidium, and potassium;
a to f indicate the atomic ratio of each element to the Mo12 atom, 1.5 ≦ a ≦ 6.0, 1.5 ≦ b ≦ 7.0, 2.0 ≦ c ≦ 8.0, 0.50 ≦ satisfy d ≦ 6.0, 0.010 ≦ e ≦ 2.0, and 0 ≦ f <2.0,
g is the number of oxygen atoms determined by the valence of the constituent elements other than oxygen. )
前記原料スラリーを乾燥して乾燥体を得る乾燥工程と、
前記乾燥体を仮焼成して仮焼成体を得る仮焼成工程と、
前記仮焼成体を不活性ガス雰囲気下で本焼成して本焼成体を得る本焼成工程と、
前記本焼成体を、酸素を含む雰囲気で酸化安定化処理して、酸化物触媒を得る酸化安定化処理工程と、
を有する、
酸化物触媒の製造方法。 A mixing step of mixing a raw material containing molybdenum, bismuth, iron, cobalt, and a lanthanoid element and a chelating agent to obtain a raw material slurry;
A drying step of drying the raw slurry to obtain a dried body;
A pre-baking step of pre-baking the dried body to obtain a pre-fired body;
A main firing step of obtaining a main fired body by subjecting the temporary fired body to a main fire in an inert gas atmosphere;
An oxidation stabilization treatment step of obtaining an oxide catalyst by subjecting the main fired body to an oxidation stabilization treatment in an atmosphere containing oxygen;
Having
A method for producing an oxide catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014066762A JP6204242B2 (en) | 2014-03-27 | 2014-03-27 | Oxide catalyst and method for producing the same, and method for producing unsaturated aldehyde or unsaturated nitrile |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014066762A JP6204242B2 (en) | 2014-03-27 | 2014-03-27 | Oxide catalyst and method for producing the same, and method for producing unsaturated aldehyde or unsaturated nitrile |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2015188801A true JP2015188801A (en) | 2015-11-02 |
| JP6204242B2 JP6204242B2 (en) | 2017-09-27 |
Family
ID=54423799
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2014066762A Expired - Fee Related JP6204242B2 (en) | 2014-03-27 | 2014-03-27 | Oxide catalyst and method for producing the same, and method for producing unsaturated aldehyde or unsaturated nitrile |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6204242B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019536627A (en) * | 2016-10-11 | 2019-12-19 | イネオス ユーロープ アクチェンゲゼルシャフト | Ammoxidation catalyst with selective by-product HCN production |
| WO2020039985A1 (en) * | 2018-08-24 | 2020-02-27 | 旭化成株式会社 | Method for producing ammoxidation catalyst, and method for producing acrylonitrile |
| WO2020039998A1 (en) * | 2018-08-23 | 2020-02-27 | 旭化成株式会社 | Method of producing ammoxidation catalyst and method of producing acrylonitrile |
| JPWO2019012920A1 (en) * | 2017-07-14 | 2020-04-09 | 旭化成株式会社 | Method for producing catalyst and method for producing unsaturated nitrile |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005330205A (en) * | 2004-05-19 | 2005-12-02 | Mitsubishi Chemicals Corp | Method for producing (meth)acrolein or (meth)acrylic acid |
| JP2009514829A (en) * | 2005-11-03 | 2009-04-09 | ビーエーエスエフ ソシエタス・ヨーロピア | Method for carrying out the process of continuously producing acrolein or acrylic acid or mixtures thereof from propane in a stable manner |
| WO2013002029A1 (en) * | 2011-06-28 | 2013-01-03 | 旭化成ケミカルズ株式会社 | Oxide catalyst |
| JP2013017917A (en) * | 2011-07-07 | 2013-01-31 | Asahi Kasei Chemicals Corp | Ammoxidation catalyst and method for producing acrylonitrile by using the same |
| JP2014031321A (en) * | 2012-08-01 | 2014-02-20 | Asahi Kasei Chemicals Corp | Method for manufacturing an oxidation product |
-
2014
- 2014-03-27 JP JP2014066762A patent/JP6204242B2/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005330205A (en) * | 2004-05-19 | 2005-12-02 | Mitsubishi Chemicals Corp | Method for producing (meth)acrolein or (meth)acrylic acid |
| JP2009514829A (en) * | 2005-11-03 | 2009-04-09 | ビーエーエスエフ ソシエタス・ヨーロピア | Method for carrying out the process of continuously producing acrolein or acrylic acid or mixtures thereof from propane in a stable manner |
| WO2013002029A1 (en) * | 2011-06-28 | 2013-01-03 | 旭化成ケミカルズ株式会社 | Oxide catalyst |
| JP2013017917A (en) * | 2011-07-07 | 2013-01-31 | Asahi Kasei Chemicals Corp | Ammoxidation catalyst and method for producing acrylonitrile by using the same |
| JP2014031321A (en) * | 2012-08-01 | 2014-02-20 | Asahi Kasei Chemicals Corp | Method for manufacturing an oxidation product |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019536627A (en) * | 2016-10-11 | 2019-12-19 | イネオス ユーロープ アクチェンゲゼルシャフト | Ammoxidation catalyst with selective by-product HCN production |
| JPWO2019012920A1 (en) * | 2017-07-14 | 2020-04-09 | 旭化成株式会社 | Method for producing catalyst and method for producing unsaturated nitrile |
| US11446643B2 (en) | 2017-07-14 | 2022-09-20 | Asahi Kasei Kabushiki Kaisha | Method for producing catalyst and method for producing unsaturated nitrile |
| WO2020039998A1 (en) * | 2018-08-23 | 2020-02-27 | 旭化成株式会社 | Method of producing ammoxidation catalyst and method of producing acrylonitrile |
| KR20210032514A (en) * | 2018-08-23 | 2021-03-24 | 아사히 가세이 가부시키가이샤 | Method for producing catalyst for ammoxidation and method for producing acrylonitrile |
| JPWO2020039998A1 (en) * | 2018-08-23 | 2021-08-10 | 旭化成株式会社 | A method for producing an ammoxidation catalyst and a method for producing acrylonitrile. |
| US20210316292A1 (en) * | 2018-08-23 | 2021-10-14 | Asahi Kasei Kabushiki Kaisha | Method for producing catalyst for ammoxidation, and method for producing acrylonitrile |
| RU2761968C1 (en) * | 2018-08-23 | 2021-12-14 | Асахи Касеи Кабусики Кайся | Method for producing ammoxidation catalyst and method for producing acrylonitrile |
| JP7109551B2 (en) | 2018-08-23 | 2022-07-29 | 旭化成株式会社 | Method for producing ammoxidation catalyst and method for producing acrylonitrile |
| US11701648B2 (en) | 2018-08-23 | 2023-07-18 | Asahi Kasei Kabushiki Kaisha | Method for producing catalyst for ammoxidation, and method for producing acrylonitrile |
| KR102642674B1 (en) * | 2018-08-23 | 2024-02-29 | 아사히 가세이 가부시키가이샤 | Method for producing a catalyst for ammonia oxidation and method for producing acrylonitrile |
| WO2020039985A1 (en) * | 2018-08-24 | 2020-02-27 | 旭化成株式会社 | Method for producing ammoxidation catalyst, and method for producing acrylonitrile |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6204242B2 (en) | 2017-09-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US9346036B2 (en) | Oxide catalyst | |
| JP6205044B2 (en) | Method for producing oxide catalyst | |
| JP6271317B2 (en) | Oxide catalyst and method for producing the same, and method for producing acrylonitrile | |
| KR101821023B1 (en) | 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 | |
| JP5794862B2 (en) | Oxides containing molybdenum, bismuth, iron and cobalt | |
| JP6180754B2 (en) | Oxide catalyst, method for producing the same, and method for producing unsaturated aldehyde | |
| JP5919870B2 (en) | Method for producing acrylonitrile production catalyst and method for producing acrylonitrile using the acrylonitrile production catalyst | |
| JP4954750B2 (en) | Method for producing molybdenum, bismuth, iron, silica-containing composite oxide catalyst | |
| JP6204242B2 (en) | Oxide catalyst and method for producing the same, and method for producing unsaturated aldehyde or unsaturated nitrile | |
| JP6961358B2 (en) | Oxide catalyst, method for producing oxide catalyst, and method for producing unsaturated aldehyde | |
| JP6185255B2 (en) | Oxide catalyst, method for producing the same, and method for producing unsaturated aldehyde | |
| JP6122278B2 (en) | Oxide catalyst | |
| JP4863436B2 (en) | Catalysts for the synthesis of unsaturated aldehydes and unsaturated carboxylic acids | |
| JP3939187B2 (en) | Process for producing unsaturated aldehyde | |
| JP5378041B2 (en) | Method for producing composite oxide catalyst for acrylonitrile synthesis | |
| JP2018158287A (en) | Method for producing catalyst | |
| JP2008237963A (en) | Method for preparing catalyst for manufacturing acrylonitrile | |
| JP2013226546A (en) | Method for producing catalyst | |
| US20190060884A1 (en) | Method for preparing catalyst | |
| RU2575346C2 (en) | Oxide catalyst | |
| WO2020203789A1 (en) | Method for producing catalyst for unsaturated carboxylic acid synthesis | |
| JP2020163383A (en) | Method of producing catalyst for synthesizing unsaturated carboxylic acid | |
| JP2021133272A (en) | Catalyst precursor and complex oxide catalyst | |
| JP2021154222A (en) | Catalyst precursor and complex oxide catalyst | |
| JP2009226270A (en) | Catalyst for producing methacrylic acid, its manufacturing method, and method for producing methacrylic acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A711 | Notification of change in applicant |
Free format text: JAPANESE INTERMEDIATE CODE: A712 Effective date: 20160401 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20160523 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20170210 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20170703 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20170726 |
|
| 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: 20170808 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20170831 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6204242 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| 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 |
|
| LAPS | Cancellation because of no payment of annual fees |