JP2005185977A - Method for manufacturing mixed metal oxide catalyst - Google Patents
Method for manufacturing mixed metal oxide catalyst Download PDFInfo
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- JP2005185977A JP2005185977A JP2003431778A JP2003431778A JP2005185977A JP 2005185977 A JP2005185977 A JP 2005185977A JP 2003431778 A JP2003431778 A JP 2003431778A JP 2003431778 A JP2003431778 A JP 2003431778A JP 2005185977 A JP2005185977 A JP 2005185977A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 44
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title abstract description 11
- 229910003455 mixed metal oxide Inorganic materials 0.000 title abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 64
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 15
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000001294 propane Substances 0.000 claims abstract description 12
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 9
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 8
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 8
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 7
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 7
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 6
- 239000001273 butane Substances 0.000 claims abstract description 6
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims abstract description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 19
- 150000004706 metal oxides Chemical class 0.000 claims description 19
- 229910052750 molybdenum Inorganic materials 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 5
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-L Oxalate Chemical compound [O-]C(=O)C([O-])=O MUBZPKHOEPUJKR-UHFFFAOYSA-L 0.000 claims 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims 1
- 238000010304 firing Methods 0.000 abstract description 2
- 239000012071 phase Substances 0.000 description 30
- 239000007787 solid Substances 0.000 description 16
- 239000002131 composite material Substances 0.000 description 14
- 239000010955 niobium Substances 0.000 description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 239000002002 slurry Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- -1 propane or butane Chemical class 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 3
- AXIFGFAGYFPNFC-UHFFFAOYSA-I 2-hydroxy-2-oxoacetate;niobium(5+) Chemical compound [Nb+5].OC(=O)C([O-])=O.OC(=O)C([O-])=O.OC(=O)C([O-])=O.OC(=O)C([O-])=O.OC(=O)C([O-])=O AXIFGFAGYFPNFC-UHFFFAOYSA-I 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000001282 iso-butane Substances 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- FXADMRZICBQPQY-UHFFFAOYSA-N orthotelluric acid Chemical compound O[Te](O)(O)(O)(O)O FXADMRZICBQPQY-UHFFFAOYSA-N 0.000 description 2
- 150000002926 oxygen Chemical class 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- 150000003682 vanadium compounds Chemical class 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 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
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 1
- 229910000379 antimony sulfate Inorganic materials 0.000 description 1
- MVMLTMBYNXHXFI-UHFFFAOYSA-H antimony(3+);trisulfate Chemical compound [Sb+3].[Sb+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O MVMLTMBYNXHXFI-UHFFFAOYSA-H 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 1
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- GSWAOPJLTADLTN-UHFFFAOYSA-N oxidanimine Chemical compound [O-][NH3+] GSWAOPJLTADLTN-UHFFFAOYSA-N 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- LAJZODKXOMJMPK-UHFFFAOYSA-N tellurium dioxide Chemical compound O=[Te]=O LAJZODKXOMJMPK-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 125000005287 vanadyl group Chemical group 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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Abstract
Description
本発明は、プロパン又はブタン等のアルカン類やプロピレン又はブテン等のアルケン類、アクロレイン又はメタアクロレイン等の不飽和アルデヒドから気相接触酸化によりアクリル酸又はメタクリル酸等の不飽和含酸素化合物を製造するために適した複合金属酸化物触媒の製造方法に関する。 The present invention produces an unsaturated oxygen-containing compound such as acrylic acid or methacrylic acid by vapor-phase catalytic oxidation from an alkane such as propane or butane, an alkene such as propylene or butene, or an unsaturated aldehyde such as acrolein or metaacrolein. The present invention relates to a method for producing a composite metal oxide catalyst suitable for the purpose.
アクリル酸及びメタクリル酸等の不飽和含酸素化合物の製造は一般に２段酸化反応で行われている。即ち、アクリル酸またはメタクリル酸を例に採ると、まず１段目反応ではＢｉ−Ｍｏ系複合酸化物触媒を使用して原料ガスであるプロピレンまたはイソブチレンからアクロレインまたはメタクロレインを製造し、引き続き２段目反応ではＭｏ−Ｖ系複合酸化物触媒を使用してアクリル酸またはメタクリル酸をそれぞれ製造している。
ところが、近年プロピレン、イソブチレンより安価なプロパン、イソブタン等のアルカンを原料に不飽和含酸素化合物を効率よく製造する方法への関心が高まり、これらプロセスに使用する触媒として、ＭｏＶＴｅ系触媒やＭｏＶＳｂ系触媒が報告されている。これらのＭｏＶＴｅ及びＭｏＶＳｂ系触媒は数種類の結晶構造が含まれ、代表的には斜方晶相及び六方晶相の２つの結晶構造が存在する。その中で主反応をつかさどる結晶構造は斜方晶相であり、この結晶構造を選択的に調製する方法が知られている。
The production of unsaturated oxygenated compounds such as acrylic acid and methacrylic acid is generally carried out by a two-stage oxidation reaction. That is, taking acrylic acid or methacrylic acid as an example, in the first stage reaction, first, acrolein or methacrolein is produced from propylene or isobutylene, which is a raw material gas, using a Bi-Mo composite oxide catalyst, and then the second stage reaction. In the eye reaction, Mo-V composite oxide catalyst is used to produce acrylic acid or methacrylic acid, respectively.
However, in recent years, interest in methods for efficiently producing unsaturated oxygenated compounds from raw materials of alkanes such as propane and isobutane, which are cheaper than propylene and isobutylene, has increased, and MoVTe catalysts and MoVSb catalysts have been used as catalysts for these processes. Has been reported. These MoVTe and MoVSb-based catalysts include several types of crystal structures, and typically have two crystal structures, an orthorhombic phase and a hexagonal phase. Among them, the crystal structure that controls the main reaction is an orthorhombic phase, and a method for selectively preparing this crystal structure is known.
例えば特許文献１では、Ｍｏ−Ｖ−Ｓｂ−Ｘ−Ｏ（Ｘは、Ｔｉ、Ｚｒ、Ｎｂ、Ｔａ、Ｃｒ、Ｗ、Ｍｎ、Ｆｅ、Ｒｕ、Ｃｏ、Ｒｈ、Ｉｒ、Ｎｉ、Ｐｄ、Ｐｔ、Ｃｕ、Ａｇ、Ｚｎ、Ｉｎ、Ｓｎ、Ｐｂ、Ｂｉ、Ｃｅ、及びアルカリ土類金属の中から選ばれた１種以上の金属元素）で表される斜方晶相及び六方晶相を含む複合酸化物に、蓚酸やエチレングリコール、または過酸化水素を加える事により六方晶相を選択的に除去することで、結果として斜方晶相を製造する方法が開示されている。 For example, in Patent Document 1, Mo—V—Sb—X—O (X is Ti, Zr, Nb, Ta, Cr, W, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu. , Ag, Zn, In, Sn, Pb, Bi, Ce, and one or more metal elements selected from alkaline earth metals) and complex oxides including orthorhombic and hexagonal phases In addition, a method for producing an orthorhombic phase by selectively removing the hexagonal phase by adding oxalic acid, ethylene glycol, or hydrogen peroxide is disclosed.
また特許文献２では、Ａ−Ｖ−Ｎ−Ｘ−Ｏ（ＡはＭｏ及びＷからなる群から選択される少なくとも１つの元素であり、ＮはＴｅ及びＳｅからなる群から選択される少なくとも１つの元素であり、さらにＸはＮｂ、Ｔａ、Ｔｉなどからなる群から選択される少なくとも１つの元素である）を有する混合金属酸化物を、有機酸、アルコール、無機酸に接触させた後、不溶性物質を回収して斜方晶相を形成させ、この物質で触媒前駆体溶液をシーディングすることにより定量的な収量で斜方晶相を製造する方法が開示されている。 In Patent Document 2, AVNXO (A is at least one element selected from the group consisting of Mo and W, and N is at least one selected from the group consisting of Te and Se. An insoluble substance after contacting a mixed metal oxide having an element, and X is at least one element selected from the group consisting of Nb, Ta, Ti, etc.) with an organic acid, alcohol, or inorganic acid Is collected to form an orthorhombic phase, and a method of producing an orthorhombic phase in a quantitative yield is disclosed by seeding a catalyst precursor solution with this material.
特許文献１では２つ以上の結晶をもつ触媒を溶媒で洗浄する事により、六方晶相等を溶解除去して斜方晶相のみを固体として回収しているが、この洗浄方法は洗浄後の斜方晶相を持つ触媒量が少なくなることが欠点である。また特許文献２では特許文献１のように溶媒で斜方晶相以外を洗浄除去した後、残った固体をシード材として触媒前駆体溶液に入れて斜方晶相を選択的に調製している。しかし、この調製工程は煩雑であり作業性に問題がある。また、上記２つの特許文献では洗浄した後の有用な金属を含む洗浄液は廃棄するか又は再利用する場合においても処理が必要となり、触媒調製全体の製造コストが高くなる。 In Patent Document 1, a catalyst having two or more crystals is washed with a solvent to dissolve and remove the hexagonal crystal phase and the like, and only the orthorhombic phase is recovered as a solid. The disadvantage is that the amount of catalyst having a tetragonal phase is reduced. In Patent Document 2, as in Patent Document 1, other than the orthorhombic phase is washed away with a solvent, and the remaining solid is used as a seed material in the catalyst precursor solution to selectively prepare the orthorhombic phase. . However, this preparation process is complicated and has a problem in workability. Further, in the above two patent documents, the cleaning liquid containing useful metal after cleaning requires treatment even when it is discarded or reused, and the manufacturing cost of the entire catalyst preparation becomes high.
本発明者等は、気相接触酸化反応によりプロパン及びイソブタンから、各々アクロレイン、アクリル酸及びメタクロレイン、メタクリル酸を製造するのに適した斜方晶相を選択的に含む複合金属酸化物触媒、更にアクロレイン及びメタクロレインから、各々アクリル酸、メタクリル酸を製造するのに適した斜方晶相を選択的に含む複合金属酸化物触媒を製造する方法について種々検討した。その結果、モリブデン、バナジウム及び特定の金属を含むスラリーを静置する事によって溶液部とゲル部を分離すると目的とする斜方晶相複合金属酸化物触媒が選択的に製造できることを見出し、本発明を完成させた。 The inventors of the present invention provide a composite metal oxide catalyst that selectively contains an orthorhombic phase suitable for producing acrolein, acrylic acid and methacrolein, and methacrylic acid, respectively, from propane and isobutane by a gas phase catalytic oxidation reaction, Furthermore, various methods for producing a composite metal oxide catalyst selectively containing an orthorhombic phase suitable for producing acrylic acid and methacrylic acid from acrolein and methacrolein were investigated. As a result, it was found that by separating a solution part and a gel part by allowing a slurry containing molybdenum, vanadium and a specific metal to stand, an intended orthorhombic phase complex metal oxide catalyst can be selectively produced. Was completed.
すなわち、本発明は
（１）
（ａ）Ｍｏ含有化合物、Ｖ含有化合物
並びに
（ｂ）Ｘ含有化合物（Ｘは、ＴｅまたはＳｂを示す。）及び／またはＹ含有化合物（ＹはＮｂ、Ｗ、ＺｒまたはＴｉを示す。）
と水との混合物を調製し、得られた混合物をゲル部と溶液部に分離し、該ゲル部を焼成処理することを特徴とする
下記一般式（１）
Ｍｏ６ＶａＸｂＹｃＯｄ（１）
（式中Ｍｏ及びＶはそれぞれモリブデン、バナジウムを、ＸはＴｅまたはＳｂを、ＹはＮｂ、Ｗ、ＺｒまたはＴｉをそれぞれ表す。ａ〜ｄは各元素の組成比を表し、０．１＜ａ＜６、０≦ｂ＜６、０≦ｃ＜６の正数であるが、ｂとｃが同時に０となることはない。また、ｄは他の元素の酸化状態により変化する数である。）
で表される斜方晶相複合金属酸化物触媒の製造方法、
（２）ａが０．９以上、１．５以下、ｂが１以上、２以下、ｃが０．５以上、１．５以下である上記（１）記載の製造方法、
（３）Ｙ含有化合物を蓚酸イオンを含む状態で使用する上記（１）または（２）記載の製造方法。、
（４）Ｔｅ含有化合物とＮｂ含有化合物を使用する上記（１）〜（３）のいずれか1項に記載の製造方法、
（５）斜方晶相複合金属酸化物触媒が、プロパンまたはブタンから気相接触反応によりアクロレイン及びアクリル酸、またはメタクロレイン及びメタクリル酸を製造するための触媒である上記（１）〜（４）のいずれか１項に記載の製造方法
に関する。
That is, the present invention provides (1)
(A) Mo-containing compound, V-containing compound and (b) X-containing compound (X represents Te or Sb) and / or Y-containing compound (Y represents Nb, W, Zr or Ti).
A mixture of water and water is prepared, the obtained mixture is separated into a gel part and a solution part, and the gel part is subjected to a baking treatment, and the following general formula (1)
Mo 6 V a X b Y c O d (1)
(Wherein Mo and V are molybdenum and vanadium, X is Te or Sb, Y is Nb, W, Zr or Ti, respectively, ad represents the composition ratio of each element, and 0.1 <a <6, 0 ≦ b <6, 0 ≦ c <6, but b and c are not 0 at the same time, and d is a number that varies depending on the oxidation state of other elements. )
A process for producing an orthorhombic phase complex metal oxide catalyst represented by:
(2) The production method according to (1), wherein a is 0.9 or more and 1.5 or less, b is 1 or more and 2 or less, and c is 0.5 or more and 1.5 or less,
(3) The production method according to (1) or (2), wherein the Y-containing compound is used in a state containing oxalate ions. ,
(4) The production method according to any one of (1) to (3), wherein a Te-containing compound and an Nb-containing compound are used.
(5) The above (1) to (4), wherein the orthorhombic phase complex metal oxide catalyst is a catalyst for producing acrolein and acrylic acid, or methacrolein and methacrylic acid from propane or butane by a gas phase catalytic reaction. The manufacturing method of any one of these.
本発明により、気相接触酸化反応によりプロパン又はブタン等のアルカン類やプロピレン又はブテン等のアルケン類、アクロレイン又はメタアクロレイン等の不飽和アルデヒドから気相接触酸化によりアクリル酸又はメタクリル酸等の不飽和含酸素化合物を製造するのに適した複合金属酸化物触媒が容易に製造できる。 According to the present invention, an unsaturated compound such as acrylic acid or methacrylic acid is obtained by gas phase catalytic oxidation from an alkane such as propane or butane, an alkene such as propylene or butene, an unsaturated aldehyde such as acrolein or metaacrolein by a gas phase catalytic oxidation reaction A composite metal oxide catalyst suitable for producing an oxygen-containing compound can be easily produced.
以下、本発明を詳細に説明する。
本発明により得られる触媒は前記式（１）で表されるが、前記式（１）において、１＜ａ＜４、０．５＜ｂ＜２、０．１＜ｃ＜２である範囲が好ましく、０．９≦ａ≦１．５、１≦ｂ≦２、０．５≦ｃ≦１．５である範囲が特に好ましい。これらの組成比はプラズマ発光分析によって測定することができる。
Hereinafter, the present invention will be described in detail.
The catalyst obtained by the present invention is represented by the above formula (1). In the above formula (1), there are ranges where 1 <a <4, 0.5 <b <2, 0.1 <c <2. The ranges of 0.9 ≦ a ≦ 1.5, 1 ≦ b ≦ 2, and 0.5 ≦ c ≦ 1.5 are particularly preferable. These composition ratios can be measured by plasma emission analysis.
本発明においてはまず、（ａ）モリブデン含有化合物及びバナジウム含有化合物（以下（ａ）群化合物と言うこともある）並びに（ｂ）Ｘ含有化合物（Ｘは、ＴｅまたはＳｂを示し、２種を併用することも可能である。）及び／またはＹ含有化合物（ＹはＮｂ、Ｗ、Ｚｒ、Ｔｉを示し、２種以上を併用することも可能である。）（以下（ｂ）群化合物と言うこともある）と水との混合物を調製する。これら（ａ）群または（ｂ）群化合物としては、空気中で焼成することにより酸化物に分解できるものであれば特に制限はなく、例えば（ａ）群化合物のうち、モリブデン含有化合物としてはモリブデン酸アンモニウム、三酸化モリブデン、モリブデン酸、モリブデン酸ナトリウム等が、バナジウムの化合物としては酸化バナジウム、バナジン酸アンモニウム、オキソ硫酸バナジル等が挙げられる。また、（ｂ）群化合物としては、金属ＸまたはＹの酸化物、塩化物、硫酸塩、硝酸塩、蓚酸塩等が挙げられる。（ｂ）群化合物のうち、Ｘ含有化合物としては、三酸化アンチモン、硫酸アンチモン、酢酸アンチモン等のＳｂ含有化合物、二酸化テルル、テルル酸等のＴｅ含有化合物が、また、Ｙ含有化合物としては、ニオブ酸、酸化ニオブ、蓚酸水素ニオブ等のＮｂ含有化合物、パラタングステン酸アンモニウム、タングステン酸、酸化タングステン等のＷ含有化合物、酸化ジルコニウム、硝酸ジルコニウム、酢酸ジルコニウム等のＺｒ含有化合物、酸化チタン、蓚酸チタンアンモニウム、硫酸チタン等のＴｉ含有化合物がそれぞれ好ましい化合物として挙げられる。（ｂ）群化合物のうち、Ｘ含有化合物とＹ含有化合物は、少なくともどちらか一方を使用するが、両者を併用する方が好ましく、Ｔｅ含有化合物とＮｂ含有化合物を併用するのが特に好ましい。 In the present invention, first, (a) a molybdenum-containing compound and a vanadium-containing compound (hereinafter sometimes referred to as (a) group compound) and (b) an X-containing compound (X represents Te or Sb, and two types are used in combination. And / or a Y-containing compound (Y represents Nb, W, Zr, Ti, and two or more types can be used in combination) (hereinafter referred to as a group compound (b)) Prepare a mixture of water). These (a) group or (b) group compounds are not particularly limited as long as they can be decomposed into oxides by firing in air. For example, among the (a) group compounds, molybdenum-containing compounds include molybdenum. Examples of vanadium compounds include ammonium oxide, molybdenum trioxide, molybdic acid, sodium molybdate, and the like. Examples of vanadium compounds include vanadium oxide, ammonium vanadate, and vanadyl oxosulfate. Examples of the (b) group compound include metal X or Y oxides, chlorides, sulfates, nitrates, and oxalates. Among (b) group compounds, X-containing compounds include Sb-containing compounds such as antimony trioxide, antimony sulfate and antimony acetate, Te-containing compounds such as tellurium dioxide and telluric acid, and Y-containing compounds include niobium. Nb-containing compounds such as acid, niobium oxide, niobium hydrogen oxalate, W-containing compounds such as ammonium paratungstate, tungstic acid, tungsten oxide, Zr-containing compounds such as zirconium oxide, zirconium nitrate, zirconium acetate, titanium oxide, ammonium ammonium oxalate Ti-containing compounds such as titanium sulfate are preferred compounds. Among the (b) group compounds, at least one of the X-containing compound and the Y-containing compound is used, but it is preferable to use both in combination, and it is particularly preferable to use the Te-containing compound and the Nb-containing compound in combination.
（ａ）群化合物と（ｂ）群化合物は、両者をあわせて、常温〜１００℃で水に溶解及び／又は分散してスラリーとされる。水の使用量は、これら原料化合物を溶解できるか、溶解できなくても均一なスラリー状にできる程度であれば特に制限はない。（ｂ）群化合物のうち、Ｘ含有化合物とＹ含有化合物を併用する場合、（ａ）群化合物とＸ含有化合物と水を混合したスラリー液にＹ含有化合物を添加する。この場合Ｙ含有化合物は固体状で加えても良いし、各種溶媒、好ましくは水に溶解又は分散させた後、加えても良い。また、Ｙ含有化合物をこのように別途添加する場合、Ｙ含有化合物は蓚酸を含んだ化合物、好ましくは蓚酸塩もしくは蓚酸を含む水溶液にＹ含有化合物を加えて溶解及び／又はスラリーとして添加する事が好ましい。 The (a) group compound and the (b) group compound are combined and dissolved and / or dispersed in water at room temperature to 100 ° C. to form a slurry. The amount of water used is not particularly limited as long as these raw material compounds can be dissolved or can be dissolved even if they cannot be dissolved. (B) When using together an X containing compound and a Y containing compound among group compounds, a Y containing compound is added to the slurry liquid which mixed the (a) group compound, X containing compound, and water. In this case, the Y-containing compound may be added in a solid state, or may be added after being dissolved or dispersed in various solvents, preferably water. In addition, when the Y-containing compound is added separately as described above, the Y-containing compound may be added as a solution containing oxalic acid, preferably dissolved and / or slurry by adding the Y-containing compound to an aqueous solution containing oxalate or oxalic acid. preferable.
スラリー調製後、攪拌を続けるとゲル状物質が生成し、このゲル状物質を含むスラリーは静置することで溶液部とゲル部に分離する。静置時間は特に制限はないが、５分〜１００時間、好ましくは３０分〜４８時間である。また、静置している時の温度は５０℃以下が好ましい。静置後、溶液部を取り除きゲル部を分離するが、その方法は一般的な濾過方法で良く、例えば自然濾過や吸引濾過等で良い。
なお、溶液部に（ａ）群または（ｂ）群化合物を加え、スラリーとして再び使用することも可能である。
When stirring is continued after slurry preparation, a gel-like substance is generated, and the slurry containing the gel-like substance is allowed to stand to separate into a solution part and a gel part. The standing time is not particularly limited, but is 5 minutes to 100 hours, preferably 30 minutes to 48 hours. Further, the temperature at the time of standing is preferably 50 ° C. or less. After standing, the solution part is removed and the gel part is separated. The method may be a general filtration method, for example, natural filtration or suction filtration.
In addition, it is also possible to add (a) group or (b) group compound to a solution part, and to use again as a slurry.
続いて取り出したゲル部を好ましくは乾燥し、焼成する。
焼成処理は、温度差が１５０〜４００℃程度になるような２段階の温度で行うのが好ましい。第一の焼成処理は、酸素ガスの存在下（例えば空気中）で、２５０℃以上、好ましくは２５０〜３５０℃の温度で０．５〜１２時間行い、第二の焼成処理は窒素、ヘリウム等不活性ガス中で４００℃以上、好ましくは５００〜６５０℃で０．５〜１０時間行う。２回に分けて実施する焼成処理において、焼成温度、時間が上記範囲からはずれると触媒性能は低下する場合がある。特にアクロレイン、アクリル酸、メタクロレイン、メタクリル酸といった不飽和含酸素化合物の選択性が低下するので好ましくない。
Subsequently, the taken-out gel part is preferably dried and fired.
The baking treatment is preferably performed at a two-stage temperature such that the temperature difference is about 150 to 400 ° C. The first baking treatment is performed in the presence of oxygen gas (for example, in the air) at a temperature of 250 ° C. or higher, preferably 250 to 350 ° C. for 0.5 to 12 hours, and the second baking treatment is nitrogen, helium, or the like. It is carried out in an inert gas at 400 ° C. or higher, preferably at 500 to 650 ° C. for 0.5 to 10 hours. In the calcination treatment carried out in two steps, the catalyst performance may be lowered if the calcination temperature and time deviate from the above ranges. In particular, the selectivity of unsaturated oxygen-containing compounds such as acrolein, acrylic acid, methacrolein, and methacrylic acid is not preferable.
こうして得られた酸化物は、通常、Ｘ線回折（Ｃｕ−Ｋα線を使用）の２θ値に６．６°、７．８°、９．０°、２２．２°（各±０．３°）の主な回折ピークを示す斜方晶相を持つ複合金属酸化物である。 The oxide thus obtained usually has 6.6 °, 7.8 °, 9.0 °, 22.2 ° (± 0.3 each) on the 2θ value of X-ray diffraction (using Cu—Kα ray). °) is a complex metal oxide with an orthorhombic phase showing the main diffraction peaks.
本発明の製造方法で得られる複合金属酸化物触媒は、そのまま触媒として使用することができるが、粉砕して使用することが好ましい。本発明により得られる触媒は固定床、流動床、移動床等のいずれの反応様式にも適用できるが、固定床の場合、好ましくはシリカ、アルミナ、シリコンカーバイト等の球状担体に粉末状の本発明の複合金属酸化物触媒を担持成型した被覆触媒または粉末状の複合金属酸化物を打錠成型等の成型機で成型した触媒が有利となる。また、流動床、移動床反応器には、耐摩耗性を向上させるためにさらにシリカ成分等を複合金属酸化物触媒に添加して調製した数十ミクロン程度の均一な触媒の使用が有利となる。 The composite metal oxide catalyst obtained by the production method of the present invention can be used as it is, but is preferably used after being pulverized. The catalyst obtained by the present invention can be applied to any reaction mode such as a fixed bed, a fluidized bed, and a moving bed. However, in the case of a fixed bed, it is preferably a powdery material on a spherical support such as silica, alumina, or silicon carbide. A coated catalyst obtained by supporting and molding the composite metal oxide catalyst of the invention or a catalyst obtained by molding a powdered composite metal oxide with a molding machine such as tableting molding is advantageous. In addition, for fluidized bed and moving bed reactors, it is advantageous to use a uniform catalyst of about several tens of microns prepared by adding a silica component or the like to the composite metal oxide catalyst in order to improve wear resistance. .
本発明により得られた触媒は、プロパン又はブタン等のアルカン類やプロピレン又はブテン等のアルケン類、アクロレイン又はメタアクロレイン等の不飽和アルデヒドから気相接触酸化によりアクリル酸又はメタクリル酸等の不飽和含酸素化合物を製造するために好ましく使用できる。 The catalyst obtained by the present invention contains an unsaturated compound such as acrylic acid or methacrylic acid by gas phase catalytic oxidation from an alkane such as propane or butane, an alkene such as propylene or butene, or an unsaturated aldehyde such as acrolein or metaacrolein. It can be preferably used for producing an oxygen compound.
以下に実施例により本発明をより具体的に説明するが、本発明は、その趣旨を越えない限り、以下の実施例に限定されるものではない。 EXAMPLES The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to the following examples unless it exceeds the gist.
実施例１
蒸留水６００ｍｌにモリブデン酸アンモニウム５０．００ｇを室温で溶解した。この水溶液を８０℃に加熱してメタバナジン酸アンモニウム９．３９ｇ、テルル酸１４．７４ｇを添加して１０分間攪拌し、その後４０℃以下まで放冷し調合液Ａを得た。また、別の容器で蒸留水２００ｍｌに蓚酸水素ニオブ２９．４７ｇ（Ｎｂ２Ｏ５換算で１５重量％含有）を添加して煮沸溶解させ、その後４０℃以下まで放冷し調合液Ｂを得た。調合液Ｂを調合液Ａに添加して充分に攪拌すると、時間と共にゲルが生成した。このゲル状スラリーを２４時間静置すると溶液部とゲル部に分離した。そのゲル部を分取して吸引濾過した後、濾紙上に残った固形物を乾燥させ固体を得た。その固体を空気雰囲気下で３００℃、２時間の焼成を行い、引き続き窒素流通下で６００℃、６時間の焼成を行い複合金属酸化物触媒を得た。
得られた触媒についてＸ線回折（Ｃｕ−Ｋα線を使用）を行った結果を図１に示す。得られた固形物は、２θ値で６．６°、７．８°、９．０°、２２．２°（各±０．３°）の斜方晶相を選択的に含む複合金属酸化物であることを確認した。また得られた固形物につきプラズマ発光分析により組成を分析した結果、Ｍｏ６Ｖ１．１Ｔｅ１．６Ｎｂ０．９（酸素を除く）であった。
Example 1
In 600 ml of distilled water, 50.00 g of ammonium molybdate was dissolved at room temperature. This aqueous solution was heated to 80 ° C., 9.39 g of ammonium metavanadate and 14.74 g of telluric acid were added and stirred for 10 minutes, and then allowed to cool to 40 ° C. or lower to obtain Formulation A. In another container, 29.47 g of niobium hydrogen oxalate (containing 15% by weight in terms of Nb 2 O 5 ) was added to 200 ml of distilled water and dissolved by boiling, and then allowed to cool to 40 ° C. or lower to obtain Formulation B . When the preparation liquid B was added to the preparation liquid A and sufficiently stirred, a gel was formed with time. When this gel slurry was allowed to stand for 24 hours, it separated into a solution part and a gel part. The gel part was collected and subjected to suction filtration, and the solid remaining on the filter paper was dried to obtain a solid. The solid was calcined at 300 ° C. for 2 hours in an air atmosphere, and subsequently calcined at 600 ° C. for 6 hours under a nitrogen flow to obtain a composite metal oxide catalyst.
FIG. 1 shows the result of X-ray diffraction (using Cu—Kα ray) for the obtained catalyst. The obtained solid was a composite metal oxide selectively containing an orthorhombic phase of 6.6 °, 7.8 °, 9.0 °, 22.2 ° (each ± 0.3 °) in terms of 2θ values. It was confirmed to be a thing. As a result of analyzing the composition of the obtained solid by plasma emission analysis, it was Mo 6 V 1.1 Te 1.6 Nb 0.9 (excluding oxygen).
比較例１
実施例１で２４時間静置後分離した溶液部をエバポレーターで乾燥させ固体を得た。その固体を空気雰囲気下で３００℃、２時間の焼成を行い、引き続き窒素流通下で６００℃、６時間の焼成を行った。
焼成したサンプルについてＸ線回折（Ｃｕ−Ｋα線を使用）を行った結果を図２に示す。得られた固形物は、２θ値で２２．２°、２８．２°、３６．２°（各±０．３°）の六方晶相を多く含む複合金属酸化物であることを確認した。また得られた固形物につきプラズマ発光分析により組成を分析した結果、Ｍｏ６Ｖ１．６Ｔｅ０．９Ｎｂ０．０４（酸素を除く）であった。
Comparative Example 1
The solution part separated after standing for 24 hours in Example 1 was dried by an evaporator to obtain a solid. The solid was calcined at 300 ° C. for 2 hours in an air atmosphere, and subsequently calcined at 600 ° C. for 6 hours under a nitrogen flow.
FIG. 2 shows the result of X-ray diffraction (using Cu—Kα ray) for the fired sample. It was confirmed that the obtained solid was a complex metal oxide containing a lot of hexagonal phases of 22.2 °, 28.2 °, and 36.2 ° (each ± 0.3 °) in terms of 2θ values. The results for each resulting solid was analyzed composition by plasma emission analysis, was Mo 6 V 1.6 Te 0.9 Nb 0.04 ( excluding oxygen).
比較例２
実施例１で調合したゲル状スラリー全量をすぐにエバポレーターで蒸発乾固して固体を得た。その固体を空気雰囲気下で３００℃、２時間の焼成を行い、引き続き窒素流通下で６００℃、６時間の焼成を行った。
焼成したサンプルについてＸ線回折（Ｃｕ−Ｋα線を使用）を行った結果を図３に示す。
得られた固形物は、２θ値で６．６°、７．８°、９．０°、２２．２°（各±０．３°）の斜方晶相、及び２θ値で２２．２°、２８．２°、３６．２°（各±０．３°）の六方晶相の両結晶相を含む複合金属酸化物であることを確認した。また得られた固形物につきプラズマ発光分析により組成を分析した結果、Ｍｏ６Ｖ１．７Ｔｅ１．３Ｎｂ０．７（酸素を除く）であった。
Comparative Example 2
The entire gel slurry prepared in Example 1 was immediately evaporated to dryness with an evaporator to obtain a solid. The solid was calcined at 300 ° C. for 2 hours in an air atmosphere, and subsequently calcined at 600 ° C. for 6 hours under a nitrogen flow.
FIG. 3 shows the result of X-ray diffraction (using Cu—Kα ray) for the fired sample.
The obtained solid had an orthorhombic phase of 6.6 °, 7.8 °, 9.0 °, 22.2 ° (each ± 0.3 °) in 2θ value, and 22.2 in 2θ value. It was confirmed to be a composite metal oxide containing both hexagonal crystal phases of °, 28.2 °, and 36.2 ° (each ± 0.3 °). As a result of analyzing the composition of the obtained solid by plasma emission analysis, it was Mo 6 V 1.7 Te 1.3 Nb 0.7 (excluding oxygen).
試験例
固定床流通式反応装置を使用し、内径１２ｍｍの耐熱ガラス管に充分に粉砕した実施例１、比較例１〜２で得られた各複合金属酸化物（触媒）１．２ｍｌを炭化ケイ素粉末３．６ｍｌで希釈しそれぞれ充填し、プロパン／酸素／水蒸気／窒素＝４．５／１０．１／３１．５／２３．６（ｍｌ／ｍｉｎ）からなる原料混合ガスを流しながら、反応温度４００℃で反応試験を行った。反応生成物はガスクロマトグラフィーで分析した。結果を下記に示す。
Test Example Using a fixed bed flow type reactor, 1.2 ml of each composite metal oxide (catalyst) obtained in Example 1 and Comparative Examples 1 and 2 sufficiently ground in a heat-resistant glass tube having an inner diameter of 12 mm was silicon carbide. While being diluted with 3.6 ml of powder and filled with each, a raw material mixed gas consisting of propane / oxygen / water vapor / nitrogen = 4.5 / 10.1 / 31.5 / 23.6 (ml / min) is flowed, A reaction test was conducted at 400 ° C. The reaction product was analyzed by gas chromatography. The results are shown below.
サンプル プロパン転化率（％） アクリル酸選択率（％）
実施例１ ４４．９ ５２．４
比較例１ １．７ ０．０
比較例２ ３３．６ ４１．７
Sample Propane conversion (%) Acrylic acid selectivity (%)
Example 1 44.9 52.4
Comparative Example 1 1.7 0.0
Comparative Example 2 33.6 41.7
試験結果から、本発明で得られた触媒は斜方晶相を主成分とするためプロパン転化率、アクリル酸選択率共に優れるが、六方晶相を主成分とする比較例１の触媒はプロパン転化率が非常に低く触媒としての機能が低く、目的物も全く生成していないため、触媒として使用できないことは明らかである。 From the test results, the catalyst obtained in the present invention has an orthorhombic phase as a main component and thus is excellent in both propane conversion and acrylic acid selectivity, but the catalyst of Comparative Example 1 having a hexagonal phase as a main component is propane conversion. The rate is very low, the function as a catalyst is low, and the target product is not produced at all, so it is clear that it cannot be used as a catalyst.
Claims (5)
並びに
（ｂ）Ｘ含有化合物（Ｘは、ＴｅまたはＳｂを示す。）及び／またはＹ含有化合物（ＹはＮｂ、Ｗ、ＺｒまたはＴｉを示す。）
と水との混合物を調製し、得られた混合物をゲル部と溶液部に分離し、該ゲル部を焼成処理することを特徴とする
下記一般式（１）
Ｍｏ６ＶａＸｂＹｃＯｄ（１）
（式中Ｍｏ及びＶはそれぞれモリブデン、バナジウムを、ＸはＴｅまたはＳｂを、ＹはＮｂ、Ｗ、ＺｒまたはＴｉをそれぞれ表す。ａ〜ｄは各元素の組成比を表し、０．１＜ａ＜６、０≦ｂ＜６、０≦ｃ＜６の正数であるが、ｂとｃが同時に０となることはない。また、ｄは他の元素の酸化状態により変化する数である。）
で表される斜方晶相複合金属酸化物触媒の製造方法。 (A) Mo-containing compound, V-containing compound and (b) X-containing compound (X represents Te or Sb) and / or Y-containing compound (Y represents Nb, W, Zr or Ti).
A mixture of water and water is prepared, the obtained mixture is separated into a gel part and a solution part, and the gel part is subjected to a baking treatment, and the following general formula (1)
Mo 6 V a X b Y c O d (1)
(Wherein Mo and V are molybdenum and vanadium, X is Te or Sb, Y is Nb, W, Zr or Ti, respectively, ad represents the composition ratio of each element, and 0.1 <a <6, 0 ≦ b <6, 0 ≦ c <6, but b and c are not 0 at the same time, and d is a number that varies depending on the oxidation state of other elements. )
The manufacturing method of the orthorhombic phase complex metal oxide catalyst represented by these.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7208445B2 (en) * | 2001-04-25 | 2007-04-24 | Rohm And Haas Company | Single crystalline phase catalyst |
| JP2007216222A (en) * | 2006-01-31 | 2007-08-30 | Rohm & Haas Co | Regenerated mixed metal oxide catalyst |
| JP2009523609A (en) * | 2006-01-17 | 2009-06-25 | サウディ ベーシック インダストリーズ コーポレイション | Process for producing mixed metal oxide catalysts for producing unsaturated aldehydes from olefins |
| JP2009183897A (en) * | 2008-02-07 | 2009-08-20 | Asahi Kasei Chemicals Corp | Method of manufacturing compound oxide and method of manufacturing unsaturated acid or nitrile |
| JP2015120133A (en) * | 2013-12-25 | 2015-07-02 | 株式会社日本触媒 | Catalyst for producing acrylic acid, and method for producing acrylic acid by using catalyst |
| JP2018043197A (en) * | 2016-09-15 | 2018-03-22 | 日本化薬株式会社 | Catalyst for manufacturing acrylic acid |
| CN112439441A (en) * | 2019-09-05 | 2021-03-05 | 中石油吉林化工工程有限公司 | Preparation method of catalyst for preparing acrylic acid by acrolein oxidation |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7208445B2 (en) * | 2001-04-25 | 2007-04-24 | Rohm And Haas Company | Single crystalline phase catalyst |
| US7326668B2 (en) | 2001-04-25 | 2008-02-05 | Rohm And Haas Company | Single crystalline phase catalyst |
| JP2009523609A (en) * | 2006-01-17 | 2009-06-25 | サウディ ベーシック インダストリーズ コーポレイション | Process for producing mixed metal oxide catalysts for producing unsaturated aldehydes from olefins |
| JP2007216222A (en) * | 2006-01-31 | 2007-08-30 | Rohm & Haas Co | Regenerated mixed metal oxide catalyst |
| JP2009183897A (en) * | 2008-02-07 | 2009-08-20 | Asahi Kasei Chemicals Corp | Method of manufacturing compound oxide and method of manufacturing unsaturated acid or nitrile |
| JP2015120133A (en) * | 2013-12-25 | 2015-07-02 | 株式会社日本触媒 | Catalyst for producing acrylic acid, and method for producing acrylic acid by using catalyst |
| JP2018043197A (en) * | 2016-09-15 | 2018-03-22 | 日本化薬株式会社 | Catalyst for manufacturing acrylic acid |
| CN112439441A (en) * | 2019-09-05 | 2021-03-05 | 中石油吉林化工工程有限公司 | Preparation method of catalyst for preparing acrylic acid by acrolein oxidation |
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