JP2008155126A - Method for producing metal component-containing catalyst - Google Patents
Method for producing metal component-containing catalyst Download PDFInfo
- Publication number
- JP2008155126A JP2008155126A JP2006346786A JP2006346786A JP2008155126A JP 2008155126 A JP2008155126 A JP 2008155126A JP 2006346786 A JP2006346786 A JP 2006346786A JP 2006346786 A JP2006346786 A JP 2006346786A JP 2008155126 A JP2008155126 A JP 2008155126A
- Authority
- JP
- Japan
- Prior art keywords
- metal component
- producing
- catalyst
- metal
- containing catalyst
- 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.)
- Pending
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 224
- 239000002184 metal Substances 0.000 title claims abstract description 224
- 239000003054 catalyst Substances 0.000 title claims abstract description 125
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 67
- 239000002245 particle Substances 0.000 claims abstract description 97
- 238000001035 drying Methods 0.000 claims abstract description 62
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000007788 liquid Substances 0.000 claims abstract description 40
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 33
- 239000011733 molybdenum Substances 0.000 claims abstract description 33
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 32
- 150000001299 aldehydes Chemical class 0.000 claims abstract description 32
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract description 30
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 230000003197 catalytic effect Effects 0.000 claims abstract description 27
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 27
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 23
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052742 iron Inorganic materials 0.000 claims abstract description 22
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910001882 dioxygen Inorganic materials 0.000 claims abstract description 20
- 230000003647 oxidation Effects 0.000 claims abstract description 20
- 239000012808 vapor phase Substances 0.000 claims abstract description 16
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 14
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims abstract description 13
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims abstract description 13
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 12
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 4
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 19
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 18
- 229910052698 phosphorus Inorganic materials 0.000 claims description 18
- 239000011574 phosphorus Substances 0.000 claims description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 17
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 17
- 230000002194 synthesizing effect Effects 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 229910017052 cobalt Inorganic materials 0.000 claims description 11
- 239000010941 cobalt Substances 0.000 claims description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 11
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 10
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 10
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 10
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 10
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 10
- 229910052787 antimony Inorganic materials 0.000 claims description 10
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 10
- 239000012736 aqueous medium Substances 0.000 claims description 10
- 229910052788 barium Inorganic materials 0.000 claims description 10
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052796 boron Inorganic materials 0.000 claims description 10
- 229910052791 calcium Inorganic materials 0.000 claims description 10
- 239000011575 calcium Substances 0.000 claims description 10
- 229910052804 chromium Inorganic materials 0.000 claims description 10
- 239000011651 chromium Substances 0.000 claims description 10
- 239000011777 magnesium Substances 0.000 claims description 10
- 229910052749 magnesium Inorganic materials 0.000 claims description 10
- 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 10
- 229910052758 niobium Inorganic materials 0.000 claims description 10
- 239000010955 niobium Substances 0.000 claims description 10
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 10
- 229910052700 potassium Inorganic materials 0.000 claims description 10
- 239000011591 potassium Substances 0.000 claims description 10
- 229910052711 selenium Inorganic materials 0.000 claims description 10
- 239000011669 selenium Substances 0.000 claims description 10
- 229910052709 silver Inorganic materials 0.000 claims description 10
- 239000004332 silver Substances 0.000 claims description 10
- 229910052715 tantalum Inorganic materials 0.000 claims description 10
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 10
- 229910052714 tellurium Inorganic materials 0.000 claims description 10
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052718 tin Inorganic materials 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 239000010936 titanium Substances 0.000 claims description 10
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 10
- 229910052721 tungsten Inorganic materials 0.000 claims description 10
- 239000010937 tungsten Substances 0.000 claims description 10
- 229910052725 zinc Inorganic materials 0.000 claims description 10
- 239000011701 zinc Substances 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 9
- 229910052720 vanadium Inorganic materials 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 229910052716 thallium Inorganic materials 0.000 claims description 8
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims description 8
- 229910052684 Cerium Inorganic materials 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052785 arsenic Inorganic materials 0.000 claims description 7
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 7
- 229910052792 caesium Inorganic materials 0.000 claims description 7
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 7
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052732 germanium Inorganic materials 0.000 claims description 7
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 7
- 239000011133 lead Substances 0.000 claims description 7
- 229910052701 rubidium Inorganic materials 0.000 claims description 7
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- 229910052712 strontium Inorganic materials 0.000 claims description 7
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical group [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 239000011593 sulfur Substances 0.000 claims description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052733 gallium Inorganic materials 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 4
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 2
- 150000002739 metals Chemical class 0.000 claims 1
- 239000002994 raw material Substances 0.000 description 22
- 239000007789 gas Substances 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 18
- 238000003756 stirring Methods 0.000 description 17
- 239000002002 slurry Substances 0.000 description 14
- 125000004429 atom Chemical group 0.000 description 13
- 239000012071 phase Substances 0.000 description 13
- 239000002609 medium Substances 0.000 description 10
- -1 phosphorus compound Chemical class 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000011964 heteropoly acid Substances 0.000 description 7
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 238000010304 firing Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
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- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 150000002736 metal compounds Chemical class 0.000 description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 4
- 125000004430 oxygen atom Chemical group O* 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
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- 150000001340 alkali metals Chemical class 0.000 description 2
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- 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 2
- 238000009826 distribution Methods 0.000 description 2
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- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229940000488 arsenic acid Drugs 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 235000010980 cellulose Nutrition 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 229940078035 curdlan Drugs 0.000 description 1
- 235000019316 curdlan Nutrition 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
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000002036 drum drying Methods 0.000 description 1
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- 238000001704 evaporation Methods 0.000 description 1
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- 239000000835 fiber Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 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
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008117 stearic acid Substances 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
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
【課題】不飽和アルデヒド及び不飽和カルボン酸、特に、メタクロレイン及びメタクリル酸を高収率で得られる触媒やその製造方法、これを用いた不飽和アルデヒド及び不飽和カルボン酸の製造方法を提供する。
【解決手段】プロピレン、イソブチレン、第三級ブチルアルコール又はメチル第三級ブチルエーテルを分子状酸素により気相接触酸化して不飽和アルデヒド及び不飽和カルボン酸を合成する際に用いる、少なくともモリブデン、ビスマス及び鉄を含む金属含有触媒の製造方法であって、少なくともモリブデン、ビスマス及び鉄を含む金属含有液を乾燥し金属含有粒子を得た後、得られた金属含有粒子の一部若しくは全部を、再度、乾燥して金属含有粒子を得る反復乾燥工程を、１回以上有する。
【選択図】なしProvided are a catalyst capable of obtaining an unsaturated aldehyde and an unsaturated carboxylic acid, particularly methacrolein and methacrylic acid in high yield, a method for producing the same, and a method for producing an unsaturated aldehyde and an unsaturated carboxylic acid using the same. .
At least molybdenum, bismuth, and bismuth used in the synthesis of unsaturated aldehyde and unsaturated carboxylic acid by vapor phase catalytic oxidation of propylene, isobutylene, tertiary butyl alcohol or methyl tertiary butyl ether with molecular oxygen. A method for producing a metal-containing catalyst containing iron, after drying a metal-containing liquid containing at least molybdenum, bismuth and iron to obtain metal-containing particles, a part or all of the obtained metal-containing particles are again It has one or more repeated drying steps to obtain metal-containing particles by drying.
[Selection figure] None
Description
本発明は、プロピレン、イソブチレンまたは第三級ブチルアルコール（以下、ＴＢＡという。）やメチル第三級ブチルエーテル（以下、ＭＴＢＥともいう）を分子状酸素を用いて気相接触酸化し、それぞれに対応する不飽和アルデヒド及び不飽和カルボン酸を合成する際に使用する金属成分含有触媒の製造方法や、得られる金属成分含有触媒、これを用いた不飽和アルデヒド及び不飽和カルボン酸の製造方法に関し、特に、メタクロレイン及びメタクリル酸を高収率で得ることができる金属成分含有触媒の製造方法や、得られる金属成分含有触媒、これを用いた不飽和アルデヒド及び不飽和カルボン酸の製造方法に関する。また、メタクロレインを分子状酸素を用いて気相接触酸化してメタクリル酸を高収率で得ることができる金属成分含有触媒の製造方法や、得られる金属成分含有触媒、これを用いたメタクリル酸の製造方法に関する。さらに、アクロレインを分子状酸素を用いて気相接触酸化してアクリル酸を高収率で得ることができる金属成分含有触媒の製造方法や、得られる金属成分含有触媒、これを用いたアクリル酸の製造方法に関する。 In the present invention, propylene, isobutylene, tertiary butyl alcohol (hereinafter referred to as TBA) or methyl tertiary butyl ether (hereinafter also referred to as MTBE) is vapor-phase catalytically oxidized using molecular oxygen, and corresponding to each. Regarding a method for producing a metal component-containing catalyst used in the synthesis of an unsaturated aldehyde and an unsaturated carboxylic acid, a metal component-containing catalyst to be obtained, and a method for producing an unsaturated aldehyde and an unsaturated carboxylic acid using the same, The present invention relates to a method for producing a metal component-containing catalyst capable of obtaining methacrolein and methacrylic acid in a high yield, a metal component-containing catalyst to be obtained, and a method for producing an unsaturated aldehyde and an unsaturated carboxylic acid using the same. Further, a method for producing a metal component-containing catalyst capable of obtaining methacrylic acid in high yield by gas-phase catalytic oxidation of methacrolein using molecular oxygen, an obtained metal component-containing catalyst, and methacrylic acid using the same It relates to the manufacturing method. Furthermore, a method for producing a metal component-containing catalyst capable of obtaining acrylic acid in a high yield by vapor-phase catalytic oxidation of acrolein with molecular oxygen, an obtained metal component-containing catalyst, and acrylic acid using the same It relates to a manufacturing method.
従来から、プロピレンを気相接触酸化してアクロレイン及びアクリル酸を製造する際に用いる触媒や、イソブチレン又はＴＢＡやＭＴＢＥ等を気相接触酸化してメタクロレイン及びメタクリル酸を製造する際に用いる触媒については、モリブデン、ビスマス、鉄等の酸化物が使用されている。これらの触媒は、モリブデン、ビスマス、鉄等の金属化合物を水性媒体等に溶解又は分散させ、これを加熱、焼成して水性媒体を除去して調製している。触媒性能の向上を図るため、触媒成分の金属を含有する混合水溶液又は水性スラリーを乾燥し粒子状とする際に、得られる乾燥物の含水率を０．３〜４％に調整した後、打錠成型する方法（特許文献１）が報告されている。 Conventionally, catalysts used for producing acrolein and acrylic acid by vapor-phase catalytic oxidation of propylene, and catalysts used for producing methacrolein and methacrylic acid by vapor-phase catalytic oxidation of isobutylene or TBA, MTBE, etc. Oxides such as molybdenum, bismuth and iron are used. These catalysts are prepared by dissolving or dispersing a metal compound such as molybdenum, bismuth, and iron in an aqueous medium or the like, and heating and baking it to remove the aqueous medium. In order to improve the catalyst performance, when the mixed aqueous solution or aqueous slurry containing the metal of the catalyst component is dried to form particles, the moisture content of the resulting dried product is adjusted to 0.3 to 4%, and then hit. A method of forming a tablet (Patent Document 1) has been reported.
また、メタクロレインを気相接触酸化してメタクリル酸を合成する際に用いる触媒として、モリブデン及びリン等を含むヘテロポリ酸系触媒が有効であることは公知である。ヘテロポリ酸系触媒は、金属化合物及びリン化合物等を水性媒体に溶解又は分散させ、これを加熱、焼成して水性媒体を除去して調製している。特に、触媒性能の向上を図るため、触媒成分のモリブデン、バナジウム、リン等を含有する混合水溶液又は水性スラリーを乾燥し粒子状とする際に、得られる乾燥物の含水率を０．５〜４％に調整した後、打錠成型する方法（特許文献２）が報告されている。 Further, it is known that a heteropolyacid catalyst containing molybdenum and phosphorus is effective as a catalyst used when synthesizing methacrylic acid by gas phase catalytic oxidation of methacrolein. The heteropolyacid catalyst is prepared by dissolving or dispersing a metal compound, a phosphorus compound, and the like in an aqueous medium, and heating and baking it to remove the aqueous medium. In particular, in order to improve the catalyst performance, when the mixed aqueous solution or aqueous slurry containing the catalyst components molybdenum, vanadium, phosphorus and the like is dried to form particles, the moisture content of the obtained dried product is 0.5-4. After adjusting to%, a method of tableting and molding (Patent Document 2) has been reported.
しかしながら、これらの方法で製造された触媒を用いた気相接触酸化反応においては、工業的生産に使用するにはメタクロレインやメタクリル酸の収率が不十分であり、これらが高収率で得られる触媒の開発が望まれている。
本発明の課題は、不飽和アルデヒド及び不飽和カルボン酸、特に、メタクロレイン及びメタクリル酸を高収率で得られる触媒やその製造方法、これを用いた不飽和アルデヒド及び不飽和カルボン酸の製造方法を提供することにある。また、メタクリル酸を高収率で得られる触媒やその製造方法、これを用いたメタクリル酸の製造方法を提供することにある。さらに、アクリル酸を高収率で得られる触媒やその製造方法、これを用いたアクリル酸の製造方法を提供することにある。 An object of the present invention is to provide a catalyst capable of obtaining unsaturated aldehydes and unsaturated carboxylic acids, particularly methacrolein and methacrylic acid in high yield, and a method for producing the same, and a method for producing unsaturated aldehydes and unsaturated carboxylic acids using the same. Is to provide. Another object of the present invention is to provide a catalyst for obtaining methacrylic acid in a high yield, a method for producing the catalyst, and a method for producing methacrylic acid using the catalyst. Furthermore, it is providing the catalyst which can obtain acrylic acid with a high yield, its manufacturing method, and the manufacturing method of acrylic acid using the same.
本発明者らは上記課題を解決すべく、鋭意研究を重ねた。その結果、触媒成分となるモリブデン等を含む金属成分含有液を調製し、これを乾燥し媒体を除去し金属成分含有粒子を得た後、その全部又は一部の金属成分含有粒子を再度、乾燥し金属成分含有粒子とすることを反復することにより、高収率で不飽和アルデヒド及び不飽和カルボン酸、又はメタクリル酸、又はアクリル酸を得ることができることを見出し本発明を完成するに至った。 The inventors of the present invention have made extensive studies to solve the above problems. As a result, after preparing a metal component-containing liquid containing molybdenum or the like as a catalyst component, drying this to remove the medium to obtain metal component-containing particles, all or some of the metal component-containing particles are again dried. It has been found that unsaturated aldehydes and unsaturated carboxylic acids, methacrylic acid, or acrylic acid can be obtained in high yields by repeating the formation of metal component-containing particles, and the present invention has been completed.
即ち、本発明は、プロピレン、イソブチレン、第三級ブチルアルコール又はメチル第三級ブチルエーテルを分子状酸素により気相接触酸化して不飽和アルデヒド及び不飽和カルボン酸を合成する際に用いる、少なくともモリブデン、ビスマス及び鉄を含む金属成分含有触媒の製造方法であって、少なくともモリブデン、ビスマス及び鉄を含む金属成分含有液を乾燥し金属成分含有粒子を得た後、得られた金属成分含有粒子の一部若しくは全部を、再度、乾燥して金属成分含有粒子を得る反復乾燥工程を１回以上有することを特徴とする金属成分含有触媒の製造方法に関する。 That is, the present invention uses at least molybdenum, which is used when synthesizing an unsaturated aldehyde and an unsaturated carboxylic acid by vapor-phase catalytic oxidation of propylene, isobutylene, tertiary butyl alcohol or methyl tertiary butyl ether with molecular oxygen. A method for producing a metal component-containing catalyst containing bismuth and iron, wherein at least a metal component-containing liquid containing at least molybdenum, bismuth and iron is dried to obtain metal component-containing particles, and then part of the obtained metal component-containing particles Alternatively, the present invention relates to a method for producing a metal component-containing catalyst characterized by having a repeated drying step for drying the whole again to obtain metal component-containing particles one or more times.
また、本発明は、メタクロレインを分子状酸素により気相接触酸化してメタクリル酸を合成する際に用いる、少なくともモリブデン及びリンを含む金属成分含有触媒の製造方法であって、少なくともモリブデン及びリンを含む金属成分含有液を乾燥し金属成分含有粒子を得た後、得られた金属成分粒子の一部若しくは全部を、再度、乾燥して金属成分含有粒子を得る反復乾燥工程を１回以上有することを特徴とする金属成分含有触媒の製造方法に関する。 The present invention also relates to a method for producing a metal component-containing catalyst containing at least molybdenum and phosphorus, which is used when synthesizing methacrylic acid by vapor-phase catalytic oxidation of methacrolein with molecular oxygen. The metal component-containing liquid is dried to obtain metal component-containing particles, and then a part or all of the obtained metal component particles are dried again to have a repeated drying step of obtaining metal component-containing particles one or more times. The present invention relates to a method for producing a metal component-containing catalyst.
さらに、本発明は、アクロレインを分子状酸素により気相接触酸化してアクリル酸を合成する際に用いる、少なくともモリブデン及びバナジウムを含む金属成分含有触媒の製造方法であって、少なくともモリブデン及びバナジウムを含む金属成分含有液を乾燥し金属成分含有粒子を得た後、得られた金属成分含有粒子の一部若しくは全部を、再度、乾燥して金属成分含有粒子を得る反復乾燥工程を１回以上有することを特徴とする金属含有触媒の製造方法に関する。 Furthermore, the present invention is a method for producing a metal component-containing catalyst containing at least molybdenum and vanadium, which is used when synthesizing acrylic acid by vapor-phase catalytic oxidation of acrolein with molecular oxygen, comprising at least molybdenum and vanadium. After the metal component-containing liquid is dried to obtain the metal component-containing particles, a part or all of the obtained metal component-containing particles are dried again to have one or more repeated drying steps to obtain the metal component-containing particles. The present invention relates to a method for producing a metal-containing catalyst.
また、本発明は、上記金属成分含有触媒の製造方法により製造された金属成分含有触媒であって、原子の組成式（１）
ＭｏaＢｉbＦｅcＭdＸeＹfＺgＳｉhＯi （１）
（式中、Ｍはコバルト又はニッケルの１種または２種を示し、Ｘはクロム、鉛、マンガン、カルシウム、マグネシウム、ニオブ、銀、バリウム、スズ、タンタル又は亜鉛のいずれか１種または２種以上を示し、Ｙはリン、ホウ素、硫黄、セレン、テルル、セリウム、タングステン、アンチモン又はチタンのいずれか１種または２種以上を示し、Ｚはリチウム、ナトリウム、カリウム、ルビジウム、セシウム又はタリウムのいずれか１種または２種以上を示し、ａ〜ｉは各原子の組成比を示し、ａが１２のとき、ｂは０．０１〜３、ｃは０．０１〜５、ｄは１〜１２、ｅは０〜８、ｆは０〜５、ｇは０．００１〜２、ｈは０〜２０を示し、ｉは金属原子全体の原子価を満足するのに必要な酸素原子比を示す。）で表される組成を有することを特徴とする金属成分含有触媒に関する。
The present invention also provides a metal component-containing catalyst produced by the above-described method for producing a metal component-containing catalyst, the atomic composition formula (1)
Mo a Bi b Fe c M d X e Y f Z g Si h O i (1)
(In the formula, M represents one or two of cobalt or nickel, and X represents one or more of chromium, lead, manganese, calcium, magnesium, niobium, silver, barium, tin, tantalum or zinc. Y represents phosphorus, boron, sulfur, selenium, tellurium, cerium, tungsten, antimony or titanium, and Z represents any of lithium, sodium, potassium, rubidium, cesium or thallium 1 type or 2 types or more are shown, ai shows the composition ratio of each atom, when a is 12, b is 0.01-3, c is 0.01-5, d is 1-12, e Is 0 to 8, f is 0 to 5, g is 0.001 to 2, h is 0 to 20, and i is an oxygen atomic ratio necessary to satisfy the valence of the entire metal atom. It has a composition represented by It relates to a metal component-containing catalysts.
また、本発明は、上記金属成分含有触媒の製造方法により製造された金属成分含有触媒であって、原子の組成式（２）
ＭｏaＰbＣｕcＶdＡeＢfＯg （２）
（式中、Ａはカリウム、ルビシウム、セシウム、又はタリウムのいずれか１種または２種以上を示し、Ｂは鉄、コバルト、ニッケル、亜鉛、マグネシウム、カルシウム、ストロンチウム、バリウム、チタン、クロム、タングステン、マンガン、銀、ホウ素、ケイ素、アルミニウム、ガリウム、ゲルマニウム、スズ、鉛、ヒ素、アンチモン、ビスマス、ニオブ、タンタル、ジルコニウム、インジウム、イオウ、セレン、テルル、ランタン、又はセリウムのいずれか１種または２種以上を示し、ａ〜ｇは各原子の組成比を示し、ａが１２のとき、ｂは０．１〜３、ｃは０．０１〜３、ｄは０．０１〜３、ｅは０．０１〜３、ｆは０〜３、ｇは金属原子全体の原子価を満足するのに必要な酸素原子比を示す。）で表される組成を有することを特徴とする金属成分含有触媒に関する。
The present invention also provides a metal component-containing catalyst produced by the above-described method for producing a metal component-containing catalyst, wherein the atomic composition formula (2)
Mo a P b Cu c V d A e B f O g (2)
(In the formula, A represents one or more of potassium, rubidium, cesium, or thallium, and B represents iron, cobalt, nickel, zinc, magnesium, calcium, strontium, barium, titanium, chromium, tungsten, One or two of manganese, silver, boron, silicon, aluminum, gallium, germanium, tin, lead, arsenic, antimony, bismuth, niobium, tantalum, zirconium, indium, sulfur, selenium, tellurium, lanthanum, or cerium In the above, a to g represent the composition ratio of each atom. When a is 12, b is 0.1 to 3, c is 0.01 to 3, d is 0.01 to 3, e is 0.3. 0 to 3; f is 0 to 3; and g is an oxygen atomic ratio necessary to satisfy the valence of the entire metal atom. That relates to a metal component-containing catalyst.
さらに、本発明は、上記金属成分含有触媒の製造方法により製造された金属成分含有触媒であって、原子の組成式（３）
ＭｏaＶbＧcＤdＥeＯf （３）
（式中、Ｇは鉄、コバルト、クロム、アルミニウム、又はストロンチウムのいずれか１種または２種以上を示し、Ｄはゲルマニウム、ホウ素、ヒ素、セレン、銀、ケイ素、ナトリウム、テルル、リチウム、アンチモン、リン、カリウム、又はバリウムのいずれか１種または２種以上を示し、Ｅはマグネシウム、チタン、マンガン、銅、亜鉛、ジルコニウム、ニオブ、タングステン、タンタル、カルシウム、スズ、又はビスマスのいずれか１種または２種以上を示す。ａ〜ｆは各原子の組成比を示し、ａが１２のときｂは０．０１〜６、ｃは０〜５、ｄは０〜１０、ｅは０〜５であり、ｆは金属原子全体の原子価を満足するのに必要な酸素原子比を示す。）で表される組成を有することを特徴とする金属成分含有触媒に関する。
Furthermore, the present invention is a metal component-containing catalyst produced by the above-described method for producing a metal component-containing catalyst, comprising an atomic composition formula (3)
Mo a V b G c D d E e O f (3)
(In the formula, G represents one or more of iron, cobalt, chromium, aluminum, or strontium, D represents germanium, boron, arsenic, selenium, silver, silicon, sodium, tellurium, lithium, antimony, One or more of phosphorus, potassium, or barium is shown, and E is any one of magnesium, titanium, manganese, copper, zinc, zirconium, niobium, tungsten, tantalum, calcium, tin, or bismuth, or A to f represent the composition ratio of each atom, and when a is 12, b is 0.01 to 6, c is 0 to 5, d is 0 to 10, e is 0 to 5. , F represents an oxygen atomic ratio necessary to satisfy the valence of the entire metal atom.), And relates to a metal component-containing catalyst characterized by having a composition represented by:
また、本発明は、上記金属成分含有触媒を用いることを特徴とする不飽和アルデヒド及び不飽和カルボン酸の製造方法や、メタクリル酸、アクリル酸の製造方法に関する。 Moreover, this invention relates to the manufacturing method of unsaturated aldehyde and unsaturated carboxylic acid characterized by using the said metal component containing catalyst, and the manufacturing method of methacrylic acid, acrylic acid.
本発明の金属含有触媒の製造方法によれば、プロピレン、イソブチレン、ＴＢＡやＭＴＢＥを分子状酸素により気相接触酸化することにより不飽和アルデヒド及び不飽和カルボン酸を高収率で得ることができる金属成分含有触媒を得ることができ、特に、メタクロレイン及びメタクリル酸を高収率で得ることができる。また、メタクロレインを分子状酸素により気相接触酸化することによりメタクリル酸を高収率で得られる。さらに、アクロレインを分子状酸素により気相接触酸化することによりアクリル酸を高収率で得られる。 According to the method for producing a metal-containing catalyst of the present invention, a metal capable of obtaining an unsaturated aldehyde and an unsaturated carboxylic acid in a high yield by subjecting propylene, isobutylene, TBA or MTBE to gas phase catalytic oxidation with molecular oxygen. A component-containing catalyst can be obtained, and in particular, methacrolein and methacrylic acid can be obtained in high yield. Further, methacrylic acid can be obtained in high yield by subjecting methacrolein to vapor phase catalytic oxidation with molecular oxygen. Furthermore, acrylic acid can be obtained in high yield by subjecting acrolein to vapor phase catalytic oxidation with molecular oxygen.
本発明の金属含有触媒の製造方法は、プロピレン、イソブチレン、第三級ブチルアルコール又はメチル第三級ブチルエーテルを分子状酸素により気相接触酸化して不飽和アルデヒド及び不飽和カルボン酸を合成する際に用いる、少なくともモリブデン、ビスマス及び鉄を含む金属成分含有触媒の製造方法であって、少なくともモリブデン、ビスマス及び鉄を含む金属成分含有液を乾燥し金属成分含有粒子を得た後、得られた金属成分含有粒子の一部若しくは全部を、再度、乾燥して金属成分含有粒子を得る反復乾燥工程を、１回以上有することを特徴とする。 The method for producing a metal-containing catalyst of the present invention comprises synthesizing an unsaturated aldehyde and an unsaturated carboxylic acid by vapor-phase catalytic oxidation of propylene, isobutylene, tertiary butyl alcohol or methyl tertiary butyl ether with molecular oxygen. A method for producing a metal component-containing catalyst containing at least molybdenum, bismuth and iron to be used, the metal component-containing liquid containing at least molybdenum, bismuth and iron being dried to obtain metal component-containing particles, and then the obtained metal component It is characterized by having one or more repeated drying steps in which part or all of the contained particles are dried again to obtain metal component-containing particles.
本発明の金属成分含有触媒の製造方法において、製造の対象である金属成分含有触媒は少なくとも、モリブデン、ビスマス及び鉄を含むものである。かかる金属成分含有触媒としては、更に、コバルト、ニッケルや、アルカリ金属、タリウム等を含有することが好ましい。具体的には、原子の組成式（１）
ＭｏaＢｉbＦｅcＭdＸeＹfＺgＳｉhＯi （１）
で表される組成物であることが、高収率で不飽和アルデヒド及び不飽和カルボン酸を得られるため好ましい。式（１）中、Ｍはコバルト若しくはニッケルの何れか１種又は２種を示す。Ｘは、クロム、鉛、マンガン、カルシウム、マグネシウム、ニオブ、銀、バリウム、スズ、タンタル、又は亜鉛の何れか１種、又は２種以上を示す。Ｙは、リン、ホウ素、硫黄、セレン、テルル、セリウム、タングステン、アンチモン、又はチタンの何れか１種又は２種以上を示す。Ｚは、リチウム、ナトリウム、カリウム、ルビジウム、セシウム、又はタリウムの何れか１種又は２種以上を示す。更に、ａ〜ｉは原子組成比を示し、ａが１２のとき、ｂは０．０１〜３、ｃは０．０１〜５、ｄは１〜１２、ｅは０〜８、ｆは０〜５、ｇは０．００１〜２、ｈは０〜２０であり、ｉは金属原子全体の原子価を満足するのに必要な酸素原子比を示す。
In the method for producing a metal component-containing catalyst of the present invention, the metal component-containing catalyst to be produced contains at least molybdenum, bismuth and iron. The metal component-containing catalyst preferably further contains cobalt, nickel, alkali metal, thallium and the like. Specifically, atomic composition formula (1)
Mo a Bi b Fe c M d X e Y f Z g Si h O i (1)
It is preferable that an unsaturated aldehyde and an unsaturated carboxylic acid can be obtained in a high yield. In the formula (1), M represents one or two of cobalt and nickel. X represents one or more of chromium, lead, manganese, calcium, magnesium, niobium, silver, barium, tin, tantalum, or zinc. Y represents one or more of phosphorus, boron, sulfur, selenium, tellurium, cerium, tungsten, antimony, or titanium. Z represents one or more of lithium, sodium, potassium, rubidium, cesium, and thallium. Further, a to i represent an atomic composition ratio. When a is 12, b is 0.01 to 3, c is 0.01 to 5, d is 1 to 12, e is 0 to 8, and f is 0 to 0. 5, g is 0.001-2, h is 0-20, i represents the oxygen atom ratio required to satisfy the valence of the entire metal atom.
本発明の金属成分含有触媒の製造方法において、少なくともモリブデン、ビスマス及び鉄を含む金属成分含有液を乾燥し金属成分含有粒子を得た後、得られた金属成分含有粒子の一部若しくは全部を、再度、乾燥して金属成分含有粒子を得る反復乾燥工程を、１回以上有する。 In the method for producing a metal component-containing catalyst of the present invention, after drying a metal component-containing liquid containing at least molybdenum, bismuth and iron to obtain metal component-containing particles, a part or all of the obtained metal component-containing particles are obtained. The drying process is repeated once to obtain the metal component-containing particles once or more.
少なくともモリブデン、ビスマス及び鉄を含む金属成分含有液の調製には、媒体としては水性媒体を用いることが好ましい。水性媒体としては、水の他、エチルアルコール等の低級アルコール、アセトン等でもよく、水と低級アルコール、アセトン等の混合物でもよいが、水が好ましい。媒質としては、少なくともモリブデン、ビスマス及び鉄を含むものであり、原子の組成式（１）中に含まれる金属成分等を含有することが好ましい。これらの金属成分は硝酸塩、炭酸塩、酢酸塩、アンモニウム塩、酸化物、ハロゲン化物等として、これらを適宜組み合わせて使用することができる。具体的には、モリブデンとしては、例えば、パラ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、塩化モリブデン等を使用することができる。ビスマスとしては、例えば、硝酸ビスマス、酸化ビスマス等を使用することができ、鉄としては、例えば、硝酸第二鉄、水酸化鉄、三酸化鉄等を使用することができ、リンとしては、例えば、リン酸、五酸化リン、リン酸アンモニウム等を使用することができる。 For the preparation of the metal component-containing liquid containing at least molybdenum, bismuth and iron, an aqueous medium is preferably used as the medium. The aqueous medium may be water, a lower alcohol such as ethyl alcohol, acetone or the like, or a mixture of water and a lower alcohol, acetone or the like, but water is preferred. The medium contains at least molybdenum, bismuth and iron, and preferably contains a metal component or the like contained in the atomic composition formula (1). These metal components can be used in appropriate combinations as nitrates, carbonates, acetates, ammonium salts, oxides, halides, and the like. Specifically, as molybdenum, for example, ammonium paramolybdate, molybdenum trioxide, molybdic acid, molybdenum chloride, or the like can be used. As bismuth, for example, bismuth nitrate, bismuth oxide, and the like can be used. As iron, for example, ferric nitrate, iron hydroxide, iron trioxide, and the like can be used, and as phosphorus, for example, Phosphoric acid, phosphorus pentoxide, ammonium phosphate, and the like can be used.
上記金属成分含有液は、これらの金属成分を溶解した溶液であっても、分散した分散液、スラリーであってもよい。金属成分含有液中の液成分の含有量は、２０〜９０質量％であることが好ましい。 The metal component-containing liquid may be a solution in which these metal components are dissolved, or a dispersed dispersion or slurry. It is preferable that content of the liquid component in a metal component containing liquid is 20-90 mass%.
上記金属成分含有液の調製には、上記媒体に上記金属塩等を適宜混合して調製することができ、例えば、共沈法、酸化物混合法等によることができ、攪拌装置を使用することができる。かかる装置としては、流体を入れる容器（攪拌槽）と流体をかき混ぜる可動部（攪拌翼）から構成される装置であり、加熱手段を有するものであってもよい。その形式は、例えば攪拌槽は円筒皿底、オートクレーブなど、攪拌翼はパドル翼（多段翼を含む）、大型翼など一般的に用いられるものを用いることができる。 The metal component-containing liquid can be prepared by appropriately mixing the metal salt and the like in the medium. For example, a coprecipitation method, an oxide mixing method, or the like can be used, and a stirrer is used. Can do. Such an apparatus is an apparatus including a container (stirring tank) for storing a fluid and a movable part (stirring blade) for stirring the fluid, and may include a heating unit. As for the type, for example, a generally used thing such as a cylindrical dish bottom and an autoclave for a stirring tank, a paddle blade (including a multistage blade), a large blade, etc. can be used as a stirring blade.
金属成分含有液の好ましい調製方法としては、具体的には、モリブデン酸化物やパラモリブデン酸アンモニウム等の上記モリブデン化合物を水に懸濁させた後に、その他の金属化合物を混合する。その他の金属化合物は、固体で、または、水性媒体等に適宜溶解または懸濁させて混合してもよい。金属成分含有液は、これらの媒質を混合中または混合後にアンモニア、ヒドラジン、ヒドロキシルアミン等のアルカリを用い、ｐＨを調整することもできる。金属成分含有液のｐＨとしては、例えば、０．５〜１０とすることができる。ｐＨが低いほど活性が高い触媒となる。 As a preferred method for preparing the metal component-containing liquid, specifically, the molybdenum compound such as molybdenum oxide or ammonium paramolybdate is suspended in water, and then the other metal compound is mixed. Other metal compounds may be mixed in solid form or appropriately dissolved or suspended in an aqueous medium or the like. The pH of the metal component-containing liquid can be adjusted by using an alkali such as ammonia, hydrazine, or hydroxylamine during or after mixing these media. As pH of a metal component containing liquid, it can be set as 0.5-10, for example. The lower the pH, the higher the activity of the catalyst.
このようにして得られた金属成分含有液を乾燥し金属成分含有粒子を得る方法としては、その含有液を加熱して媒体を揮発させ濃縮し、乾燥する方法を挙げることができる。濃縮、乾燥には、金属成分含有液の調製に用いた同じ攪拌槽を使用し、電気ヒーターや蒸気等の熱源を用いて金属成分含有液を収納する攪拌槽等を、例えば、５０℃〜１２０℃、好ましくは９０℃〜１１０℃に加熱して行うことができる。また、金属成分含有液を濃縮した後、更に媒体を揮発させ金属成分含有粒子を得るには、金属成分含有液の調製に用いた攪拌装置と異なる装置を使用することもでき、具体的には、後述する連続乾燥装置、不連続乾燥装置を問わず公知の装置を使用することもできる。 Examples of the method for drying the metal component-containing liquid thus obtained to obtain metal component-containing particles include a method of heating the liquid to volatilize and concentrate the medium, followed by drying. For the concentration and drying, the same stirring tank used for the preparation of the metal component-containing liquid is used, and a stirring tank for storing the metal component-containing liquid using a heat source such as an electric heater or steam, for example, 50 ° C to 120 ° C. It can be carried out by heating to a temperature of 90 ° C, preferably 90 ° C to 110 ° C. In addition, after concentrating the metal component-containing liquid, in order to further volatilize the medium to obtain metal component-containing particles, an apparatus different from the stirring apparatus used for the preparation of the metal component-containing liquid can be used. A known apparatus can be used regardless of a continuous drying apparatus or a discontinuous drying apparatus described later.
このような乾燥により金属成分含有液の媒体を揮発させ金属成分含有粒子を得る。金属成分含有液の媒体が水性媒体の場合、この最初の乾燥により得られる金属成分含有粒子中に残留する水の含有量が５質量％以下であることが好ましく、４質量％以下であることがより好ましい。 By such drying, the medium of the metal component-containing liquid is volatilized to obtain metal component-containing particles. When the medium of the metal component-containing liquid is an aqueous medium, the content of water remaining in the metal component-containing particles obtained by the first drying is preferably 5% by mass or less, and preferably 4% by mass or less. More preferred.
得られた金属成分含有粒子を再度、乾燥する反復乾燥工程においては、金属成分含有液を乾燥して得られた金属成分含有粒子の一部若しくは全量について行う。金属成分含有液の乾燥により得られた金属成分含有粒子のうち、反復乾燥に供する金属成分含有粒子としては、具体的には、最初の乾燥により得られた金属成分含有粒子全量であることが最も好ましいが、金属成分含有粒子全量に対し、１０質量％以上であることが好ましく、より好ましくは２０質量％以上である。 In the repeated drying step of drying the obtained metal component-containing particles again, a part or all of the metal component-containing particles obtained by drying the metal component-containing liquid is performed. Among the metal component-containing particles obtained by drying the metal component-containing liquid, the metal component-containing particles used for repeated drying are specifically the total amount of metal component-containing particles obtained by the first drying. Although it is preferable, it is preferable that it is 10 mass% or more with respect to the metal component containing particle whole quantity, More preferably, it is 20 mass% or more.
反復乾燥工程としては、金属成分含有粒子を、そのまま加熱することにより、残留する媒体の除去を行う方法が好ましい。金属成分含有液の媒体が水性媒体の場合、反復乾燥工程により得られる金属成分含有粒子中に残留する水の含有量が、１質量％以下となるまで行うことが好ましく、０．８質量％以下まで行うことがより好ましい。金属成分含有粒子中の水の含有量が１質量％以下であれば、性能の優れた触媒を得ることがきる。反復乾燥を一部の金属成分含有粒子について行った場合、得られた金属成分含有粒子と、反復乾燥を行っていない金属成分含有粒子とをよく混合することが好ましい。 As the repeated drying step, a method of removing the remaining medium by heating the metal component-containing particles as they are is preferable. When the medium of the metal component-containing liquid is an aqueous medium, it is preferable to carry out until the content of water remaining in the metal component-containing particles obtained by the repeated drying step is 1% by mass or less, and 0.8% by mass or less. Is more preferable. If the content of water in the metal component-containing particles is 1% by mass or less, a catalyst having excellent performance can be obtained. When repeated drying is performed on some of the metal component-containing particles, it is preferable that the obtained metal component-containing particles are well mixed with the metal component-containing particles that have not been repeatedly dried.
ここで、金属成分含有粒子中の水の含有量は、赤外線分水計等の水分量測定装置により測定した値を採用することができる。 Here, as the water content in the metal component-containing particles, a value measured by a water content measuring device such as an infrared water meter can be adopted.
反復乾燥工程は得られる金属成分含有粒子中の含水量が１質量％以下になるまで、１回以上、何度行ってもよい。このように反復乾燥工程を経て得られる金属成分含有粒子は、反復乾燥工程を経ないものと比較して、不飽和アルデヒド及び不飽和カルボン酸を高収率で得ることがき、特にメタクロレイン及びメタクリル酸を高収率で得ることができる。この理由としては、定かではないが、触媒表面の成分の分布、触媒粒子内の細孔構造が変化するためと考えられる。 The repeated drying step may be performed once or more times until the water content in the obtained metal component-containing particles is 1% by mass or less. In this way, the metal component-containing particles obtained through the repeated drying step can obtain unsaturated aldehydes and unsaturated carboxylic acids in a higher yield than those not subjected to the repeated drying steps, particularly methacrolein and methacrylic acid. The acid can be obtained in high yield. The reason for this is not clear, but is thought to be because the distribution of components on the catalyst surface and the pore structure in the catalyst particles change.
上記反復乾燥工程において使用可能な乾燥装置としては、連続乾燥装置、不連続乾燥装置を問わず公知の装置を挙げることができる。具体的には、噴霧乾燥法、気流乾燥法、ドラム乾燥法などの連続乾燥装置、必要量だけ別の容器に移液する箱型乾燥法、蒸発乾固法などの不連続乾燥装置を挙げることができる。 As a drying apparatus that can be used in the repeated drying step, a known apparatus can be used regardless of whether it is a continuous drying apparatus or a discontinuous drying apparatus. Specific examples include continuous drying equipment such as spray drying, airflow drying, drum drying, etc., box drying that transfers only the required amount to another container, and discontinuous drying equipment such as evaporation to dryness. Can do.
乾燥温度は特に限定されないが、１００℃〜５００℃が好ましく、１１０℃〜４００℃がより好ましい。乾燥時間は特に限定されず、連続の場合は原料の供給が続く限り連続して乾燥してもよいし、短い時間で乾燥を断続的に行ってもよいが、連続的に運転するほうが安定した乾燥には好ましい。具体的には、金属成分含有粒子の材質により適宜選択することができ、例えば、１回の反復乾燥時間として、０．１〜４８時間等を挙げることができ、０．３〜２４時間がより好ましい。 Although drying temperature is not specifically limited, 100 to 500 degreeC is preferable and 110 to 400 degreeC is more preferable. The drying time is not particularly limited. In the case of continuous drying, as long as the supply of raw materials continues, drying may be performed continuously, or drying may be performed intermittently in a short time, but continuous operation is more stable. Preferred for drying. Specifically, it can be selected as appropriate depending on the material of the metal component-containing particles. For example, the time for repeated drying can be 0.1 to 48 hours, and more preferably 0.3 to 24 hours. preferable.
得られる金属成分含有粒子の粒子径は、スラリー調製条件や乾燥方法および条件によって異なるが、通常は０．１〜３００μｍとなる。 The particle diameter of the obtained metal component-containing particles varies depending on the slurry preparation conditions, the drying method and the conditions, but is usually 0.1 to 300 μm.
得られた金属成分含有粒子は予め目的とする形状に成形し、得られた成形物を焼成することができる。金属成形含有粒子の焼成は、金属成分含有粒子中に残留する硝酸塩等を分解し、含有する金属を酸化物に形成する。金属成分含有粒子の焼成は３００〜５００℃で行うことができ、好ましくは３００〜４５０℃である。焼成は、空気等の酸素含有ガス流通下および／または不活性ガス流通下で行うことができる。焼成時間は０．５時間以上が好ましく、より好ましくは１〜４０時間である。 The obtained metal component-containing particles can be formed into a desired shape in advance, and the obtained molded product can be fired. The firing of the metal-forming-containing particles decomposes nitrates and the like remaining in the metal component-containing particles, and forms the contained metal into an oxide. The firing of the metal component-containing particles can be performed at 300 to 500 ° C, preferably 300 to 450 ° C. Calcination can be performed under a flow of oxygen-containing gas such as air and / or under a flow of inert gas. The firing time is preferably 0.5 hours or more, more preferably 1 to 40 hours.
成形は、上記反復乾燥工程で得られた金属成分含有粒子を焼成する前に行うことが好ましいが、上記反復工程で得られた金属成分含有粒子の焼成後に行ってもよい。成形は金属成分含有粒子又はその焼成物を、例えば、打錠成形、押出成形、造粒等の成形方法を用いることができる。成形に際しては、比表面積、細孔容積および細孔分布の揃った成形物を再現性よく製造するため、また、成形物の機械的強度を高める等の目的で添加剤を添加してもよい。添加剤としては、具体的に、硫酸バリウム、硫酸アンモニウム等の無機塩類、グラファイト等の滑剤、セルロース類、でんぷん、ポリビニルアルコール、ステアリン酸等の有機物、シリカゾル、アルミナゾル等の水酸化物ゾル、ウィスカー、ガラス繊維、炭素繊維等の無機質繊維等を用いることができる。触媒成形物の形状としては、例えば、球状、円柱状、リング状、板状等を挙げることができる。 The molding is preferably performed before firing the metal component-containing particles obtained in the repeated drying step, but may be performed after firing the metal component-containing particles obtained in the repeated step. For molding, the metal component-containing particles or the fired product thereof can be used, for example, by a molding method such as tableting, extrusion, or granulation. In molding, an additive may be added for the purpose of producing a molded product having a uniform specific surface area, pore volume and pore distribution with good reproducibility, and for the purpose of increasing the mechanical strength of the molded product. Specific examples of additives include inorganic salts such as barium sulfate and ammonium sulfate, lubricants such as graphite, organic substances such as celluloses, starch, polyvinyl alcohol and stearic acid, hydroxide sols such as silica sol and alumina sol, whiskers and glass Inorganic fibers such as fibers and carbon fibers can be used. Examples of the shape of the catalyst molded product include a spherical shape, a cylindrical shape, a ring shape, and a plate shape.
本発明の金属成分含有触媒は上記製造方法により得られたものであり、原子の組成式（１）で表される組成を有するものである。 The metal component-containing catalyst of the present invention is obtained by the above production method and has a composition represented by the atomic composition formula (1).
また、本発明の不飽和アルデヒド及び不飽和カルボン酸の製造方法は、上記金属成分含有触媒を用いることを特徴とする。上記金属成分含有触媒の存在下、原料のプロピレン、イソブチレン、ＴＢＡ又はＭＴＢＥを分子状酸素により気相接触酸化させて行う。かかる反応は、触媒を充填した管式反応器を使用することが好ましく、多管式反応器を用いることもできる。 Moreover, the manufacturing method of the unsaturated aldehyde and unsaturated carboxylic acid of this invention uses the said metal component containing catalyst, It is characterized by the above-mentioned. In the presence of the metal component-containing catalyst, the raw material propylene, isobutylene, TBA or MTBE is subjected to gas phase catalytic oxidation with molecular oxygen. For this reaction, a tubular reactor filled with a catalyst is preferably used, and a multitubular reactor can also be used.
原料ガスの分子状酸素としては、空気を用いるのが工業的に有利であるが、必要に応じて純酸素を混合して用いることもできる。原料ガスは、窒素、炭酸ガス等の不活性ガス、水蒸気等で希釈して使用することが経済的である。原料ガス中のプロピレン等の濃度は広い範囲で変えることができ、例えば、１〜２０容量％とすることができ、好ましくは３〜１０容量％である。原料ガス中のプロピレン等と酸素とのモル比は、１：０．４〜４の範囲が好ましく、特に１：０．５〜３の範囲が好ましい。反応器中に充填する上記金属成分含有触媒は、必要に応じてシリカ、アルミナ、シリカ−アルミナ、マグネシア、チタニア、シリコンカーバイト等の不活性物質で希釈して用いることもできる。 Although it is industrially advantageous to use air as the molecular oxygen of the source gas, pure oxygen can be mixed and used as necessary. It is economical to use the source gas diluted with an inert gas such as nitrogen or carbon dioxide, water vapor or the like. The concentration of propylene or the like in the raw material gas can be varied within a wide range, and can be, for example, 1 to 20% by volume, preferably 3 to 10% by volume. The molar ratio between propylene and the like in the raw material gas and oxygen is preferably in the range of 1: 0.4 to 4, particularly preferably in the range of 1: 0.5 to 3. The metal component-containing catalyst charged in the reactor can be diluted with an inert substance such as silica, alumina, silica-alumina, magnesia, titania, silicon carbide, etc., if necessary.
気相接触反応における反応圧力は大気圧〜５気圧が好ましく、より好ましくは大気圧〜３気圧である。反応温度は２００〜４５０℃が好ましく、より好ましくは２５０〜４００℃である。原料ガスと触媒の接触時間は１．５〜１５秒が好ましく、より好ましくは２〜７秒である。 The reaction pressure in the gas phase contact reaction is preferably atmospheric pressure to 5 atmospheric pressure, more preferably atmospheric pressure to 3 atmospheric pressure. 200-450 degreeC of reaction temperature is preferable, More preferably, it is 250-400 degreeC. The contact time between the raw material gas and the catalyst is preferably 1.5 to 15 seconds, more preferably 2 to 7 seconds.
このような気相接触酸化反応において、本発明の金属成分含有触媒の製造方法により得られる金属成分含有触媒を用いることにより、プロピレンを原料としてアクロレイン及びアクリル酸を、イソブチレン、ＴＢＡ、ＭＴＢＥを原料としてメタクロレイン及びメタクリル酸を高収率で合成することができ、特に、メタクロレイン及びメタクリル酸を高収率で得ることができる。 In such a gas phase catalytic oxidation reaction, by using the metal component-containing catalyst obtained by the method for producing a metal component-containing catalyst of the present invention, acrolein and acrylic acid are used as raw materials, and isobutylene, TBA, and MTBE are used as raw materials. Methacrolein and methacrylic acid can be synthesized in a high yield, and in particular, methacrolein and methacrylic acid can be obtained in a high yield.
また、本発明の他の金属成分含有触媒の製造方法は、メタクロレインを分子状酸素により気相接触酸化してメタクリル酸を合成する際に用いる、少なくともモリブデン及びリンを含む金属成分含有触媒の製造方法であって、少なくともモリブデン及びリンを含む金属成分含有液を乾燥し金属成分含有粒子を得た後、得られた金属成分含有粒子の一部若しくは全部を、再度、乾燥して金属含有粒子を得る反復乾燥工程を、１回以上有することを特徴とする。あるいは、本発明の他の金属成分含有触媒の製造方法は、アクロレインを分子状酸素により気相接触酸化してアクリル酸を合成する際に用いる、少なくともモリブデン及びバナジウムを含む金属成分含有触媒の製造方法であって、少なくともモリブデン及びバナジウムを含む金属成分含有液を乾燥し金属成分含有粒子を得た後、得られた金属成分含有粒子の一部若しくは全部を、再度、乾燥して金属含有粒子を得る反復乾燥工程を、１回以上有することを特徴とする。 Another method for producing a metal component-containing catalyst according to the present invention is the production of a metal component-containing catalyst containing at least molybdenum and phosphorus, which is used when synthesizing methacrylic acid by vapor-phase catalytic oxidation of methacrolein with molecular oxygen. A method comprising drying a metal component-containing liquid containing at least molybdenum and phosphorus to obtain metal component-containing particles, and then drying part or all of the obtained metal component-containing particles again to obtain metal-containing particles. It is characterized by having one or more repeated drying steps. Alternatively, another metal component-containing catalyst production method of the present invention is a method for producing a metal component-containing catalyst containing at least molybdenum and vanadium, which is used when synthesizing acrylic acid by vapor-phase catalytic oxidation of acrolein with molecular oxygen. The metal component-containing liquid containing at least molybdenum and vanadium is dried to obtain metal component-containing particles, and then part or all of the obtained metal component-containing particles are dried again to obtain metal-containing particles. It has the repeated drying process once or more.
本発明の他の金属成分含有触媒の製造方法において、製造の対象である金属成分含有触媒は少なくとも、モリブデン及びリンを含むものである。かかる金属含有触媒としては、更に、カリウム、ルビジウム、セシウム、タリウム等のアルカリ金属を含んでいることが好ましく、さらにこれ以外に、銅、バナジウム、鉄、コバルト、ニッケル、亜鉛、マグネシウム、カルシウム、ストロンチウム、バリウム、チタン、クロム、タングステン、マンガン、銀、ホウ素、ケイ素、アルミニウム、ガリウム、ゲルマニウム、スズ、鉛、ヒ素、アンチモン、ビスマス、ニオブ、タンタル、ジルコニウム、インジウム、イオウ、セレン、テルル、ランタン、セリウム等を含有することが好ましい。具体的には、原子の組成式（２）
ＭｏaＰbＣｕcＶdＡeＢfＯg （２）
で表される組成物であることが、高収率でメタクリル酸を得られるため好ましい。式（２）中、Ａはカリウム、ルビシウム、セシウム、又はタリウムのいずれか１種または２種以上を示し、Ｂは鉄、コバルト、ニッケル、亜鉛、マグネシウム、カルシウム、ストロンチウム、バリウム、チタン、クロム、タングステン、マンガン、銀、ホウ素、ケイ素、アルミニウム、ガリウム、ゲルマニウム、スズ、鉛、ヒ素、アンチモン、ビスマス、ニオブ、タンタル、ジルコニウム、インジウム、イオウ、セレン、テルル、ランタン、又はセリウムのいずれか１種または２種以上を示し、ａ〜ｇは各原子の組成比を示し、ａが１２のとき、ｂは０．１〜３、ｃは０．０１〜３、ｄは０．０１〜３、ｅは０．０１〜３、ｆは０〜３、ｇは金属原子全体の原子価を満足するのに必要な酸素原子比を示す。このような金属成分含有触媒には、上記金属のヘテロポリ酸若しくはヘテロポリ酸塩、又はこれらの双方を含むことが好ましい。金属含有粒子が、複合酸化物であること、ヘテロポリ酸やその塩を含むことはＸ線回折装置（ＸＲＤ）により確認することができる。
In the method for producing another metal component-containing catalyst of the present invention, the metal component-containing catalyst to be produced contains at least molybdenum and phosphorus. Such a metal-containing catalyst preferably further contains an alkali metal such as potassium, rubidium, cesium, thallium, etc. In addition to this, copper, vanadium, iron, cobalt, nickel, zinc, magnesium, calcium, strontium , Barium, titanium, chromium, tungsten, manganese, silver, boron, silicon, aluminum, gallium, germanium, tin, lead, arsenic, antimony, bismuth, niobium, tantalum, zirconium, indium, sulfur, selenium, tellurium, lanthanum, cerium Etc. are preferably contained. Specifically, atomic composition formula (2)
Mo a P b Cu c V d A e B f O g (2)
The composition represented by the formula is preferred because methacrylic acid can be obtained in a high yield. In formula (2), A represents one or more of potassium, rubidium, cesium, or thallium, and B represents iron, cobalt, nickel, zinc, magnesium, calcium, strontium, barium, titanium, chromium, Tungsten, manganese, silver, boron, silicon, aluminum, gallium, germanium, tin, lead, arsenic, antimony, bismuth, niobium, tantalum, zirconium, indium, sulfur, selenium, tellurium, lanthanum, or cerium 2 or more types are shown, ag shows the composition ratio of each atom, when a is 12, b is 0.1-3, c is 0.01-3, d is 0.01-3, e is 0.01 to 3, f is 0 to 3, and g is an oxygen atomic ratio necessary to satisfy the valence of the entire metal atom. Such a metal component-containing catalyst preferably contains a heteropolyacid or heteropolyacid salt of the above metal or both of them. It can be confirmed by an X-ray diffractometer (XRD) that the metal-containing particles are a complex oxide and contain a heteropolyacid or a salt thereof.
本発明の他の金属成分含有触媒の製造方法において、製造の対象である金属成分含有触媒は少なくとも、モリブデン及びバナジウムを含むものであり、原子の組成式（３）
ＭｏaＶbＧcＤdＥeＯf （３）
で表される組成物は、高収率でアクリル酸を得られるため好ましい。式（３）中、Ｇは鉄、コバルト、クロム、アルミニウム、又はストロンチウムのいずれか１種または２種以上を示し、Ｄはゲルマニウム、ホウ素、ヒ素、セレン、銀、ケイ素、ナトリウム、テルル、リチウム、アンチモン、リン、カリウム、又はバリウムのいずれか１種または２種以上を示し、Ｅはマグネシウム、チタン、マンガン、銅、亜鉛、ジルコニウム、ニオブ、タングステン、タンタル、カルシウム、スズ又はビスマスのいずれか１種または２種以上を示し、ａ〜ｆは各元素の原子比率を表し、ａが１２のときｂは０．０１〜６、ｃは０〜５、ｄは０〜１０、ｅは０〜５であり、ｆは金属原子全体の原子価を満足するのに必要な酸素原子比を示す。
In the method for producing another metal component-containing catalyst of the present invention, the metal component-containing catalyst to be produced contains at least molybdenum and vanadium, and the atomic composition formula (3)
Mo a V b G c D d E e O f (3)
Is preferable because acrylic acid can be obtained in a high yield. In formula (3), G represents one or more of iron, cobalt, chromium, aluminum, or strontium, D represents germanium, boron, arsenic, selenium, silver, silicon, sodium, tellurium, lithium, One or more of antimony, phosphorus, potassium, or barium is shown, and E is any one of magnesium, titanium, manganese, copper, zinc, zirconium, niobium, tungsten, tantalum, calcium, tin, or bismuth. Or 2 or more types are shown, af represents the atomic ratio of each element, when a is 12, b is 0.01-6, c is 0-5, d is 0-10, e is 0-5. And f represents the oxygen atom ratio necessary to satisfy the valence of the entire metal atom.
本発明のメタクロレインを原料としメタクリル酸を合成する際に用いる金属成分含有触媒の製造方法の具体的方法としては、モリブデン及びリンを含有する、好ましくは原子の組成式（２）で表される組成の金属成分等を含有する金属成分含有液を用いる他は、上記飽和アルデヒド及び不飽和カルボン酸を合成する金属成分含有触媒の製造方法の具体的方法と同様の方法を挙げることができる。 A specific method for producing a metal component-containing catalyst used when synthesizing methacrylic acid using methacrolein of the present invention as a raw material contains molybdenum and phosphorus, and is preferably represented by an atomic composition formula (2). The method similar to the specific method of the manufacturing method of the metal component containing catalyst which synthesize | combines the said saturated aldehyde and unsaturated carboxylic acid can be mentioned except using the metal component containing liquid containing the metal component etc. of a composition.
また、本発明のメタクロレインを原料としメタクリル酸を合成する際に用いる金属成分含有触媒は、上記金属成分含有触媒の製造方法により製造された金属成分含有触媒であって、原子の組成式（２）で表される組成を有するものである。 The metal component-containing catalyst used when synthesizing methacrylic acid using the methacrolein of the present invention as a raw material is a metal component-containing catalyst produced by the above-described method for producing a metal component-containing catalyst, and comprises an atomic composition formula (2 ).
また、本発明のメタクリル酸の製造方法は、上記金属成分含有触媒を用いることを特徴とする。メタクリル酸の製造方法の具体的方法としては、原料にメタクロレインを使用する他は、上記不飽和アルデヒド及び不飽和カルボン酸の製造方法の具体的方法と同様の方法を挙げることができる。また、原料のメタクロレインには、水、低級飽和アルデヒド等の不純物が少量含まれている場合があるが、このようなメタクロレイン由来の不純物は、分子状酸素との反応に実質的に影響を与えることはなく、収率の低下を抑制することができる。 Moreover, the manufacturing method of methacrylic acid of this invention uses the said metal component containing catalyst. Specific methods for producing methacrylic acid include the same methods as the specific methods for producing unsaturated aldehydes and unsaturated carboxylic acids except that methacrolein is used as a raw material. In addition, the raw material methacrolein may contain a small amount of impurities such as water and lower saturated aldehyde, but such methacrolein-derived impurities substantially affect the reaction with molecular oxygen. It does not give, and the fall of a yield can be suppressed.
本発明のアクロレインを原料としアクリル酸を合成する際に用いる金属成分含有触媒の製造方法の具体的方法としては、モリブデン及びリンを含有する、好ましくは原子の組成式（３）で表される組成の金属成分等を含有する金属成分含有液を用いる他は、上記飽和アルデヒド及び不飽和カルボン酸を合成する金属成分含有触媒の製造方法の具体的方法と同様の方法を挙げることができる。 As a specific method for producing a metal component-containing catalyst used when synthesizing acrylic acid using acrolein of the present invention as a raw material, a composition containing molybdenum and phosphorus, preferably represented by an atomic composition formula (3). Other than using the metal component-containing liquid containing the above metal components and the like, the same method as the specific method for producing the metal component-containing catalyst for synthesizing the saturated aldehyde and unsaturated carboxylic acid can be exemplified.
更に、本発明のアクロレインを原料としアクリル酸を合成する際に用いる金属成分含有触媒は、上記金属成分含有触媒の製造方法により製造された金属成分含有触媒であって、原子の組成式（３）で表される組成を有するものである。 Furthermore, the metal component-containing catalyst used when synthesizing acrylic acid using the acrolein of the present invention as a raw material is a metal component-containing catalyst produced by the above-described method for producing a metal component-containing catalyst, and the atomic composition formula (3) It has a composition represented by these.
また、本発明のアクリル酸の製造方法は、上記金属成分含有触媒を用いることを特徴とする。アクリル酸の製造方法の具体的方法としては、原料にアクロレインを使用する他は、上記不飽和アルデヒド及び不飽和カルボン酸の製造方法の具体的方法と同様の方法を挙げることができる。また、原料のアクロレインには、水、低級飽和アルデヒド等の不純物が少量含まれている場合があるが、このようなアクロレイン由来の不純物は、分子状酸素との反応に実質的に影響を与えることはなく、収率の低下を抑制することができる。 Moreover, the manufacturing method of acrylic acid of this invention uses the said metal component containing catalyst. As a specific method for producing acrylic acid, there can be mentioned the same method as the specific method for producing unsaturated aldehyde and unsaturated carboxylic acid except that acrolein is used as a raw material. In addition, the raw material acrolein may contain a small amount of impurities such as water and lower saturated aldehydes, but such acrolein-derived impurities may substantially affect the reaction with molecular oxygen. No reduction in yield can be suppressed.
以下、本発明の金属成分含有触媒の製造方法を具体的に説明するが、本発明の技術的範囲は以下の実施例に限定されるものではない。以下、実施例において「部」は「質量部」を示す。 Hereinafter, although the manufacturing method of the metal component containing catalyst of this invention is demonstrated concretely, the technical scope of this invention is not limited to a following example. Hereinafter, in the examples, “part” means “part by mass”.
原料ガスおよび生成物の分析はガスクロマトグラフィーによる。 Source gas and product analysis is by gas chromatography.
原料（オレフィン、ＴＢＡ、ＭＴＢＥ又はメタクロレイン）の反応率、生成する不飽和アルデヒドと不飽和カルボン酸の選択率、生成する不飽和アルデヒド及び不飽和カルボン酸の合計収率（以下、合計収率という。）は次式により算出した。 Reaction rate of raw materials (olefin, TBA, MTBE or methacrolein), selectivity of unsaturated aldehyde and unsaturated carboxylic acid to be produced, total yield of unsaturated aldehyde and unsaturated carboxylic acid to be produced (hereinafter referred to as total yield) .) Was calculated by the following equation.
反応率（％）＝Ｍｒ／Ｍｓ×１００、
不飽和アルデヒドの選択率（％）＝（Ｐａ／Ｍｒ）×１００、
不飽和カルボン酸の選択率（％）＝（Ｐｃ／Ｍｒ）×１００、
合計収率（％）＝｛（Ｐａ＋Ｐｃ）／Ｍｓ｝×１００。
Reaction rate (%) = Mr / Ms × 100,
Unsaturated aldehyde selectivity (%) = (Pa / Mr) × 100,
Unsaturated carboxylic acid selectivity (%) = (Pc / Mr) × 100,
Total yield (%) = {(Pa + Pc) / Ms} × 100.
式中、Ｍｒは反応したプロピレン、イソブチレン、ＴＢＡ、ＭＴＢＥ又はメタクロレインのモル数、Ｍｓは供給したプロピレン、イソブチレン、ＴＢＡ、ＭＴＢＥ又はメタクロレインのモル数、Ｐａは生成した不飽和アルデヒドのモル数、Ｐｃは生成した不飽和カルボン酸のモル数である。 In the formula, Mr is the number of moles of reacted propylene, isobutylene, TBA, MTBE or methacrolein, Ms is the number of moles of supplied propylene, isobutylene, TBA, MTBE or methacrolein, Pa is the number of moles of the unsaturated aldehyde produced, Pc is the number of moles of the unsaturated carboxylic acid produced.
金属成分含有粒子中の水の含有量は、赤外線水分計（（株）Kett科学研究所製FD−６００）により金属成分含有粒子約１０ｇを９０℃、３０分測定することにより求めた。
［実施例１］
［触媒の調製］
攪拌槽に純水と、純水１０００部に対してパラモリブデン酸アンモニウム５００部、パラタングステン酸アンモニウム６．２部、硝酸セシウム２３．０部、三酸化アンチモン２４．０部及び三酸化ビスマス３３．０部を加え、加熱攪拌した（Ａ液）。別の攪拌槽に、純水１０００部に対して硝酸第二鉄２０９．８部、硝酸ニッケル７５．５部、硝酸コバルト４５３．３部および硝酸鉛３１．３部を順次加え、溶解した（Ｂ液）。ついで、Ａ液にＢ液を加えて水性スラリーとして、このスラリーを１０１℃まで加熱し、濃縮を行った。
The water content in the metal component-containing particles was determined by measuring about 10 g of the metal component-containing particles at 90 ° C. for 30 minutes with an infrared moisture meter (FD-600, manufactured by Kett Scientific Laboratory).
[Example 1]
[Preparation of catalyst]
Pure water in a stirring tank, 500 parts of ammonium paramolybdate, 6.2 parts of ammonium paratungstate, 23.0 parts of cesium nitrate, 24.0 parts of antimony trioxide, and bismuth trioxide 33. 0 parts were added, and it heated and stirred (A liquid). In another stirring tank, 209.8 parts of ferric nitrate, 75.5 parts of nickel nitrate, 453.3 parts of cobalt nitrate, and 31.3 parts of lead nitrate were sequentially added to 1000 parts of pure water and dissolved (B liquid). Next, liquid B was added to liquid A to form an aqueous slurry, which was heated to 101 ° C. and concentrated.
次いで、この濃縮スラリーを噴霧乾燥機にて乾燥した。乾燥は入口熱風温度３００℃、出口温度１２０〜１３０℃でロータリーアトマイザー回転数１５，０００ｒｐｍの条件で行い、サイクロン１箇所で金属成分含有粒子を回収した。得られた金属成分含有粒子中の水含有量は、１．２質量％であった。この金属成分含有粒子全量を回収し、全量金属バット上に移して、箱型乾燥機中１４５℃、１２時間再乾燥し、最終的な金属成分含有粒子を得た。最終乾燥粉体中に含有される水分は０．９質量％であった。 Subsequently, this concentrated slurry was dried with a spray dryer. Drying was performed under conditions of an inlet hot air temperature of 300 ° C. and an outlet temperature of 120 to 130 ° C. and a rotary atomizer rotating speed of 15,000 rpm, and the metal component-containing particles were collected at one cyclone. The water content in the obtained metal component-containing particles was 1.2% by mass. The total amount of the metal component-containing particles was collected, transferred to a metal vat, and re-dried in a box dryer at 145 ° C. for 12 hours to obtain final metal component-containing particles. The moisture contained in the final dry powder was 0.9% by mass.
このようにして得られた最終金属成分含有粒子５００部に対してヒドロキシプロピルメチルセルロース２０部およびカードラン５部を添加した後、よく乾式混合した。この混合物と純水１９０部を双腕式ニーダーに投入し、粘土状物質になるまで混練を行った。得られた粘土状物質を押出成形機により、外形５ｍｍ、内径２ｍｍ、平均長さ５ｍｍのリング状に成形し、空気流通下１１０℃の熱風乾燥機を用いて乾燥後、４００℃にて３時間焼成して触媒成形体を得た。得られた触媒成形体の酸素以外の原子の組成は、Ｍｏ12Ｗ0.1Ｂｉ0.6Ｆｅ2.2Ｓｂ0.7Ｎｉ1.1Ｃｏ6.6Ｐｂ0.4Ｃｓ0.6であった。 After adding 20 parts of hydroxypropyl methylcellulose and 5 parts of curdlan to 500 parts of the final metal component-containing particles obtained in this manner, the mixture was thoroughly dry-mixed. This mixture and 190 parts of pure water were put into a double-arm kneader and kneaded until a clay-like substance was obtained. The obtained clay-like substance was formed into a ring shape having an outer diameter of 5 mm, an inner diameter of 2 mm, and an average length of 5 mm by an extrusion molding machine, dried using a hot air dryer at 110 ° C. under air flow, and then at 400 ° C. for 3 hours. Calcination was performed to obtain a catalyst molded body. The composition of the atoms other than oxygen in the obtained catalyst compact was Mo 12 W 0.1 Bi 0.6 Fe 2.2 Sb 0.7 Ni 1.1 Co 6.6 Pb 0.4 Cs 0.6 .
［不飽和アルデヒド及び不飽和カルボン酸の調製］
この触媒成形体を反応管に充填し、イソブチレン５％、酸素１２％、水蒸気１０％、窒素７３％（容量％）の混合ガスを、大気圧下、反応温度３４０℃、接触時間３．６秒で通じてイソブチレンの気相接触酸化反応を行った。原料の反応率、生成する不飽和アルデヒドと不飽和カルボン酸の選択率、生成物の合計収率を求めた。結果を表１に示す。
[Preparation of unsaturated aldehyde and unsaturated carboxylic acid]
The catalyst compact was filled into a reaction tube, and a mixed gas of 5% isobutylene, 12% oxygen, 10% water vapor, and 73% nitrogen (volume%) under atmospheric pressure, a reaction temperature of 340 ° C., and a contact time of 3.6 seconds. The gas phase catalytic oxidation reaction of isobutylene was carried out. The reaction rate of the raw material, the selectivity of the unsaturated aldehyde and unsaturated carboxylic acid to be produced, and the total yield of the product were determined. The results are shown in Table 1.
［比較例１］
実施例１と同じ条件で調製した濃縮スラリーを噴霧乾燥機にて乾燥を行い、得られた金属成分含有粒子の再乾燥を行わず、実施例１と同様にして触媒成形体を成形し、これを用いてイソブチレンの気相接触酸化反応を行った。原料の反応率、生成する不飽和アルデヒドと不飽和カルボン酸の選択率、生成物の合計収率を求めた。結果を表１に示す。
[Comparative Example 1]
The concentrated slurry prepared under the same conditions as in Example 1 was dried with a spray dryer, and the resulting metal component-containing particles were not re-dried, and a catalyst molded body was molded in the same manner as in Example 1. Was used for the gas phase catalytic oxidation of isobutylene. The reaction rate of the raw material, the selectivity of the unsaturated aldehyde and unsaturated carboxylic acid to be produced, and the total yield of the product were determined. The results are shown in Table 1.
［実施例２］
攪拌槽に純水２００部を投入し９０ｒｐｍで攪拌を開始した（以下、濃縮終了まで攪拌を継続した）。そこへパラモリブデン酸アンモニウム１００部を溶解し、さらにメタバナジン酸アンモニウム３．４部、８５質量％リン酸水溶液６．６部を純水３０部に溶解した溶液を加え、１０分間攪拌を続けた。ここに、三酸化アンチモン２．１部、硝酸銅１．１部を純水３０部に溶解した溶液及び６０％砒酸水溶液２．２部を純水１０部に溶解した溶液を順次加え、これを攪拌しながら９０℃まで加熱し、液温を９０℃に保ちつつ５時間加熱攪拌した。その後、硝酸セシウム９．２部を純水１００部に溶解した溶液をこれに加え１５分間攪拌してスラリーを得た。このスラリーを１０１℃まで加熱し、攪拌しながら濃縮を行なった。
[Example 2]
200 parts of pure water was put into the stirring tank and stirring was started at 90 rpm (hereinafter, stirring was continued until the concentration was completed). Thereto, 100 parts of ammonium paramolybdate was dissolved, and a solution prepared by dissolving 3.4 parts of ammonium metavanadate and 6.6 parts of 85 mass% phosphoric acid aqueous solution in 30 parts of pure water was added, and stirring was continued for 10 minutes. A solution prepared by dissolving 2.1 parts of antimony trioxide, 1.1 parts of copper nitrate in 30 parts of pure water and a solution of 2.2 parts of a 60% aqueous arsenic acid solution in 10 parts of pure water were sequentially added thereto. The mixture was heated to 90 ° C. with stirring, and stirred for 5 hours while maintaining the liquid temperature at 90 ° C. Thereafter, a solution obtained by dissolving 9.2 parts of cesium nitrate in 100 parts of pure water was added thereto and stirred for 15 minutes to obtain a slurry. The slurry was heated to 101 ° C. and concentrated with stirring.
次いで、この濃縮スラリーを噴霧乾燥機にて乾燥した。乾燥は入口熱風温度２５０℃、出口温度１１０〜１２０℃でロータリーアトマイザー回転数２０，０００ｒｐｍの条件で行い、サイクロン１箇所で金属成分含有粒子を回収した。得られた金属成分含有粒子中の水含有量は１．０質量％であった。この金属成分含有粒子全量を回収し、全量金属バット上に移して、箱型乾燥機中１３０℃、１２時間再乾燥し最終的な金属成分含有粒子を得た。 Subsequently, this concentrated slurry was dried with a spray dryer. Drying was performed under conditions of an inlet hot air temperature of 250 ° C. and an outlet temperature of 110 to 120 ° C. and a rotary atomizer rotating speed of 20,000 rpm, and the metal component-containing particles were collected at one cyclone. The water content in the obtained metal component-containing particles was 1.0% by mass. The total amount of the metal component-containing particles was collected, transferred to a metal vat, and re-dried in a box dryer at 130 ° C. for 12 hours to obtain final metal component-containing particles.
このようにして得られた最終金属成分含有粒子１００部に対してグラファイト２部を添加した後、打錠成形機により、外形５ｍｍ、内径２ｍｍ、長さ５ｍｍのリング状に成形し、空気流通下３８０℃にて６時間焼成して触媒成形体を得た。得られた触媒成形体は、酸素原子以外の原子の組成が、Ｐ1.2Ｍｏ12Ｖ0.6Ｃｕ0.1Ｓｂ0.3Ａｓ0.2Ｃｓ1なるヘテロポリ酸およびその塩を含む酸化物であった。 After adding 2 parts of graphite to 100 parts of the final metal component-containing particles thus obtained, it was molded into a ring shape having an outer diameter of 5 mm, an inner diameter of 2 mm, and a length of 5 mm by a tableting machine. A catalyst molded body was obtained by calcination at 380 ° C. for 6 hours. The obtained catalyst molded body was an oxide containing a heteropolyacid having a composition of atoms other than oxygen atoms of P 1.2 Mo 12 V 0.6 Cu 0.1 Sb 0.3 As 0.2 Cs 1 and a salt thereof.
この触媒を反応管に充填し、メタクロレイン５％、酸素１０％、水蒸気３０％、窒素５５％（容量％）の混合ガスを、大気圧下、反応温度２８５℃、接触時間３．６秒で通じてメタクロレインの気相接触酸化反応を行った。原料の反応率、生成するメタクリル酸の選択率、生成物の収率を求めた。結果を表２に示す。 The catalyst was charged into a reaction tube, and a mixed gas of 5% methacrolein, 10% oxygen, 30% water vapor, and 55% nitrogen (volume%) was applied at atmospheric pressure, reaction temperature of 285 ° C., and contact time of 3.6 seconds. A gas phase catalytic oxidation reaction of methacrolein was performed. The reaction rate of the raw materials, the selectivity of methacrylic acid to be produced, and the yield of the product were determined. The results are shown in Table 2.
［比較例２］
実施例２と同じ条件で調製した濃縮スラリーを噴霧乾燥機にて乾燥を行い、得られた金属成分含有粒子を、再乾燥を行わずに用いて、実施例２と同様にして触媒成形体を成形し、これを用いてメタクロレインの気相接触酸化反応を行った。原料の反応率、生成するメタクリル酸の選択率、生成物の収率を求めた。結果を表２に示す。
[Comparative Example 2]
A concentrated slurry prepared under the same conditions as in Example 2 was dried with a spray dryer, and the resulting metal component-containing particles were used without re-drying, and a catalyst molded body was obtained in the same manner as in Example 2. Molding was performed and a gas phase catalytic oxidation reaction of methacrolein was performed. The reaction rate of the raw materials, the selectivity of methacrylic acid to be produced, and the yield of the product were determined. The results are shown in Table 2.
［実施例３］
攪拌槽に純水４００部を投入し、そこへ三酸化モリブデン１００部、８５質量％リン酸水溶液７．３部、五酸化バナジウム３．２部、酸化銅０．５部、酸化鉄０．２部、硝酸セリウム２．５部を加え、９５℃で５時間加熱攪拌を行った。この液を５０℃まで冷却した後、硝酸セシウム１１．３部を純水３０部に溶解した溶液を滴下し１５分間攪拌した。次いでこの液を７０℃に昇温し、２９質量％アンモニア水３７．４部を滴下し、５０℃で１５分間攪拌した。さらにこのスラリーを１０１℃まで加熱し、濃縮を行った。
[Example 3]
400 parts of pure water was put into a stirring tank, into which 100 parts of molybdenum trioxide, 7.3 parts of 85 mass% phosphoric acid aqueous solution, 3.2 parts of vanadium pentoxide, 0.5 parts of copper oxide, 0.2 parts of iron oxide were added. And 2.5 parts of cerium nitrate were added, and the mixture was heated and stirred at 95 ° C. for 5 hours. After cooling this solution to 50 ° C., a solution prepared by dissolving 11.3 parts of cesium nitrate in 30 parts of pure water was added dropwise and stirred for 15 minutes. Subsequently, this liquid was heated up to 70 degreeC, 37.4 parts of 29 mass% ammonia water was dripped, and it stirred at 50 degreeC for 15 minutes. The slurry was further heated to 101 ° C. and concentrated.
調製した濃縮スラリーをドラム乾燥機にて乾燥を行い、ドラム本体とドラム下部の２箇所で金属成分含有粒子を回収した。ドラム本体から回収した金属成分含有粒子（全金属成分含有粒子の９０質量％）の水分は０．４質量％であった。また、ドラム下部より回収した金属成分含有粒子（全金属成分含有粒子の１０質量％）の水分は７．５質量％であった。 The prepared concentrated slurry was dried with a drum dryer, and metal component-containing particles were collected at two locations, the drum body and the drum lower part. The water content of the metal component-containing particles recovered from the drum body (90% by mass of all metal component-containing particles) was 0.4% by mass. Moreover, the water | moisture content of the metal component containing particle (10 mass% of all the metal component containing particles) collect | recovered from the drum lower part was 7.5 mass%.
ドラム本体から回収した金属成分含有粒子はそのままポリエチレン製ビニール袋で保持し、ドラム下部から回収した金属成分含有粒子を箱型乾燥機中１３０℃で１２時間再度乾燥し、再乾燥金属成分含有粒子を得た。得られた再乾燥金属成分含有粒子とドラム本体から回収した金属成分含有粒子とを混合し最終金属成分含有粒子とした。最終金属成分含有粒子中に含有される水分は０．５質量％であった。 The metal component-containing particles recovered from the drum body are held in a polyethylene plastic bag as they are, and the metal component-containing particles recovered from the bottom of the drum are dried again at 130 ° C. for 12 hours in a box-type dryer. Obtained. The obtained re-dried metal component-containing particles and the metal component-containing particles recovered from the drum body were mixed to obtain final metal component-containing particles. The moisture contained in the final metal component-containing particles was 0.5% by mass.
このようにして得られた金属成分含有粒子１００部に対してヒドロキシプロピルセルロース３部及びエチルアルコール３０部を添加した後、双腕式ニーダーで混練を行った。得られた粘土状物質を押出成形機により、外形５ｍｍ、長さ５ｍｍの円柱状に成形し、空気流通下３７０℃にて１２時間焼成して触媒成形体を得た。得られた触媒成形体は、酸素原子以外の原子の組成が、Ｐ1.1Ｍｏ12Ｖ0.6Ｃｕ0.1Ｆｅ0.05Ｃｅ0.1Ｃｓ1.0なるヘテロポリ酸及びその塩を含む酸化物であった。 After adding 3 parts of hydroxypropyl cellulose and 30 parts of ethyl alcohol to 100 parts of the metal component-containing particles thus obtained, kneading was performed using a double-arm kneader. The obtained clay-like substance was molded into a cylindrical shape having an outer diameter of 5 mm and a length of 5 mm by an extrusion molding machine, and calcined at 370 ° C. for 12 hours under an air flow to obtain a catalyst molded body. The obtained catalyst compact was an oxide containing a heteropolyacid having a composition of atoms other than oxygen atoms of P 1.1 Mo 12 V 0.6 Cu 0.1 Fe 0.05 Ce 0.1 Cs 1.0 and a salt thereof.
この触媒を用いてメタクロレインの気相接触酸化反応を行った。原料の反応率、生成するメタクリル酸の選択率、生成物の収率を求めた。結果を表２に示す。 Using this catalyst, methacrolein was subjected to a gas phase catalytic oxidation reaction. The reaction rate of the raw materials, the selectivity of methacrylic acid to be produced, and the yield of the product were determined. The results are shown in Table 2.
［比較例３］
実施例３と同じ条件で調製した濃縮スラリーをドラム乾燥機にて乾燥を行い、得られた金属成分含有粒子を、箱型乾燥機で再乾燥を行わずに用いて、実施例３と同様にして触媒成形体を成形し、これを用いてメタクロレインの気相接触酸化反応を行った。原料の反応率、生成するメタクリル酸の選択率、生成物の収率を求めた。結果を表２に示す。
[Comparative Example 3]
The concentrated slurry prepared under the same conditions as in Example 3 was dried in a drum dryer, and the obtained metal component-containing particles were used in the same manner as in Example 3 without re-drying in a box-type dryer. Then, a catalyst molded body was molded, and a gas phase catalytic oxidation reaction of methacrolein was performed using the molded catalyst body. The reaction rate of the raw materials, the selectivity of methacrylic acid to be produced, and the yield of the product were determined. The results are shown in Table 2.
結果からも、本発明の金属含有触媒の製造方法により得られる触媒を用いることにより、不飽和アルデヒド及び不飽和カルボン酸を高収率で得られ、特にメタクロレイン及びメタクリル酸、又はメタクリル酸を高収率で得ることができる。 From the results, it is also possible to obtain unsaturated aldehydes and unsaturated carboxylic acids in high yields by using the catalyst obtained by the method for producing a metal-containing catalyst of the present invention, particularly high methacrolein and methacrylic acid or methacrylic acid. The yield can be obtained.
Claims (10)
少なくともモリブデン、ビスマス及び鉄を含む金属成分含有液を乾燥し金属成分含有粒子を得た後、
得られた金属成分含有粒子の一部若しくは全部を、再度、乾燥して金属成分含有粒子を得る反復乾燥工程を１回以上有することを特徴とする金属成分含有触媒の製造方法。 Metals containing at least molybdenum, bismuth and iron for use in the synthesis of unsaturated aldehydes and unsaturated carboxylic acids by vapor phase catalytic oxidation of propylene, isobutylene, tertiary butyl alcohol or methyl tertiary butyl ether with molecular oxygen A method for producing a component-containing catalyst comprising:
After drying the metal component-containing liquid containing at least molybdenum, bismuth and iron to obtain metal component-containing particles,
A method for producing a metal component-containing catalyst, comprising one or more repeated drying steps in which part or all of the obtained metal component-containing particles are dried again to obtain metal component-containing particles.
少なくともモリブデン及びリンを含む金属成分含有液を乾燥し金属成分含有粒子を得た後、
得られた金属成分含有粒子の一部若しくは全部を、再度、乾燥して金属成分含有粒子を得る反復乾燥工程を１回以上有することを特徴とする金属含有触媒の製造方法。 A method for producing a metal component-containing catalyst containing at least molybdenum and phosphorus, which is used for synthesizing methacrylic acid by vapor-phase catalytic oxidation of methacrolein to molecular oxygen,
After drying the metal component-containing liquid containing at least molybdenum and phosphorus to obtain metal component-containing particles,
A method for producing a metal-containing catalyst, comprising one or more repeated drying steps in which part or all of the obtained metal component-containing particles are dried again to obtain metal component-containing particles.
ＭｏaＢｉbＦｅcＭdＸeＹfＺgＳｉhＯi （１）
（式中、Ｍはコバルト又はニッケルの１種または２種を示し、Ｘはクロム、鉛、マンガン、カルシウム、マグネシウム、ニオブ、銀、バリウム、スズ、タンタル又は亜鉛のいずれか１種または２種以上を示し、Ｙはリン、ホウ素、硫黄、セレン、テルル、セリウム、タングステン、アンチモン又はチタンのいずれか１種または２種以上を示し、Ｚはリチウム、ナトリウム、カリウム、ルビジウム、セシウム又はタリウムのいずれか１種または２種以上を示し、ａ〜ｉは各原子の組成比を示し、ａが１２のとき、ｂは０．０１〜３、ｃは０．０１〜５、ｄは１〜１２、ｅは０〜８、ｆは０〜５、ｇは０．００１〜２、ｈは０〜２０を示し、ｉは金属原子全体の原子価を満足するのに必要な酸素原子比を示す。） A metal component-containing catalyst produced by the method for producing a metal component-containing catalyst according to claim 1, wherein the metal has a composition represented by an atomic composition formula (1). Component-containing catalyst.
Mo a Bi b Fe c M d X e Y f Z g Si h O i (1)
(In the formula, M represents one or two of cobalt or nickel, and X represents one or more of chromium, lead, manganese, calcium, magnesium, niobium, silver, barium, tin, tantalum or zinc. Y represents phosphorus, boron, sulfur, selenium, tellurium, cerium, tungsten, antimony or titanium, and Z represents any of lithium, sodium, potassium, rubidium, cesium or thallium 1 type or 2 types or more are shown, ai shows the composition ratio of each atom, when a is 12, b is 0.01-3, c is 0.01-5, d is 1-12, e Is 0 to 8, f is 0 to 5, g is 0.001 to 2, h is 0 to 20, and i is an oxygen atomic ratio necessary to satisfy the valence of the entire metal atom.)
ＭｏaＰbＣｕcＶdＡeＢfＯg （２）
（式中、Ａはカリウム、ルビシウム、セシウム、又はタリウムのいずれか１種または２種以上を示し、Ｂは鉄、コバルト、ニッケル、亜鉛、マグネシウム、カルシウム、ストロンチウム、バリウム、チタン、クロム、タングステン、マンガン、銀、ホウ素、ケイ素、アルミニウム、ガリウム、ゲルマニウム、スズ、鉛、ヒ素、アンチモン、ビスマス、ニオブ、タンタル、ジルコニウム、インジウム、イオウ、セレン、テルル、ランタン、又はセリウムのいずれか１種または２種以上を示し、ａ〜ｇは各原子の組成比を示し、ａが１２のとき、ｂは０．１〜３、ｃは０．０１〜３、ｄは０．０１〜３、ｅは０．０１〜３、ｆは０〜３、ｇは金属原子全体の原子価を満足するのに必要な酸素原子比を示す。） A metal component-containing catalyst produced by the method for producing a metal component-containing catalyst according to claim 2 or 4, wherein the catalyst has a composition represented by a composition formula (2) of atoms. .
Mo a P b Cu c V d A e B f O g (2)
(In the formula, A represents one or more of potassium, rubidium, cesium, or thallium, and B represents iron, cobalt, nickel, zinc, magnesium, calcium, strontium, barium, titanium, chromium, tungsten, One or two of manganese, silver, boron, silicon, aluminum, gallium, germanium, tin, lead, arsenic, antimony, bismuth, niobium, tantalum, zirconium, indium, sulfur, selenium, tellurium, lanthanum, or cerium In the above, a to g represent the composition ratio of each atom. When a is 12, b is 0.1 to 3, c is 0.01 to 3, d is 0.01 to 3, e is 0.3. 01 to 3, f is 0 to 3, and g is an oxygen atomic ratio necessary to satisfy the valence of the entire metal atom.)
ＭｏaＶbＧcＤdＥeＯf （３）
（式中、Ｇは鉄、コバルト、クロム、アルミニウム、又はストロンチウムのいずれか１種または２種以上を示し、Ｄはゲルマニウム、ホウ素、ヒ素、セレン、銀、ケイ素、ナトリウム、テルル、リチウム、アンチモン、リン、カリウム、又はバリウムのいずれか１種または２種以上を示し、Ｅはマグネシウム、チタン、マンガン、銅、亜鉛、ジルコニウム、ニオブ、タングステン、タンタル、カルシウム、スズ、又はビスマスのいずれか１種または２種以上を示す。ａ〜ｆは各原子の組成比を示し、ａが１２のときｂは０．０１〜６、ｃは０〜５、ｄは０〜１０、ｅは０〜５であり、ｆは金属原子全体の原子価を満足するのに必要な酸素原子比を示す。） A metal component-containing catalyst produced by the method for producing a metal component-containing catalyst according to claim 3 or 4, wherein the catalyst has a composition represented by a composition formula (3) of atoms. .
Mo a V b G c D d E e O f (3)
(In the formula, G represents one or more of iron, cobalt, chromium, aluminum, or strontium, D represents germanium, boron, arsenic, selenium, silver, silicon, sodium, tellurium, lithium, antimony, One or more of phosphorus, potassium, or barium is shown, and E is any one of magnesium, titanium, manganese, copper, zinc, zirconium, niobium, tungsten, tantalum, calcium, tin, or bismuth, or A to f represent the composition ratio of each atom, and when a is 12, b is 0.01 to 6, c is 0 to 5, d is 0 to 10, e is 0 to 5. , F represents the oxygen atomic ratio necessary to satisfy the valence of the entire metal atom.)
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