WO2019026640A1 - Catalyst precursor, method for producing catalyst, method for producing methacrylic acid and acrylic acid, and method for producing methacrylic acid ester and acrylic acid ester - Google Patents
Catalyst precursor, method for producing catalyst, method for producing methacrylic acid and acrylic acid, and method for producing methacrylic acid ester and acrylic acid ester Download PDFInfo
- Publication number
- WO2019026640A1 WO2019026640A1 PCT/JP2018/027205 JP2018027205W WO2019026640A1 WO 2019026640 A1 WO2019026640 A1 WO 2019026640A1 JP 2018027205 W JP2018027205 W JP 2018027205W WO 2019026640 A1 WO2019026640 A1 WO 2019026640A1
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- WIPO (PCT)
- Prior art keywords
- catalyst
- methacrylic acid
- group
- producing
- catalyst precursor
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- 239000012018 catalyst precursor Substances 0.000 title claims abstract description 89
- 239000003054 catalyst Substances 0.000 title claims abstract description 88
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 37
- 125000005397 methacrylic acid ester group Chemical group 0.000 title claims abstract description 11
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 title claims description 24
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims description 24
- 125000005396 acrylic acid ester group Chemical group 0.000 title claims description 5
- 239000011964 heteropoly acid Substances 0.000 claims abstract description 42
- 150000003839 salts Chemical class 0.000 claims abstract description 33
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims description 37
- 239000010949 copper Substances 0.000 claims description 23
- 229910052760 oxygen Inorganic materials 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 22
- 239000007789 gas Substances 0.000 claims description 21
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 19
- 239000001301 oxygen Substances 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 18
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 16
- 229910001882 dioxygen Inorganic materials 0.000 claims description 15
- 229910052750 molybdenum Inorganic materials 0.000 claims description 15
- 229910052698 phosphorus Inorganic materials 0.000 claims description 15
- 230000003197 catalytic effect Effects 0.000 claims description 14
- 238000007254 oxidation reaction Methods 0.000 claims description 14
- 230000003647 oxidation Effects 0.000 claims description 12
- 229910052720 vanadium Inorganic materials 0.000 claims description 12
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 11
- 239000011733 molybdenum Substances 0.000 claims description 11
- 239000011574 phosphorus Substances 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- 229910052792 caesium Inorganic materials 0.000 claims description 8
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 8
- 239000012071 phase Substances 0.000 claims description 8
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 8
- 239000011777 magnesium Substances 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- 229910052701 rubidium Inorganic materials 0.000 claims description 6
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 6
- 229910052716 thallium Inorganic materials 0.000 claims description 6
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims description 6
- 229910052785 arsenic Inorganic materials 0.000 claims description 5
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 5
- 239000012808 vapor phase Substances 0.000 claims description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052733 gallium Inorganic materials 0.000 claims description 4
- 229910052732 germanium Inorganic materials 0.000 claims description 4
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 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
- 229910052742 iron Inorganic materials 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
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 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 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 239000010955 niobium Substances 0.000 claims description 4
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052711 selenium Inorganic materials 0.000 claims description 4
- 239000011669 selenium Substances 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 229910052712 strontium Inorganic materials 0.000 claims description 4
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- 229910052715 tantalum Inorganic materials 0.000 claims description 4
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052714 tellurium Inorganic materials 0.000 claims description 4
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- 239000000843 powder Substances 0.000 description 67
- 239000002994 raw material Substances 0.000 description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 23
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 17
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 16
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 16
- 238000003756 stirring Methods 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000007788 liquid Substances 0.000 description 13
- 238000002156 mixing Methods 0.000 description 13
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 12
- 239000001099 ammonium carbonate Substances 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 10
- 238000005259 measurement Methods 0.000 description 10
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 9
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 9
- 239000002131 composite material Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 238000000465 moulding Methods 0.000 description 8
- 235000011007 phosphoric acid Nutrition 0.000 description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 7
- ZMCUDHNSHCRDBT-UHFFFAOYSA-M caesium bicarbonate Chemical compound [Cs+].OC([O-])=O ZMCUDHNSHCRDBT-UHFFFAOYSA-M 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 238000001694 spray drying Methods 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 235000012501 ammonium carbonate Nutrition 0.000 description 3
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000002036 drum drying Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- -1 oxides Chemical class 0.000 description 2
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910021550 Vanadium Chloride Inorganic materials 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 229940045803 cuprous chloride Drugs 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
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000020169 heat generation Effects 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
- 239000012535 impurity Substances 0.000 description 1
- 150000004715 keto acids Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000000463 material Substances 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
- 150000002823 nitrates Chemical class 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- CPWJKGIJFGMVPL-UHFFFAOYSA-K tricesium;phosphate Chemical compound [Cs+].[Cs+].[Cs+].[O-]P([O-])([O-])=O CPWJKGIJFGMVPL-UHFFFAOYSA-K 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
- B01J27/198—Vanadium
- B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
- C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
- C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
- C07C69/54—Acrylic acid esters; Methacrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B61/00—Other general methods
Definitions
- the present invention relates to a catalyst precursor, a method of producing a catalyst using the precursor, a method of producing methacrylic acid and acrylic acid, and a method of producing methacrylic acid ester and acrylic acid ester.
- the present invention also relates to a precursor of a catalyst used for producing methacrylic acid or acrylic acid by gas phase catalytic oxidation of methacrolein or acrolein using molecular oxygen, and methacrylic acid produced using this precursor.
- the present invention also relates to a method for producing a catalyst for producing acrylic acid, a method for producing methacrylic acid or acrylic acid, and a method for producing methacrylic acid ester or acrylic acid ester.
- a catalyst for producing methacrylic acid a catalyst containing a heteropolyacid such as phosphomolybdic acid, phosphomolybdate or the like or a salt thereof as a main component is known.
- the X-ray-diffraction pattern after baking is prescribed
- patent document 2 it describes about the X-ray-diffraction peak of the raw material for catalyst manufacture, and it is a mixture containing molybdenum and A element (A shows at least 1 sort (s) of elements chosen from the group which consists of phosphorus and arsenic.).
- the precipitate obtained from the solution is subjected to a heat treatment at 250 to 350 ° C. to define an XRD diffraction peak.
- an object of the present invention is to provide a catalyst precursor for producing a catalyst having a higher yield of methacrylic acid and acrylic acid than a conventional catalyst, a method for producing a catalyst from the precursor, and methacrylic acid using the catalyst And acrylic acid, and their esters.
- the present invention is as shown in the following [1] to [8] and [1 '] to [5'].
- a precursor of a catalyst wherein the catalyst comprises methacrylic acid and acrylic acid by vapor phase catalytic oxidation of at least one member selected from the group consisting of methacrolein and acrolein using molecular oxygen
- P a Mo b V c Cu d A e E f G g O h (I) (In formula (I), P, Mo, V, Cu and O are element symbols showing phosphorus, molybdenum, vanadium, copper and oxygen respectively.
- A is antimony, bismuth, arsenic, germanium, zirconium, tellurium
- silver E represents at least one element selected from the group consisting of selenium, silicon, tungsten and boron
- E represents iron, zinc, chromium, magnesium, calcium, strontium, tantalum, cobalt, nickel, manganese, barium, titanium, tin
- G is at least one type selected from the group consisting of potassium, rubidium, cesium and thallium
- [6] The method for producing a catalyst according to [5], wherein the heat treatment temperature in the heat treatment step is 300 to 450 ° C.
- [7] A method of producing at least one selected from the group consisting of methacrylic acid and acrylic acid, (1) a step of producing a catalyst by the method according to [5] or [6], and (2) using molecular oxygen in the presence of the catalyst, at least one selected from the group consisting of methacrolein and acrolein Vapor phase catalytic oxidation of one species to produce at least one species selected from the group consisting of methacrylic acid and acrylic acid, Method, including.
- a method for producing at least one selected from the group consisting of methacrylic acid esters and acrylic acid esters (1) a step of producing a catalyst by the method described in [5] or [6], (2) Gas phase catalytic oxidation of at least one member selected from the group consisting of methacrolein and acrolein using molecular oxygen in the presence of the catalyst is selected from the group consisting of methacrylic acid and acrylic acid Manufacturing at least one kind, and (3) esterifying at least one kind selected from the group consisting of the methacrylic acid and the acrylic acid, And how to contain it.
- a precursor of a heteropolyacid salt-containing catalyst which is used in the vapor phase catalytic oxidation of methacrolein with molecular oxygen to produce a catalyst for producing methacrylic acid, which comprises counter cathode Cu—K ⁇ radiation
- Production of methacrylic acid having, in the X-ray diffraction pattern used, peak P1 having 2 ⁇ of 26.16 ° ⁇ 0.06 ° and peak P2 having 2 ⁇ at a higher angle than peak P1 and not exceeding 26.44 ° Catalyst precursor.
- the catalyst precursor for methacrylic acid manufacture which has a composition represented by following formula (I).
- P, Mo, V, Cu and O are element symbols showing phosphorus, molybdenum, vanadium, copper and oxygen respectively.
- A is antimony, bismuth, arsenic, germanium, zirconium, tellurium
- silver E represents at least one element selected from the group consisting of selenium, silicon, tungsten and boron
- E represents iron, zinc, chromium, magnesium, calcium, strontium, tantalum, cobalt, nickel, manganese, barium, titanium, tin
- G is at least one type selected from the group consisting of potassium, rubidium, cesium and thallium
- [4 ′] The method for producing a catalyst for producing methacrylic acid according to [3 ′], wherein the heat treatment temperature in the heat treatment step is 300 to 450 ° C.
- a catalyst for producing methacrylic acid is produced by the method for producing a catalyst for producing methacrylic acid according to [5 '] [3'] or [4 '], and methacrolein is gas phase catalytically oxidized with molecular oxygen in the presence of the catalyst.
- Process for producing methacrylic acid The manufacturing method of the methacrylic acid ester which esterifies the methacrylic acid manufactured by the manufacturing method of methacrylic acid as described in [6 '] [5'].
- the catalyst precursor refers to a catalyst precursor which is composed of a raw material of a catalyst constituent element and which becomes a catalyst by being heat-treated.
- the catalyst produced from the catalyst precursor of the present invention can be used for various oxidation reactions, for example, it is used for the reaction of producing methacrylic acid from methacrolein or acrylic acid from acrolein, and particularly preferably And methacrolein can be used in the reaction for producing methacrylic acid.
- methacrylic acid is manufactured from methacrolein
- these are applicable also when manufacturing acrylic acid from acrolein.
- the catalyst precursor of the present invention contains a heteropoly acid salt, and in the X-ray diffraction pattern (X-ray diffraction line) using counter-cathode Cu-K ⁇ ray, peak P1 having 2 ⁇ of 26.16 ° ⁇ 0.06 ° and , And a peak P2 having a higher angle side than the peak P1 and not greater than 26.44 °.
- the peak at which 2 ⁇ appears around 26 ° in the X-ray diffraction pattern is derived from the (222) plane of the heteropolyacid salt cubic structure.
- the catalyst precursor having two or more peaks in this region has at least two kinds of heteropoly acid salts having different structures or heteropoly acid complex salts (hereinafter collectively referred to as "heteropoly acid (complex) salts").
- heteropoly acid (complex) salts meanss of containing.
- the heteropoly acid complex salt refers to a salt in which heteropoly acid salts having different structures are complexed in a specific ratio.
- the peaks P1 and P2 have a height of 5/100 or more with respect to a diffraction pattern near 25.5 ° derived from ⁇ -alumina shown below.
- the ratio (I1 / I2) of the height I1 of the peak P1 to the height I2 of the peak P2 is preferably 0.05 to 0.92 from the viewpoint of the yield of methacrylic acid.
- the lower limit of I1 / I2 is more preferably 0.1 or more, and the upper limit thereof is more preferably 0.9 or less.
- heteropoly acid (complex) salts having different structures also have different properties and contain heteropoly acid (complex) salts with different properties derived from said peaks P1 and P2 in the X-ray diffraction pattern It is considered that by doing this, an active site structure that is advantageous in the gas phase catalytic oxidation reaction of methacrolein is formed.
- a diffraction pattern originating in the (012) plane of ⁇ -alumina appears around 25.5 °.
- the angle of this diffraction pattern is 25.583 °
- the diffraction pattern appearing from around 26 ° to 26.5 ° is the angle of the diffraction pattern derived from the (222) plane of the heteropoly acid (composite) salt in the catalyst precursor
- 21 Diffraction patterns are also present around 3 to 21.5 °, 23.8 to 24.2 °, and 30.2 to 30.7 °.
- the catalyst precursor of the present invention preferably has a composition represented by the following formula (I) from the viewpoint of methacrylic acid yield.
- the molar ratio of an elemental composition be the value computed by analyzing the component which melt
- P, Mo, V, Cu and O are element symbols showing phosphorus, molybdenum, vanadium, copper and oxygen, respectively.
- A represents at least one element selected from the group consisting of antimony, bismuth, arsenic, germanium, zirconium, tellurium, silver, selenium, silicon, tungsten and boron
- E represents iron, zinc, chromium, magnesium, calcium
- G is potassium
- It represents at least one element selected from the group consisting of rubidium, cesium and thallium.
- the method for producing the catalyst precursor according to the present invention is not particularly limited, but for example, a step of preparing a dry powder K1 having the peak P1 (hereinafter, also referred to as “dry powder K1 preparation step”); A step of preparing a dry powder K2 having a peak P2 (hereinafter also referred to as “dry powder K2 preparation step”), a step of mixing the dry powder K1 and the dry powder K2 to produce a catalyst precursor (hereinafter, And “a dry powder mixing step”).
- a dry powder K1 having the peak P1 is prepared.
- a catalyst raw material is first mixed, and a heteropoly acid-containing liquid is prepared by heating and stirring.
- the catalyst raw material preferably contains at least phosphorus and molybdenum, and more preferably contains vanadium, copper, the element A, and the element E.
- the raw material compounds of the respective elements are not particularly limited, and nitrates, carbonates, acetates, ammonium salts, oxides, halides, oxo acids, oxo acid salts, etc. of the respective elements are used singly or in combination of two or more kinds. It can be used.
- a molybdenum raw material ammonium paramolybdate, molybdenum trioxide, molybdic acid, molybdenum chloride and the like can be used.
- phosphates such as orthophosphoric acid, phosphorus pentoxide, or ammonium phosphate, a cesium phosphate, can be used, for example.
- vanadium raw material for example, ammonium vanadate, ammonium metavanadate, vanadium pentoxide, vanadium chloride and the like can be used.
- a copper raw material copper sulfate, copper nitrate, copper acetate, cuprous chloride, cupric chloride etc. can be used, for example. These may use only 1 type and may use 2 or more types together.
- a heteropoly acid containing at least one element of molybdenum, phosphorus, and vanadium may be used as a raw material.
- heteropoly acids include phosphomolybdic acid, phosphovanadomolybdic acid, silicomolybdic acid and the like. These may use only 1 type and may use 2 or more types together.
- Water, ethyl alcohol, acetone or the like can be used as a solvent for dissolving or suspending the raw material compound.
- a solvent for dissolving or suspending the raw material compound One of these may be used, or two or more may be used in combination. Among these, water is preferable as the solvent.
- the temperature at the time of heating and stirring is preferably 50 to 120 ° C.
- the raw material of the element G and the ammonium raw material are added to the prepared heteropolyacid-containing liquid to prepare a heteropolyacid (composite) salt-containing liquid.
- the temperature of the heteropoly acid-containing liquid at the time of addition of the raw material of G element and the ammonium raw material is preferably 70 to 120.degree.
- the element G is at least one element selected from the group consisting of potassium, rubidium, cesium and thallium, and it is preferable to use cesium from the viewpoint of methacrylic acid yield.
- ammonium in the present invention is a generic name of ammonia (NH 3 ) which can be ammonium ion (NH 4 + ), and ammonium contained in ammonium-containing compounds such as ammonium salts.
- ammonium raw material include ammonia, ammonium nitrate, ammonium hydrogencarbonate, ammonium carbonate, ammonium acetate, ammonium vanadate and the like, and it is preferable to use ammonium hydrogencarbonate and ammonium carbonate, and it is more preferable to use ammonium carbonate. These may use only 1 type and may use 2 or more types together.
- the lower limit of the value of (Mg1 + Mn1) / Mp1 is preferably 2.8 or more, and more preferably 2.9 or more.
- the upper limit is preferably 4.0 or less, more preferably 3.5 or less.
- the pH of the heteropoly acid (complex) salt-containing solution is preferably 0.1 to 4 from the viewpoint of methacrylic acid yield, and more preferably 0.1 to 2.
- the dried powder K1 is prepared by drying the resulting heteropoly acid (complex) salt-containing solution.
- the drying method in this case is not particularly limited, and for example, evaporation to dryness, spray drying, drum drying, flash drying and the like can be used, and the spray drying is most preferable. It is preferable to carry out drying until the water content of the obtained dry powder K1 becomes 2 wt% or less.
- dry powder K2 preparation process In this step, dry powder K2 having the peak P2 is prepared.
- a heteropolyacid-containing liquid is first prepared by the same method as the dry powder K1 preparing step.
- the raw material of the element G and the ammonium raw material are added to the prepared heteropolyacid-containing liquid to prepare a heteropolyacid (composite) salt-containing liquid.
- the temperature of the heteropoly acid-containing liquid at the time of addition of the raw material of G element and the ammonium raw material is preferably 70 to 120.degree.
- the G element is at least one element selected from the group consisting of potassium, rubidium, cesium and thallium, and it is preferable to use cesium from the viewpoint of methacrylic acid yield.
- the prepared heteropoly acid (complex) salt-containing liquid when the smaller one of the number of moles of phosphorus and the number of 1/12 of the number of moles of molybdenum is defined as Mp 2, the number of moles Mg of G element to be added, And when the number Mn2 of moles of ammonium contained in the added ammonium raw material satisfies the following formulas (IV) and (V), a dry powder K2 having a peak P2 can be obtained.
- the lower limit of the value of (Mg 2 + Mn 2) / Mp 2 is preferably 2.8 or more, and more preferably 2.9 or more.
- the upper limit is preferably 4.0 or less, more preferably 3.5 or less.
- the pH of the heteropoly acid (complex) salt-containing solution is preferably 0.1 to 4 from the viewpoint of methacrylic acid yield, and more preferably 0.1 to 2.
- the dried powder K2 is prepared by drying the resulting heteropoly acid (complex) salt-containing solution.
- the drying method in this case is not particularly limited, and for example, evaporation to dryness, spray drying, drum drying, flash drying and the like can be used, and the spray drying is most preferable. It is preferable to carry out drying until the water content of the obtained dry powder K2 becomes 2 wt% or less.
- the dry powder K1 and the dry powder K2 are mixed to prepare a catalyst precursor.
- the mixing method is not particularly limited, but when dry powder K1 and dry powder K2 are dried using a spray drying method, it is only necessary to dry mix dry powder K1 and dry powder K2.
- the dried powder K1 and the dried powder K2 are dried using the evaporation to dryness method or the drum drying method, it is preferable to perform mixing by crushing using a grinder.
- the value of I1 / I2 can be adjusted by the mixing ratio of the dry powders K1 and K2. It is preferable to mix such that the K1 mixing ratio calculated by the following equation is 5 to 95%.
- the lower limit of the K1 mixing ratio is more preferably 10% or more, and the upper limit is more preferably 94% or less.
- K1 mixing ratio mass of dried powder K1 / (mass of dried powder K1 + mass of dried powder K2) ⁇ 100
- the stirring speed at the time of adding the raw material of G element and an ammonium raw material to heteropoly acid containing liquid besides the method of preparing and mixing two types of dry powder as mentioned above, temperature of heteropoly acid containing liquid, G element
- the catalyst precursor having both of the peak P1 and the peak P2 may be prepared in one step by adjusting the addition rates of the raw material and the ammonium raw material.
- the catalyst precursor obtained by the dry powder mixing step may be shaped before the heat treatment step described later.
- the molding method is not particularly limited, and known dry or wet molding methods can be applied. For example, tablet molding, press molding, extrusion molding, granulation molding and the like can be mentioned.
- the shape of the molded article is not particularly limited, and examples thereof include a cylindrical shape, a ring shape, and a spherical shape. Further, at the time of molding, it is preferable to mold only the catalyst precursor without adding a carrier, a binder or the like to the catalyst precursor, but if necessary, for example, known additives such as graphite and talc, or known materials derived from organic substances and inorganic substances Binders may be added.
- catalyst precursor obtained in the dry powder mixing step or the molded product of the catalyst precursor obtained in the molding step (hereinafter collectively referred to as “catalyst precursor”) is heat-treated. It is preferable to include a step (hereinafter also referred to as “heat treatment step”).
- the heat treatment process In this step, the catalyst precursor is heat-treated to produce a catalyst.
- the heat treatment step it is possible to obtain a catalyst with less local heat generation under industrial use conditions and high activity per reactor.
- the heat treatment method and conditions are not particularly limited, and known methods and conditions can be applied.
- the heat treatment temperature is preferably 300 to 450 ° C. By setting the heat treatment temperature to 300 ° C. or higher, the ammonium in the catalyst can be removed and the catalyst activity can be made favorable. By setting the heat treatment temperature to 450 ° C. or less, the thermal decomposition of the heteropoly acid is suppressed, and the rapid catalytic activity is achieved. Can be suppressed.
- 0.5 hour or more is preferable and, as for the minimum of heat processing time, 1 hour or more is more preferable.
- the upper limit of heat processing time 40 hours or less are preferable.
- the heat treatment can be performed, for example, in the flow of at least one of air and an inert gas.
- the inert gas indicates a gas which does not reduce the catalytic activity, and examples thereof include nitrogen, carbon dioxide gas, helium, argon and the like. One of these may be used, or two or more may be mixed and used.
- the heat treatment is preferably performed in the flow of an oxygen-containing gas such as air.
- the method for producing methacrylic acid according to the present invention produces methacrylic acid by catalytic oxidation of methacrolein with molecular oxygen in the presence of a catalyst obtained from the catalyst precursor according to the present invention. According to this method, methacrylic acid can be produced in high yield. Methacrylic acid may be produced after a given period of time has elapsed since the catalyst was obtained. Also, the production site of the catalyst and the production site of methacrylic acid may be different.
- methacrylic acid can be produced by contacting a source gas containing methacrolein and molecular oxygen with the catalyst according to the present invention.
- the reaction is preferably carried out in a fixed bed.
- the catalyst may be used as it is without dilution or may be used after diluting it with an inert carrier, or it may be used by laminating a non-diluted layer and a diluted layer to form a plurality of layers.
- the concentration of methacrolein in the raw material gas is not particularly limited, but is preferably 1 to 20% by volume, the lower limit is 3% by volume or more, and the upper limit is 10% by volume or less.
- Methacrolein may contain a small amount of impurities such as lower saturated aldehyde which do not substantially affect the reaction.
- the molar ratio of methacrolein to molecular oxygen in the raw material gas is preferably 0.5 to 4.0 mol with respect to 1.0 mol of methacrolein, and the lower limit is 1.0 mol or more and the upper limit is 3.0 mol The following are more preferable. While it is economical to use air as a molecular oxygen source, air enriched with pure oxygen can also be used if desired.
- the source gas may dilute methacrolein and molecular oxygen with an inert gas such as nitrogen or carbon dioxide gas. Further, the source gas may contain water vapor.
- methacrylic acid can be obtained with higher selectivity.
- the concentration of water vapor in the raw material gas is preferably 0.1 to 50.0% by volume, and more preferably 1.0 to 40.0% by volume.
- the contact time between the raw material gas and the catalyst is preferably 1.5 to 15.0 seconds, the lower limit is preferably 2.0 seconds or more, and the upper limit is more preferably 5.0 seconds or less.
- the reaction pressure can be set in the range from atmospheric pressure to several hundreds kPa (G). However, (G) means being gauge pressure.
- the reaction temperature is preferably 200 ° C. to 450 ° C., the lower limit is more than 250 ° C., and the upper limit is more preferably 400 ° C. or less.
- the method for producing a methacrylic acid ester according to the present invention can be carried out by esterification of methacrylic acid obtained by the method according to the present invention.
- a methacrylic acid ester can be obtained using methacrylic acid obtained by gas phase catalytic oxidation of methacrolein.
- the alcohol to be reacted with methacrylic acid include methanol, ethanol, isopropanol, n-butanol, isobutanol and the like.
- Examples of the methacrylic acid ester to be obtained include methyl methacrylate, ethyl methacrylate, propyl methacrylate and butyl methacrylate.
- the reaction can be carried out in the presence of an acidic catalyst such as a sulfonic acid type cation exchange resin.
- the reaction temperature is preferably 50 to 200 ° C.
- A represents the number of moles of methacrolein supplied
- B represents the number of moles of methacrolein reacted
- C represents the number of moles of methacrylic acid formed.
- Example 1 100 parts of molybdenum trioxide, 6.67 parts of 85 mass% phosphoric acid, 3.36 parts of ammonium metavanadate and 2.10 parts of cupric nitrate were dissolved in 600 parts of pure water. The temperature was raised while stirring, and stirred under reflux at 100 ° C. for 5 hours. While keeping the temperature at 80 ° C., add 24.14 parts of cesium bicarbonate dissolved in 200 parts of pure water, stir for 15 minutes, and then 3.84 parts of ammonium bicarbonate dissolved in 200 parts of pure water Was added. The resulting heteropoly acid (composite) salt-containing solution was spray-dried at an outlet temperature of 250 ° C., and further dried at 130 ° C.
- the resulting heteropoly acid (composite) salt-containing solution was spray-dried at an outlet temperature of 250 ° C., and further dried at 130 ° C. for 16 hours to obtain a dry powder K2a.
- 90 parts of the dry powder K1a and 10 parts of the dry powder K2a were mixed to obtain a catalyst precursor.
- peaks shown in Table 1 were confirmed.
- the catalyst precursor was molded by a tableting machine and placed in a cylindrical quartz glass baking container with an inner diameter of 3 cm. Under air flow, the temperature was raised at 10 ° C./h, and the catalyst was prepared by heat treatment at 380 ° C. for 2 hours.
- the composition of the catalyst excluding hydrogen, nitrogen and oxygen was P 1 Mo 12 V 0.5 Cu 0.15 Cs 1.97 .
- the molar ratio of the elemental composition was calculated by analyzing a component obtained by dissolving the catalyst precursor in aqueous ammonia by ICP emission analysis.
- the catalyst is charged in a reaction tube, and a raw material gas consisting of 5% by volume of methacrolein, 10% by volume of oxygen, 30% by volume of steam and 30% by volume of steam and 55% by volume of nitrogen is used.
- the reaction was done in seconds. The results are shown in Table 1.
- Example 2 100 parts of molybdenum trioxide, 6.67 parts of 85 mass% phosphoric acid, 3.36 parts of ammonium metavanadate and 2.10 parts of cupric nitrate were dissolved in 600 parts of pure water. The temperature was raised while stirring, and stirred under reflux at 100 ° C. for 5 hours. While maintaining the temperature at 80 ° C., add 30.10 parts of cesium bicarbonate dissolved in 200 parts of pure water, stir for 15 minutes, and then dissolve 1.45 parts of ammonium bicarbonate dissolved in 200 parts of pure water Was added. The resulting heteropoly acid (composite) salt-containing solution was spray-dried at an outlet temperature of 250 ° C., and further dried at 130 ° C.
- the catalyst precursor was shaped and heat-treated in the same manner as in Example 1 to prepare a catalyst. Using this catalyst, methacrylic acid was produced in the same manner as in Example 1. The results are shown in Table 1.
- Example 3 100 parts of molybdenum trioxide, 6.67 parts of 85 mass% phosphoric acid, 3.36 parts of ammonium metavanadate and 2.10 parts of cupric nitrate were dissolved in 600 parts of pure water. The temperature was raised while stirring, and stirred under reflux at 100 ° C. for 5 hours. While maintaining the temperature at 80 ° C., add 21.56 parts of cesium bicarbonate dissolved in 200 parts of pure water, stir for 15 minutes, and then dissolve 4.88 parts of ammonium bicarbonate dissolved in 200 parts of pure water Was added. The resulting heteropoly acid (composite) salt-containing solution was spray-dried at an outlet temperature of 250 ° C. and further dried at 130 ° C.
- the catalyst precursor was shaped and heat-treated in the same manner as in Example 1 to prepare a catalyst. Using this catalyst, methacrylic acid was produced in the same manner as in Example 1. The results are shown in Table 1.
- Example 4 Dry powder K1a and dry powder K2a were obtained in the same manner as in Example 1. Next, 6 parts of dry powder K2a was mixed with 94 parts of dry powder K1a to obtain a catalyst precursor. The composition except hydrogen, nitrogen, and oxygen of the obtained catalyst precursor was P 1 Mo 12 V 0.5 Cu 0.15 Cs 2.04 . As a result of X-ray diffraction pattern measurement using an anticathode Cu-K ⁇ ray for the catalyst precursor, peaks shown in Table 1 were confirmed.
- the catalyst precursor was shaped and heat-treated in the same manner as in Example 1 to prepare a catalyst. Using this catalyst, methacrylic acid was produced in the same manner as in Example 1. The results are shown in Table 1.
- Example 5 Dry powder K1a and dry powder K2a were obtained in the same manner as in Example 1. Next, the dry powder K1a was mixed with 97 parts of dry powder K2a at a ratio of 3 parts to obtain a catalyst precursor. The composition except hydrogen, nitrogen, and oxygen of the obtained catalyst precursor was P 1 Mo 12 V 0.5 Cu 0.15 Cs 2.10 . As a result of X-ray diffraction pattern measurement using an anticathode Cu-K ⁇ ray for the catalyst precursor, peaks shown in Table 1 were confirmed.
- the catalyst precursor was shaped and heat-treated in the same manner as in Example 1 to prepare a catalyst. Using this catalyst, methacrylic acid was produced in the same manner as in Example 1. The results are shown in Table 1.
- Example 6 Dry powder K1a and dry powder K2a were obtained in the same manner as in Example 1. Next, 90 parts of dry powder K2a was mixed with 10 parts of dry powder K1a to obtain a catalyst precursor. The composition of the obtained catalyst precursor excluding hydrogen, nitrogen and oxygen was P 1 Mo 12 V 0.5 Cu 0.15 Cs 0.54 . As a result of X-ray diffraction pattern measurement using an anticathode Cu-K ⁇ ray for the catalyst precursor, peaks shown in Table 1 were confirmed.
- the catalyst precursor was shaped and heat-treated in the same manner as in Example 1 to prepare a catalyst. Using this catalyst, methacrylic acid was produced in the same manner as in Example 1. The results are shown in Table 1.
- Comparative Example 1 A dry powder K1a was obtained by the same method as in Example 1 and used as a catalyst precursor.
- the composition of the catalyst precursor excluding hydrogen, nitrogen and oxygen was P 1 Mo 12 V 0.5 Cu 0.15 Cs 2.15 .
- peaks shown in Table 1 were confirmed.
- the catalyst precursor was shaped and heat-treated in the same manner as in Example 1 to prepare a catalyst. Using this catalyst, methacrylic acid was produced in the same manner as in Example 1. The results are shown in Table 1.
- Comparative Example 2 A dry powder K2a was obtained by the same method as in Example 1 and used as a catalyst precursor.
- the composition except hydrogen, nitrogen and oxygen of the catalyst precursor was P 1 Mo 12 V 0.5 Cu 0.15 Cs 0.36 .
- peaks shown in Table 1 were confirmed.
- the catalyst precursor was shaped and heat-treated in the same manner as in Example 1 to prepare a catalyst. Using this catalyst, methacrylic acid was produced in the same manner as in Example 1. The results are shown in Table 1.
- the catalyst precursor was shaped and heat-treated in the same manner as in Example 1 to prepare a catalyst. Using this catalyst, methacrylic acid was produced in the same manner as in Example 1. The results are shown in Table 1.
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Abstract
Provided are a catalyst precursor for producing a catalyst having a high yield of methacrylic acid, a catalyst, and a method for producing methacrylic acid and a methacrylic acid ester. A catalyst precursor including a heteropoly acid salt is used, the catalyst precursor having, in an X-ray diffraction pattern in which an anti-cathode Cu-Kα line is used, a peak P1 in which 2θ is 26.16° ± 0.06° and a peak P2 that is further toward the high-angle side than the peak P1 and is equal to or less than 26.44°. Moreover, a catalyst precursor is prepared in which the ratio (I1/I2) of the height I1 of peak P1 relative to the height I2 of peak P2 is 0.05-0.92. In addition, a catalyst is produced from the catalyst precursor, and methacrylic acid is produced from methacrolein using the catalyst.
Description
本発明は、触媒前駆体、及びこの前駆体を用いた触媒の製造方法、メタクリル酸及びアクリル酸の製造方法、並びにメタクリル酸エステル及びアクリル酸エステルの製造方法に関する。
また本発明は、分子状酸素を用いてメタクロレイン又はアクロレインを気相接触酸化してメタクリル酸又はアクリル酸を製造する際に用いる触媒の前駆体、及び、この前駆体を用いて製造するメタクリル酸又はアクリル酸製造用触媒の製造方法、メタクリル酸又はアクリル酸の製造方法、並びにメタクリル酸エステル又はアクリル酸エステルの製造方法に関する。 The present invention relates to a catalyst precursor, a method of producing a catalyst using the precursor, a method of producing methacrylic acid and acrylic acid, and a method of producing methacrylic acid ester and acrylic acid ester.
The present invention also relates to a precursor of a catalyst used for producing methacrylic acid or acrylic acid by gas phase catalytic oxidation of methacrolein or acrolein using molecular oxygen, and methacrylic acid produced using this precursor. The present invention also relates to a method for producing a catalyst for producing acrylic acid, a method for producing methacrylic acid or acrylic acid, and a method for producing methacrylic acid ester or acrylic acid ester.
また本発明は、分子状酸素を用いてメタクロレイン又はアクロレインを気相接触酸化してメタクリル酸又はアクリル酸を製造する際に用いる触媒の前駆体、及び、この前駆体を用いて製造するメタクリル酸又はアクリル酸製造用触媒の製造方法、メタクリル酸又はアクリル酸の製造方法、並びにメタクリル酸エステル又はアクリル酸エステルの製造方法に関する。 The present invention relates to a catalyst precursor, a method of producing a catalyst using the precursor, a method of producing methacrylic acid and acrylic acid, and a method of producing methacrylic acid ester and acrylic acid ester.
The present invention also relates to a precursor of a catalyst used for producing methacrylic acid or acrylic acid by gas phase catalytic oxidation of methacrolein or acrolein using molecular oxygen, and methacrylic acid produced using this precursor. The present invention also relates to a method for producing a catalyst for producing acrylic acid, a method for producing methacrylic acid or acrylic acid, and a method for producing methacrylic acid ester or acrylic acid ester.
化学反応に用いられる触媒の構造については、数多くの検討がなされている。例えばメタクリル酸製造用触媒としては、リンモリブデン酸、リンモリブデン酸塩等のヘテロポリ酸又はその塩を主成分とする触媒が知られている。
特許文献１では、ヘテロポリ酸塩を含む気相酸化触媒について、焼成後のＸ線回折パターンを規定している。
また特許文献２では、触媒製造用原料のＸ線回折ピークについて記載されており、モリブデン及びＡ元素（Ａは、リン及びヒ素からなる群より選ばれる少なくとも１種の元素を示す。）を含む混合液から得られる沈殿を、２５０～３５０℃で熱処理した後のＸＲＤ回折ピークを規定している。 Numerous studies have been made on the structure of catalysts used in chemical reactions. For example, as a catalyst for producing methacrylic acid, a catalyst containing a heteropolyacid such as phosphomolybdic acid, phosphomolybdate or the like or a salt thereof as a main component is known.
In patent document 1, the X-ray-diffraction pattern after baking is prescribed | regulated about the gas phase oxidation catalyst containing heteropoly acid salt.
Moreover, in patent document 2, it describes about the X-ray-diffraction peak of the raw material for catalyst manufacture, and it is a mixture containing molybdenum and A element (A shows at least 1 sort (s) of elements chosen from the group which consists of phosphorus and arsenic.). The precipitate obtained from the solution is subjected to a heat treatment at 250 to 350 ° C. to define an XRD diffraction peak.
特許文献１では、ヘテロポリ酸塩を含む気相酸化触媒について、焼成後のＸ線回折パターンを規定している。
また特許文献２では、触媒製造用原料のＸ線回折ピークについて記載されており、モリブデン及びＡ元素（Ａは、リン及びヒ素からなる群より選ばれる少なくとも１種の元素を示す。）を含む混合液から得られる沈殿を、２５０～３５０℃で熱処理した後のＸＲＤ回折ピークを規定している。 Numerous studies have been made on the structure of catalysts used in chemical reactions. For example, as a catalyst for producing methacrylic acid, a catalyst containing a heteropolyacid such as phosphomolybdic acid, phosphomolybdate or the like or a salt thereof as a main component is known.
In patent document 1, the X-ray-diffraction pattern after baking is prescribed | regulated about the gas phase oxidation catalyst containing heteropoly acid salt.
Moreover, in patent document 2, it describes about the X-ray-diffraction peak of the raw material for catalyst manufacture, and it is a mixture containing molybdenum and A element (A shows at least 1 sort (s) of elements chosen from the group which consists of phosphorus and arsenic.). The precipitate obtained from the solution is subjected to a heat treatment at 250 to 350 ° C. to define an XRD diffraction peak.
しかし、これらの方法で得られた触媒を使用してメタクリル酸やアクリル酸を製造する場合、収率が十分ではない問題があった。
そこで、本発明の目的は、従来の触媒よりもメタクリル酸およびアクリル酸の収率の高い触媒を製造するための触媒前駆体、前記前駆体から触媒を製造する方法、前記触媒を用いてメタクリル酸およびアクリル酸、並びにそれらのエステルを提供することにある。 However, when producing methacrylic acid or acrylic acid using the catalyst obtained by these methods, there was a problem that the yield was not sufficient.
Therefore, an object of the present invention is to provide a catalyst precursor for producing a catalyst having a higher yield of methacrylic acid and acrylic acid than a conventional catalyst, a method for producing a catalyst from the precursor, and methacrylic acid using the catalyst And acrylic acid, and their esters.
そこで、本発明の目的は、従来の触媒よりもメタクリル酸およびアクリル酸の収率の高い触媒を製造するための触媒前駆体、前記前駆体から触媒を製造する方法、前記触媒を用いてメタクリル酸およびアクリル酸、並びにそれらのエステルを提供することにある。 However, when producing methacrylic acid or acrylic acid using the catalyst obtained by these methods, there was a problem that the yield was not sufficient.
Therefore, an object of the present invention is to provide a catalyst precursor for producing a catalyst having a higher yield of methacrylic acid and acrylic acid than a conventional catalyst, a method for producing a catalyst from the precursor, and methacrylic acid using the catalyst And acrylic acid, and their esters.
本発明者らは上記目的を達成するために、メタクリル酸およびアクリル酸の収率の高い触媒を製造する技術について鋭意検討を進めた。
この結果、特定の構造を有する触媒前駆体を製造し、これを熱処理して触媒を製造することで、メタクリル酸およびアクリル酸の収率の高い触媒を製造することが可能なことを見出し、本発明に至った。 Means for Solving the Problems In order to achieve the above object, the present inventors diligently studied about a technology for producing a catalyst with a high yield of methacrylic acid and acrylic acid.
As a result, it has been found that it is possible to produce a catalyst with high yield of methacrylic acid and acrylic acid by producing a catalyst precursor having a specific structure and subjecting it to heat treatment to produce a catalyst. It came to the invention.
この結果、特定の構造を有する触媒前駆体を製造し、これを熱処理して触媒を製造することで、メタクリル酸およびアクリル酸の収率の高い触媒を製造することが可能なことを見出し、本発明に至った。 Means for Solving the Problems In order to achieve the above object, the present inventors diligently studied about a technology for producing a catalyst with a high yield of methacrylic acid and acrylic acid.
As a result, it has been found that it is possible to produce a catalyst with high yield of methacrylic acid and acrylic acid by producing a catalyst precursor having a specific structure and subjecting it to heat treatment to produce a catalyst. It came to the invention.
本発明は、以下の［１］～［８］及び［１’］～［５’］に示すとおりである。
The present invention is as shown in the following [1] to [8] and [1 '] to [5'].
［１］ヘテロポリ酸塩を含む触媒前駆体であって、対陰極Ｃｕ－Ｋα線を用いたＸ線回折パターンにおいて、２θが２６．１６°±０．０６°であるピークＰ１と、２θがピークＰ１よりも高角側にあり２６．４４°以下にあるピークＰ２とを有する触媒前駆体。
［２］前記ピークＰ２の高さＩ２に対する前記ピークＰ１の高さＩ１の比（Ｉ１／Ｉ２）が、０．０５～０．９２である、［１］に記載の触媒前駆体。
［３］触媒の前駆体であって、前記触媒が、分子状酸素を用いてメタクロレイン及びアクロレインからなる群より選択される少なくとも１種を気相接触酸化して、メタクリル酸及びアクリル酸からなる群より選択される少なくとも１種を製造する際に用いれる、［１］又は［２］に記載の触媒前駆体。
［４］下記式（Ｉ）で表される組成を有する［１］～［３］のいずれか１つに記載の触媒前駆体。
ＰａＭｏｂＶｃＣｕｄＡｅＥｆＧｇＯｈ （Ｉ）
（式（Ｉ）中、Ｐ、Ｍｏ、Ｖ、Ｃｕ及びＯは、それぞれリン、モリブデン、バナジウム、銅及び酸素を示す元素記号である。Ａはアンチモン、ビスマス、砒素、ゲルマニウム、ジルコニウム、テルル、銀、セレン、ケイ素、タングステン及びホウ素からなる群より選ばれた少なくとも１種類の元素を示し、Ｅは鉄、亜鉛、クロム、マグネシウム、カルシウム、ストロンチウム、タンタル、コバルト、ニッケル、マンガン、バリウム、チタン、スズ、鉛、ニオブ、インジウム、硫黄、パラジウム、ガリウム、セリウム及びランタンからなる群より選ばれた少なくとも１種類の元素を示し、Ｇはカリウム、ルビジウム、セシウム及びタリウムからなる群より選ばれた少なくとも１種類の元素を示す。ａ、ｂ、ｃ、ｄ、ｅ、ｆ、ｇ及びｈは各元素の原子比率を示し、ｂ＝１２の時ａ＝０．５～３、ｃ＝０．０１～３、ｄ＝０．０１～２、ｅ＝０～３、ｆ＝０～３、ｇ＝０．０１～３であり、ｈは前記各成分の原子価を満足するのに必要な酸素の原子比率である。）
［５］［１］～［４］のいずれか１つに記載の触媒前駆体を熱処理する工程を含む、触媒の製造方法。
［６］前記熱処理工程における熱処理温度が３００～４５０℃である、［５］に記載の触媒の製造方法。
［７］メタクリル酸及びアクリル酸からなる群より選択される少なくとも１種を製造する方法であって、
（１）［５］又は［６］に記載の方法により触媒を製造する工程、及び
（２）前記触媒の存在下で分子状酸素を用いて、メタクロレイン及びアクロレインからなる群より選択される少なくとも１種を気相接触酸化して、メタクリル酸及びアクリル酸からなる群より選択される少なくとも１種を製造する工程、
を含む、方法。
［８］メタクリル酸エステル及びアクリル酸エステルからなる群より選択される少なくとも１種を製造する方法であって、
（１）［５］又は［６］に記載の方法により触媒を製造する工程、
（２）前記触媒の存在下で分子状酸素を用いて、メタクロレイン及びアクロレインからなる群より選択される少なくとも１種を気相接触酸化して、メタクリル酸及びアクリル酸からなる郡より選択される少なくとも１種を製造する工程、及び
（３）前記メタクリル酸及び前記アクリル酸からなる群より選択される少なくとも１種をエステル化する工程、
を、含む方法。 [1] It is a catalyst precursor containing a heteropoly acid salt, and in the X-ray diffraction pattern using counter-cathode Cu-Kα rays, peak P1 having 2θ of 26.16 ° ± 0.06 ° and peak of 2θ A catalyst precursor having a peak P2 located on the higher angle side than P1 and not more than 26.44 °.
[2] The catalyst precursor according to [1], wherein the ratio (I1 / I2) of the height I1 of the peak P1 to the height I2 of the peak P2 is 0.05 to 0.92.
[3] A precursor of a catalyst, wherein the catalyst comprises methacrylic acid and acrylic acid by vapor phase catalytic oxidation of at least one member selected from the group consisting of methacrolein and acrolein using molecular oxygen The catalyst precursor as described in [1] or [2] used when manufacturing at least 1 sort (s) selected from a group.
[4] The catalyst precursor according to any one of [1] to [3], which has a composition represented by the following formula (I).
P a Mo b V c Cu d A e E f G g O h (I)
(In formula (I), P, Mo, V, Cu and O are element symbols showing phosphorus, molybdenum, vanadium, copper and oxygen respectively. A is antimony, bismuth, arsenic, germanium, zirconium, tellurium, silver E represents at least one element selected from the group consisting of selenium, silicon, tungsten and boron, E represents iron, zinc, chromium, magnesium, calcium, strontium, tantalum, cobalt, nickel, manganese, barium, titanium, tin And at least one element selected from the group consisting of lead, niobium, indium, sulfur, palladium, gallium, cerium and lanthanum, and G is at least one type selected from the group consisting of potassium, rubidium, cesium and thallium A, b, c, d, e, f, g and h of each element Child ratio, and when b = 12, a = 0.5 to 3, c = 0.01 to 3, d = 0.01 to 2, e = 0 to 3, f = 0 to 3, g = 0 01 to 3, and h is an atomic ratio of oxygen necessary to satisfy the valences of the respective components.)
[5] A method for producing a catalyst, comprising the step of heat-treating the catalyst precursor according to any one of [1] to [4].
[6] The method for producing a catalyst according to [5], wherein the heat treatment temperature in the heat treatment step is 300 to 450 ° C.
[7] A method of producing at least one selected from the group consisting of methacrylic acid and acrylic acid,
(1) a step of producing a catalyst by the method according to [5] or [6], and (2) using molecular oxygen in the presence of the catalyst, at least one selected from the group consisting of methacrolein and acrolein Vapor phase catalytic oxidation of one species to produce at least one species selected from the group consisting of methacrylic acid and acrylic acid,
Method, including.
[8] A method for producing at least one selected from the group consisting of methacrylic acid esters and acrylic acid esters,
(1) a step of producing a catalyst by the method described in [5] or [6],
(2) Gas phase catalytic oxidation of at least one member selected from the group consisting of methacrolein and acrolein using molecular oxygen in the presence of the catalyst is selected from the group consisting of methacrylic acid and acrylic acid Manufacturing at least one kind, and (3) esterifying at least one kind selected from the group consisting of the methacrylic acid and the acrylic acid,
And how to contain it.
［２］前記ピークＰ２の高さＩ２に対する前記ピークＰ１の高さＩ１の比（Ｉ１／Ｉ２）が、０．０５～０．９２である、［１］に記載の触媒前駆体。
［３］触媒の前駆体であって、前記触媒が、分子状酸素を用いてメタクロレイン及びアクロレインからなる群より選択される少なくとも１種を気相接触酸化して、メタクリル酸及びアクリル酸からなる群より選択される少なくとも１種を製造する際に用いれる、［１］又は［２］に記載の触媒前駆体。
［４］下記式（Ｉ）で表される組成を有する［１］～［３］のいずれか１つに記載の触媒前駆体。
ＰａＭｏｂＶｃＣｕｄＡｅＥｆＧｇＯｈ （Ｉ）
（式（Ｉ）中、Ｐ、Ｍｏ、Ｖ、Ｃｕ及びＯは、それぞれリン、モリブデン、バナジウム、銅及び酸素を示す元素記号である。Ａはアンチモン、ビスマス、砒素、ゲルマニウム、ジルコニウム、テルル、銀、セレン、ケイ素、タングステン及びホウ素からなる群より選ばれた少なくとも１種類の元素を示し、Ｅは鉄、亜鉛、クロム、マグネシウム、カルシウム、ストロンチウム、タンタル、コバルト、ニッケル、マンガン、バリウム、チタン、スズ、鉛、ニオブ、インジウム、硫黄、パラジウム、ガリウム、セリウム及びランタンからなる群より選ばれた少なくとも１種類の元素を示し、Ｇはカリウム、ルビジウム、セシウム及びタリウムからなる群より選ばれた少なくとも１種類の元素を示す。ａ、ｂ、ｃ、ｄ、ｅ、ｆ、ｇ及びｈは各元素の原子比率を示し、ｂ＝１２の時ａ＝０．５～３、ｃ＝０．０１～３、ｄ＝０．０１～２、ｅ＝０～３、ｆ＝０～３、ｇ＝０．０１～３であり、ｈは前記各成分の原子価を満足するのに必要な酸素の原子比率である。）
［５］［１］～［４］のいずれか１つに記載の触媒前駆体を熱処理する工程を含む、触媒の製造方法。
［６］前記熱処理工程における熱処理温度が３００～４５０℃である、［５］に記載の触媒の製造方法。
［７］メタクリル酸及びアクリル酸からなる群より選択される少なくとも１種を製造する方法であって、
（１）［５］又は［６］に記載の方法により触媒を製造する工程、及び
（２）前記触媒の存在下で分子状酸素を用いて、メタクロレイン及びアクロレインからなる群より選択される少なくとも１種を気相接触酸化して、メタクリル酸及びアクリル酸からなる群より選択される少なくとも１種を製造する工程、
を含む、方法。
［８］メタクリル酸エステル及びアクリル酸エステルからなる群より選択される少なくとも１種を製造する方法であって、
（１）［５］又は［６］に記載の方法により触媒を製造する工程、
（２）前記触媒の存在下で分子状酸素を用いて、メタクロレイン及びアクロレインからなる群より選択される少なくとも１種を気相接触酸化して、メタクリル酸及びアクリル酸からなる郡より選択される少なくとも１種を製造する工程、及び
（３）前記メタクリル酸及び前記アクリル酸からなる群より選択される少なくとも１種をエステル化する工程、
を、含む方法。 [1] It is a catalyst precursor containing a heteropoly acid salt, and in the X-ray diffraction pattern using counter-cathode Cu-Kα rays, peak P1 having 2θ of 26.16 ° ± 0.06 ° and peak of 2θ A catalyst precursor having a peak P2 located on the higher angle side than P1 and not more than 26.44 °.
[2] The catalyst precursor according to [1], wherein the ratio (I1 / I2) of the height I1 of the peak P1 to the height I2 of the peak P2 is 0.05 to 0.92.
[3] A precursor of a catalyst, wherein the catalyst comprises methacrylic acid and acrylic acid by vapor phase catalytic oxidation of at least one member selected from the group consisting of methacrolein and acrolein using molecular oxygen The catalyst precursor as described in [1] or [2] used when manufacturing at least 1 sort (s) selected from a group.
[4] The catalyst precursor according to any one of [1] to [3], which has a composition represented by the following formula (I).
P a Mo b V c Cu d A e E f G g O h (I)
(In formula (I), P, Mo, V, Cu and O are element symbols showing phosphorus, molybdenum, vanadium, copper and oxygen respectively. A is antimony, bismuth, arsenic, germanium, zirconium, tellurium, silver E represents at least one element selected from the group consisting of selenium, silicon, tungsten and boron, E represents iron, zinc, chromium, magnesium, calcium, strontium, tantalum, cobalt, nickel, manganese, barium, titanium, tin And at least one element selected from the group consisting of lead, niobium, indium, sulfur, palladium, gallium, cerium and lanthanum, and G is at least one type selected from the group consisting of potassium, rubidium, cesium and thallium A, b, c, d, e, f, g and h of each element Child ratio, and when b = 12, a = 0.5 to 3, c = 0.01 to 3, d = 0.01 to 2, e = 0 to 3, f = 0 to 3, g = 0 01 to 3, and h is an atomic ratio of oxygen necessary to satisfy the valences of the respective components.)
[5] A method for producing a catalyst, comprising the step of heat-treating the catalyst precursor according to any one of [1] to [4].
[6] The method for producing a catalyst according to [5], wherein the heat treatment temperature in the heat treatment step is 300 to 450 ° C.
[7] A method of producing at least one selected from the group consisting of methacrylic acid and acrylic acid,
(1) a step of producing a catalyst by the method according to [5] or [6], and (2) using molecular oxygen in the presence of the catalyst, at least one selected from the group consisting of methacrolein and acrolein Vapor phase catalytic oxidation of one species to produce at least one species selected from the group consisting of methacrylic acid and acrylic acid,
Method, including.
[8] A method for producing at least one selected from the group consisting of methacrylic acid esters and acrylic acid esters,
(1) a step of producing a catalyst by the method described in [5] or [6],
(2) Gas phase catalytic oxidation of at least one member selected from the group consisting of methacrolein and acrolein using molecular oxygen in the presence of the catalyst is selected from the group consisting of methacrylic acid and acrylic acid Manufacturing at least one kind, and (3) esterifying at least one kind selected from the group consisting of the methacrylic acid and the acrylic acid,
And how to contain it.
［１’］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製造用触媒を製造する際に用いられる、ヘテロポリ酸塩を含む触媒の前駆体であって、対陰極Ｃｕ－Ｋα線を用いたＸ線回折パターンにおいて、２θが２６．１６°±０．０６°であるピークＰ１と、２θがピークＰ１よりも高角側にあり２６．４４°以下にあるピークＰ２とを有するメタクリル酸製造用触媒前駆体。
［２’］［１’］に記載のメタクリル酸製造用触媒の前駆体であって、下記式（Ｉ）で表される組成を有するメタクリル酸製造用触媒前駆体。
ＰａＭｏｂＶｃＣｕｄＡｅＥｆＧｇＯｈ （Ｉ）
（式（Ｉ）中、Ｐ、Ｍｏ、Ｖ、Ｃｕ及びＯは、それぞれリン、モリブデン、バナジウム、銅及び酸素を示す元素記号である。Ａはアンチモン、ビスマス、砒素、ゲルマニウム、ジルコニウム、テルル、銀、セレン、ケイ素、タングステン及びホウ素からなる群より選ばれた少なくとも１種類の元素を示し、Ｅは鉄、亜鉛、クロム、マグネシウム、カルシウム、ストロンチウム、タンタル、コバルト、ニッケル、マンガン、バリウム、チタン、スズ、鉛、ニオブ、インジウム、硫黄、パラジウム、ガリウム、セリウム及びランタンからなる群より選ばれた少なくとも１種類の元素を示し、Ｇはカリウム、ルビジウム、セシウム及びタリウムからなる群より選ばれた少なくとも１種類の元素を示す。ａ、ｂ、ｃ、ｄ、ｅ、ｆ、ｇ及びｈは各元素の原子比率を示し、ｂ＝１２の時ａ＝０．５～３、ｃ＝０．０１～３、ｄ＝０．０１～２、ｅ＝０～３、ｆ＝０～３、ｇ＝０．０１～３であり、ｈは前記各成分の原子価を満足するのに必要な酸素の原子比率である。）
［３’］［１’］又は［２’］に記載のメタクリル酸製造用触媒の前駆体を熱処理する工程を含むメタクリル酸製造用触媒の製造方法。
［４’］前記熱処理工程における熱処理温度が３００～４５０℃である［３’］に記載のメタクリル酸製造用触媒の製造方法。
［５’］［３’］又は［４’］に記載のメタクリル酸製造用触媒の製造方法によりメタクリル酸製造用触媒を製造し、その存在下で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製造するメタクリル酸の製造方法。
［６’］［５’］に記載のメタクリル酸の製造方法により製造されたメタクリル酸をエステル化するメタクリル酸エステルの製造方法。 [1 ′] A precursor of a heteropolyacid salt-containing catalyst, which is used in the vapor phase catalytic oxidation of methacrolein with molecular oxygen to produce a catalyst for producing methacrylic acid, which comprises counter cathode Cu—Kα radiation Production of methacrylic acid having, in the X-ray diffraction pattern used, peak P1 having 2θ of 26.16 ° ± 0.06 ° and peak P2 having 2θ at a higher angle than peak P1 and not exceeding 26.44 ° Catalyst precursor.
It is a precursor of the catalyst for methacrylic acid manufacture as described in [2 '] [1'], Comprising: The catalyst precursor for methacrylic acid manufacture which has a composition represented by following formula (I).
P a Mo b V c Cu d A e E f G g O h (I)
(In formula (I), P, Mo, V, Cu and O are element symbols showing phosphorus, molybdenum, vanadium, copper and oxygen respectively. A is antimony, bismuth, arsenic, germanium, zirconium, tellurium, silver E represents at least one element selected from the group consisting of selenium, silicon, tungsten and boron, E represents iron, zinc, chromium, magnesium, calcium, strontium, tantalum, cobalt, nickel, manganese, barium, titanium, tin And at least one element selected from the group consisting of lead, niobium, indium, sulfur, palladium, gallium, cerium and lanthanum, and G is at least one type selected from the group consisting of potassium, rubidium, cesium and thallium A, b, c, d, e, f, g and h of each element Child ratio, and when b = 12, a = 0.5 to 3, c = 0.01 to 3, d = 0.01 to 2, e = 0 to 3, f = 0 to 3, g = 0 01 to 3, and h is an atomic ratio of oxygen necessary to satisfy the valences of the respective components.)
The manufacturing method of the catalyst for methacrylic acid manufacture including the process of heat-processing the precursor of the catalyst for methacrylic acid manufacture as described in [3 '] [1'] or [2 '].
[4 ′] The method for producing a catalyst for producing methacrylic acid according to [3 ′], wherein the heat treatment temperature in the heat treatment step is 300 to 450 ° C.
A catalyst for producing methacrylic acid is produced by the method for producing a catalyst for producing methacrylic acid according to [5 '] [3'] or [4 '], and methacrolein is gas phase catalytically oxidized with molecular oxygen in the presence of the catalyst. Process for producing methacrylic acid.
The manufacturing method of the methacrylic acid ester which esterifies the methacrylic acid manufactured by the manufacturing method of methacrylic acid as described in [6 '] [5'].
［２’］［１’］に記載のメタクリル酸製造用触媒の前駆体であって、下記式（Ｉ）で表される組成を有するメタクリル酸製造用触媒前駆体。
ＰａＭｏｂＶｃＣｕｄＡｅＥｆＧｇＯｈ （Ｉ）
（式（Ｉ）中、Ｐ、Ｍｏ、Ｖ、Ｃｕ及びＯは、それぞれリン、モリブデン、バナジウム、銅及び酸素を示す元素記号である。Ａはアンチモン、ビスマス、砒素、ゲルマニウム、ジルコニウム、テルル、銀、セレン、ケイ素、タングステン及びホウ素からなる群より選ばれた少なくとも１種類の元素を示し、Ｅは鉄、亜鉛、クロム、マグネシウム、カルシウム、ストロンチウム、タンタル、コバルト、ニッケル、マンガン、バリウム、チタン、スズ、鉛、ニオブ、インジウム、硫黄、パラジウム、ガリウム、セリウム及びランタンからなる群より選ばれた少なくとも１種類の元素を示し、Ｇはカリウム、ルビジウム、セシウム及びタリウムからなる群より選ばれた少なくとも１種類の元素を示す。ａ、ｂ、ｃ、ｄ、ｅ、ｆ、ｇ及びｈは各元素の原子比率を示し、ｂ＝１２の時ａ＝０．５～３、ｃ＝０．０１～３、ｄ＝０．０１～２、ｅ＝０～３、ｆ＝０～３、ｇ＝０．０１～３であり、ｈは前記各成分の原子価を満足するのに必要な酸素の原子比率である。）
［３’］［１’］又は［２’］に記載のメタクリル酸製造用触媒の前駆体を熱処理する工程を含むメタクリル酸製造用触媒の製造方法。
［４’］前記熱処理工程における熱処理温度が３００～４５０℃である［３’］に記載のメタクリル酸製造用触媒の製造方法。
［５’］［３’］又は［４’］に記載のメタクリル酸製造用触媒の製造方法によりメタクリル酸製造用触媒を製造し、その存在下で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製造するメタクリル酸の製造方法。
［６’］［５’］に記載のメタクリル酸の製造方法により製造されたメタクリル酸をエステル化するメタクリル酸エステルの製造方法。 [1 ′] A precursor of a heteropolyacid salt-containing catalyst, which is used in the vapor phase catalytic oxidation of methacrolein with molecular oxygen to produce a catalyst for producing methacrylic acid, which comprises counter cathode Cu—Kα radiation Production of methacrylic acid having, in the X-ray diffraction pattern used, peak P1 having 2θ of 26.16 ° ± 0.06 ° and peak P2 having 2θ at a higher angle than peak P1 and not exceeding 26.44 ° Catalyst precursor.
It is a precursor of the catalyst for methacrylic acid manufacture as described in [2 '] [1'], Comprising: The catalyst precursor for methacrylic acid manufacture which has a composition represented by following formula (I).
P a Mo b V c Cu d A e E f G g O h (I)
(In formula (I), P, Mo, V, Cu and O are element symbols showing phosphorus, molybdenum, vanadium, copper and oxygen respectively. A is antimony, bismuth, arsenic, germanium, zirconium, tellurium, silver E represents at least one element selected from the group consisting of selenium, silicon, tungsten and boron, E represents iron, zinc, chromium, magnesium, calcium, strontium, tantalum, cobalt, nickel, manganese, barium, titanium, tin And at least one element selected from the group consisting of lead, niobium, indium, sulfur, palladium, gallium, cerium and lanthanum, and G is at least one type selected from the group consisting of potassium, rubidium, cesium and thallium A, b, c, d, e, f, g and h of each element Child ratio, and when b = 12, a = 0.5 to 3, c = 0.01 to 3, d = 0.01 to 2, e = 0 to 3, f = 0 to 3, g = 0 01 to 3, and h is an atomic ratio of oxygen necessary to satisfy the valences of the respective components.)
The manufacturing method of the catalyst for methacrylic acid manufacture including the process of heat-processing the precursor of the catalyst for methacrylic acid manufacture as described in [3 '] [1'] or [2 '].
[4 ′] The method for producing a catalyst for producing methacrylic acid according to [3 ′], wherein the heat treatment temperature in the heat treatment step is 300 to 450 ° C.
A catalyst for producing methacrylic acid is produced by the method for producing a catalyst for producing methacrylic acid according to [5 '] [3'] or [4 '], and methacrolein is gas phase catalytically oxidized with molecular oxygen in the presence of the catalyst. Process for producing methacrylic acid.
The manufacturing method of the methacrylic acid ester which esterifies the methacrylic acid manufactured by the manufacturing method of methacrylic acid as described in [6 '] [5'].
本発明によれば、分子状酸素を用いて、メタクロレイン及びアクロレインを気相接触酸化してメタクリル酸及びアクリル酸を製造する際に、メタクリル酸及びアクリル酸の収率が高い触媒を製造することが可能な触媒前駆体を製造することができる。
According to the present invention, when producing methacrylic acid and acrylic acid by vapor phase catalytic oxidation of methacrolein and acrolein using molecular oxygen, producing a catalyst having a high yield of methacrylic acid and acrylic acid Can be produced.
［触媒前駆体］
本発明において、触媒前駆体とは触媒構成元素の原料から構成されるものであり、熱処理されることによって触媒となる、触媒前駆体を示す。 [Catalyst precursor]
In the present invention, the catalyst precursor refers to a catalyst precursor which is composed of a raw material of a catalyst constituent element and which becomes a catalyst by being heat-treated.
本発明において、触媒前駆体とは触媒構成元素の原料から構成されるものであり、熱処理されることによって触媒となる、触媒前駆体を示す。 [Catalyst precursor]
In the present invention, the catalyst precursor refers to a catalyst precursor which is composed of a raw material of a catalyst constituent element and which becomes a catalyst by being heat-treated.
本発明の触媒前駆体から製造される触媒は、様々な酸化反応に用いることができるが、例えば、メタクロレインからメタクリル酸を、又は、アクロレインからアクリル酸を製造する反応に用いられ、特に好ましくは、メタクロレインからメタクリル酸を製造する反応に用いることができる。
The catalyst produced from the catalyst precursor of the present invention can be used for various oxidation reactions, for example, it is used for the reaction of producing methacrylic acid from methacrolein or acrylic acid from acrolein, and particularly preferably And methacrolein can be used in the reaction for producing methacrylic acid.
以下、メタクロレインからメタクリル酸を製造する場合を例として記載するが、これらは、アクロレインからアクリル酸を製造する際にも適用できるものである。
Hereinafter, although the case where methacrylic acid is manufactured from methacrolein is described as an example, these are applicable also when manufacturing acrylic acid from acrolein.
本発明の触媒前駆体はヘテロポリ酸塩を含み、対陰極Ｃｕ－Ｋα線を用いたＸ線回折パターン（Ｘ線回折線）において、２θが２６．１６°±０．０６°であるピークＰ１と、２θがピークＰ１よりも高角側にあり２６．４４°以下にあるピークＰ２とを有する。
The catalyst precursor of the present invention contains a heteropoly acid salt, and in the X-ray diffraction pattern (X-ray diffraction line) using counter-cathode Cu-Kα ray, peak P1 having 2θ of 26.16 ° ± 0.06 ° and , And a peak P2 having a higher angle side than the peak P1 and not greater than 26.44 °.
Ｘ線回折パターンにおいて、２θが２６°付近に出現するピークは、ヘテロポリ酸塩の立方晶構造の（２２２）面に由来するものである。この領域に２つ以上のピークが存在する触媒前駆体は、異なる構造を有するヘテロポリ酸塩、又はヘテロポリ酸複合塩（以下、まとめて「ヘテロポリ酸（複合）塩」とも示す。）を少なくとも２種類含有することを意味する。ここでヘテロポリ酸複合塩とは、異なる構造を有するヘテロポリ酸塩が特定の割合で複合した塩を示す。本発明の触媒前駆体を熱処理して製造した触媒を用いてメタクロレインの酸化を行うことで、高い収率でメタクリル酸を製造することができる。なお、ピークＰ１、ピークＰ２は、下記に示すα－アルミナを由来とする２５．５°付近の回折パターンに対し、５／１００以上の高さを有するものとする。
前記ピークＰ２の高さＩ２に対するピークＰ１の高さＩ１の比（Ｉ１／Ｉ２）は、０．０５～０．９２であることがメタクリル酸の収率の観点から好ましい。Ｉ１／Ｉ２の下限は０．１以上、上限は０．９以下がより好ましい。 The peak at which 2θ appears around 26 ° in the X-ray diffraction pattern is derived from the (222) plane of the heteropolyacid salt cubic structure. The catalyst precursor having two or more peaks in this region has at least two kinds of heteropoly acid salts having different structures or heteropoly acid complex salts (hereinafter collectively referred to as "heteropoly acid (complex) salts"). Means of containing. Here, the heteropoly acid complex salt refers to a salt in which heteropoly acid salts having different structures are complexed in a specific ratio. By oxidizing methacrolein using a catalyst produced by heat-treating the catalyst precursor of the present invention, methacrylic acid can be produced in a high yield. The peaks P1 and P2 have a height of 5/100 or more with respect to a diffraction pattern near 25.5 ° derived from α-alumina shown below.
The ratio (I1 / I2) of the height I1 of the peak P1 to the height I2 of the peak P2 is preferably 0.05 to 0.92 from the viewpoint of the yield of methacrylic acid. The lower limit of I1 / I2 is more preferably 0.1 or more, and the upper limit thereof is more preferably 0.9 or less.
前記ピークＰ２の高さＩ２に対するピークＰ１の高さＩ１の比（Ｉ１／Ｉ２）は、０．０５～０．９２であることがメタクリル酸の収率の観点から好ましい。Ｉ１／Ｉ２の下限は０．１以上、上限は０．９以下がより好ましい。 The peak at which 2θ appears around 26 ° in the X-ray diffraction pattern is derived from the (222) plane of the heteropolyacid salt cubic structure. The catalyst precursor having two or more peaks in this region has at least two kinds of heteropoly acid salts having different structures or heteropoly acid complex salts (hereinafter collectively referred to as "heteropoly acid (complex) salts"). Means of containing. Here, the heteropoly acid complex salt refers to a salt in which heteropoly acid salts having different structures are complexed in a specific ratio. By oxidizing methacrolein using a catalyst produced by heat-treating the catalyst precursor of the present invention, methacrylic acid can be produced in a high yield. The peaks P1 and P2 have a height of 5/100 or more with respect to a diffraction pattern near 25.5 ° derived from α-alumina shown below.
The ratio (I1 / I2) of the height I1 of the peak P1 to the height I2 of the peak P2 is preferably 0.05 to 0.92 from the viewpoint of the yield of methacrylic acid. The lower limit of I1 / I2 is more preferably 0.1 or more, and the upper limit thereof is more preferably 0.9 or less.
この理由は明らかではないが、異なる構造を有するヘテロポリ酸（複合）塩は特性も異なっており、Ｘ線回折パターンにおける前記ピークＰ１及びＰ２に由来する、特性の異なるヘテロポリ酸（複合）塩を含有することにより、メタクロレインの気相接触酸化反応において有利な活性点構造が形成されるためと考えられる。
Although the reason for this is not clear, heteropoly acid (complex) salts having different structures also have different properties and contain heteropoly acid (complex) salts with different properties derived from said peaks P1 and P2 in the X-ray diffraction pattern It is considered that by doing this, an active site structure that is advantageous in the gas phase catalytic oxidation reaction of methacrolein is formed.
Ｘ線回折パターンは、まず触媒前駆体を粉状とし、触媒前駆体の質量：α－アルミナの質量＝１：４となるようにα－アルミナを混合して得られる混合粉について測定する。測定はＰＡＮａｌｔｉｃａｌ社製の「商品名：Ｘ‘Ｐｅｒｔ Ｐｒｏ ＭＰＤ」を用い、線源：ＣｕＫα線（λ＝０．１５４０６ｎｍ）、管電圧：４５ｋＶ、管電流：４０ｍＡ、散乱スリット：１°、拡散防止スリット：２°、スキャンステップ：０．００８°で行う。得られたデータはＰＡＮａｌｙｔｉｃａｌ社製のＸ線回折装置用データ収集ソフトウエア「商品名：Ｘ‘Ｐｅｒｔ」を用いてＫα２線の除去操作を実施する。この時、２５．５°付近にα―アルミナの（０１２）面に起因する回折パターンが現れる。この回折パターンの角度を２５．５８３°として、２６°付近から２６．５°付近に現れる回折パターンを、触媒前駆体中のヘテロポリ酸（複合）塩の（２２２）面に由来する回折パターンの角度として算出する。なおヘテロポリ酸（複合）塩は、他に２θ＝１０．６～１０．７°、１３．０～１３．２°、１５．１～１５．３°、１８．４～１８．６°、２１．３～２１．５°、２３．８～２４．２°、３０．２～３０．７°付近にも回折パターンを有する。
The X-ray diffraction pattern is first measured on a powder mixture obtained by powdering the catalyst precursor and mixing α-alumina so that the mass of the catalyst precursor: mass of α-alumina = 1: 4. Measurement is performed using "trade name: X'Pert Pro MPD" manufactured by PANaltical, using a radiation source: CuKα ray (λ = 0.15406 nm), tube voltage: 45 kV, tube current: 40 mA, scattering slit: 1 °, diffusion prevention Slit: 2 °, scan step: 0.008 °. The obtained data is subjected to the removal operation of the Kα2 line using data acquisition software for X-ray diffractometer "trade name: X‘Pert" manufactured by PANalytical. At this time, a diffraction pattern originating in the (012) plane of α-alumina appears around 25.5 °. Assuming that the angle of this diffraction pattern is 25.583 °, the diffraction pattern appearing from around 26 ° to 26.5 ° is the angle of the diffraction pattern derived from the (222) plane of the heteropoly acid (composite) salt in the catalyst precursor Calculated as Other heteropoly acid (complex) salts are 2θ = 10.6-10.7 °, 13.0-13.2 °, 15.1-15.3 °, 18.4-18.6 °, 21 Diffraction patterns are also present around 3 to 21.5 °, 23.8 to 24.2 °, and 30.2 to 30.7 °.
本発明の触媒前駆体は、メタクリル酸収率の観点から下記式（Ｉ）で表される組成を有することが好ましい。なお、元素組成のモル比は、触媒前駆体をアンモニア水に溶解した成分をＩＣＰ発光分析法で分析することによって算出した値とする。
ＰａＭｏｂＶｃＣｕｄＡｅＥｆＧｇＯｈ （Ｉ）
式（Ｉ）中、Ｐ、Ｍｏ、Ｖ、Ｃｕ及びＯは、それぞれリン、モリブデン、バナジウム、銅及び酸素を示す元素記号である。Ａはアンチモン、ビスマス、砒素、ゲルマニウム、ジルコニウム、テルル、銀、セレン、ケイ素、タングステン及びホウ素からなる群より選ばれた少なくとも１種類の元素を示し、Ｅは鉄、亜鉛、クロム、マグネシウム、カルシウム、ストロンチウム、タンタル、コバルト、ニッケル、マンガン、バリウム、チタン、スズ、鉛、ニオブ、インジウム、硫黄、パラジウム、ガリウム、セリウム及びランタンからなる群より選ばれた少なくとも１種類の元素を示し、Ｇはカリウム、ルビジウム、セシウム及びタリウムからなる群より選ばれた少なくとも１種類の元素を示す。ａ、ｂ、ｃ、ｄ、ｅ、ｆ、ｇ及びｈは各元素の原子比率を示し、ｂ＝１２の時ａ＝０．５～３、ｃ＝０．０１～３、ｄ＝０．０１～２、ｅ＝０～３、ｆ＝０～３、ｇ＝０．０１～３であり、ｈは前記各成分の原子価を満足するのに必要な酸素の原子比率である。 The catalyst precursor of the present invention preferably has a composition represented by the following formula (I) from the viewpoint of methacrylic acid yield. In addition, let the molar ratio of an elemental composition be the value computed by analyzing the component which melt | dissolved the catalyst precursor in ammonia water by ICP emission spectrometry.
P a Mo b V c Cu d A e E f G g O h (I)
In formula (I), P, Mo, V, Cu and O are element symbols showing phosphorus, molybdenum, vanadium, copper and oxygen, respectively. A represents at least one element selected from the group consisting of antimony, bismuth, arsenic, germanium, zirconium, tellurium, silver, selenium, silicon, tungsten and boron, and E represents iron, zinc, chromium, magnesium, calcium, At least one element selected from the group consisting of strontium, tantalum, cobalt, nickel, manganese, barium, titanium, tin, lead, niobium, indium, sulfur, palladium, gallium, cerium and lanthanum, and G is potassium, It represents at least one element selected from the group consisting of rubidium, cesium and thallium. a, b, c, d, e, f, g and h indicate atomic ratios of respective elements, and when b = 12, a = 0.5 to 3, c = 0.01 to 3, d = 0.01 It is ̃2, e = 0 ̃3, f = 0 ̃3, g = 0.01 ̃3 and h is an atomic ratio of oxygen necessary to satisfy the valence of each component.
ＰａＭｏｂＶｃＣｕｄＡｅＥｆＧｇＯｈ （Ｉ）
式（Ｉ）中、Ｐ、Ｍｏ、Ｖ、Ｃｕ及びＯは、それぞれリン、モリブデン、バナジウム、銅及び酸素を示す元素記号である。Ａはアンチモン、ビスマス、砒素、ゲルマニウム、ジルコニウム、テルル、銀、セレン、ケイ素、タングステン及びホウ素からなる群より選ばれた少なくとも１種類の元素を示し、Ｅは鉄、亜鉛、クロム、マグネシウム、カルシウム、ストロンチウム、タンタル、コバルト、ニッケル、マンガン、バリウム、チタン、スズ、鉛、ニオブ、インジウム、硫黄、パラジウム、ガリウム、セリウム及びランタンからなる群より選ばれた少なくとも１種類の元素を示し、Ｇはカリウム、ルビジウム、セシウム及びタリウムからなる群より選ばれた少なくとも１種類の元素を示す。ａ、ｂ、ｃ、ｄ、ｅ、ｆ、ｇ及びｈは各元素の原子比率を示し、ｂ＝１２の時ａ＝０．５～３、ｃ＝０．０１～３、ｄ＝０．０１～２、ｅ＝０～３、ｆ＝０～３、ｇ＝０．０１～３であり、ｈは前記各成分の原子価を満足するのに必要な酸素の原子比率である。 The catalyst precursor of the present invention preferably has a composition represented by the following formula (I) from the viewpoint of methacrylic acid yield. In addition, let the molar ratio of an elemental composition be the value computed by analyzing the component which melt | dissolved the catalyst precursor in ammonia water by ICP emission spectrometry.
P a Mo b V c Cu d A e E f G g O h (I)
In formula (I), P, Mo, V, Cu and O are element symbols showing phosphorus, molybdenum, vanadium, copper and oxygen, respectively. A represents at least one element selected from the group consisting of antimony, bismuth, arsenic, germanium, zirconium, tellurium, silver, selenium, silicon, tungsten and boron, and E represents iron, zinc, chromium, magnesium, calcium, At least one element selected from the group consisting of strontium, tantalum, cobalt, nickel, manganese, barium, titanium, tin, lead, niobium, indium, sulfur, palladium, gallium, cerium and lanthanum, and G is potassium, It represents at least one element selected from the group consisting of rubidium, cesium and thallium. a, b, c, d, e, f, g and h indicate atomic ratios of respective elements, and when b = 12, a = 0.5 to 3, c = 0.01 to 3, d = 0.01 It is ̃2, e = 0 ̃3, f = 0 ̃3, g = 0.01 ̃3 and h is an atomic ratio of oxygen necessary to satisfy the valence of each component.
［触媒前駆体の製造方法］
本発明に係る触媒前駆体の製造方法は特に限定されるものではないが、例えば前記ピークＰ１を有する乾燥粉Ｋ１を調製する工程（以下、「乾燥粉Ｋ１調製工程」とも示す。）と、前記ピークＰ２を有する乾燥粉Ｋ２を調製する工程（以下、「乾燥粉Ｋ２調製工程」とも示す。）と、前記乾燥粉Ｋ１と前記乾燥粉Ｋ２を混合し、触媒前駆体を製造する工程（以下、「乾燥粉混合工程」とも示す。）と、を含む方法が挙げられる。 [Method of producing catalyst precursor]
The method for producing the catalyst precursor according to the present invention is not particularly limited, but for example, a step of preparing a dry powder K1 having the peak P1 (hereinafter, also referred to as "dry powder K1 preparation step"); A step of preparing a dry powder K2 having a peak P2 (hereinafter also referred to as "dry powder K2 preparation step"), a step of mixing the dry powder K1 and the dry powder K2 to produce a catalyst precursor (hereinafter, And “a dry powder mixing step”).
本発明に係る触媒前駆体の製造方法は特に限定されるものではないが、例えば前記ピークＰ１を有する乾燥粉Ｋ１を調製する工程（以下、「乾燥粉Ｋ１調製工程」とも示す。）と、前記ピークＰ２を有する乾燥粉Ｋ２を調製する工程（以下、「乾燥粉Ｋ２調製工程」とも示す。）と、前記乾燥粉Ｋ１と前記乾燥粉Ｋ２を混合し、触媒前駆体を製造する工程（以下、「乾燥粉混合工程」とも示す。）と、を含む方法が挙げられる。 [Method of producing catalyst precursor]
The method for producing the catalyst precursor according to the present invention is not particularly limited, but for example, a step of preparing a dry powder K1 having the peak P1 (hereinafter, also referred to as "dry powder K1 preparation step"); A step of preparing a dry powder K2 having a peak P2 (hereinafter also referred to as "dry powder K2 preparation step"), a step of mixing the dry powder K1 and the dry powder K2 to produce a catalyst precursor (hereinafter, And “a dry powder mixing step”).
（乾燥粉Ｋ１調製工程）
本工程では、前記ピークＰ１を有する乾燥粉Ｋ１を調製する。
乾燥粉Ｋ１を調製する方法としては、例えば、まず触媒原料を混合し、加熱撹拌することでヘテロポリ酸含有液を調製する。前記触媒原料は、少なくともリン及びモリブデンを含むことが好ましく、バナジウム、銅、前記Ａ元素、及び前記Ｅ元素を含むことがより好ましい。 (Dried powder K1 preparation process)
In this step, a dry powder K1 having the peak P1 is prepared.
As a method of preparing the dry powder K1, for example, a catalyst raw material is first mixed, and a heteropoly acid-containing liquid is prepared by heating and stirring. The catalyst raw material preferably contains at least phosphorus and molybdenum, and more preferably contains vanadium, copper, the element A, and the element E.
本工程では、前記ピークＰ１を有する乾燥粉Ｋ１を調製する。
乾燥粉Ｋ１を調製する方法としては、例えば、まず触媒原料を混合し、加熱撹拌することでヘテロポリ酸含有液を調製する。前記触媒原料は、少なくともリン及びモリブデンを含むことが好ましく、バナジウム、銅、前記Ａ元素、及び前記Ｅ元素を含むことがより好ましい。 (Dried powder K1 preparation process)
In this step, a dry powder K1 having the peak P1 is prepared.
As a method of preparing the dry powder K1, for example, a catalyst raw material is first mixed, and a heteropoly acid-containing liquid is prepared by heating and stirring. The catalyst raw material preferably contains at least phosphorus and molybdenum, and more preferably contains vanadium, copper, the element A, and the element E.
各元素の原料化合物は、特に限定されず、各元素の硝酸塩、炭酸塩、酢酸塩、アンモニウム塩、酸化物、ハロゲン化物、オキソ酸、オキソ酸塩等を単独で、又は２種類以上を組み合わせて使用することができる。例えばモリブデン原料としては、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、塩化モリブデン等が使用できる。リン原料としては、例えば正リン酸、五酸化リン、又は、リン酸アンモニウム、リン酸セシウム等のリン酸塩が使用できる。バナジウム原料としては、例えばバナジン酸アンモニウム、メタバナジン酸アンモニウム、五酸化バナジウム、塩化バナジウム等が使用できる。銅原料としては、例えば硫酸銅、硝酸銅、酢酸銅、塩化第一銅、塩化第二銅等が使用できる。これらは１種のみを用いてもよく、２種以上を併用してもよい。
The raw material compounds of the respective elements are not particularly limited, and nitrates, carbonates, acetates, ammonium salts, oxides, halides, oxo acids, oxo acid salts, etc. of the respective elements are used singly or in combination of two or more kinds. It can be used. For example, as a molybdenum raw material, ammonium paramolybdate, molybdenum trioxide, molybdic acid, molybdenum chloride and the like can be used. As a phosphorus raw material, phosphates, such as orthophosphoric acid, phosphorus pentoxide, or ammonium phosphate, a cesium phosphate, can be used, for example. As the vanadium raw material, for example, ammonium vanadate, ammonium metavanadate, vanadium pentoxide, vanadium chloride and the like can be used. As a copper raw material, copper sulfate, copper nitrate, copper acetate, cuprous chloride, cupric chloride etc. can be used, for example. These may use only 1 type and may use 2 or more types together.
また、モリブデン、リン、バナジウムの原料としては、モリブデン、リン、バナジウムのうちの少なくとも一つの元素を含むヘテロポリ酸を原料として用いてもよい。ヘテロポリ酸としては、例えばリンモリブデン酸、リンバナドモリブデン酸、ケイモリブデン酸等が挙げられる。これらは１種のみを用いてもよく、２種以上を併用してもよい。
In addition, as a raw material of molybdenum, phosphorus, and vanadium, a heteropoly acid containing at least one element of molybdenum, phosphorus, and vanadium may be used as a raw material. Examples of heteropoly acids include phosphomolybdic acid, phosphovanadomolybdic acid, silicomolybdic acid and the like. These may use only 1 type and may use 2 or more types together.
前記原料化合物を溶解又は懸濁する溶媒としては、水、エチルアルコール、アセトン等を用いることができる。これらは１種を用いてもよく、２種以上を併用してもよい。これらの中でも、溶媒としては水が好ましい。
Water, ethyl alcohol, acetone or the like can be used as a solvent for dissolving or suspending the raw material compound. One of these may be used, or two or more may be used in combination. Among these, water is preferable as the solvent.
加熱撹拌時の温度は、５０～１２０℃であることが望ましい。
The temperature at the time of heating and stirring is preferably 50 to 120 ° C.
続いて、調製されたヘテロポリ酸含有液に前記Ｇ元素の原料及びアンモニウム原料を添加し、ヘテロポリ酸（複合）塩含有液を調製する。Ｇ元素の原料及びアンモニウム原料添加時におけるヘテロポリ酸含有液の温度は、７０～１２０℃であることが好ましい。
Subsequently, the raw material of the element G and the ammonium raw material are added to the prepared heteropolyacid-containing liquid to prepare a heteropolyacid (composite) salt-containing liquid. The temperature of the heteropoly acid-containing liquid at the time of addition of the raw material of G element and the ammonium raw material is preferably 70 to 120.degree.
Ｇ元素は、カリウム、ルビジウム、セシウム及びタリウムからなる群から選択される少なくとも１種の元素であり、セシウムを用いることがメタクリル酸収率の観点から好ましい。
The element G is at least one element selected from the group consisting of potassium, rubidium, cesium and thallium, and it is preferable to use cesium from the viewpoint of methacrylic acid yield.
ここで、本発明におけるアンモニウムとは、アンモニウムイオン（ＮＨ４
＋）になり得るアンモニア（ＮＨ３）、及びアンモニウム塩などのアンモニウム含有化合物に含まれるアンモニウムの総称である。アンモニウム原料としては、例えばアンモニア、硝酸アンモニウム、炭酸水素アンモニウム、炭酸アンモニウム、酢酸アンモニウム、バナジン酸アンモニウム等が挙げられるが、炭酸水素アンモニウム、炭酸アンモニウムを用いることが好ましく、炭酸アンモニウムを用いることがより好ましい。これらは１種のみを用いてもよく、２種以上を併用してもよい。
Here, ammonium in the present invention is a generic name of ammonia (NH 3 ) which can be ammonium ion (NH 4 + ), and ammonium contained in ammonium-containing compounds such as ammonium salts. Examples of the ammonium raw material include ammonia, ammonium nitrate, ammonium hydrogencarbonate, ammonium carbonate, ammonium acetate, ammonium vanadate and the like, and it is preferable to use ammonium hydrogencarbonate and ammonium carbonate, and it is more preferable to use ammonium carbonate. These may use only 1 type and may use 2 or more types together.
調製されたヘテロポリ酸（複合）塩含有液において、リンのモル数と、モリブデンのモル数の１／１２のうち小さい方の値をＭｐ１と定義したときに、添加するＧ元素のモル数Ｍｇ１、及び添加するアンモニウム原料に含まれるアンモニウムのモル数Ｍｎ１が下記式（ＩＩ）及び（ＩＩＩ）を満たすことで、ピークＰ１を有する乾燥粉Ｋ１を得ることができる。
１．８５≦Ｍｇ１／Ｍｐ１≦２．７５ （ＩＩ）
２．７≦（Ｍｇ１＋Ｍｎ１）／Ｍｐ１≦６．０ （ＩＩＩ） In the prepared heteropoly acid (complex) salt-containing liquid, when the smaller one of the number of moles of phosphorus and the number of 1/12 of the number of moles of molybdenum is defined as Mp 1, the number of moles of G element Mg 1 to be added And when the number of moles Mn of ammonium contained in the added ammonium raw material satisfies the following formulas (II) and (III), it is possible to obtain a dry powder K1 having a peak P1.
1.85 ≦ Mg1 / Mp1 ≦ 2.75 (II)
2.7 ≦ (Mg1 + Mn1) /Mp1≦6.0 (III)
１．８５≦Ｍｇ１／Ｍｐ１≦２．７５ （ＩＩ）
２．７≦（Ｍｇ１＋Ｍｎ１）／Ｍｐ１≦６．０ （ＩＩＩ） In the prepared heteropoly acid (complex) salt-containing liquid, when the smaller one of the number of moles of phosphorus and the number of 1/12 of the number of moles of molybdenum is defined as Mp 1, the number of moles of G element Mg 1 to be added And when the number of moles Mn of ammonium contained in the added ammonium raw material satisfies the following formulas (II) and (III), it is possible to obtain a dry powder K1 having a peak P1.
1.85 ≦ Mg1 / Mp1 ≦ 2.75 (II)
2.7 ≦ (Mg1 + Mn1) /Mp1≦6.0 (III)
なお、（Ｍｇ１＋Ｍｎ１）／Ｍｐ１の値の下限は、２．８以上であることが好ましく、２．９以上であることがより好ましい。また上限は４．０以下であることが好ましく、３．５以下であることがより好ましい。
The lower limit of the value of (Mg1 + Mn1) / Mp1 is preferably 2.8 or more, and more preferably 2.9 or more. The upper limit is preferably 4.0 or less, more preferably 3.5 or less.
ヘテロポリ酸（複合）塩含有液のｐＨは、メタクリル酸収率の観点から０．１～４が好ましく、０．１～２がより好ましい。
The pH of the heteropoly acid (complex) salt-containing solution is preferably 0.1 to 4 from the viewpoint of methacrylic acid yield, and more preferably 0.1 to 2.
得られたヘテロポリ酸（複合）塩含有液を乾燥することで、乾燥粉Ｋ１を調製する。この際の乾燥方法は特に限定されず、例えば蒸発乾固法、噴霧乾燥法、ドラム乾燥法、気流乾燥法等を用いることができるが、噴霧乾燥法が最も好適である。得られる乾燥粉Ｋ１の水分量が２ｗｔ％以下になるまで乾燥を行うことが好ましい。
The dried powder K1 is prepared by drying the resulting heteropoly acid (complex) salt-containing solution. The drying method in this case is not particularly limited, and for example, evaporation to dryness, spray drying, drum drying, flash drying and the like can be used, and the spray drying is most preferable. It is preferable to carry out drying until the water content of the obtained dry powder K1 becomes 2 wt% or less.
（乾燥粉Ｋ２調製工程）
本工程では、前記ピークＰ２を有する乾燥粉Ｋ２を調製する。
乾燥粉Ｋ２を調製する方法としては、例えば、まず乾燥粉Ｋ１調製工程と同様の方法により、ヘテロポリ酸含有液を調製する。 (Dried powder K2 preparation process)
In this step, dry powder K2 having the peak P2 is prepared.
As a method of preparing dry powder K2, for example, a heteropolyacid-containing liquid is first prepared by the same method as the dry powder K1 preparing step.
本工程では、前記ピークＰ２を有する乾燥粉Ｋ２を調製する。
乾燥粉Ｋ２を調製する方法としては、例えば、まず乾燥粉Ｋ１調製工程と同様の方法により、ヘテロポリ酸含有液を調製する。 (Dried powder K2 preparation process)
In this step, dry powder K2 having the peak P2 is prepared.
As a method of preparing dry powder K2, for example, a heteropolyacid-containing liquid is first prepared by the same method as the dry powder K1 preparing step.
続いて、調製されたヘテロポリ酸含有液に前記Ｇ元素の原料及びアンモニウム原料を添加し、ヘテロポリ酸（複合）塩含有液を調製する。Ｇ元素の原料及びアンモニウム原料添加時におけるヘテロポリ酸含有液の温度は、７０～１２０℃であることが好ましい。
Subsequently, the raw material of the element G and the ammonium raw material are added to the prepared heteropolyacid-containing liquid to prepare a heteropolyacid (composite) salt-containing liquid. The temperature of the heteropoly acid-containing liquid at the time of addition of the raw material of G element and the ammonium raw material is preferably 70 to 120.degree.
Ｇ元素は、カリウム、ルビジウム、セシウム及びタリウムからなる群から選択される少なくとも１種の元素であり、セシウムを用いることがメタクリル酸収率の観点からが好ましい。
The G element is at least one element selected from the group consisting of potassium, rubidium, cesium and thallium, and it is preferable to use cesium from the viewpoint of methacrylic acid yield.
調製されたヘテロポリ酸（複合）塩含有液において、リンのモル数と、モリブデンのモル数の１／１２のうち小さい方の値をＭｐ２と定義したときに、添加するＧ元素のモル数Ｍｇ２、及び添加するアンモニウム原料に含まれるアンモニウムのモル数Ｍｎ２が下記式（ＩＶ）及び（Ｖ）を満たすことで、ピークＰ２を有する乾燥粉Ｋ２を得ることができる。
０．１５≦Ｍｇ２／Ｍｐ２＜Ｍｇ１／Ｍｐ１ （ＩＶ）
２．７≦（Ｍｇ２＋Ｍｎ２）／Ｍｐ２≦６．０ （Ｖ）
なお、（Ｍｇ２＋Ｍｎ２）／Ｍｐ２の値の下限は、２．８以上であることが好ましく、２．９以上であることがより好ましい。また上限は４．０以下であることが好ましく、３．５以下であることがより好ましい。 In the prepared heteropoly acid (complex) salt-containing liquid, when the smaller one of the number of moles of phosphorus and the number of 1/12 of the number of moles of molybdenum is defined as Mp 2, the number of moles Mg of G element to be added, And when the number Mn2 of moles of ammonium contained in the added ammonium raw material satisfies the following formulas (IV) and (V), a dry powder K2 having a peak P2 can be obtained.
0.15 ≦ Mg2 / Mp2 <Mg1 / Mp1 (IV)
2.7 ≦ (Mg2 + Mn2) /Mp2≦6.0 (V)
The lower limit of the value of (Mg 2 + Mn 2) / Mp 2 is preferably 2.8 or more, and more preferably 2.9 or more. The upper limit is preferably 4.0 or less, more preferably 3.5 or less.
０．１５≦Ｍｇ２／Ｍｐ２＜Ｍｇ１／Ｍｐ１ （ＩＶ）
２．７≦（Ｍｇ２＋Ｍｎ２）／Ｍｐ２≦６．０ （Ｖ）
なお、（Ｍｇ２＋Ｍｎ２）／Ｍｐ２の値の下限は、２．８以上であることが好ましく、２．９以上であることがより好ましい。また上限は４．０以下であることが好ましく、３．５以下であることがより好ましい。 In the prepared heteropoly acid (complex) salt-containing liquid, when the smaller one of the number of moles of phosphorus and the number of 1/12 of the number of moles of molybdenum is defined as Mp 2, the number of moles Mg of G element to be added, And when the number Mn2 of moles of ammonium contained in the added ammonium raw material satisfies the following formulas (IV) and (V), a dry powder K2 having a peak P2 can be obtained.
0.15 ≦ Mg2 / Mp2 <Mg1 / Mp1 (IV)
2.7 ≦ (Mg2 + Mn2) /Mp2≦6.0 (V)
The lower limit of the value of (Mg 2 + Mn 2) / Mp 2 is preferably 2.8 or more, and more preferably 2.9 or more. The upper limit is preferably 4.0 or less, more preferably 3.5 or less.
ヘテロポリ酸（複合）塩含有液のｐＨは、メタクリル酸収率の観点から０．１～４が好ましく、０．１～２がより好ましい。
The pH of the heteropoly acid (complex) salt-containing solution is preferably 0.1 to 4 from the viewpoint of methacrylic acid yield, and more preferably 0.1 to 2.
得られたヘテロポリ酸（複合）塩含有液を乾燥することで、乾燥粉Ｋ２を調製する。この際の乾燥方法は特に限定されず、例えば蒸発乾固法、噴霧乾燥法、ドラム乾燥法、気流乾燥法等を用いることができるが、噴霧乾燥法が最も好適である。得られる乾燥粉Ｋ２の水分量が２ｗｔ％以下になるまで乾燥を行うことが好ましい。
The dried powder K2 is prepared by drying the resulting heteropoly acid (complex) salt-containing solution. The drying method in this case is not particularly limited, and for example, evaporation to dryness, spray drying, drum drying, flash drying and the like can be used, and the spray drying is most preferable. It is preferable to carry out drying until the water content of the obtained dry powder K2 becomes 2 wt% or less.
（乾燥粉混合工程）
本工程では、前記乾燥粉Ｋ１と前記乾燥粉Ｋ２を混合し、触媒前駆体を調製する。混合方法は特に限定されないが、噴霧乾燥法を用いて乾燥粉Ｋ１及び乾燥粉Ｋ２を乾燥している場合は、単に乾燥粉Ｋ１及び乾燥粉Ｋ２を乾式混合するだけでよい。蒸発乾固法やドラム乾燥法を用いて乾燥粉Ｋ１及び乾燥粉Ｋ２を乾燥している場合には、擂潰器を用いて擂潰による混合を行うことが好ましい。
乾燥粉Ｋ１とＫ２の混合比率により、前記Ｉ１／Ｉ２の値を調整することができる。下記式により算出されるＫ１混合比が、５～９５％となるように混合することが好ましい。Ｋ１混合比の下限は１０％以上、上限は９４％以下がより好ましい。
Ｋ１混合比＝乾燥粉Ｋ１の質量／（乾燥粉Ｋ１の質量＋乾燥粉Ｋ２の質量）×１００
なお、上述のように２種類の乾燥粉を調製し混合する方法以外にも、ヘテロポリ酸含有液へＧ元素の原料及びアンモニウム原料を添加する際の撹拌速度、ヘテロポリ酸含有液の温度、Ｇ元素の原料及びアンモニウム原料の添加速度を調節することにより、１工程でピークＰ１及びピークＰ２の両方を有する触媒前駆体を調製しても良い。 (Dried powder mixing process)
In this step, the dry powder K1 and the dry powder K2 are mixed to prepare a catalyst precursor. The mixing method is not particularly limited, but when dry powder K1 and dry powder K2 are dried using a spray drying method, it is only necessary to dry mix dry powder K1 and dry powder K2. When the dried powder K1 and the dried powder K2 are dried using the evaporation to dryness method or the drum drying method, it is preferable to perform mixing by crushing using a grinder.
The value of I1 / I2 can be adjusted by the mixing ratio of the dry powders K1 and K2. It is preferable to mix such that the K1 mixing ratio calculated by the following equation is 5 to 95%. The lower limit of the K1 mixing ratio is more preferably 10% or more, and the upper limit is more preferably 94% or less.
K1 mixing ratio = mass of dried powder K1 / (mass of dried powder K1 + mass of dried powder K2) × 100
In addition, the stirring speed at the time of adding the raw material of G element and an ammonium raw material to heteropoly acid containing liquid besides the method of preparing and mixing two types of dry powder as mentioned above, temperature of heteropoly acid containing liquid, G element The catalyst precursor having both of the peak P1 and the peak P2 may be prepared in one step by adjusting the addition rates of the raw material and the ammonium raw material.
本工程では、前記乾燥粉Ｋ１と前記乾燥粉Ｋ２を混合し、触媒前駆体を調製する。混合方法は特に限定されないが、噴霧乾燥法を用いて乾燥粉Ｋ１及び乾燥粉Ｋ２を乾燥している場合は、単に乾燥粉Ｋ１及び乾燥粉Ｋ２を乾式混合するだけでよい。蒸発乾固法やドラム乾燥法を用いて乾燥粉Ｋ１及び乾燥粉Ｋ２を乾燥している場合には、擂潰器を用いて擂潰による混合を行うことが好ましい。
乾燥粉Ｋ１とＫ２の混合比率により、前記Ｉ１／Ｉ２の値を調整することができる。下記式により算出されるＫ１混合比が、５～９５％となるように混合することが好ましい。Ｋ１混合比の下限は１０％以上、上限は９４％以下がより好ましい。
Ｋ１混合比＝乾燥粉Ｋ１の質量／（乾燥粉Ｋ１の質量＋乾燥粉Ｋ２の質量）×１００
なお、上述のように２種類の乾燥粉を調製し混合する方法以外にも、ヘテロポリ酸含有液へＧ元素の原料及びアンモニウム原料を添加する際の撹拌速度、ヘテロポリ酸含有液の温度、Ｇ元素の原料及びアンモニウム原料の添加速度を調節することにより、１工程でピークＰ１及びピークＰ２の両方を有する触媒前駆体を調製しても良い。 (Dried powder mixing process)
In this step, the dry powder K1 and the dry powder K2 are mixed to prepare a catalyst precursor. The mixing method is not particularly limited, but when dry powder K1 and dry powder K2 are dried using a spray drying method, it is only necessary to dry mix dry powder K1 and dry powder K2. When the dried powder K1 and the dried powder K2 are dried using the evaporation to dryness method or the drum drying method, it is preferable to perform mixing by crushing using a grinder.
The value of I1 / I2 can be adjusted by the mixing ratio of the dry powders K1 and K2. It is preferable to mix such that the K1 mixing ratio calculated by the following equation is 5 to 95%. The lower limit of the K1 mixing ratio is more preferably 10% or more, and the upper limit is more preferably 94% or less.
K1 mixing ratio = mass of dried powder K1 / (mass of dried powder K1 + mass of dried powder K2) × 100
In addition, the stirring speed at the time of adding the raw material of G element and an ammonium raw material to heteropoly acid containing liquid besides the method of preparing and mixing two types of dry powder as mentioned above, temperature of heteropoly acid containing liquid, G element The catalyst precursor having both of the peak P1 and the peak P2 may be prepared in one step by adjusting the addition rates of the raw material and the ammonium raw material.
（成形工程）
後述する熱処理工程の前に、前記乾燥粉混合工程により得られた触媒前駆体を成形してもよい。成形方法は特に制限されず、公知の乾式又は湿式の成形方法が適用できる。例えば、打錠成形、プレス成形、押出成形、造粒成形等が挙げられる。成形品の形状は特に限定されず、例えば、円柱状、リング状、球状等が挙げられる。また、成形時には触媒前駆体に担体やバインダー等を添加せず、触媒前駆体のみを成形することが好ましいが、必要に応じて例えばグラファイト、タルク等の公知の添加剤や有機物、無機物由来の公知のバインダーを添加してもよい。 (Molding process)
The catalyst precursor obtained by the dry powder mixing step may be shaped before the heat treatment step described later. The molding method is not particularly limited, and known dry or wet molding methods can be applied. For example, tablet molding, press molding, extrusion molding, granulation molding and the like can be mentioned. The shape of the molded article is not particularly limited, and examples thereof include a cylindrical shape, a ring shape, and a spherical shape. Further, at the time of molding, it is preferable to mold only the catalyst precursor without adding a carrier, a binder or the like to the catalyst precursor, but if necessary, for example, known additives such as graphite and talc, or known materials derived from organic substances and inorganic substances Binders may be added.
後述する熱処理工程の前に、前記乾燥粉混合工程により得られた触媒前駆体を成形してもよい。成形方法は特に制限されず、公知の乾式又は湿式の成形方法が適用できる。例えば、打錠成形、プレス成形、押出成形、造粒成形等が挙げられる。成形品の形状は特に限定されず、例えば、円柱状、リング状、球状等が挙げられる。また、成形時には触媒前駆体に担体やバインダー等を添加せず、触媒前駆体のみを成形することが好ましいが、必要に応じて例えばグラファイト、タルク等の公知の添加剤や有機物、無機物由来の公知のバインダーを添加してもよい。 (Molding process)
The catalyst precursor obtained by the dry powder mixing step may be shaped before the heat treatment step described later. The molding method is not particularly limited, and known dry or wet molding methods can be applied. For example, tablet molding, press molding, extrusion molding, granulation molding and the like can be mentioned. The shape of the molded article is not particularly limited, and examples thereof include a cylindrical shape, a ring shape, and a spherical shape. Further, at the time of molding, it is preferable to mold only the catalyst precursor without adding a carrier, a binder or the like to the catalyst precursor, but if necessary, for example, known additives such as graphite and talc, or known materials derived from organic substances and inorganic substances Binders may be added.
［触媒又はメタクリル酸製造用触媒の製造方法］
触媒を製造するには、前記乾燥粉混合工程により得られた触媒前駆体、又は前記成形工程により得られる触媒前駆体の成形物（以下、まとめて「触媒前駆体」とも示す。）を熱処理する工程（以下、「熱処理工程」とも示す。）を含むことが好ましい。 [Method for producing catalyst or catalyst for producing methacrylic acid]
In order to produce the catalyst, the catalyst precursor obtained in the dry powder mixing step or the molded product of the catalyst precursor obtained in the molding step (hereinafter collectively referred to as "catalyst precursor") is heat-treated. It is preferable to include a step (hereinafter also referred to as “heat treatment step”).
触媒を製造するには、前記乾燥粉混合工程により得られた触媒前駆体、又は前記成形工程により得られる触媒前駆体の成形物（以下、まとめて「触媒前駆体」とも示す。）を熱処理する工程（以下、「熱処理工程」とも示す。）を含むことが好ましい。 [Method for producing catalyst or catalyst for producing methacrylic acid]
In order to produce the catalyst, the catalyst precursor obtained in the dry powder mixing step or the molded product of the catalyst precursor obtained in the molding step (hereinafter collectively referred to as "catalyst precursor") is heat-treated. It is preferable to include a step (hereinafter also referred to as “heat treatment step”).
（熱処理工程）
本工程では、前記触媒前駆体を熱処理して触媒を製造する。熱処理工程により、工業的使用条件下で局所発熱が少なく、かつ、反応器あたりの活性の高い触媒を得ることができる。熱処理方法や条件は特に制限されず、公知の方法及び条件を適用することができる。熱処理温度は、３００～４５０℃であることが好ましい。熱処理温度を３００℃以上にすることで、触媒中のアンモニウムが除去されて触媒活性を良好とすることができ、４５０℃以下とすることで、ヘテロポリ酸の熱分解を抑制し、急激な触媒活性の低下を抑制することができる。また、熱処理時間の下限は０．５時間以上が好ましく、１時間以上がより好ましい。また、熱処理時間の上限は、４０時間以下が好ましい。 (Heat treatment process)
In this step, the catalyst precursor is heat-treated to produce a catalyst. By the heat treatment step, it is possible to obtain a catalyst with less local heat generation under industrial use conditions and high activity per reactor. The heat treatment method and conditions are not particularly limited, and known methods and conditions can be applied. The heat treatment temperature is preferably 300 to 450 ° C. By setting the heat treatment temperature to 300 ° C. or higher, the ammonium in the catalyst can be removed and the catalyst activity can be made favorable. By setting the heat treatment temperature to 450 ° C. or less, the thermal decomposition of the heteropoly acid is suppressed, and the rapid catalytic activity is achieved. Can be suppressed. Moreover, 0.5 hour or more is preferable and, as for the minimum of heat processing time, 1 hour or more is more preferable. Moreover, as for the upper limit of heat processing time, 40 hours or less are preferable.
本工程では、前記触媒前駆体を熱処理して触媒を製造する。熱処理工程により、工業的使用条件下で局所発熱が少なく、かつ、反応器あたりの活性の高い触媒を得ることができる。熱処理方法や条件は特に制限されず、公知の方法及び条件を適用することができる。熱処理温度は、３００～４５０℃であることが好ましい。熱処理温度を３００℃以上にすることで、触媒中のアンモニウムが除去されて触媒活性を良好とすることができ、４５０℃以下とすることで、ヘテロポリ酸の熱分解を抑制し、急激な触媒活性の低下を抑制することができる。また、熱処理時間の下限は０．５時間以上が好ましく、１時間以上がより好ましい。また、熱処理時間の上限は、４０時間以下が好ましい。 (Heat treatment process)
In this step, the catalyst precursor is heat-treated to produce a catalyst. By the heat treatment step, it is possible to obtain a catalyst with less local heat generation under industrial use conditions and high activity per reactor. The heat treatment method and conditions are not particularly limited, and known methods and conditions can be applied. The heat treatment temperature is preferably 300 to 450 ° C. By setting the heat treatment temperature to 300 ° C. or higher, the ammonium in the catalyst can be removed and the catalyst activity can be made favorable. By setting the heat treatment temperature to 450 ° C. or less, the thermal decomposition of the heteropoly acid is suppressed, and the rapid catalytic activity is achieved. Can be suppressed. Moreover, 0.5 hour or more is preferable and, as for the minimum of heat processing time, 1 hour or more is more preferable. Moreover, as for the upper limit of heat processing time, 40 hours or less are preferable.
熱処理は、例えば空気及び不活性ガスの少なくとも一方の流通下で行うことができる。ここで、不活性ガスとは触媒活性を低下させない気体のことを示し、例えば窒素、炭酸ガス、ヘリウム、アルゴン等が挙げられる。これらは一種を用いてもよく、二種以上を混合して使用してもよい。熱処理は、空気等の酸素含有ガス流通下で行われることが好ましい。
The heat treatment can be performed, for example, in the flow of at least one of air and an inert gas. Here, the inert gas indicates a gas which does not reduce the catalytic activity, and examples thereof include nitrogen, carbon dioxide gas, helium, argon and the like. One of these may be used, or two or more may be mixed and used. The heat treatment is preferably performed in the flow of an oxygen-containing gas such as air.
［メタクリル酸の製造方法］
本発明に係るメタクリル酸の製造方法は、本発明に係る触媒前駆体から得られる触媒の存在下で、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製造する。該方法によれば、高い収率でメタクリル酸を製造することができる。
なお、触媒を得てから一定期間経過後にメタクリル酸を製造してもよい。また触媒の製造場所とメタクリル酸の製造場所は異なっていてもよい。 [Method for producing methacrylic acid]
The method for producing methacrylic acid according to the present invention produces methacrylic acid by catalytic oxidation of methacrolein with molecular oxygen in the presence of a catalyst obtained from the catalyst precursor according to the present invention. According to this method, methacrylic acid can be produced in high yield.
Methacrylic acid may be produced after a given period of time has elapsed since the catalyst was obtained. Also, the production site of the catalyst and the production site of methacrylic acid may be different.
本発明に係るメタクリル酸の製造方法は、本発明に係る触媒前駆体から得られる触媒の存在下で、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製造する。該方法によれば、高い収率でメタクリル酸を製造することができる。
なお、触媒を得てから一定期間経過後にメタクリル酸を製造してもよい。また触媒の製造場所とメタクリル酸の製造場所は異なっていてもよい。 [Method for producing methacrylic acid]
The method for producing methacrylic acid according to the present invention produces methacrylic acid by catalytic oxidation of methacrolein with molecular oxygen in the presence of a catalyst obtained from the catalyst precursor according to the present invention. According to this method, methacrylic acid can be produced in high yield.
Methacrylic acid may be produced after a given period of time has elapsed since the catalyst was obtained. Also, the production site of the catalyst and the production site of methacrylic acid may be different.
具体的には、メタクロレイン及び分子状酸素を含む原料ガスと、本発明に係る触媒とを接触させることでメタクリル酸を製造することができる。この反応は固定床で行うことが好ましい。
Specifically, methacrylic acid can be produced by contacting a source gas containing methacrolein and molecular oxygen with the catalyst according to the present invention. The reaction is preferably carried out in a fixed bed.
触媒はそのまま無希釈で使用しても、不活性担体で希釈して使用しても良く、無希釈層と希釈層とを積層し複数層を形成して使用しても良い。
The catalyst may be used as it is without dilution or may be used after diluting it with an inert carrier, or it may be used by laminating a non-diluted layer and a diluted layer to form a plurality of layers.
原料ガス中のメタクロレインの濃度は特に限定されないが、１～２０容量％が好ましく、下限は３容量％以上、上限は１０容量％以下がより好ましい。メタクロレインは、低級飽和アルデヒド等の本反応に実質的な影響を与えない不純物を少量含んでいてもよい。原料ガス中のメタクロレインと分子状酸素とのモル比は、メタクロレイン１．０モルに対して０．５～４．０モルが好ましく、下限は１．０モル以上、上限は３．０モル以下がより好ましい。分子状酸素源としては空気を用いるのが経済的であるが、必要であれば、純酸素で富化した空気も用いることができる。
The concentration of methacrolein in the raw material gas is not particularly limited, but is preferably 1 to 20% by volume, the lower limit is 3% by volume or more, and the upper limit is 10% by volume or less. Methacrolein may contain a small amount of impurities such as lower saturated aldehyde which do not substantially affect the reaction. The molar ratio of methacrolein to molecular oxygen in the raw material gas is preferably 0.5 to 4.0 mol with respect to 1.0 mol of methacrolein, and the lower limit is 1.0 mol or more and the upper limit is 3.0 mol The following are more preferable. While it is economical to use air as a molecular oxygen source, air enriched with pure oxygen can also be used if desired.
原料ガスは、メタクロレイン及び分子状酸素を、窒素、炭酸ガス等の不活性ガスにより希釈してもよい。また、前記原料ガスは水蒸気を含んでもよい。水蒸気の存在下で反応を行うことにより、メタクリル酸をより高い選択率で得ることができる。原料ガス中の水蒸気の濃度は、０．１～５０．０容量％が好ましく、１．０～４０．０容量％がより好ましい。原料ガスと触媒との接触時間は、１．５～１５．０秒が好ましく、下限は２．０秒以上、上限は５．０秒以下がより好ましい。反応圧力は大気圧～数百ｋＰａ（Ｇ）までの範囲内で設定されることができる。ただし、（Ｇ）はゲージ圧であることを意味する。反応温度は２００℃～４５０℃が好ましく、下限は２５０℃以上、上限は４００℃以下がより好ましい。
The source gas may dilute methacrolein and molecular oxygen with an inert gas such as nitrogen or carbon dioxide gas. Further, the source gas may contain water vapor. By carrying out the reaction in the presence of steam, methacrylic acid can be obtained with higher selectivity. The concentration of water vapor in the raw material gas is preferably 0.1 to 50.0% by volume, and more preferably 1.0 to 40.0% by volume. The contact time between the raw material gas and the catalyst is preferably 1.5 to 15.0 seconds, the lower limit is preferably 2.0 seconds or more, and the upper limit is more preferably 5.0 seconds or less. The reaction pressure can be set in the range from atmospheric pressure to several hundreds kPa (G). However, (G) means being gauge pressure. The reaction temperature is preferably 200 ° C. to 450 ° C., the lower limit is more than 250 ° C., and the upper limit is more preferably 400 ° C. or less.
［メタクリル酸エステルの製造方法］
本発明に係るメタクリル酸エステルの製造方法は、本発明に係る方法により得られるメタクリル酸のエステル化により行うことができる。該方法によれば、メタクロレインの気相接触酸化により得られるメタクリル酸を用いて、メタクリル酸エステルを得ることができる。メタクリル酸と反応させるアルコールとしては、メタノール、エタノール、イソプロパノール、ｎ－ブタノール、イソブタノール等が挙げられる。得られるメタクリル酸エステルとしては、例えばメタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸ブチル等が挙げられる。反応は、スルホン酸型カチオン交換樹脂等の酸性触媒の存在下で行うことができる。反応温度は５０～２００℃が好ましい。 [Method for producing methacrylic acid ester]
The method for producing a methacrylic acid ester according to the present invention can be carried out by esterification of methacrylic acid obtained by the method according to the present invention. According to this method, a methacrylic acid ester can be obtained using methacrylic acid obtained by gas phase catalytic oxidation of methacrolein. Examples of the alcohol to be reacted with methacrylic acid include methanol, ethanol, isopropanol, n-butanol, isobutanol and the like. Examples of the methacrylic acid ester to be obtained include methyl methacrylate, ethyl methacrylate, propyl methacrylate and butyl methacrylate. The reaction can be carried out in the presence of an acidic catalyst such as a sulfonic acid type cation exchange resin. The reaction temperature is preferably 50 to 200 ° C.
本発明に係るメタクリル酸エステルの製造方法は、本発明に係る方法により得られるメタクリル酸のエステル化により行うことができる。該方法によれば、メタクロレインの気相接触酸化により得られるメタクリル酸を用いて、メタクリル酸エステルを得ることができる。メタクリル酸と反応させるアルコールとしては、メタノール、エタノール、イソプロパノール、ｎ－ブタノール、イソブタノール等が挙げられる。得られるメタクリル酸エステルとしては、例えばメタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸ブチル等が挙げられる。反応は、スルホン酸型カチオン交換樹脂等の酸性触媒の存在下で行うことができる。反応温度は５０～２００℃が好ましい。 [Method for producing methacrylic acid ester]
The method for producing a methacrylic acid ester according to the present invention can be carried out by esterification of methacrylic acid obtained by the method according to the present invention. According to this method, a methacrylic acid ester can be obtained using methacrylic acid obtained by gas phase catalytic oxidation of methacrolein. Examples of the alcohol to be reacted with methacrylic acid include methanol, ethanol, isopropanol, n-butanol, isobutanol and the like. Examples of the methacrylic acid ester to be obtained include methyl methacrylate, ethyl methacrylate, propyl methacrylate and butyl methacrylate. The reaction can be carried out in the presence of an acidic catalyst such as a sulfonic acid type cation exchange resin. The reaction temperature is preferably 50 to 200 ° C.
以下、実施例及び比較例により本発明を詳細に説明するが、本発明はこれらの実施例に限定されるものではない。実施例及び比較例において、「部」は質量部を意味する。Ｘ線回折は、Ｘ線構造解析装置（商品名：Ｘ‘Ｐｅｒｔ ＰＲＯ ＭＰＤ、ＰＡＮａｌｙｔｉｃａｌ社製）にて測定した。原料ガス及び生成物の分析は、ガスクロマトグラフィーを用いて行った。ガスクロマトグラフィーの結果から、メタクロレインの転化率、生成するメタクリル酸の選択率及びメタクリル酸の収率は下記式にて求めた。
メタクロレイン転化率（％）＝（Ｂ／Ａ）×１００
メタクリル酸選択率（％）＝（Ｃ／Ｂ）×１００
メタクリル酸収率（％）＝（Ｃ／Ａ）×１００
式中、Ａは供給したメタクロレインのモル数、Ｂは反応したメタクロレインのモル数、Ｃは生成したメタクリル酸のモル数を示す。 Hereinafter, the present invention will be described in detail by way of examples and comparative examples, but the present invention is not limited to these examples. In Examples and Comparative Examples, "parts" means parts by mass. The X-ray diffraction was measured by an X-ray structural analyzer (trade name: X'Pert PRO MPD, manufactured by PANalytical). The analysis of the source gas and the product was performed using gas chromatography. From the results of gas chromatography, the conversion of methacrolein, the selectivity of the formed methacrylic acid and the yield of methacrylic acid were determined by the following equations.
Methacrolein conversion rate (%) = (B / A) x 100
Methacrylic acid selectivity (%) = (C / B) × 100
Methacrylic acid yield (%) = (C / A) × 100
In the formula, A represents the number of moles of methacrolein supplied, B represents the number of moles of methacrolein reacted, and C represents the number of moles of methacrylic acid formed.
メタクロレイン転化率（％）＝（Ｂ／Ａ）×１００
メタクリル酸選択率（％）＝（Ｃ／Ｂ）×１００
メタクリル酸収率（％）＝（Ｃ／Ａ）×１００
式中、Ａは供給したメタクロレインのモル数、Ｂは反応したメタクロレインのモル数、Ｃは生成したメタクリル酸のモル数を示す。 Hereinafter, the present invention will be described in detail by way of examples and comparative examples, but the present invention is not limited to these examples. In Examples and Comparative Examples, "parts" means parts by mass. The X-ray diffraction was measured by an X-ray structural analyzer (trade name: X'Pert PRO MPD, manufactured by PANalytical). The analysis of the source gas and the product was performed using gas chromatography. From the results of gas chromatography, the conversion of methacrolein, the selectivity of the formed methacrylic acid and the yield of methacrylic acid were determined by the following equations.
Methacrolein conversion rate (%) = (B / A) x 100
Methacrylic acid selectivity (%) = (C / B) × 100
Methacrylic acid yield (%) = (C / A) × 100
In the formula, A represents the number of moles of methacrolein supplied, B represents the number of moles of methacrolein reacted, and C represents the number of moles of methacrylic acid formed.
［実施例１］
純水６００部に、三酸化モリブデン１００部、８５質量％リン酸６．６７部、メタバナジン酸アンモニウム３．３６部、硝酸第二銅２．１０部を溶解した。これを撹拌しながら昇温し、１００℃の還流下で５時間攪拌した。降温し液温を８０℃に保ちつつ、純水２００部に溶解した重炭酸セシウム２４．１４部を添加して１５分間撹拌し、続いて純水２００部に溶解した重炭酸アンモニウム３．８４部を添加した。得られたヘテロポリ酸（複合）塩含有液を、出口温度２５０℃で噴霧乾燥を行い、さらに１３０℃で１６時間乾燥して乾燥粉Ｋ１ａを得た。一方、純水６００部に、三酸化モリブデン１００部、８５質量％リン酸６．６７部、メタバナジン酸アンモニウム３．３６部、硝酸第二銅２．１０部を溶解した。これを撹拌しながら昇温し、１００℃の還流下で５時間攪拌した。降温し液温を８０℃に保ちつつ、純水２００部に溶解した重炭酸セシウム４．０４部を添加して１５分間撹拌し、続いて純水２００部に溶解した重炭酸アンモニウム１１．９３部を添加した。得られたヘテロポリ酸（複合）塩含有液を、出口温度２５０℃で噴霧乾燥を行い、さらに１３０℃で１６時間乾燥して乾燥粉Ｋ２ａを得た。次に、乾燥粉Ｋ１ａを９０部に対し、乾燥粉Ｋ２ａを１０部の割合で混合し、触媒前駆体を得た。該触媒前駆体について、対陰極Ｃｕ－Ｋα線を用いたＸ線回折パターン測定を行った結果、表１に示すピークが確認された。 Example 1
100 parts of molybdenum trioxide, 6.67 parts of 85 mass% phosphoric acid, 3.36 parts of ammonium metavanadate and 2.10 parts of cupric nitrate were dissolved in 600 parts of pure water. The temperature was raised while stirring, and stirred under reflux at 100 ° C. for 5 hours. While keeping the temperature at 80 ° C., add 24.14 parts of cesium bicarbonate dissolved in 200 parts of pure water, stir for 15 minutes, and then 3.84 parts of ammonium bicarbonate dissolved in 200 parts of pure water Was added. The resulting heteropoly acid (composite) salt-containing solution was spray-dried at an outlet temperature of 250 ° C., and further dried at 130 ° C. for 16 hours to obtain a dry powder K1a. On the other hand, 100 parts of molybdenum trioxide, 6.67 parts of 85% by mass phosphoric acid, 3.36 parts of ammonium metavanadate and 2.10 parts of cupric nitrate were dissolved in 600 parts of pure water. The temperature was raised while stirring, and stirred under reflux at 100 ° C. for 5 hours. While maintaining the temperature at 80 ° C., add 4.04 parts of cesium bicarbonate dissolved in 200 parts of pure water, stir for 15 minutes, and then 11.93 parts of ammonium bicarbonate dissolved in 200 parts of pure water Was added. The resulting heteropoly acid (composite) salt-containing solution was spray-dried at an outlet temperature of 250 ° C., and further dried at 130 ° C. for 16 hours to obtain a dry powder K2a. Next, 90 parts of the dry powder K1a and 10 parts of the dry powder K2a were mixed to obtain a catalyst precursor. As a result of X-ray diffraction pattern measurement using an anticathode Cu-Kα ray for the catalyst precursor, peaks shown in Table 1 were confirmed.
純水６００部に、三酸化モリブデン１００部、８５質量％リン酸６．６７部、メタバナジン酸アンモニウム３．３６部、硝酸第二銅２．１０部を溶解した。これを撹拌しながら昇温し、１００℃の還流下で５時間攪拌した。降温し液温を８０℃に保ちつつ、純水２００部に溶解した重炭酸セシウム２４．１４部を添加して１５分間撹拌し、続いて純水２００部に溶解した重炭酸アンモニウム３．８４部を添加した。得られたヘテロポリ酸（複合）塩含有液を、出口温度２５０℃で噴霧乾燥を行い、さらに１３０℃で１６時間乾燥して乾燥粉Ｋ１ａを得た。一方、純水６００部に、三酸化モリブデン１００部、８５質量％リン酸６．６７部、メタバナジン酸アンモニウム３．３６部、硝酸第二銅２．１０部を溶解した。これを撹拌しながら昇温し、１００℃の還流下で５時間攪拌した。降温し液温を８０℃に保ちつつ、純水２００部に溶解した重炭酸セシウム４．０４部を添加して１５分間撹拌し、続いて純水２００部に溶解した重炭酸アンモニウム１１．９３部を添加した。得られたヘテロポリ酸（複合）塩含有液を、出口温度２５０℃で噴霧乾燥を行い、さらに１３０℃で１６時間乾燥して乾燥粉Ｋ２ａを得た。次に、乾燥粉Ｋ１ａを９０部に対し、乾燥粉Ｋ２ａを１０部の割合で混合し、触媒前駆体を得た。該触媒前駆体について、対陰極Ｃｕ－Ｋα線を用いたＸ線回折パターン測定を行った結果、表１に示すピークが確認された。 Example 1
100 parts of molybdenum trioxide, 6.67 parts of 85 mass% phosphoric acid, 3.36 parts of ammonium metavanadate and 2.10 parts of cupric nitrate were dissolved in 600 parts of pure water. The temperature was raised while stirring, and stirred under reflux at 100 ° C. for 5 hours. While keeping the temperature at 80 ° C., add 24.14 parts of cesium bicarbonate dissolved in 200 parts of pure water, stir for 15 minutes, and then 3.84 parts of ammonium bicarbonate dissolved in 200 parts of pure water Was added. The resulting heteropoly acid (composite) salt-containing solution was spray-dried at an outlet temperature of 250 ° C., and further dried at 130 ° C. for 16 hours to obtain a dry powder K1a. On the other hand, 100 parts of molybdenum trioxide, 6.67 parts of 85% by mass phosphoric acid, 3.36 parts of ammonium metavanadate and 2.10 parts of cupric nitrate were dissolved in 600 parts of pure water. The temperature was raised while stirring, and stirred under reflux at 100 ° C. for 5 hours. While maintaining the temperature at 80 ° C., add 4.04 parts of cesium bicarbonate dissolved in 200 parts of pure water, stir for 15 minutes, and then 11.93 parts of ammonium bicarbonate dissolved in 200 parts of pure water Was added. The resulting heteropoly acid (composite) salt-containing solution was spray-dried at an outlet temperature of 250 ° C., and further dried at 130 ° C. for 16 hours to obtain a dry powder K2a. Next, 90 parts of the dry powder K1a and 10 parts of the dry powder K2a were mixed to obtain a catalyst precursor. As a result of X-ray diffraction pattern measurement using an anticathode Cu-Kα ray for the catalyst precursor, peaks shown in Table 1 were confirmed.
該触媒前駆体を、打錠成形機により成形し、内径３ｃｍの円筒状石英ガラス製焼成容器に入れた。空気流通下、１０℃／ｈで昇温し、３８０℃にて２時間熱処理して触媒を調製した。該触媒の水素、窒素、酸素を除く組成は、Ｐ１Ｍｏ１２Ｖ０．５Ｃｕ０．１５Ｃｓ１．９７であった。なお、該元素組成のモル比は、触媒前駆体をアンモニア水に溶解した成分をＩＣＰ発光分析法で分析することによって算出した。
The catalyst precursor was molded by a tableting machine and placed in a cylindrical quartz glass baking container with an inner diameter of 3 cm. Under air flow, the temperature was raised at 10 ° C./h, and the catalyst was prepared by heat treatment at 380 ° C. for 2 hours. The composition of the catalyst excluding hydrogen, nitrogen and oxygen was P 1 Mo 12 V 0.5 Cu 0.15 Cs 1.97 . The molar ratio of the elemental composition was calculated by analyzing a component obtained by dissolving the catalyst precursor in aqueous ammonia by ICP emission analysis.
該触媒を反応管に充填し、メタクロレイン５容量％、酸素１０容量％、水蒸気３０容量％及び窒素５５容量％からなる原料ガスを通じて、反応温度２９０℃、反応圧力２５６ｋＰａ、接触時間：３．６秒で反応を行った。結果を表１に示す。
The catalyst is charged in a reaction tube, and a raw material gas consisting of 5% by volume of methacrolein, 10% by volume of oxygen, 30% by volume of steam and 30% by volume of steam and 55% by volume of nitrogen is used. The reaction was done in seconds. The results are shown in Table 1.
［実施例２］
純水６００部に、三酸化モリブデン１００部、８５質量％リン酸６．６７部、メタバナジン酸アンモニウム３．３６部、硝酸第二銅２．１０部を溶解した。これを撹拌しながら昇温し、１００℃の還流下で５時間攪拌した。降温し液温を８０℃に保ちつつ、純水２００部に溶解した重炭酸セシウム３０．１０部を添加して１５分間撹拌し、続いて純水２００部に溶解した重炭酸アンモニウム１．４５部を添加した。得られたヘテロポリ酸（複合）塩含有液を、出口温度２５０℃で噴霧乾燥を行い、さらに１３０℃で１６時間乾燥して乾燥粉Ｋ１ｂを得た。一方、純水６００部に、三酸化モリブデン１００部、８５質量％リン酸６．６７部、メタバナジン酸アンモニウム３．３６部、硝酸第二銅２．１０部を溶解した。これを撹拌しながら昇温し、１００℃の還流下で５時間攪拌した。降温し液温を８０℃に８０℃に保ちつつ、純水２００部に溶解した重炭酸セシウム３．１４部を添加して１５分間撹拌し、続いて純水２００部に溶解した重炭酸アンモニウム１２．２９部を添加した。得られたヘテロポリ酸（複合）塩含有液を、出口温度２５０℃で噴霧乾燥を行い、さらに１３０℃で１６時間乾燥して乾燥粉Ｋ２ｂを得た。 Example 2
100 parts of molybdenum trioxide, 6.67 parts of 85 mass% phosphoric acid, 3.36 parts of ammonium metavanadate and 2.10 parts of cupric nitrate were dissolved in 600 parts of pure water. The temperature was raised while stirring, and stirred under reflux at 100 ° C. for 5 hours. While maintaining the temperature at 80 ° C., add 30.10 parts of cesium bicarbonate dissolved in 200 parts of pure water, stir for 15 minutes, and then dissolve 1.45 parts of ammonium bicarbonate dissolved in 200 parts of pure water Was added. The resulting heteropoly acid (composite) salt-containing solution was spray-dried at an outlet temperature of 250 ° C., and further dried at 130 ° C. for 16 hours to obtain a dry powder K1b. On the other hand, 100 parts of molybdenum trioxide, 6.67 parts of 85% by mass phosphoric acid, 3.36 parts of ammonium metavanadate and 2.10 parts of cupric nitrate were dissolved in 600 parts of pure water. The temperature was raised while stirring, and stirred under reflux at 100 ° C. for 5 hours. While keeping the temperature at 80 ° C. and maintaining the temperature at 80 ° C., 3.14 parts of cesium bicarbonate dissolved in 200 parts of pure water is added and stirred for 15 minutes, and then ammonium bicarbonate 12 dissolved in 200 parts of pure water .29 parts were added. The resulting heteropoly acid (complex) salt-containing solution was spray-dried at an outlet temperature of 250 ° C., and further dried at 130 ° C. for 16 hours to obtain a dry powder K2b.
純水６００部に、三酸化モリブデン１００部、８５質量％リン酸６．６７部、メタバナジン酸アンモニウム３．３６部、硝酸第二銅２．１０部を溶解した。これを撹拌しながら昇温し、１００℃の還流下で５時間攪拌した。降温し液温を８０℃に保ちつつ、純水２００部に溶解した重炭酸セシウム３０．１０部を添加して１５分間撹拌し、続いて純水２００部に溶解した重炭酸アンモニウム１．４５部を添加した。得られたヘテロポリ酸（複合）塩含有液を、出口温度２５０℃で噴霧乾燥を行い、さらに１３０℃で１６時間乾燥して乾燥粉Ｋ１ｂを得た。一方、純水６００部に、三酸化モリブデン１００部、８５質量％リン酸６．６７部、メタバナジン酸アンモニウム３．３６部、硝酸第二銅２．１０部を溶解した。これを撹拌しながら昇温し、１００℃の還流下で５時間攪拌した。降温し液温を８０℃に８０℃に保ちつつ、純水２００部に溶解した重炭酸セシウム３．１４部を添加して１５分間撹拌し、続いて純水２００部に溶解した重炭酸アンモニウム１２．２９部を添加した。得られたヘテロポリ酸（複合）塩含有液を、出口温度２５０℃で噴霧乾燥を行い、さらに１３０℃で１６時間乾燥して乾燥粉Ｋ２ｂを得た。 Example 2
100 parts of molybdenum trioxide, 6.67 parts of 85 mass% phosphoric acid, 3.36 parts of ammonium metavanadate and 2.10 parts of cupric nitrate were dissolved in 600 parts of pure water. The temperature was raised while stirring, and stirred under reflux at 100 ° C. for 5 hours. While maintaining the temperature at 80 ° C., add 30.10 parts of cesium bicarbonate dissolved in 200 parts of pure water, stir for 15 minutes, and then dissolve 1.45 parts of ammonium bicarbonate dissolved in 200 parts of pure water Was added. The resulting heteropoly acid (composite) salt-containing solution was spray-dried at an outlet temperature of 250 ° C., and further dried at 130 ° C. for 16 hours to obtain a dry powder K1b. On the other hand, 100 parts of molybdenum trioxide, 6.67 parts of 85% by mass phosphoric acid, 3.36 parts of ammonium metavanadate and 2.10 parts of cupric nitrate were dissolved in 600 parts of pure water. The temperature was raised while stirring, and stirred under reflux at 100 ° C. for 5 hours. While keeping the temperature at 80 ° C. and maintaining the temperature at 80 ° C., 3.14 parts of cesium bicarbonate dissolved in 200 parts of pure water is added and stirred for 15 minutes, and then ammonium bicarbonate 12 dissolved in 200 parts of pure water .29 parts were added. The resulting heteropoly acid (complex) salt-containing solution was spray-dried at an outlet temperature of 250 ° C., and further dried at 130 ° C. for 16 hours to obtain a dry powder K2b.
次に、乾燥粉Ｋ１ｂを７０部に対し、乾燥粉Ｋ２ｂを３０部の割合で混合し、触媒前駆体を得た。得られた触媒前駆体の水素、窒素、酸素を除く組成は、Ｐ１Ｍｏ１２Ｖ０．５Ｃｕ０．１５Ｃｓ１．９６であった。該触媒前駆体について、対陰極Ｃｕ－Ｋα線を用いたＸ線回折パターン測定を行った結果、表１に示すピークが確認された。
Next, 70 parts of the dry powder K1b was mixed with 30 parts of the dry powder K2b to obtain a catalyst precursor. The composition except hydrogen, nitrogen, and oxygen of the obtained catalyst precursor was P 1 Mo 12 V 0.5 Cu 0.15 Cs 1.96 . As a result of X-ray diffraction pattern measurement using an anticathode Cu-Kα ray for the catalyst precursor, peaks shown in Table 1 were confirmed.
該触媒前駆体を実施例１と同様の方法により成形し熱処理して、触媒を調製した。
該触媒を用いて、実施例１と同様の方法によりメタクリル酸の製造を行った。結果を表１に示す。 The catalyst precursor was shaped and heat-treated in the same manner as in Example 1 to prepare a catalyst.
Using this catalyst, methacrylic acid was produced in the same manner as in Example 1. The results are shown in Table 1.
該触媒を用いて、実施例１と同様の方法によりメタクリル酸の製造を行った。結果を表１に示す。 The catalyst precursor was shaped and heat-treated in the same manner as in Example 1 to prepare a catalyst.
Using this catalyst, methacrylic acid was produced in the same manner as in Example 1. The results are shown in Table 1.
［実施例３］
純水６００部に、三酸化モリブデン１００部、８５質量％リン酸６．６７部、メタバナジン酸アンモニウム３．３６部、硝酸第二銅２．１０部を溶解した。これを撹拌しながら昇温し、１００℃の還流下で５時間攪拌した。降温し液温を８０℃に保ちつつ、純水２００部に溶解した重炭酸セシウム２１．５６部を添加して１５分間撹拌し、続いて純水２００部に溶解した重炭酸アンモニウム４．８８部を添加した。得られたヘテロポリ酸（複合）塩含有液を、出口温度２５０℃で噴霧乾燥を行い、さらに１３０℃で１６時間乾燥して乾燥粉Ｋ１ｃを得た。一方、純水６００部に、三酸化モリブデン１００部、８５質量％リン酸６．６７部、メタバナジン酸アンモニウム３．３６部、硝酸第二銅２．１０部を溶解した。これを撹拌しながら昇温し、１００℃の還流下で５時間攪拌した。降温し液温を８０℃に８０℃に保ちつつ、純水２００部に溶解した重炭酸セシウム５．６２部を添加して１５分間撹拌し、続いて純水２００部に溶解した重炭酸アンモニウム１１．３０部を添加した。得られたヘテロポリ酸（複合）塩含有液を、出口温度２５０℃で噴霧乾燥を行い、さらに１３０℃で１６時間乾燥して乾燥粉Ｋ２ｃを得た。 [Example 3]
100 parts of molybdenum trioxide, 6.67 parts of 85 mass% phosphoric acid, 3.36 parts of ammonium metavanadate and 2.10 parts of cupric nitrate were dissolved in 600 parts of pure water. The temperature was raised while stirring, and stirred under reflux at 100 ° C. for 5 hours. While maintaining the temperature at 80 ° C., add 21.56 parts of cesium bicarbonate dissolved in 200 parts of pure water, stir for 15 minutes, and then dissolve 4.88 parts of ammonium bicarbonate dissolved in 200 parts of pure water Was added. The resulting heteropoly acid (composite) salt-containing solution was spray-dried at an outlet temperature of 250 ° C. and further dried at 130 ° C. for 16 hours to obtain a dry powder K1c. On the other hand, 100 parts of molybdenum trioxide, 6.67 parts of 85% by mass phosphoric acid, 3.36 parts of ammonium metavanadate and 2.10 parts of cupric nitrate were dissolved in 600 parts of pure water. The temperature was raised while stirring, and stirred under reflux at 100 ° C. for 5 hours. While maintaining the temperature at 80 ° C. at 80 ° C., add 5.62 parts of cesium bicarbonate dissolved in 200 parts of pure water, stir for 15 minutes, and then dissolve ammonium bicarbonate 11 dissolved in 200 parts of pure water. .30 parts were added. The resulting heteropoly acid (composite) salt-containing solution was spray-dried at an outlet temperature of 250 ° C. and further dried at 130 ° C. for 16 hours to obtain a dry powder K2c.
純水６００部に、三酸化モリブデン１００部、８５質量％リン酸６．６７部、メタバナジン酸アンモニウム３．３６部、硝酸第二銅２．１０部を溶解した。これを撹拌しながら昇温し、１００℃の還流下で５時間攪拌した。降温し液温を８０℃に保ちつつ、純水２００部に溶解した重炭酸セシウム２１．５６部を添加して１５分間撹拌し、続いて純水２００部に溶解した重炭酸アンモニウム４．８８部を添加した。得られたヘテロポリ酸（複合）塩含有液を、出口温度２５０℃で噴霧乾燥を行い、さらに１３０℃で１６時間乾燥して乾燥粉Ｋ１ｃを得た。一方、純水６００部に、三酸化モリブデン１００部、８５質量％リン酸６．６７部、メタバナジン酸アンモニウム３．３６部、硝酸第二銅２．１０部を溶解した。これを撹拌しながら昇温し、１００℃の還流下で５時間攪拌した。降温し液温を８０℃に８０℃に保ちつつ、純水２００部に溶解した重炭酸セシウム５．６２部を添加して１５分間撹拌し、続いて純水２００部に溶解した重炭酸アンモニウム１１．３０部を添加した。得られたヘテロポリ酸（複合）塩含有液を、出口温度２５０℃で噴霧乾燥を行い、さらに１３０℃で１６時間乾燥して乾燥粉Ｋ２ｃを得た。 [Example 3]
100 parts of molybdenum trioxide, 6.67 parts of 85 mass% phosphoric acid, 3.36 parts of ammonium metavanadate and 2.10 parts of cupric nitrate were dissolved in 600 parts of pure water. The temperature was raised while stirring, and stirred under reflux at 100 ° C. for 5 hours. While maintaining the temperature at 80 ° C., add 21.56 parts of cesium bicarbonate dissolved in 200 parts of pure water, stir for 15 minutes, and then dissolve 4.88 parts of ammonium bicarbonate dissolved in 200 parts of pure water Was added. The resulting heteropoly acid (composite) salt-containing solution was spray-dried at an outlet temperature of 250 ° C. and further dried at 130 ° C. for 16 hours to obtain a dry powder K1c. On the other hand, 100 parts of molybdenum trioxide, 6.67 parts of 85% by mass phosphoric acid, 3.36 parts of ammonium metavanadate and 2.10 parts of cupric nitrate were dissolved in 600 parts of pure water. The temperature was raised while stirring, and stirred under reflux at 100 ° C. for 5 hours. While maintaining the temperature at 80 ° C. at 80 ° C., add 5.62 parts of cesium bicarbonate dissolved in 200 parts of pure water, stir for 15 minutes, and then dissolve ammonium bicarbonate 11 dissolved in 200 parts of pure water. .30 parts were added. The resulting heteropoly acid (composite) salt-containing solution was spray-dried at an outlet temperature of 250 ° C. and further dried at 130 ° C. for 16 hours to obtain a dry powder K2c.
次に、乾燥粉Ｋ１ｃを８０部に対し、乾燥粉Ｋ２ｃを２０部の割合で混合し、触媒前駆体を得た。得られた触媒前駆体の水素、窒素、酸素を除く組成は、Ｐ１Ｍｏ１２Ｖ０．５Ｃｕ０．１５Ｃｓ１．６４であった。該触媒前駆体について、対陰極Ｃｕ－Ｋα線を用いたＸ線回折パターン測定を行った結果、表１に示すピークが確認された。
Next, 20 parts of dry powder K2c was mixed with 80 parts of dry powder K1c to obtain a catalyst precursor. The composition except hydrogen, nitrogen and oxygen of the obtained catalyst precursor was P 1 Mo 12 V 0.5 Cu 0.15 Cs 1.64 . As a result of X-ray diffraction pattern measurement using an anticathode Cu-Kα ray for the catalyst precursor, peaks shown in Table 1 were confirmed.
該触媒前駆体を実施例１と同様の方法により成形し熱処理して、触媒を調製した。
該触媒を用いて、実施例１と同様の方法によりメタクリル酸の製造を行った。結果を表１に示す。 The catalyst precursor was shaped and heat-treated in the same manner as in Example 1 to prepare a catalyst.
Using this catalyst, methacrylic acid was produced in the same manner as in Example 1. The results are shown in Table 1.
該触媒を用いて、実施例１と同様の方法によりメタクリル酸の製造を行った。結果を表１に示す。 The catalyst precursor was shaped and heat-treated in the same manner as in Example 1 to prepare a catalyst.
Using this catalyst, methacrylic acid was produced in the same manner as in Example 1. The results are shown in Table 1.
［実施例４］
実施例１と同様の方法により乾燥粉Ｋ１ａ及び乾燥粉Ｋ２ａを得た。次に、乾燥粉Ｋ１ａを９４部に対し、乾燥粉Ｋ２ａを６部の割合で混合し、触媒前駆体を得た。得られた触媒前駆体の水素、窒素、酸素を除く組成は、Ｐ１Ｍｏ１２Ｖ０．５Ｃｕ０．１５Ｃｓ２．０４であった。該触媒前駆体について、対陰極Ｃｕ－Ｋα線を用いたＸ線回折パターン測定を行った結果、表１に示すピークが確認された。 Example 4
Dry powder K1a and dry powder K2a were obtained in the same manner as in Example 1. Next, 6 parts of dry powder K2a was mixed with 94 parts of dry powder K1a to obtain a catalyst precursor. The composition except hydrogen, nitrogen, and oxygen of the obtained catalyst precursor was P 1 Mo 12 V 0.5 Cu 0.15 Cs 2.04 . As a result of X-ray diffraction pattern measurement using an anticathode Cu-Kα ray for the catalyst precursor, peaks shown in Table 1 were confirmed.
実施例１と同様の方法により乾燥粉Ｋ１ａ及び乾燥粉Ｋ２ａを得た。次に、乾燥粉Ｋ１ａを９４部に対し、乾燥粉Ｋ２ａを６部の割合で混合し、触媒前駆体を得た。得られた触媒前駆体の水素、窒素、酸素を除く組成は、Ｐ１Ｍｏ１２Ｖ０．５Ｃｕ０．１５Ｃｓ２．０４であった。該触媒前駆体について、対陰極Ｃｕ－Ｋα線を用いたＸ線回折パターン測定を行った結果、表１に示すピークが確認された。 Example 4
Dry powder K1a and dry powder K2a were obtained in the same manner as in Example 1. Next, 6 parts of dry powder K2a was mixed with 94 parts of dry powder K1a to obtain a catalyst precursor. The composition except hydrogen, nitrogen, and oxygen of the obtained catalyst precursor was P 1 Mo 12 V 0.5 Cu 0.15 Cs 2.04 . As a result of X-ray diffraction pattern measurement using an anticathode Cu-Kα ray for the catalyst precursor, peaks shown in Table 1 were confirmed.
該触媒前駆体を実施例１と同様の方法により成形し熱処理して、触媒を調製した。
該触媒を用いて、実施例１と同様の方法によりメタクリル酸の製造を行った。結果を表１に示す。 The catalyst precursor was shaped and heat-treated in the same manner as in Example 1 to prepare a catalyst.
Using this catalyst, methacrylic acid was produced in the same manner as in Example 1. The results are shown in Table 1.
該触媒を用いて、実施例１と同様の方法によりメタクリル酸の製造を行った。結果を表１に示す。 The catalyst precursor was shaped and heat-treated in the same manner as in Example 1 to prepare a catalyst.
Using this catalyst, methacrylic acid was produced in the same manner as in Example 1. The results are shown in Table 1.
［実施例５］
実施例１と同様の方法により乾燥粉Ｋ１ａ及び乾燥粉Ｋ２ａを得た。次に、乾燥粉Ｋ１ａを９７部に対し、乾燥粉Ｋ２ａを３部の割合で混合し、触媒前駆体を得た。得られた触媒前駆体の水素、窒素、酸素を除く組成は、Ｐ１Ｍｏ１２Ｖ０．５Ｃｕ０．１５Ｃｓ２．１０であった。該触媒前駆体について、対陰極Ｃｕ－Ｋα線を用いたＸ線回折パターン測定を行った結果、表１に示すピークが確認された。 [Example 5]
Dry powder K1a and dry powder K2a were obtained in the same manner as in Example 1. Next, the dry powder K1a was mixed with 97 parts of dry powder K2a at a ratio of 3 parts to obtain a catalyst precursor. The composition except hydrogen, nitrogen, and oxygen of the obtained catalyst precursor was P 1 Mo 12 V 0.5 Cu 0.15 Cs 2.10 . As a result of X-ray diffraction pattern measurement using an anticathode Cu-Kα ray for the catalyst precursor, peaks shown in Table 1 were confirmed.
実施例１と同様の方法により乾燥粉Ｋ１ａ及び乾燥粉Ｋ２ａを得た。次に、乾燥粉Ｋ１ａを９７部に対し、乾燥粉Ｋ２ａを３部の割合で混合し、触媒前駆体を得た。得られた触媒前駆体の水素、窒素、酸素を除く組成は、Ｐ１Ｍｏ１２Ｖ０．５Ｃｕ０．１５Ｃｓ２．１０であった。該触媒前駆体について、対陰極Ｃｕ－Ｋα線を用いたＸ線回折パターン測定を行った結果、表１に示すピークが確認された。 [Example 5]
Dry powder K1a and dry powder K2a were obtained in the same manner as in Example 1. Next, the dry powder K1a was mixed with 97 parts of dry powder K2a at a ratio of 3 parts to obtain a catalyst precursor. The composition except hydrogen, nitrogen, and oxygen of the obtained catalyst precursor was P 1 Mo 12 V 0.5 Cu 0.15 Cs 2.10 . As a result of X-ray diffraction pattern measurement using an anticathode Cu-Kα ray for the catalyst precursor, peaks shown in Table 1 were confirmed.
該触媒前駆体を実施例１と同様の方法により成形し熱処理して、触媒を調製した。
該触媒を用いて、実施例１と同様の方法によりメタクリル酸の製造を行った。結果を表１に示す。 The catalyst precursor was shaped and heat-treated in the same manner as in Example 1 to prepare a catalyst.
Using this catalyst, methacrylic acid was produced in the same manner as in Example 1. The results are shown in Table 1.
該触媒を用いて、実施例１と同様の方法によりメタクリル酸の製造を行った。結果を表１に示す。 The catalyst precursor was shaped and heat-treated in the same manner as in Example 1 to prepare a catalyst.
Using this catalyst, methacrylic acid was produced in the same manner as in Example 1. The results are shown in Table 1.
［実施例６］
実施例１と同様の方法により乾燥粉Ｋ１ａ及び乾燥粉Ｋ２ａを得た。次に、乾燥粉Ｋ１ａを１０部に対し、乾燥粉Ｋ２ａを９０部の割合で混合し、触媒前駆体を得た。得られた触媒前駆体の水素、窒素、酸素を除く組成は、Ｐ１Ｍｏ１２Ｖ０．５Ｃｕ０．１５Ｃｓ０．５４であった。該触媒前駆体について、対陰極Ｃｕ－Ｋα線を用いたＸ線回折パターン測定を行った結果、表１に示すピークが確認された。 [Example 6]
Dry powder K1a and dry powder K2a were obtained in the same manner as in Example 1. Next, 90 parts of dry powder K2a was mixed with 10 parts of dry powder K1a to obtain a catalyst precursor. The composition of the obtained catalyst precursor excluding hydrogen, nitrogen and oxygen was P 1 Mo 12 V 0.5 Cu 0.15 Cs 0.54 . As a result of X-ray diffraction pattern measurement using an anticathode Cu-Kα ray for the catalyst precursor, peaks shown in Table 1 were confirmed.
実施例１と同様の方法により乾燥粉Ｋ１ａ及び乾燥粉Ｋ２ａを得た。次に、乾燥粉Ｋ１ａを１０部に対し、乾燥粉Ｋ２ａを９０部の割合で混合し、触媒前駆体を得た。得られた触媒前駆体の水素、窒素、酸素を除く組成は、Ｐ１Ｍｏ１２Ｖ０．５Ｃｕ０．１５Ｃｓ０．５４であった。該触媒前駆体について、対陰極Ｃｕ－Ｋα線を用いたＸ線回折パターン測定を行った結果、表１に示すピークが確認された。 [Example 6]
Dry powder K1a and dry powder K2a were obtained in the same manner as in Example 1. Next, 90 parts of dry powder K2a was mixed with 10 parts of dry powder K1a to obtain a catalyst precursor. The composition of the obtained catalyst precursor excluding hydrogen, nitrogen and oxygen was P 1 Mo 12 V 0.5 Cu 0.15 Cs 0.54 . As a result of X-ray diffraction pattern measurement using an anticathode Cu-Kα ray for the catalyst precursor, peaks shown in Table 1 were confirmed.
該触媒前駆体を実施例１と同様の方法により成形し熱処理して、触媒を調製した。
該触媒を用いて、実施例１と同様の方法によりメタクリル酸の製造を行った。結果を表１に示す。 The catalyst precursor was shaped and heat-treated in the same manner as in Example 1 to prepare a catalyst.
Using this catalyst, methacrylic acid was produced in the same manner as in Example 1. The results are shown in Table 1.
該触媒を用いて、実施例１と同様の方法によりメタクリル酸の製造を行った。結果を表１に示す。 The catalyst precursor was shaped and heat-treated in the same manner as in Example 1 to prepare a catalyst.
Using this catalyst, methacrylic acid was produced in the same manner as in Example 1. The results are shown in Table 1.
［比較例１］
実施例１と同様の方法により乾燥粉Ｋ１ａを得て、触媒前駆体とした。該触媒前駆体の水素、窒素、酸素を除く組成は、Ｐ１Ｍｏ１２Ｖ０．５Ｃｕ０．１５Ｃｓ２．１５であった。該触媒前駆体について、対陰極Ｃｕ－Ｋα線を用いたＸ線回折パターン測定を行った結果、表１に示すピークが確認された。 Comparative Example 1
A dry powder K1a was obtained by the same method as in Example 1 and used as a catalyst precursor. The composition of the catalyst precursor excluding hydrogen, nitrogen and oxygen was P 1 Mo 12 V 0.5 Cu 0.15 Cs 2.15 . As a result of X-ray diffraction pattern measurement using an anticathode Cu-Kα ray for the catalyst precursor, peaks shown in Table 1 were confirmed.
実施例１と同様の方法により乾燥粉Ｋ１ａを得て、触媒前駆体とした。該触媒前駆体の水素、窒素、酸素を除く組成は、Ｐ１Ｍｏ１２Ｖ０．５Ｃｕ０．１５Ｃｓ２．１５であった。該触媒前駆体について、対陰極Ｃｕ－Ｋα線を用いたＸ線回折パターン測定を行った結果、表１に示すピークが確認された。 Comparative Example 1
A dry powder K1a was obtained by the same method as in Example 1 and used as a catalyst precursor. The composition of the catalyst precursor excluding hydrogen, nitrogen and oxygen was P 1 Mo 12 V 0.5 Cu 0.15 Cs 2.15 . As a result of X-ray diffraction pattern measurement using an anticathode Cu-Kα ray for the catalyst precursor, peaks shown in Table 1 were confirmed.
該触媒前駆体を実施例１と同様の方法により成形し熱処理して、触媒を調製した。
該触媒を用いて、実施例１と同様の方法によりメタクリル酸の製造を行った。結果を表１に示す。 The catalyst precursor was shaped and heat-treated in the same manner as in Example 1 to prepare a catalyst.
Using this catalyst, methacrylic acid was produced in the same manner as in Example 1. The results are shown in Table 1.
該触媒を用いて、実施例１と同様の方法によりメタクリル酸の製造を行った。結果を表１に示す。 The catalyst precursor was shaped and heat-treated in the same manner as in Example 1 to prepare a catalyst.
Using this catalyst, methacrylic acid was produced in the same manner as in Example 1. The results are shown in Table 1.
［比較例２］
実施例１と同様の方法により乾燥粉Ｋ２ａを得て、触媒前駆体とした。該触媒前駆体の水素、窒素、酸素を除く組成は、Ｐ１Ｍｏ１２Ｖ０．５Ｃｕ０．１５Ｃｓ０．３６であった。該触媒前駆体について、対陰極Ｃｕ－Ｋα線を用いたＸ線回折パターン測定を行った結果、表１に示すピークが確認された。 Comparative Example 2
A dry powder K2a was obtained by the same method as in Example 1 and used as a catalyst precursor. The composition except hydrogen, nitrogen and oxygen of the catalyst precursor was P 1 Mo 12 V 0.5 Cu 0.15 Cs 0.36 . As a result of X-ray diffraction pattern measurement using an anticathode Cu-Kα ray for the catalyst precursor, peaks shown in Table 1 were confirmed.
実施例１と同様の方法により乾燥粉Ｋ２ａを得て、触媒前駆体とした。該触媒前駆体の水素、窒素、酸素を除く組成は、Ｐ１Ｍｏ１２Ｖ０．５Ｃｕ０．１５Ｃｓ０．３６であった。該触媒前駆体について、対陰極Ｃｕ－Ｋα線を用いたＸ線回折パターン測定を行った結果、表１に示すピークが確認された。 Comparative Example 2
A dry powder K2a was obtained by the same method as in Example 1 and used as a catalyst precursor. The composition except hydrogen, nitrogen and oxygen of the catalyst precursor was P 1 Mo 12 V 0.5 Cu 0.15 Cs 0.36 . As a result of X-ray diffraction pattern measurement using an anticathode Cu-Kα ray for the catalyst precursor, peaks shown in Table 1 were confirmed.
該触媒前駆体を実施例１と同様の方法により成形し熱処理して、触媒を調製した。
該触媒を用いて、実施例１と同様の方法によりメタクリル酸の製造を行った。結果を表１に示す。 The catalyst precursor was shaped and heat-treated in the same manner as in Example 1 to prepare a catalyst.
Using this catalyst, methacrylic acid was produced in the same manner as in Example 1. The results are shown in Table 1.
該触媒を用いて、実施例１と同様の方法によりメタクリル酸の製造を行った。結果を表１に示す。 The catalyst precursor was shaped and heat-treated in the same manner as in Example 1 to prepare a catalyst.
Using this catalyst, methacrylic acid was produced in the same manner as in Example 1. The results are shown in Table 1.
［比較例３］
実施例１と同様の方法により乾燥粉Ｋ１ａを得た。一方、純水６００部に、三酸化モリブデン１００部、８５質量％リン酸６．６７部、メタバナジン酸アンモニウム３．３６部、硝酸第二銅２．１０部を溶解した。これを撹拌しながら昇温し、１００℃の還流下で５時間攪拌した。降温し液温を８０℃に８０℃に保ちつつ、純水２００部に溶解した重炭酸セシウム１．４６部を添加して１５分間撹拌し、続いて純水２００部に溶解した重炭酸アンモニウム１２．９７部を添加した。得られたヘテロポリ酸塩含有液を、出口温度２５０℃で噴霧乾燥を行い、さらに１３０℃で１６時間乾燥して乾燥粉Ｋ２ｅを得た。 Comparative Example 3
Dry powder K1a was obtained in the same manner as in Example 1. On the other hand, 100 parts of molybdenum trioxide, 6.67 parts of 85% by mass phosphoric acid, 3.36 parts of ammonium metavanadate and 2.10 parts of cupric nitrate were dissolved in 600 parts of pure water. The temperature was raised while stirring, and stirred under reflux at 100 ° C. for 5 hours. While keeping the temperature at 80 ° C. and keeping the temperature at 80 ° C., add 1.46 parts of cesium bicarbonate dissolved in 200 parts of pure water, stir for 15 minutes, and then dissolve ammonium bicarbonate 12 dissolved in 200 parts of pure water .97 parts were added. The resulting heteropolyacid salt-containing liquid was spray-dried at an outlet temperature of 250 ° C. and further dried at 130 ° C. for 16 hours to obtain a dry powder K2e.
実施例１と同様の方法により乾燥粉Ｋ１ａを得た。一方、純水６００部に、三酸化モリブデン１００部、８５質量％リン酸６．６７部、メタバナジン酸アンモニウム３．３６部、硝酸第二銅２．１０部を溶解した。これを撹拌しながら昇温し、１００℃の還流下で５時間攪拌した。降温し液温を８０℃に８０℃に保ちつつ、純水２００部に溶解した重炭酸セシウム１．４６部を添加して１５分間撹拌し、続いて純水２００部に溶解した重炭酸アンモニウム１２．９７部を添加した。得られたヘテロポリ酸塩含有液を、出口温度２５０℃で噴霧乾燥を行い、さらに１３０℃で１６時間乾燥して乾燥粉Ｋ２ｅを得た。 Comparative Example 3
Dry powder K1a was obtained in the same manner as in Example 1. On the other hand, 100 parts of molybdenum trioxide, 6.67 parts of 85% by mass phosphoric acid, 3.36 parts of ammonium metavanadate and 2.10 parts of cupric nitrate were dissolved in 600 parts of pure water. The temperature was raised while stirring, and stirred under reflux at 100 ° C. for 5 hours. While keeping the temperature at 80 ° C. and keeping the temperature at 80 ° C., add 1.46 parts of cesium bicarbonate dissolved in 200 parts of pure water, stir for 15 minutes, and then dissolve ammonium bicarbonate 12 dissolved in 200 parts of pure water .97 parts were added. The resulting heteropolyacid salt-containing liquid was spray-dried at an outlet temperature of 250 ° C. and further dried at 130 ° C. for 16 hours to obtain a dry powder K2e.
次に、乾燥粉Ｋ１ａを９０部に対し、乾燥粉Ｋ２ｅを１０部の割合で混合し、触媒前駆体を得た。得られた触媒前駆体の水素、窒素、酸素を除く組成は、Ｐ１Ｍｏ１２Ｖ０．５Ｃｕ０．１５Ｃｓ１．９５であった。該触媒前駆体について、対陰極Ｃｕ－Ｋα線を用いたＸ線回折パターン測定を行った結果、表１に示すピークが確認された。
Next, 10 parts of dry powder K2a was mixed with 90 parts of dry powder K1a to obtain a catalyst precursor. The composition except hydrogen, nitrogen, and oxygen of the obtained catalyst precursor was P 1 Mo 12 V 0.5 Cu 0.15 Cs 1.95 . As a result of X-ray diffraction pattern measurement using an anticathode Cu-Kα ray for the catalyst precursor, peaks shown in Table 1 were confirmed.
該触媒前駆体を実施例１と同様の方法により成形し熱処理して、触媒を調製した。
該触媒を用いて、実施例１と同様の方法によりメタクリル酸の製造を行った。結果を表１に示す。 The catalyst precursor was shaped and heat-treated in the same manner as in Example 1 to prepare a catalyst.
Using this catalyst, methacrylic acid was produced in the same manner as in Example 1. The results are shown in Table 1.
該触媒を用いて、実施例１と同様の方法によりメタクリル酸の製造を行った。結果を表１に示す。 The catalyst precursor was shaped and heat-treated in the same manner as in Example 1 to prepare a catalyst.
Using this catalyst, methacrylic acid was produced in the same manner as in Example 1. The results are shown in Table 1.
表１に示すように、ピークＰ１及びＰ２が本発明の規定範囲である実施例１～６により得られた触媒前駆体を熱処理したものを触媒として使用した結果、メタクリル酸収率が高いものとなった。その中でも、Ｉ１／Ｉ２の値が０．０５～０．９２の範囲内である実施例１～４及び６において特に高いメタクリル酸収率を示しており、Ｉ１／Ｉ２の値に最適な範囲があることが分かった。
一方、比較例１により得られる触媒前駆体のＸ線回折パターンにはピークＰ２が、比較例２により得られる触媒前駆体のＸ線回折パターンにはピークＰ１が現れず、また比較例３により得られる触媒前駆体はピークＰ２の２θが規定範囲外である。このような触媒前駆体を熱処理したものを触媒として使用した結果、いずれも実施例と比較してメタクリル酸収率が低いものとなった。
As shown in Table 1, as a result of using, as a catalyst, those obtained by heat-treating the catalyst precursors obtained in Examples 1 to 6 in which the peaks P1 and P2 fall within the defined range of the present invention, became. Among them, particularly high methacrylic acid yield is shown in Examples 1 to 4 and 6 in which the value of I1 / I2 is in the range of 0.05 to 0.92, and the optimum range for the value of I1 / I2 is It turned out that there is.
On the other hand, the peak P2 does not appear in the X-ray diffraction pattern of the catalyst precursor obtained by Comparative Example 1, and the peak P1 does not appear in the X-ray diffraction pattern of the catalyst precursor obtained by Comparative Example 2. The catalyst precursor to be prepared has a peak P2 of 2θ outside the specified range. As a result of using such a catalyst precursor subjected to heat treatment as a catalyst, in any case, the yield of methacrylic acid was lower than in the examples.
一方、比較例１により得られる触媒前駆体のＸ線回折パターンにはピークＰ２が、比較例２により得られる触媒前駆体のＸ線回折パターンにはピークＰ１が現れず、また比較例３により得られる触媒前駆体はピークＰ２の２θが規定範囲外である。このような触媒前駆体を熱処理したものを触媒として使用した結果、いずれも実施例と比較してメタクリル酸収率が低いものとなった。
As shown in Table 1, as a result of using, as a catalyst, those obtained by heat-treating the catalyst precursors obtained in Examples 1 to 6 in which the peaks P1 and P2 fall within the defined range of the present invention, became. Among them, particularly high methacrylic acid yield is shown in Examples 1 to 4 and 6 in which the value of I1 / I2 is in the range of 0.05 to 0.92, and the optimum range for the value of I1 / I2 is It turned out that there is.
On the other hand, the peak P2 does not appear in the X-ray diffraction pattern of the catalyst precursor obtained by Comparative Example 1, and the peak P1 does not appear in the X-ray diffraction pattern of the catalyst precursor obtained by Comparative Example 2. The catalyst precursor to be prepared has a peak P2 of 2θ outside the specified range. As a result of using such a catalyst precursor subjected to heat treatment as a catalyst, in any case, the yield of methacrylic acid was lower than in the examples.
Claims (8)
- ヘテロポリ酸塩を含む触媒前駆体であって、対陰極Ｃｕ－Ｋα線を用いたＸ線回折パターンにおいて、２θが２６．１６°±０．０６°であるピークＰ１と、２θがピークＰ１よりも高角側にあり２６．４４°以下にあるピークＰ２とを有する触媒前駆体。 A catalyst precursor containing a heteropolyacid salt, and in an X-ray diffraction pattern using counter-cathode Cu-Kα rays, peak P1 having 2θ of 26.16 ° ± 0.06 ° and 2θ more than peak P1 A catalyst precursor having a peak P2 on the high angle side and not more than 26.44 °.
- 前記ピークＰ２の高さＩ２に対する前記ピークＰ１の高さＩ１の比（Ｉ１／Ｉ２）が、０．０５～０．９２である、請求項１に記載の触媒前駆体。 The catalyst precursor according to claim 1, wherein the ratio (I1 / I2) of the height I1 of the peak P1 to the height I2 of the peak P2 is 0.05 to 0.92.
- 触媒の前駆体であって、前記触媒が、分子状酸素を用いてメタクロレイン及びアクロレインからなる群より選択される少なくとも１種を気相接触酸化して、メタクリル酸及びアクリル酸からなる群より選択される少なくとも１種を製造する際に用いられる、請求項１又は２に記載の触媒前駆体。 It is a precursor of a catalyst, wherein the catalyst is selected from the group consisting of methacrylic acid and acrylic acid by vapor phase catalytic oxidation of at least one member selected from the group consisting of methacrolein and acrolein using molecular oxygen. The catalyst precursor according to claim 1 or 2, which is used in the production of at least one selected from the group consisting of
- 下記式（Ｉ）で表される組成を有する請求項１～３のいずれか１項に記載の触媒前駆体。
ＰａＭｏｂＶｃＣｕｄＡｅＥｆＧｇＯｈ （Ｉ）
（式（Ｉ）中、Ｐ、Ｍｏ、Ｖ、Ｃｕ及びＯは、それぞれリン、モリブデン、バナジウム、銅及び酸素を示す元素記号である。Ａはアンチモン、ビスマス、砒素、ゲルマニウム、ジルコニウム、テルル、銀、セレン、ケイ素、タングステン及びホウ素からなる群より選ばれた少なくとも１種類の元素を示し、Ｅは鉄、亜鉛、クロム、マグネシウム、カルシウム、ストロンチウム、タンタル、コバルト、ニッケル、マンガン、バリウム、チタン、スズ、鉛、ニオブ、インジウム、硫黄、パラジウム、ガリウム、セリウム及びランタンからなる群より選ばれた少なくとも１種類の元素を示し、Ｇはカリウム、ルビジウム、セシウム及びタリウムからなる群より選ばれた少なくとも１種類の元素を示す。ａ、ｂ、ｃ、ｄ、ｅ、ｆ、ｇ及びｈは各元素の原子比率を示し、ｂ＝１２の時ａ＝０．５～３、ｃ＝０．０１～３、ｄ＝０．０１～２、ｅ＝０～３、ｆ＝０～３、ｇ＝０．０１～３であり、ｈは前記各成分の原子価を満足するのに必要な酸素の原子比率である。） The catalyst precursor according to any one of claims 1 to 3, which has a composition represented by the following formula (I).
P a Mo b V c Cu d A e E f G g O h (I)
(In formula (I), P, Mo, V, Cu and O are element symbols showing phosphorus, molybdenum, vanadium, copper and oxygen respectively. A is antimony, bismuth, arsenic, germanium, zirconium, tellurium, silver E represents at least one element selected from the group consisting of selenium, silicon, tungsten and boron, E represents iron, zinc, chromium, magnesium, calcium, strontium, tantalum, cobalt, nickel, manganese, barium, titanium, tin And at least one element selected from the group consisting of lead, niobium, indium, sulfur, palladium, gallium, cerium and lanthanum, and G is at least one type selected from the group consisting of potassium, rubidium, cesium and thallium A, b, c, d, e, f, g and h of each element Child ratio, and when b = 12, a = 0.5 to 3, c = 0.01 to 3, d = 0.01 to 2, e = 0 to 3, f = 0 to 3, g = 0 01 to 3, and h is an atomic ratio of oxygen necessary to satisfy the valences of the respective components.) - 請求項１～４のいずれか１項に記載の触媒前駆体を熱処理する工程を含む、触媒の製造方法。 A method for producing a catalyst, comprising the step of heat treating the catalyst precursor according to any one of claims 1 to 4.
- 前記熱処理工程における熱処理温度が３００～４５０℃である、請求項５に記載の触媒の製造方法。 The method for producing a catalyst according to claim 5, wherein the heat treatment temperature in the heat treatment step is 300 to 450 属 C.
- メタクリル酸及びアクリル酸からなる群より選択される少なくとも１種を製造する方法であって、
（１）請求項５又は６に記載の方法により触媒を製造する工程、及び
（２）前記触媒の存在下で分子状酸素を用いて、メタクロレイン及びアクロレインからなる群より選択される少なくとも１種を気相接触酸化して、メタクリル酸及びアクリル酸からなる群より選択される少なくとも１種を製造する工程、
を含む、方法。 A method of producing at least one selected from the group consisting of methacrylic acid and acrylic acid,
(1) a step of producing a catalyst by the method according to claim 5 or 6, and (2) at least one member selected from the group consisting of methacrolein and acrolein using molecular oxygen in the presence of the catalyst. Gas phase catalytic oxidation to produce at least one selected from the group consisting of methacrylic acid and acrylic acid,
Method, including. - メタクリル酸エステル及びアクリル酸エステルからなる群より選択される少なくとも１種を製造する方法であって、
（１）請求項５又は６に記載の方法により触媒を製造する工程、
（２）前記触媒の存在下で分子状酸素を用いて、メタクロレイン及びアクロレインからなる群より選択される少なくとも１種を気相接触酸化して、メタクリル酸及びアクリル酸からなる郡より選択される少なくとも１種を製造する工程、及び
（３）前記メタクリル酸及び前記アクリル酸からなる群より選択される少なくとも１種をエステル化する工程、
を、含む方法。
A method of producing at least one selected from the group consisting of methacrylic acid esters and acrylic acid esters,
(1) A process for producing a catalyst by the method according to claim 5 or 6,
(2) Gas phase catalytic oxidation of at least one member selected from the group consisting of methacrolein and acrolein using molecular oxygen in the presence of the catalyst is selected from the group consisting of methacrylic acid and acrylic acid Manufacturing at least one kind, and (3) esterifying at least one kind selected from the group consisting of the methacrylic acid and the acrylic acid,
And how to contain it.
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| SG11201911738QA SG11201911738QA (en) | 2017-07-31 | 2018-07-20 | Catalyst precursors, methods for producing catalysts, methods for producing methacrylic acid and acrylic acid, and methods for producing methacrylic acid esters and acrylic acid esters |
| JP2019534035A JP6769557B2 (en) | 2017-07-31 | 2018-07-20 | Catalyst precursor, catalyst production method, methacrylic acid and acrylic acid production method, and methacrylic acid ester and acrylic acid ester production method. |
| CN201880048701.9A CN110944747B (en) | 2017-07-31 | 2018-07-20 | Catalyst precursor for production of methacrylic acid, acrylic acid and esters thereof, and method for production of catalyst |
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| JPH0615178A (en) * | 1991-11-28 | 1994-01-25 | Tosoh Corp | Method for preparing catalyst for methacrylic acid production |
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| WO2018051840A1 (en) * | 2016-09-14 | 2018-03-22 | 三菱ケミカル株式会社 | Methacrylic acid production catalyst and method for producing same, and method for producing methacrylic acid and methacrylic acid ester |
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| JP4222721B2 (en) * | 2000-12-25 | 2009-02-12 | 三菱レイヨン株式会社 | Method for producing methacrylic acid |
| FR2969509B1 (en) * | 2010-12-22 | 2012-12-28 | IFP Energies Nouvelles | SPHERICAL MATERIAL BASED ON TRAPPED HETEROPOLYANIONS IN A MESOSTRUCTURED OXIDE MATRIX AND ITS USE AS CATALYST IN REFINING PROCESSES |
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| JPH0615178A (en) * | 1991-11-28 | 1994-01-25 | Tosoh Corp | Method for preparing catalyst for methacrylic acid production |
| JP2009022945A (en) * | 2007-06-20 | 2009-02-05 | Mitsubishi Rayon Co Ltd | Raw material for catalyst production, method for producing the same, method for producing the catalyst, and method for producing methacrylic acid |
| WO2018051840A1 (en) * | 2016-09-14 | 2018-03-22 | 三菱ケミカル株式会社 | Methacrylic acid production catalyst and method for producing same, and method for producing methacrylic acid and methacrylic acid ester |
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