CN112004597A - Method for producing catalyst for methacrylic acid production, and method for producing methacrylic acid and methacrylic acid ester - Google Patents
Method for producing catalyst for methacrylic acid production, and method for producing methacrylic acid and methacrylic acid ester Download PDFInfo
- Publication number
- CN112004597A CN112004597A CN201980027507.7A CN201980027507A CN112004597A CN 112004597 A CN112004597 A CN 112004597A CN 201980027507 A CN201980027507 A CN 201980027507A CN 112004597 A CN112004597 A CN 112004597A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- methacrylic acid
- ltoreq
- producing
- molybdenum
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 146
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 68
- 125000005397 methacrylic acid ester group Chemical group 0.000 title claims description 14
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 64
- 239000002994 raw material Substances 0.000 claims abstract description 58
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 39
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 37
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 36
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000011574 phosphorus Substances 0.000 claims abstract description 36
- 239000011733 molybdenum Substances 0.000 claims abstract description 34
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims abstract description 29
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002002 slurry Substances 0.000 claims abstract description 26
- 238000001354 calcination Methods 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000011964 heteropoly acid Substances 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 32
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 31
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 claims description 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 18
- 239000001301 oxygen Substances 0.000 claims description 18
- 229910052760 oxygen Inorganic materials 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 15
- 239000010949 copper Substances 0.000 claims description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 13
- 230000001590 oxidative effect Effects 0.000 claims description 12
- 229910052720 vanadium Inorganic materials 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910003202 NH4 Inorganic materials 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-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
- 229910052785 arsenic Inorganic materials 0.000 claims description 4
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper 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
- 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
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon 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
- 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
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229910052792 caesium Inorganic materials 0.000 claims description 3
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 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 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910052701 rubidium Inorganic materials 0.000 claims description 3
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052711 selenium Inorganic materials 0.000 claims description 3
- 239000011669 selenium Substances 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 229910052714 tellurium Inorganic materials 0.000 claims description 3
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052716 thallium Inorganic materials 0.000 claims description 3
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 239000011133 lead Substances 0.000 claims description 2
- 239000011135 tin Substances 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- 239000007789 gas Substances 0.000 description 20
- 239000000243 solution Substances 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- DDXPLCBTGWFAIG-UHFFFAOYSA-N triazanium;phosphate;trihydrate Chemical compound [NH4+].[NH4+].[NH4+].O.O.O.[O-]P([O-])([O-])=O DDXPLCBTGWFAIG-UHFFFAOYSA-N 0.000 description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 9
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 9
- 238000000465 moulding Methods 0.000 description 9
- 229910001882 dioxygen Inorganic materials 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 7
- 235000011007 phosphoric acid Nutrition 0.000 description 7
- 230000001747 exhibiting effect Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000004254 Ammonium phosphate Substances 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 235000019289 ammonium phosphates Nutrition 0.000 description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 4
- 238000007696 Kjeldahl method Methods 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- -1 alkali metal salt Chemical class 0.000 description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-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
- 239000005696 Diammonium phosphate Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-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
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 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 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 2
- 235000019838 diammonium phosphate Nutrition 0.000 description 2
- 238000007865 diluting Methods 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
- 238000002036 drum drying Methods 0.000 description 2
- 238000004993 emission spectroscopy Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000006012 monoammonium phosphate Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- ZFYIQPIHXRFFCZ-QMMMGPOBSA-N (2s)-2-(cyclohexylamino)butanedioic acid Chemical compound OC(=O)C[C@@H](C(O)=O)NC1CCCCC1 ZFYIQPIHXRFFCZ-QMMMGPOBSA-N 0.000 description 1
- 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910021550 Vanadium Chloride Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- ZMCUDHNSHCRDBT-UHFFFAOYSA-M caesium bicarbonate Chemical compound [Cs+].OC([O-])=O ZMCUDHNSHCRDBT-UHFFFAOYSA-M 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 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
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 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
- 238000011049 filling Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 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
- 150000004677 hydrates Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000004715 keto acids Chemical class 0.000 description 1
- 239000012046 mixed solvent 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
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 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
- 239000002243 precursor Substances 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
- 238000010298 pulverizing process Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- ROUPZXDBSPQFLE-UHFFFAOYSA-N triazanium;phosphate;hydrate Chemical compound [NH4+].[NH4+].[NH4+].O.[O-]P([O-])([O-])=O ROUPZXDBSPQFLE-UHFFFAOYSA-N 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
-
- 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
- B01J27/24—Nitrogen compounds
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B61/00—Other general methods
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention provides a catalyst for methacrylic acid production which can improve the yield of methacrylic acid and can be used as an industrial catalyst. A method for producing a catalyst containing at least phosphorus and molybdenum, comprising the steps of: (I) a step of mixing at least a molybdenum raw material and a phosphorus raw material with a solvent to prepare a solution or slurry, (II) a step of drying the solution or slurry to obtain a catalyst precursor, and (III) a step of calcining the catalyst precursor to obtain a catalyst, wherein triammonium phosphate is used as at least a part of the phosphorus raw material in the step (I).
Description
Technical Field
The present invention relates to a method for producing a catalyst for methacrylic acid production, and a method for producing methacrylic acid and methacrylic acid esters using the produced catalyst for methacrylic acid production.
Background
As a catalyst for methacrylic acid production (hereinafter also simply referred to as "catalyst") used for producing methacrylic acid by oxidizing methacrolein, for example, a heteropoly acid-based catalyst containing molybdenum and phosphorus is known. Examples of the heteropoly acid-based catalyst include a proton-type heteropoly acid in which a counter cation is a proton, and a heteropoly acid salt in which a part of the proton is replaced with a cation other than a proton (hereinafter, the proton-type heteropoly acid is also referred to as "heteropoly acid", and the proton-type heteropoly acid and/or heteropoly acid salt is also referred to as "heteropoly acid (salt)").
Heteropoly acids (salts) are condensed oxo acids (salts) formed from oxides of hetero atoms and coordinating atoms (hereinafter, referred to as polyatomic atoms) forming the basic skeleton of the polyhydrates. Phosphorus, silicon, arsenic, germanium, titanium, antimony, etc. may become heteroatoms, and tungsten, molybdenum, vanadium, niobium, tantalum, etc. may become polyatomic. Basic structures of heteropoly acids (salts) include Keggin type, Dawson type, Preyssler type, and the like (non-patent document 1).
In the heteropoly acid-based catalyst, the catalyst has also been improved for the purpose of increasing the yield of methacrylic acid. For example, an attempt to improve the catalyst and increase the yield of methacrylic acid by controlling the basic structure and crystal structure of a heteropoly-acid has also been reported (non-patent document 2). In the above-mentioned non-patent document 2, it is reported that the basic structures of the Keggin type, Dawson type and defect type thereof exist in the heteropoly acid composed of phosphorus and molybdenum, and these basic structures change depending on the ionic strength, pH and the like of the heteropoly acid aqueous solution.
In addition, patent document 1 discloses that a catalyst prepared by a specific production method is advantageous for the yield of methacrylic acid. Specifically disclosed is a catalyst produced by a production method comprising the following steps (i) to (iv).
(i) A step of adding at least a molybdenum raw material and a raw material of an element X to water to prepare an aqueous slurry or an aqueous solution containing a heteropoly acid;
(ii) adding an alkali metal compound to the aqueous slurry or aqueous solution to precipitate a heteropolyacid salt which is at least a part of the alkali metal salt of the heteropolyacid;
(iii) adding a phosphorus raw material selected from at least one of orthophosphoric acid, phosphorus pentoxide and ammonium phosphate to the aqueous slurry or aqueous solution from which the heteropolyacid salt has precipitated;
(iv) a step of drying an aqueous slurry or an aqueous solution containing all the raw materials to obtain a dried product; and
(v) and a step of heat-treating the dried product.
Documents of the prior art
Patent document
Patent document 1: international publication No. 2010/013749
Non-patent document
Non-patent document 1: yuyuan Shengcheng Cheng, Qianbaizhen, catalyst, vol.34, No.3(1992)
Non-patent document 2: lege Patterson, Ingerarb Andersson, Lars-Olof Ohman, Inorgnic Chemistry, vol.25, 4726-
Disclosure of Invention
However, in order to increase the yield of methacrylic acid, it is desired to further improve the catalyst.
The present invention provides a method for producing a catalyst for methacrylic acid production, which can be used as an industrial catalyst, for the purpose of improving the yield of methacrylic acid. Another object of the present invention is to provide a method for producing methacrylic acid and methacrylic acid ester using the catalyst.
The present inventors have conducted extensive studies in view of the above-mentioned problems, and as a result, have found that the above-mentioned problems can be solved by using a catalyst produced by a specific production method as a catalyst for methacrylic acid production, and have completed the present invention.
That is, the present invention includes the following configurations [1] to [10 ].
[1]: a method for producing a catalyst used for producing methacrylic acid by oxidizing methacrolein, comprising the steps of:
(I) a step of mixing at least a molybdenum material and a phosphorus material with a solvent to prepare a solution or slurry,
(II) a step of drying the solution or slurry to obtain a catalyst precursor,
(III) a step of calcining the catalyst precursor to obtain a catalyst,
in the step (I), triammonium phosphate is used as at least a part of the phosphorus raw material.
[2]: the method for producing a catalyst according to [1], wherein the catalyst precursor obtained in the step (II) has a Keggin-type heteropoly acid structure.
[3]: the method for producing a catalyst according to [1] or [2], wherein the catalyst obtained in the step (III) satisfies the following formula (1) with a molar ratio of phosphorus to 12 moles of molybdenum being a.
0.5≤a≤3 (1)
[4]: the method for producing a catalyst according to any one of [1] to [3], wherein the catalyst obtained in the step (III) satisfies the following formula (2) when a molar ratio of phosphorus to 12 moles of molybdenum is represented by "a" and a molar ratio of phosphorus derived from triammonium phosphate to 12 moles of molybdenum is represented by "a".
0.1≤a’/a≤1 (2)
[5]: the method for producing a catalyst according to any one of [1] to [4], wherein the catalyst precursor obtained in the step (II) satisfies the following formula (3) when the molar ratio of ammonium groups to 12 moles of molybdenum is h2 and the molar ratio of ammonium groups derived from triammonium phosphate to 12 moles of molybdenum is h 2'.
0.2≤h2’/h2≤1 (3)
[6]: the method for producing a catalyst according to any one of [1] to [5], wherein the catalyst obtained in the step (III) is a catalyst having a composition represented by the following formula (4).
PaMobVcCudAeEfGg(NH4)hOi (4)
(in the formula (4), P, Mo, V, Cu, NH4And O represents phosphorus, molybdenum, vanadium, copper, ammonium, and oxygen, respectively.
A represents at least 1 element selected from antimony, bismuth, arsenic, germanium, zirconium, tellurium, silver, selenium, silicon, tungsten and boron.
E represents at least 1 element selected from iron, zinc, chromium, calcium, strontium, tantalum, cobalt, nickel, manganese, titanium, tin, lead, niobium, indium, sulfur, palladium, gallium, cerium and lanthanum.
G represents at least 1 element selected from potassium, rubidium, cesium, thallium, magnesium, and barium.
a to i represent the molar ratio of each component, and when b is 12, a is 0.5. ltoreq. a.ltoreq.3, c is 0.01. ltoreq.3, d is 0.01. ltoreq.2, e is 0. ltoreq.3, f is 0. ltoreq. f.ltoreq.3, g is 0.01. ltoreq. g.ltoreq.3, h is 0. ltoreq. h.ltoreq.20, and i represents the molar ratio of oxygen necessary for satisfying the valence of each component. )
[7]: a method for producing methacrylic acid, comprising a step of oxidizing methacrolein in the presence of the catalyst produced by any one of the methods described in [1] to [6 ].
[8]: a method for producing methacrylic acid, comprising a step of producing a catalyst by the method according to any one of [1] to [6], and a step of oxidizing methacrolein with the catalyst.
[9]: a method for producing a methacrylic acid ester, comprising the step of esterifying methacrylic acid produced by the method of [7] or [8 ].
[10]: a method for producing a methacrylic acid ester, comprising the steps of producing a catalyst by the method according to any one of [1] to [6], oxidizing methacrolein with the catalyst, and esterifying methacrylic acid.
According to the present invention, it is possible to provide a catalyst for methacrylic acid production, which can be expected to further improve the yield of methacrylic acid when methacrylic acid is produced by oxidizing methacrolein. Further, a method for producing methacrylic acid and methacrylic acid ester using the catalyst can be provided.
Detailed Description
The present invention will be described in detail below.
[ catalyst for methacrylic acid production ]
The catalyst obtained by the production method of the present invention is used for producing methacrylic acid by oxidizing methacrolein. The catalyst contains at least phosphorus atoms and molybdenum atoms, and preferably satisfies the following formula (1) where a is a molar ratio of phosphorus atoms to molybdenum atoms of 12 moles.
0.5≤a≤3 (1)
By satisfying the above formula (1), a heteropoly acid structure suitable for the production of methacrylic acid can be formed.
From the viewpoint of improving the yield of methacrylic acid, the catalyst preferably has a composition represented by the following formula (4). The molar ratio of each element in the catalyst can be determined by analyzing the components obtained by dissolving the catalyst in aqueous ammonia by ICP emission spectrometry. The molar ratio of ammonium groups can be determined by analyzing the catalyst by kjeldahl method.
PaMobVcCudAeEfGg(NH4)hOi (4)
(in the formula (4), P, Mo, V, Cu, NH4And O represents phosphorus, molybdenum, vanadium, copper, ammonium, and oxygen, respectively.
A represents at least 1 element selected from antimony, bismuth, arsenic, germanium, zirconium, tellurium, silver, selenium, silicon, tungsten and boron.
E represents at least 1 element selected from iron, zinc, chromium, magnesium, calcium, strontium, tantalum, cobalt, nickel, manganese, barium, titanium, tin, thallium, lead, niobium, indium, sulfur, palladium, gallium, cerium and lanthanum.
G represents at least 1 element selected from potassium, rubidium and cesium.
a to i represent the molar ratio of each component, and when b is 12, a is 0.5. ltoreq. a.ltoreq.3, c is 0.01. ltoreq.3, d is 0.01. ltoreq.2, e is 0. ltoreq.3, f is 0. ltoreq. f.ltoreq.3, g is 0.01. ltoreq. g.ltoreq.3, h is 0. ltoreq. h.ltoreq.20, and i represents the molar ratio of oxygen necessary for satisfying the valence of each component. )
The term "ammonium group" as used herein means that the ammonium group may be converted into ammonium ion (NH)4 +) Ammonia (NH)3) And ammonium contained in an ammonium-containing compound such as an ammonium salt.
In the formula (4), when b is 12, the lower limit of a is preferably 1 or more. The upper limit is preferably 2.5 or less, and more preferably 2 or less.
The lower limit of c is preferably 0.1 or more, and the upper limit is preferably 2.5 or less. The lower limit of d is preferably 0.05 or more, and the upper limit is preferably 1.5 or less. The lower limit of e is preferably 0.01 or more, and the upper limit is preferably 2.5 or less. The upper limit of f is preferably 2 or less, and more preferably 1 or less. The lower limit of g is more preferably 0.1 or more, and the upper limit is more preferably 2.5 or less. The upper limit of h is preferably 5 or less, more preferably 3 or less.
[ method for producing catalyst for methacrylic acid production ]
The present invention relates to a method for producing a catalyst used for producing methacrylic acid by oxidizing methacrolein, which comprises the following steps (I) to (III),
(I) a step of mixing at least a molybdenum material and a phosphorus material with a solvent to prepare a solution or slurry;
(II) drying the solution or slurry to obtain a catalyst precursor; and
(III) calcining the catalyst precursor to obtain a catalyst.
Triammonium phosphate is used as at least a part of the phosphorus raw material in the step (I).
The method is characterized in that triammonium phosphate is used as at least a part of the phosphorus raw material in the step (I). Thus, a catalyst for methacrylic acid production which can be used as an industrial catalyst can be produced.
It is known to use ammonium phosphate in a step of mixing at least a molybdenum raw material and a phosphorus raw material with a solvent to prepare a solution or slurry (for example, patent document 1). However, the expression "ammonium phosphate" generally refers to ammonium phosphate salts having high versatility, i.e., ammonium dihydrogen phosphate and ammonium hydrogen phosphate.
The present inventors have found that a catalyst having a high methacrylic acid yield can be obtained by using triammonium phosphate as at least a part of a phosphorus raw material. This is considered to be because triammonium phosphate functions as a buffer, maintains pH stably, and can obtain a catalyst precursor having a Keggin-type heteropoly acid structure suitable for methacrylic acid production reaction. By using a catalyst obtained by calcining the precursor, the yield of methacrylic acid is improved.
Hereinafter, each step will be described in detail.
(Process (I))
In the step (I), at least the molybdenum raw material and the phosphorus raw material are mixed with a solvent to prepare a solution or slurry. At this time, triammonium phosphate is used as at least a part of the phosphorus raw material.
< molybdenum raw Material >
Examples of the molybdenum raw material include ammonium paramolybdate, molybdenum trioxide, molybdic acid, molybdenum chloride, and the like.
< phosphorus raw Material >
Examples of the triammonium phosphate include triammonium phosphate anhydride and triammonium phosphate hydrate. By producing a catalyst using such triammonium phosphate as at least a part of the phosphorus raw material, a catalyst exhibiting a high methacrylic acid yield can be obtained.
The triammonium phosphate can be used alone or in combination with other phosphorus starting materials. Examples of the other phosphorus raw material include phosphates such as orthophosphoric acid, phosphorus pentoxide, ammonium phosphate (monoammonium phosphate, diammonium phosphate), and cesium phosphate.
The amount of the phosphorus raw material containing triammonium phosphate is preferably such that the amounts satisfy the following formulae (2) and (3). This can provide a catalyst exhibiting a high methacrylic acid yield.
< other raw materials >
As described above, the catalyst produced in the present invention preferably has a composition represented by formula (4). Thus, it is preferable to further use a raw material containing an element constituting the composition. These raw materials may be used singly or in combination of two or more kinds of nitrate, carbonate, acetate, ammonium salt, oxide, halide, oxoacid salt, and the like of each element.
Specifically, examples of the vanadium raw material include ammonium metavanadate, vanadium pentoxide, vanadium chloride, and the like. Examples of the copper raw material include copper sulfate, copper nitrate, copper oxide, copper carbonate, copper acetate, and copper chloride. The starting material for the ammonium group is not particularly limited as long as it is an ammonium-containing compound. Examples thereof include triammonium phosphate and hydrates thereof, ammonium hydroxide, aqueous ammonia, ammonium nitrate, ammonium carbonate, and ammonium bicarbonate. These raw materials may be used alone or in combination of 2 or more.
< solvent >
As the solvent, water, an organic solvent, a mixed solvent of water and an organic solvent, or the like can be used, and water is preferably used from an industrial viewpoint.
< mixing of raw materials with solvent >
The above raw materials are mixed by adding a part or all of them to a solvent. The order of adding the raw materials is not particularly limited, and it is preferable to add the raw materials so that the pH of the solution or slurry is in the range of 0.1 to 6.5 from the viewpoint of obtaining a catalyst exhibiting a high methacrylic acid yield. The lower limit of the pH is more preferably 0.5 or more, and still more preferably 1 or more. The upper limit is more preferably 6 or less, and still more preferably 3 or less. The pH of the solution or slurry does not need to be strictly measured by titration and may be adjusted while measuring it with a commercially available pH meter or the like. The pH can be adjusted by using an acid (sulfuric acid, nitric acid, hydrochloric acid, or the like) or a base containing the same ions as the raw materials as described above, as necessary.
The temperature of the solvent when the raw materials are added to the solvent is preferably 10 to 60 ℃ from the viewpoint of avoiding unnecessary reactions of the raw materials, and the upper limit is more preferably 50 ℃ or lower. In addition, if the temperature is within the above range, the raw material may be added while raising the temperature.
After the addition of the raw materials, a solution or slurry is prepared by stirring while heating. The heating temperature is not particularly limited, but is preferably 75 to 130 ℃, and more preferably 95 to 130 ℃. By setting the heating temperature to 75 ℃ or higher, the reaction rate of the compound contained in the solution or slurry can be sufficiently increased. Further, by setting the heating temperature to 130 ℃ or lower, evaporation of water in the solution or slurry can be suppressed. Depending on the vapor pressure of the solvent used, the solvent may be concentrated or refluxed during heating, or may be heated under a pressurized condition by operating in a closed vessel.
The rate of temperature rise is not particularly limited, but is preferably 0.8 to 15 ℃/min. The time required for the step (I) can be shortened by setting the temperature rise rate to 0.8 ℃/min or more. Further, the temperature can be raised by using a normal temperature raising means by setting the temperature raising rate to 15 ℃/min or less.
The stirring power is preferably 0.01kW/m3The above is preferably carried out at 0.05kW/m3This is done. By making the stirring power 0.01kW/m3As described above, local variations in the temperature, components, and temperature of the solution or slurry are reduced, and a structure suitable as a catalyst for methacrylic acid production can be stably formed. In addition, from the viewpoint of the production cost of the catalyst, the stirring is usually carried out with a stirring power of 3.5kW/m3The process is carried out.
The pH of the solution or slurry obtained in the step (I) is preferably 0.2 to 3, the lower limit is more preferably 0.5 or more, and the upper limit is more preferably 2.5 or less. Thus, in step (II) described later, a catalyst precursor having a Keggin-type heteropoly acid structure suitable for the production of methacrylic acid can be obtained.
As a method of controlling the pH of the solution and the slurry within the above range, there is a method of appropriately selecting the amount of each raw material containing the catalyst constituent and appropriately adding nitric acid, oxalic acid, or the like.
(Process (II))
In the step (II), the solution or slurry obtained in the step (I) is dried to obtain a catalyst precursor.
The drying method is not particularly limited, and drum drying, freeze drying, spray drying, evaporative drying and the like can be mentioned. Among these, drum drying, spray drying or evaporation drying is preferable from the viewpoint of drying ability. The drying temperature is preferably 120 to 500 ℃, the lower limit is more preferably 140 ℃ or higher, and the upper limit is more preferably 350 ℃ or lower. Drying is carried out until the solution or slurry is dry. The moisture content of the catalyst precursor obtained by drying is preferably 0.1 to 4.5% by mass.
The conditions such as the drying method, the drying temperature, and the moisture content can be appropriately selected depending on the shape and size of the catalyst precursor to be used.
The catalyst precursor obtained in step (II) preferably has a Keggin-type heteropoly acid structure suitable for the production of methacrylic acid, as described above.
The structure of the catalyst precursor can be judged by infrared absorption spectroscopy. When the catalyst precursor has a Keggin type heteropoly acid structure, the obtained infrared absorption spectrum is 1060, 960, 870 and 780cm-1With characteristic peaks in the vicinity.
In the catalyst precursor, the molar ratio of ammonium groups to 12 moles of molybdenum is preferably h2, and 1. ltoreq. h 2. ltoreq.5 is satisfied. The value of h2 is obtained by analyzing the catalyst precursor by kjeldahl method. The value of h2 can be controlled by changing the amounts of the molybdenum raw material and the ammonium raw material charged in the step (I). When h2 is 1 or more, a catalyst precursor having a crystal structure suitable for the production of methacrylic acid is obtained in step (II). Further, by setting h2 to 5 or less, a Keggin-type heteropoly acid structure suitable for the production of methacrylic acid can be easily formed. The lower limit of h2 is more preferably 1.5 or more, and the upper limit is more preferably 4.5 or less.
In the catalyst precursor, when the molar ratio of the ammonium group derived from triammonium phosphate to 12 moles of molybdenum is h 2', the following formula (3) is preferably satisfied from the viewpoint that a catalyst exhibiting a high methacrylic acid yield can be obtained. The value of h 2' is determined from the amounts of the molybdenum raw material and the triammonium phosphate charged.
0.2≤h2’/h2≤1 (3)
The value of h 2'/h 2 can be controlled by varying the amounts of the triammonium phosphate and the ammonium salt starting materials charged in step (I) above. The lower limit of h 2'/h 2 is preferably 0.5 or more, more preferably 0.6 or more, particularly preferably 0.7 or more, and most preferably 0.8 or more.
The catalyst precursor obtained in step (II) is then molded in a molding step. The molding may be performed after the step (III) described later.
(Molding Process)
In the molding step, the catalyst precursor or the catalyst obtained in the step (III) described later is molded. The molding method is not particularly limited, and a known dry or wet molding method can be used. For example, tablet forming, extrusion forming, pressure forming, rotary granulation, and the like can be mentioned. The shape of the molded article is not particularly limited, and may be any shape such as spherical particles, annular particles, cylindrical particles, star-like particles, and particles obtained by crushing and classifying after molding.
Examples of the pulverization include a method using a pulverizer such as a ball mill, a high-speed rotary mill, a jet mill, or a kneader. Examples of the classification include methods using a classifier such as a mesh-fixed sieve, a vibrating sieve, or a flat-surface moving sieve.
The size of the molded article is preferably 0.1 to 10mm in diameter. By setting the diameter of the molded product to 0.1mm or more, the pressure loss in the reaction tube can be reduced. Further, by setting the diameter of the molded product to 10mm or less, the activity of the catalyst is further improved, and the yield of methacrylic acid is improved. The carrier may be supported during molding, or other additives may be mixed.
(Process (III))
In the step (III), the catalyst precursor obtained in the step (II) or the molded product of the catalyst precursor obtained in the molding step (hereinafter, collectively referred to as a catalyst precursor) is calcined to obtain a catalyst. The catalyst precursor can be calcined to further improve the catalytic activity.
The calcination method is not particularly limited, and a suitable method can be appropriately selected from static calcination, fluidized calcination, and the like. Examples of the static calcination include calcination using a box furnace, a ring calciner, or the like. Examples of the fluidized calcination include a method of calcination using a fluidized calciner, a rotary kiln, or the like.
The calcination is performed, for example, in an atmosphere of an oxygen-containing gas such as air or an inert gas, and preferably in an atmosphere of an oxygen-containing gas such as air. The "inert gas" means a gas that does not lower the catalytic activity, and examples thereof include nitrogen, carbon dioxide, helium, and argon. One kind of them may be used, or two or more kinds of them may be mixed and used. The atmosphere of the calcination may be a flow of the calcination gas or a non-flow of the calcination gas, as long as the required atmosphere of the calcination gas can be maintained.
From the viewpoint of obtaining a catalyst exhibiting a high methacrylic acid yield, the calcination temperature is preferably 200 to 500 ℃, the lower limit is more preferably 300 ℃ or more, and the upper limit is more preferably 450 ℃ or less. The calcination time is preferably 1 to 40 hours, and the lower limit is more preferably 2 hours or more.
In the catalyst obtained in the step (III), in view of obtaining a catalyst exhibiting a high methacrylic acid yield, it is preferable that the above formula (1) is satisfied when the molar ratio of phosphorus to molybdenum 12 moles is denoted by a, and the following formula (2) is satisfied when the molar ratio of phosphorus derived from triammonium phosphate to molybdenum 12 moles is denoted by a'. The value of a' is determined from the amounts of the molybdenum raw material and the triammonium phosphate charged.
0.1≤a’/a≤1 (2)
The value of a'/a can be controlled by changing the amounts of the triammonium phosphate and the other phosphorus raw materials charged in the step (I) as described above. The lower limit of a'/a is preferably 0.4 or more, more preferably 0.5 or more, particularly preferably 0.6 or more, and most preferably 0.7 or more.
[ method for producing methacrylic acid ]
Methacrolein is oxidized, particularly by gas phase contact oxidation with molecular oxygen, in the presence of the catalyst produced by the method of the present invention. That is, the method for producing methacrylic acid according to the present invention comprises: a step of producing a catalyst by the method according to the present invention, and a step of subjecting methacrolein to gas phase contact oxidation with molecular oxygen using the catalyst. By using the catalyst for methacrylic acid production produced by the method of the present invention, methacrylic acid can be produced in a higher yield than in the conventional method.
The method for producing methacrylic acid according to the present invention produces methacrylic acid by bringing a raw material gas containing methacrolein and molecular oxygen into contact with the catalyst according to the present invention. A fixed bed type reactor may be used in the reaction. The reaction can be carried out by filling a catalyst into the reaction tube and supplying a raw material gas to the reactor. The catalyst layer may be 1 layer, or a plurality of catalysts having different activities may be packed in a plurality of layers. In addition, in order to control the activity, the catalyst for methacrylic acid production may be diluted and packed with an inactive carrier.
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 more preferably 3% by volume, and the upper limit is more preferably 10% by volume or less. The raw material methacrolein may contain a small amount of impurities such as water and lower saturated aldehydes which do not substantially affect the reaction.
The concentration of molecular oxygen in the raw material gas is preferably 0.4 to 4 mol, the lower limit is more preferably 0.5 mol or more, and the upper limit is more preferably 3 mol or less, based on 1 mol of methacrolein. From the viewpoint of economy, air is preferred as the molecular oxygen source. If necessary, a gas obtained by enriching molecular oxygen by adding pure oxygen to air may be used.
The raw material gas may be a gas obtained by diluting methacrolein and molecular oxygen with an inert gas such as nitrogen or carbon dioxide. Further, water vapor may be added to the raw material gas. By carrying out the reaction in the presence of water vapor, methacrylic acid can be obtained in a higher yield. The concentration of water vapor in the raw material gas is preferably 0.1 to 50% by volume, the lower limit is more preferably 1% by volume, and the upper limit is more preferably 40% by volume or less.
The contact time between the raw material gas and the methacrylic acid production catalyst is preferably 1.5 to 15 seconds, the lower limit is more preferably 2 seconds or more, and the upper limit is more preferably 10 seconds or less. The reaction pressure is preferably 0.1 to 1MPa (G). Wherein (G) is gauge pressure. The reaction temperature is preferably 200 to 450 ℃, the lower limit is more preferably 250 ℃ or higher, and the upper limit is more preferably 400 ℃ or lower.
[ method for producing methacrylic acid ester ]
The method for producing a methacrylic acid ester according to the present invention is a method for esterifying methacrylic acid produced by the method according to the present invention. That is, the method for producing a methacrylic acid ester according to the present invention comprises: the process for producing a catalyst for methacrylic acid production by the method of the present invention, the process for gas-phase contact oxidation of methacrolein with molecular oxygen using the catalyst, and the process for esterifying methacrylic acid. By using the catalyst for methacrylic acid production according to the present invention, methacrylic acid can be obtained in high yield by gas-phase contact oxidation of methacrolein, and methacrylic acid ester can be obtained in high yield from methacrolein as a raw material.
The alcohol to be reacted with methacrylic acid is not particularly limited, and examples thereof include methanol, ethanol, isopropanol, n-butanol, and isobutanol. Examples of the obtained methacrylic acid ester include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, and the like. The reaction may be carried out in the presence of an acidic catalyst such as a sulfonic acid type cation exchange resin. The reaction temperature is preferably 50-200 ℃.
Examples
The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. "parts" in examples and comparative examples represent parts by mass.
The structure of the catalyst precursor was judged by infrared absorption analysis using NICOLET6700 FT-IR (product name, manufactured by Thermo electron Co., Ltd.).
The molar ratio of each element in the catalyst and the catalyst precursor was calculated by analyzing the components obtained by dissolving the catalyst and the catalyst precursor in aqueous ammonia by ICP emission spectrometry.
The molar ratio of ammonium groups was calculated by analyzing the catalyst and the catalyst precursor by kjeldahl method. The values of a 'and h 2' were calculated from the amounts of the molybdenum raw material and the triammonium phosphate charged.
The raw material gas and the product were analyzed by gas chromatography (device: GC-2014 manufactured by Shimadzu, column: Agilent J & W, trade name: DB-FFAP, 30 m. times.0.32 mm, film thickness 1.0 μm). From the results of the gas chromatography, the yield of methacrylic acid was determined by the following formula.
Yield (%) of methacrylic acid (number of moles of methacrylic acid produced/moles of methacrolein supplied) × 100
[ example 1]
To 1200 parts of pure water at room temperature were added 300 parts of molybdenum trioxide and 10.2 parts of ammonium metavanadate, followed by dispersion with stirring, and added 42.1 parts of triammonium phosphate trihydrate, 8.9 parts of 85% aqueous phosphoric acid solution, a diluted product obtained by diluting 40.2 parts of cesium bicarbonate with 175 parts of pure water, and a dissolved product obtained by dissolving 6.2 parts of copper (II) nitrate trihydrate in 9.0 parts of pure water. The resulting slurry was heated at 2 ℃/min and stirred for 2 hours while being maintained at 95 ℃. The resulting slurry was heated to evaporate and dry it to obtain a catalyst precursor. The obtained catalyst precursor has a Keggin type heteropoly acid structure.
The catalyst precursor was press-molded and pulverized, and classified with a sieve so that the particle diameter thereof was in the range of 710 μm to 2.36 mm. The obtained molded product was calcined at 380 ℃ for 5 hours under air circulation to produce a catalyst. The composition of the obtained catalyst other than oxygen was P1.6Mo12V0.5Cu0.15Cs1.2. The molar ratio of ammonium groups in the catalyst is 0. ltoreq. h.ltoreq.1.
The catalyst is filled in a reactor so that the reaction rate of methacrolein is in the range of 37 to 60%, and a raw material gas consisting of 5% by volume of methacrolein, 10% by volume of oxygen, 30% by volume of water vapor and 55% by volume of nitrogen is passed through the reactor to carry out a reaction at a reaction temperature of 285 ℃. The product was collected and analyzed by gas chromatography to calculate the yield of methacrylic acid. The results are shown in Table 1.
[ example 2]
A catalyst precursor was obtained in the same manner as in example 1, except that 42.1 parts of triammonium phosphate trihydrate was changed to 38.8 parts in example 1. The obtained catalyst precursor has a Keggin type heteropoly acid structure.
This catalyst precursor was molded and calcined in the same manner as in example 1 to obtain a catalyst. The composition of the obtained catalyst other than oxygen was P1.5Mo12V0.5Cu0.15Cs1.2. The molar ratio of ammonium groups in the catalyst is 0. ltoreq. h.ltoreq.1.
Using this catalyst, methacrylic acid was produced in the same manner as in example 1, and the yield of methacrylic acid was calculated. The results are shown in Table 1.
[ example 3]
A catalyst precursor was obtained in the same manner as in example 1, except that in example 1, 42.1 parts of triammonium phosphate trihydrate was changed to 31.0 parts and no 85% aqueous phosphoric acid solution was added. The obtained catalyst precursor has a Keggin type heteropoly acid structure.
This catalyst precursor was molded and calcined in the same manner as in example 1 to obtain a catalyst. The obtained catalyst has oxygen-free propertyHas the composition of P0.9Mo12V0.5Cu0.15Cs1.2. The molar ratio of ammonium groups in the catalyst is 0. ltoreq. h.ltoreq.1.
Using this catalyst, methacrylic acid was produced in the same manner as in example 1, and the yield of methacrylic acid was calculated. The results are shown in Table 1.
[ example 4]
A catalyst precursor was obtained in the same manner as in example 1, except that in example 1, 38.8 parts of triammonium phosphate trihydrate was used as 42.1 parts, and 4.3 parts of an 85% aqueous phosphoric acid solution was used as 8.9 parts. The obtained catalyst precursor has a Keggin type heteropoly acid structure.
This catalyst precursor was molded and calcined in the same manner as in example 1 to obtain a catalyst. The composition of the obtained catalyst other than oxygen was P1.3Mo12V0.5Cu0.15Cs1.2. The molar ratio of ammonium groups in the catalyst is 0. ltoreq. h.ltoreq.1.
Using this catalyst, methacrylic acid was produced in the same manner as in example 1, and the yield of methacrylic acid was calculated. The results are shown in Table 1.
[ example 5]
A catalyst precursor was obtained in the same manner as in example 1, except that 42.1 parts of triammonium phosphate trihydrate was changed to 62.2 parts in example 1. The obtained catalyst precursor has a Keggin type heteropoly acid structure.
This catalyst precursor was molded and calcined in the same manner as in example 1 to obtain a catalyst. The composition of the obtained catalyst other than oxygen was P2.2Mo12V0.5Cu0.15Cs1.2. The molar ratio of ammonium groups in the catalyst is 0. ltoreq. h.ltoreq.1.
Using this catalyst, methacrylic acid was produced in the same manner as in example 1, and the yield of methacrylic acid was calculated. The results are shown in Table 1.
[ example 6]
A catalyst precursor was obtained in the same manner as in example 1, except that 38.8 parts of triammonium phosphate trihydrate and 11.6 parts of 28% aqueous ammonia were used in place of 42.1 parts of triammonium phosphate trihydrate in example 1. The obtained catalyst precursor has a Keggin type heteropoly acid structure.
This catalyst precursor was molded and calcined in the same manner as in example 1 to obtain a catalyst. The composition of the obtained catalyst other than oxygen was P1.5Mo12V0.5Cu0.15Cs1.2. The molar ratio of ammonium groups in the catalyst is 0. ltoreq. h.ltoreq.1.
Using this catalyst, methacrylic acid was produced in the same manner as in example 1, and the yield of methacrylic acid was calculated. The results are shown in Table 1.
Comparative example 1
A catalyst precursor was obtained in the same manner as in example 1, except that in example 1, 23.5 parts of diammonium phosphate and 10.6 parts of 28% aqueous ammonia were used instead of 42.1 parts of triammonium phosphate trihydrate. The obtained catalyst precursor has a Keggin type heteropoly acid structure.
This catalyst precursor was molded and calcined in the same manner as in example 1 to obtain a catalyst. The composition of the obtained catalyst other than oxygen was P1.5Mo12V0.5Cu0.15Cs1.2. The molar ratio of ammonium groups in the catalyst is 0. ltoreq. h.ltoreq.1.
Using this catalyst, methacrylic acid was produced in the same manner as in example 1, and the yield of methacrylic acid was calculated. The results are shown in Table 1.
Comparative example 2
A catalyst precursor was obtained in the same manner as in example 1 except that 31.6 parts of 28% aqueous ammonia was used instead of 40.2 parts of triammonium phosphate trihydrate in example 1 and 8.9 parts of 85% aqueous phosphoric acid was changed to 30.6 parts. The obtained catalyst precursor has a Keggin type heteropoly acid structure.
This catalyst precursor was molded and calcined in the same manner as in example 1 to obtain a catalyst. The composition of the obtained catalyst other than oxygen was P1.5Mo12V0.5Cu0.15Cs1.2. The molar ratio of ammonium groups in the catalyst is 0. ltoreq. h.ltoreq.1.
Using this catalyst, methacrylic acid was produced in the same manner as in example 1, and the yield of methacrylic acid was calculated. The results are shown in Table 1.
Comparative example 3
A catalyst precursor was obtained in the same manner as in example 1 except that 46.7 parts of 28% aqueous ammonia was used instead of 40.2 parts of triammonium phosphate trihydrate in example 1 and 8.9 parts of 85% aqueous phosphoric acid was changed to 30.6 parts. The obtained catalyst precursor has a Keggin type heteropoly acid structure.
This catalyst precursor was molded and calcined in the same manner as in example 1 to obtain a catalyst. The composition of the obtained catalyst other than oxygen was P1.5Mo12V0.5Cu0.15Cs1.2. The molar ratio of ammonium groups in the catalyst is 0. ltoreq. h.ltoreq.1.
Using this catalyst, methacrylic acid was produced in the same manner as in example 1, and the yield of methacrylic acid was calculated. The results are shown in Table 1.
Comparative example 4
A catalyst precursor was obtained in the same manner as in example 1, except that in example 1, 21.7 parts of monoammonium phosphate and 20.5 parts of 28% aqueous ammonia were used instead of 42.1 parts of triammonium phosphate trihydrate. The obtained catalyst precursor has a Keggin type heteropoly acid structure.
This catalyst precursor was molded and calcined in the same manner as in example 1 to obtain a catalyst. The composition of the obtained catalyst other than oxygen was P1.5Mo12V0.5Cu0.15Cs1.2. The molar ratio of ammonium groups in the catalyst is 0. ltoreq. h.ltoreq.1.
Using this catalyst, methacrylic acid was produced in the same manner as in example 1, and the yield of methacrylic acid was calculated. The results are shown in Table 1.
[ Table 1]
As shown in Table 1, it was confirmed that examples 1 to 6 using triammonium phosphate as at least a part of the phosphorus raw material are catalysts having a high methacrylic acid yield as compared with comparative examples 1 to 4.
Industrial applicability
The catalyst for methacrylic acid production according to the present invention is useful for industrial production of methacrylic acid because methacrylic acid can be produced in a higher yield than in the conventional art.
Claims (10)
1. A method for producing a catalyst used for producing methacrylic acid by oxidizing methacrolein, comprising the steps of:
(I) a step of mixing at least a molybdenum material and a phosphorus material with a solvent to prepare a solution or slurry,
(II) a step of drying the solution or slurry to obtain a catalyst precursor,
(III) a step of calcining the catalyst precursor to obtain a catalyst,
in the step (I), triammonium phosphate is used as at least a part of the phosphorus raw material.
2. The method for producing a catalyst according to claim 1, wherein the catalyst precursor obtained in the step (II) has a Keggin-type heteropoly acid structure.
3. The method for producing a catalyst according to claim 1 or 2, wherein the catalyst obtained in the step (III) satisfies the following formula (1) where a represents a molar ratio of phosphorus to 12 moles of molybdenum,
0.5≤a≤3 (1)。
4. the method for producing a catalyst according to any one of claims 1 to 3, wherein the catalyst obtained in the step (III) satisfies the following formula (2) when a represents a molar ratio of phosphorus to 12 moles of molybdenum and a' represents a molar ratio of phosphorus derived from triammonium phosphate to 12 moles of molybdenum,
0.1≤a’/a≤1 (2)。
5. the method for producing a catalyst according to any one of claims 1 to 4, wherein the catalyst precursor obtained in the step (II) satisfies the following formula (3) when the molar ratio of ammonium groups to molybdenum (12 mol) is h2 and the molar ratio of ammonium groups derived from triammonium phosphate to molybdenum (12 mol) is h 2',
0.2≤h2’/h2≤1 (3)。
6. the method for producing a catalyst according to any one of claims 1 to 5, wherein the catalyst obtained in the step (III) is a catalyst having a composition represented by the following formula (4),
PaMobVcCudAeEfGg(NH4)hOi (4)
in the formula (4), P, Mo, V, Cu, NH4And O represents phosphorus, molybdenum, vanadium, copper, ammonium and oxygen, respectively,
a represents at least 1 element selected from antimony, bismuth, arsenic, germanium, zirconium, tellurium, silver, selenium, silicon, tungsten and boron,
e represents at least 1 element selected from the group consisting of iron, zinc, chromium, calcium, strontium, tantalum, cobalt, nickel, manganese, titanium, tin, lead, niobium, indium, sulfur, palladium, gallium, cerium and lanthanum,
g represents at least 1 element selected from potassium, rubidium, cesium, thallium, magnesium and barium,
a to i represent the molar ratio of each component, and when b is 12, a is 0.5. ltoreq. a.ltoreq.3, c is 0.01. ltoreq. c.ltoreq.3, d is 0.01. ltoreq. d.ltoreq.2, e is 0. ltoreq. e.ltoreq.3, f is 0. ltoreq. f.ltoreq.3, g is 0.01. ltoreq. g.ltoreq.3, h is 0. ltoreq. h.ltoreq.20, and i is the molar ratio of oxygen necessary for satisfying the valence.
7. A method for producing methacrylic acid, comprising a step of oxidizing methacrolein in the presence of the catalyst produced by the method according to any one of claims 1 to 6.
8. A method for producing methacrylic acid, comprising a step of producing a catalyst by the method according to any one of claims 1 to 6, and a step of oxidizing methacrolein with the catalyst.
9. A method for producing a methacrylic acid ester, comprising the step of esterifying methacrylic acid produced by the method according to claim 7 or 8.
10. A method for producing a methacrylic acid ester, comprising the step of producing a catalyst by the method according to any one of claims 1 to 6, the step of oxidizing methacrolein with the catalyst, and the step of esterifying methacrylic acid.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018085196 | 2018-04-26 | ||
| JP2018-085196 | 2018-04-26 | ||
| PCT/JP2019/017719 WO2019208715A1 (en) | 2018-04-26 | 2019-04-25 | Method for producing catalyst for methacrylic-acid production and methods for producing methacrylic acid and methacryic ester |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112004597A true CN112004597A (en) | 2020-11-27 |
Family
ID=68294061
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201980027507.7A Pending CN112004597A (en) | 2018-04-26 | 2019-04-25 | Method for producing catalyst for methacrylic acid production, and method for producing methacrylic acid and methacrylic acid ester |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP7031737B2 (en) |
| KR (1) | KR102463952B1 (en) |
| CN (1) | CN112004597A (en) |
| SG (1) | SG11202009571VA (en) |
| WO (1) | WO2019208715A1 (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5579044A (en) * | 1978-12-07 | 1980-06-14 | Toyo Soda Mfg Co Ltd | Catalyst for methacrylic acid production |
| WO2004105941A1 (en) * | 2003-05-30 | 2004-12-09 | Nippon Kayaku Kabushiki Kaisha | Process for producing catalyst for methacrylic acid production |
| CN1662304A (en) * | 2002-07-05 | 2005-08-31 | 三菱丽阳株式会社 | Process for producing catalysts for the production of methacrylic acid |
| CN1874842A (en) * | 2003-10-27 | 2006-12-06 | 三菱丽阳株式会社 | Process for producing catalyst for methacrylic acid production, catalyst for methacrylic acid production, and process for producing methacrylic acid |
| CN101073776A (en) * | 2006-05-15 | 2007-11-21 | 北京化工大学 | Catalyst for producing methyl-acrylate from methyl-acrolein and its production |
| WO2010013749A1 (en) * | 2008-07-29 | 2010-02-04 | 三菱レイヨン株式会社 | Catalyst for methacrylic acid production, process for producing same, and process for producing methacrylic acid |
| JP2011173114A (en) * | 2010-01-28 | 2011-09-08 | Mitsubishi Rayon Co Ltd | Catalyst for manufacturing methacrylic acid, manufacturing method of the same, and manufacturing method of methacrylic acid |
| JP2013006162A (en) * | 2011-06-27 | 2013-01-10 | Mitsubishi Rayon Co Ltd | Method of manufacturing methacrylic acid manufacturing catalyst |
| CN103459022A (en) * | 2011-04-11 | 2013-12-18 | 三菱丽阳株式会社 | Method for preparing catalyst for production of 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 |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3101821B2 (en) * | 1990-02-15 | 2000-10-23 | 三菱レイヨン株式会社 | Preparation of catalyst for methacrylic acid production |
| JPH08157414A (en) * | 1994-12-01 | 1996-06-18 | Mitsui Toatsu Chem Inc | Catalyst for methacrylic acid production and production of methacrylic acid |
| JP3482476B2 (en) * | 1995-07-12 | 2003-12-22 | 住友化学工業株式会社 | Method for producing catalyst for producing methacrylic acid and method for producing methacrylic acid |
| JPH0938495A (en) * | 1995-08-02 | 1997-02-10 | Mitsubishi Chem Corp | Oxidation dehydrogenation catalyst and production of unsaturated carboxylic acids using the same |
| WO2000072964A1 (en) | 1999-05-27 | 2000-12-07 | Mitsubishi Rayon Co., Ltd. | Catalyst for methacrylic acid production and process for producing methacrylic acid |
| KR100915078B1 (en) * | 2006-12-01 | 2009-09-02 | 주식회사 엘지화학 | Novel heteropoly acid catalyst and preparing method thereof |
| US9527792B2 (en) * | 2014-04-30 | 2016-12-27 | Mitsubishi Rayon Co., Ltd. | Method for producing (meth)acrylic acid |
-
2019
- 2019-04-25 KR KR1020207033334A patent/KR102463952B1/en active IP Right Grant
- 2019-04-25 CN CN201980027507.7A patent/CN112004597A/en active Pending
- 2019-04-25 JP JP2020515577A patent/JP7031737B2/en active Active
- 2019-04-25 SG SG11202009571VA patent/SG11202009571VA/en unknown
- 2019-04-25 WO PCT/JP2019/017719 patent/WO2019208715A1/en active Application Filing
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5579044A (en) * | 1978-12-07 | 1980-06-14 | Toyo Soda Mfg Co Ltd | Catalyst for methacrylic acid production |
| CN1662304A (en) * | 2002-07-05 | 2005-08-31 | 三菱丽阳株式会社 | Process for producing catalysts for the production of methacrylic acid |
| WO2004105941A1 (en) * | 2003-05-30 | 2004-12-09 | Nippon Kayaku Kabushiki Kaisha | Process for producing catalyst for methacrylic acid production |
| CN1874842A (en) * | 2003-10-27 | 2006-12-06 | 三菱丽阳株式会社 | Process for producing catalyst for methacrylic acid production, catalyst for methacrylic acid production, and process for producing methacrylic acid |
| CN101073776A (en) * | 2006-05-15 | 2007-11-21 | 北京化工大学 | Catalyst for producing methyl-acrylate from methyl-acrolein and its production |
| WO2010013749A1 (en) * | 2008-07-29 | 2010-02-04 | 三菱レイヨン株式会社 | Catalyst for methacrylic acid production, process for producing same, and process for producing methacrylic acid |
| CN102105223A (en) * | 2008-07-29 | 2011-06-22 | 三菱丽阳株式会社 | Catalyst for methacrylic acid production, process for producing same, and process for producing methacrylic acid |
| JP2011173114A (en) * | 2010-01-28 | 2011-09-08 | Mitsubishi Rayon Co Ltd | Catalyst for manufacturing methacrylic acid, manufacturing method of the same, and manufacturing method of methacrylic acid |
| CN103459022A (en) * | 2011-04-11 | 2013-12-18 | 三菱丽阳株式会社 | Method for preparing catalyst for production of methacrylic acid |
| JP2013006162A (en) * | 2011-06-27 | 2013-01-10 | Mitsubishi Rayon Co Ltd | Method of manufacturing methacrylic acid manufacturing catalyst |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| KR102463952B1 (en) | 2022-11-04 |
| WO2019208715A1 (en) | 2019-10-31 |
| JPWO2019208715A1 (en) | 2021-05-20 |
| KR20210002576A (en) | 2021-01-08 |
| SG11202009571VA (en) | 2020-10-29 |
| JP7031737B2 (en) | 2022-03-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109641192B (en) | Catalyst for methacrylic acid production, method for producing same, and method for producing methacrylic acid and methacrylic acid ester | |
| CN110300622B (en) | Catalyst for methacrylic acid production, catalyst precursor for methacrylic acid production, processes for producing these, process for producing methacrylic acid, and process for producing methacrylic acid ester | |
| KR20110044266A (en) | Catalyst for methacrylic acid production, process for producing same, and process for producing methacrylic acid | |
| KR101735862B1 (en) | Process for production of composite oxide catalyst | |
| JP7006477B2 (en) | A method for producing a catalyst for producing methacrylic acid, and a method for producing methacrylic acid. | |
| CN112004597A (en) | Method for producing catalyst for methacrylic acid production, and method for producing methacrylic acid and methacrylic acid ester | |
| CN110062656B (en) | Method for producing catalyst precursor for production of alpha, beta-unsaturated carboxylic acid | |
| KR102318486B1 (en) | Method for preparing catalyst for preparing α,β-unsaturated carboxylic acid, method for preparing α,β-unsaturated carboxylic acid, and method for preparing α,β-unsaturated carboxylic acid ester | |
| CN111770795B (en) | Method for producing catalyst for producing alpha, beta-unsaturated carboxylic acid, and method for producing alpha, beta-unsaturated carboxylic acid | |
| KR102573437B1 (en) | Catalyst for producing methacrylic acid, method for producing same, and method for producing methacrylic acid and methacrylic acid ester | |
| JP2013128878A (en) | Method for producing catalyst for producing methacrylic acid | |
| KR102346234B1 (en) | Catalyst precursor, method for preparing catalyst, method for preparing methacrylic acid and acrylic acid, and method for preparing methacrylic acid ester and acrylic acid ester | |
| WO2023182425A1 (en) | Catalyst for methacrylic acid production, method for producing same, and method for producing methacrylic acid and methacrylic acid esters using catalyst | |
| JP5609396B2 (en) | Catalyst for methacrylic acid production |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20201127 |