KR20200069340A - Method for preparing catalyst for production of α,β-unsaturated carboxylic acid, method for producing α,β-unsaturated carboxylic acid, and method for producing α,β-unsaturated carboxylic acid ester - Google Patents
Method for preparing catalyst for production of α,β-unsaturated carboxylic acid, method for producing α,β-unsaturated carboxylic acid, and method for producing α,β-unsaturated carboxylic acid ester Download PDFInfo
- Publication number
- KR20200069340A KR20200069340A KR1020207013491A KR20207013491A KR20200069340A KR 20200069340 A KR20200069340 A KR 20200069340A KR 1020207013491 A KR1020207013491 A KR 1020207013491A KR 20207013491 A KR20207013491 A KR 20207013491A KR 20200069340 A KR20200069340 A KR 20200069340A
- Authority
- KR
- South Korea
- Prior art keywords
- unsaturated carboxylic
- carboxylic acid
- catalyst
- producing
- molybdenum
- Prior art date
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- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 title claims abstract description 92
- 239000003054 catalyst Substances 0.000 title claims abstract description 90
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims description 57
- 239000002245 particle Substances 0.000 claims abstract description 63
- 239000002994 raw material Substances 0.000 claims abstract description 63
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 39
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000011733 molybdenum Substances 0.000 claims abstract description 36
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims abstract description 31
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000009826 distribution Methods 0.000 claims abstract description 26
- 238000005259 measurement Methods 0.000 claims abstract description 8
- 239000002002 slurry Substances 0.000 claims description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 28
- 239000007789 gas Substances 0.000 claims description 27
- 239000007864 aqueous solution Substances 0.000 claims description 26
- 150000001299 aldehydes Chemical class 0.000 claims description 23
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 21
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 20
- 229910001882 dioxygen Inorganic materials 0.000 claims description 20
- 239000011964 heteropoly acid Substances 0.000 claims description 17
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims description 16
- 239000012018 catalyst precursor Substances 0.000 claims description 16
- 230000003647 oxidation Effects 0.000 claims description 15
- 238000007254 oxidation reaction Methods 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- 229910052698 phosphorus Inorganic materials 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 239000010949 copper Substances 0.000 claims description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 239000011574 phosphorus Substances 0.000 claims description 10
- 230000003197 catalytic effect Effects 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 8
- 150000001768 cations Chemical class 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 229910052720 vanadium Inorganic materials 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052792 caesium Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 239000011133 lead Substances 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 229910052701 rubidium Inorganic materials 0.000 claims description 4
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052716 thallium Inorganic materials 0.000 claims description 4
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 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 group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical group [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 group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-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
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052785 arsenic Inorganic materials 0.000 claims description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-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
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Chemical group 0.000 claims 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 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Chemical group 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Chemical group 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 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
- 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
- 239000011777 magnesium Chemical group 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical group [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
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 239000010955 niobium Substances 0.000 claims description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052711 selenium Inorganic materials 0.000 claims description 3
- 239000011669 selenium Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon 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 group [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
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical group [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 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
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 239000011135 tin Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 239000011701 zinc Chemical group 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 150000001735 carboxylic acids Chemical class 0.000 claims 2
- 239000003377 acid catalyst Substances 0.000 claims 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims 1
- 239000000047 product Substances 0.000 description 19
- 238000010438 heat treatment Methods 0.000 description 12
- 239000012071 phase Substances 0.000 description 12
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical group CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000000465 moulding Methods 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- 150000003863 ammonium salts Chemical class 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 150000003868 ammonium compounds Chemical class 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000001099 ammonium carbonate Substances 0.000 description 3
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 3
- 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 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 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
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 235000012501 ammonium carbonate Nutrition 0.000 description 2
- 238000004458 analytical method Methods 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
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 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
- 238000001914 filtration Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- AMWVZPDSWLOFKA-UHFFFAOYSA-N phosphanylidynemolybdenum Chemical compound [Mo]#P AMWVZPDSWLOFKA-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000002360 preparation method Methods 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
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 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
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 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
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- AXMVYSVVTMKQSL-UHFFFAOYSA-N UNPD142122 Natural products OC1=CC=C(C=CC=O)C=C1O AXMVYSVVTMKQSL-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
- 239000000654 additive Substances 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ZMCUDHNSHCRDBT-UHFFFAOYSA-M caesium bicarbonate Chemical compound [Cs+].OC([O-])=O ZMCUDHNSHCRDBT-UHFFFAOYSA-M 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229940117916 cinnamic aldehyde Drugs 0.000 description 1
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 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
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 1
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- 238000010586 diagram Methods 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
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- 238000002036 drum drying Methods 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
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- 238000011049 filling Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 150000004715 keto acids Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 210000003205 muscle Anatomy 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- -1 oxides Chemical class 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- CBXWGGFGZDVPNV-UHFFFAOYSA-N so4-so4 Chemical compound OS(O)(=O)=O.OS(O)(=O)=O CBXWGGFGZDVPNV-UHFFFAOYSA-N 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 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
- 239000012808 vapor phase Substances 0.000 description 1
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- 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
- B01J37/02—Impregnation, coating or precipitation
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Abstract
높은 수율로 α,β-불포화 카복실산을 제조할 수 있는 α,β-불포화 카복실산 제조용 촉매를 제공한다. 몰리브데넘 원료로서, 입자경 분포 측정에 의해 얻어지는 빈도 분포 곡선에 있어서, 입자경이 6μm 이하인 입자의 비율이 2∼55체적%인 몰리브데넘 산화물을 사용하는 α,β-불포화 카복실산 제조용 촉매의 제조 방법.Provided is a catalyst for the production of α,β-unsaturated carboxylic acids capable of producing α,β-unsaturated carboxylic acids with high yield. Method for producing catalyst for production of α,β-unsaturated carboxylic acid using molybdenum oxide having a ratio of 2 to 55% by volume of particles having a particle diameter of 6 μm or less in a frequency distribution curve obtained by particle size distribution measurement as a molybdenum raw material .
Description
본 발명은 α,β-불포화 카복실산 제조용 촉매의 제조 방법, α,β-불포화 카복실산의 제조 방법 및 α,β-불포화 카복실산 에스터의 제조 방법에 관한 것이다.The present invention relates to a method for preparing a catalyst for producing α,β-unsaturated carboxylic acid, a method for producing α,β-unsaturated carboxylic acid, and a method for producing α,β-unsaturated carboxylic acid ester.
α,β-불포화 알데하이드를 분자상 산소에 의해 기상 접촉 산화시켜 α,β-불포화 카복실산을 제조할 때에 이용되는 촉매로서는, 인 몰리브데넘산, 인 몰리브데넘산염 등의 헤테로폴리산 또는 그의 염을 주성분으로 하는 촉매가 알려져 있다. 해당 촉매의 제조 방법에 대해서는 수많은 검토가 이루어지고 있고, 그 대부분은, 우선 촉매를 구성하는 각 원소를 포함하는 수성 슬러리 또는 수용액을 조제하고, 그 후 이것을 건조하고, 소성함으로써 촉매를 제조하고 있다.As a catalyst used in the production of α,β-unsaturated carboxylic acids by gas phase contact oxidation of α,β-unsaturated aldehydes with molecular oxygen, heteropolyacids such as phosphorus molybdenum acid and phosphorus molybdenum acid salts or main salts thereof Catalysts to be known are known. A number of studies have been conducted on the production method of the catalyst, most of which are prepared by first preparing an aqueous slurry or aqueous solution containing each element constituting the catalyst, and then drying and calcining it.
이와 같은 촉매의 기본적인 성능은, 주로 원소 조성, 결정 구조, 입자경 등에 의존하지만, 그 제어에는, 수성 슬러리 또는 수용액의 조제 과정의 조건을 제어할 것이 요구된다. 일반적으로, 수성 슬러리 또는 수용액의 조제에 이용되는 원료로서는, 수용성의 원료 및 물에 불용성인 원료 모두 사용 가능하다. 그러나, 특히 물에 불용성인 원료를 이용하는 경우, 원료의 물성이 촉매 성능에 큰 영향을 주는 것이 알려져 있다. 예를 들면 특허문헌 1에는, 압축도가 60 이하인 몰리브데넘 산화물을 원료에 이용함으로써, 높은 촉매 활성 및 선택성을 갖는 몰리브데넘 함유 고체 촉매를 제조할 수 있는 것이 기재되어 있다. 또한, 특허문헌 2에는, X선으로서 CuKα선을 이용한 X선 회절도에 있어서의 회절 피크 위치와 회절 강도가 규정된 몰리브데넘 산화물을 원료로서 사용하는 촉매의 제조 방법이 개시되어 있다.Although the basic performance of such a catalyst mainly depends on the element composition, crystal structure, particle diameter, etc., it is required to control the conditions of the preparation process of the aqueous slurry or aqueous solution for its control. Generally, as a raw material used for preparing an aqueous slurry or aqueous solution, both a water-soluble raw material and a water-insoluble raw material can be used. However, it is known that, in particular, when a raw material insoluble in water is used, the physical properties of the raw material greatly affect the catalyst performance. For example,
그러나, 특허문헌 1, 2에 개시되어 있는 몰리브데넘 산화물을 이용하여 제조한 촉매에서는, α,β-불포화 카복실산의 수율이 아직도 불충분하여, 더한층의 촉매의 개량이 요망된다.However, in the catalyst produced using the molybdenum oxide disclosed in
본 발명은 높은 수율로 α,β-불포화 카복실산을 제조할 수 있는 촉매를 제공하는 것을 목적으로 한다.It is an object of the present invention to provide a catalyst capable of producing α,β-unsaturated carboxylic acids with high yield.
본 발명은, 이하의 [1] 내지 [13]이다.The present invention is the following [1] to [13].
[1] 몰리브데넘 원료로서, 입자경 분포 측정에 의해 얻어지는 빈도 분포 곡선에 있어서, 입자경이 6μm 이하인 입자의 비율이 2∼55체적%인 몰리브데넘 산화물을 사용하는 α,β-불포화 카복실산 제조용 촉매의 제조 방법.[1] A catalyst for the production of α,β-unsaturated carboxylic acids using molybdenum oxide having a ratio of 2 to 55% by volume of particles having a particle diameter of 6 μm or less in a frequency distribution curve obtained by particle size distribution measurement as a molybdenum raw material Method of manufacture.
[2] (i) 적어도 상기 몰리브데넘 원료 및 인 원료를 포함하는 촉매 원료와 물을 혼합하여 얻어진 수성 슬러리(I)을, 90∼150℃로 가열하여 헤테로폴리산을 포함하는 수성 슬러리 또는 수용액(II)를 얻는 공정과,[2] (i) An aqueous slurry or aqueous solution containing heteropoly acid by heating the aqueous slurry (I) obtained by mixing water with at least the catalyst raw material including the molybdenum raw material and phosphorus raw material at 90 to 150°C (II ), and
(ii) 상기 수성 슬러리 또는 수용액(II)에 금속 양이온 함유 화합물을 첨가하여, 헤테로폴리산염이 석출된 수성 슬러리(III)을 얻는 공정과,(ii) adding a metal cation-containing compound to the aqueous slurry or aqueous solution (II) to obtain an aqueous slurry (III) in which heteropolyacids are precipitated,
(iii) 상기 수성 슬러리(III)을 건조하여, 촉매 전구체 건조물을 얻는 공정과,(iii) drying the aqueous slurry (III) to obtain a catalyst precursor dried product,
(iv) 상기 촉매 전구체 건조물을 열처리하여, 촉매를 얻는 공정(iv) Process of heat-treating the dried catalyst precursor to obtain a catalyst
을 갖고, 상기 공정(i)에 있어서, 상기 수성 슬러리(I)의 온도가 60℃에 도달하고 나서 90℃에 도달할 때까지의 시간이 5∼40분인, [1]에 기재된 α,β-불포화 카복실산 제조용 촉매의 제조 방법.Α, β- described in [1], in the step (i), the time from the temperature of the aqueous slurry (I) to 60° C. until reaching 90° C. is 5 to 40 minutes. Method for producing a catalyst for producing an unsaturated carboxylic acid.
[3] 상기 공정(i)에 있어서, 상기 수성 슬러리(I)의 온도가 60℃에 도달하고 나서 90℃에 도달할 때까지의 시간이 7∼30분인, [2]에 기재된 α,β-불포화 카복실산 제조용 촉매의 제조 방법.[3] The α,β- described in [2], in which the time from the temperature of the aqueous slurry (I) to 60°C to 90°C in the step (i) is 7 to 30 minutes. Method for producing a catalyst for producing an unsaturated carboxylic acid.
[4] 상기 몰리브데넘 원료가, 입자경이 6μm 이하인 입자의 비율이 2∼35체적%인 몰리브데넘 산화물인, [1] 내지 [3] 중 어느 하나에 기재된 α,β-불포화 카복실산 제조용 촉매의 제조 방법.[4] The catalyst for the production of α,β-unsaturated carboxylic acids according to any one of [1] to [3], wherein the molybdenum raw material is a molybdenum oxide having a particle size of 2 to 35% by volume with a particle diameter of 6 μm or less. Method of manufacture.
[5] 상기 몰리브데넘 원료가, 입자경이 6μm 이하인 입자의 비율이 2∼15체적%인 몰리브데넘 산화물인, [4]에 기재된 α,β-불포화 카복실산 제조용 촉매의 제조 방법.[5] The method for producing the catalyst for producing α,β-unsaturated carboxylic acids according to [4], wherein the molybdenum raw material is a molybdenum oxide having a particle diameter of 2 to 15% by volume with a particle diameter of 6 μm or less.
[6] 상기 α,β-불포화 카복실산 제조용 촉매가, 하기 식(1)로 표시되는 조성을 갖는, [1] 내지 [5] 중 어느 하나에 기재된 α,β-불포화 카복실산 제조용 촉매의 제조 방법.[6] The method for producing the catalyst for producing α,β-unsaturated carboxylic acid according to any one of [1] to [5], wherein the catalyst for producing α,β-unsaturated carboxylic acid has a composition represented by the following formula (1).
PaMobVcCudAeEfGgOh (1)P a Mo b V c Cu d A e E f G g O h (1)
(식(1) 중, P, Mo, V, Cu 및 O는 각각 인, 몰리브데넘, 바나듐, 구리 및 산소를 나타내는 원소 기호이다. A는 안티모니, 비스무트, 비소, 저마늄, 지르코늄, 텔루륨, 은, 셀레늄, 규소, 텅스텐 및 붕소로 이루어지는 군으로부터 선택되는 적어도 1종의 원소를 나타내고, E는 철, 아연, 크로뮴, 마그네슘, 칼슘, 스트론튬, 탄탈럼, 코발트, 니켈, 망가니즈, 바륨, 타이타늄, 주석, 납, 나이오븀, 인듐, 황, 팔라듐, 갈륨, 세륨 및 란타넘으로 이루어지는 군으로부터 선택되는 적어도 1종의 원소를 나타내고, G는 리튬, 나트륨, 칼륨, 루비듐, 세슘 및 탈륨으로 이루어지는 군으로부터 선택되는 적어도 1종의 원소를 나타낸다. a∼h는 각 원소의 원자 비율을 나타내고, b=12일 때, a=0.5∼3, c=0.01∼3, d=0.01∼2, e=0∼3, f=0∼3, g=0.01∼3이며, h는 상기 각 원소의 원자가를 만족하는 데 필요한 산소의 원자 비율이다.).(In formula (1), P, Mo, V, Cu, and O are elemental symbols representing phosphorus, molybdenum, vanadium, copper, and oxygen, respectively. A is antimony, bismuth, arsenic, germanium, zirconium, and tellurium. Represents at least one element selected from the group consisting of rulium, silver, selenium, silicon, tungsten and boron, E is iron, zinc, chromium, magnesium, calcium, strontium, tantalum, cobalt, nickel, manganese, barium , Titanium, tin, lead, niobium, indium, sulfur, palladium, gallium, cerium, and at least one element selected from the group consisting of lanthanum, G is lithium, sodium, potassium, rubidium, cesium and thallium Represents at least one element selected from the group consisting of: a to h represent the atomic ratio of each element, 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 the atomic ratio of oxygen required to satisfy the valence of each element.).
[7] 상기 몰리브데넘 원료로서 삼산화 몰리브데넘을 50질량% 이상 사용하는, [1] 내지 [6] 중 어느 하나에 기재된 α,β-불포화 카복실산 제조용 촉매의 제조 방법.[7] The method for producing a catalyst for producing α,β-unsaturated carboxylic acids according to any one of [1] to [6], wherein 50 mol% or more of molybdenum trioxide is used as the raw material for molybdenum.
[8] 상기 몰리브데넘 원료로서 삼산화 몰리브데넘을 70질량% 이상 사용하는, [7]에 기재된 α,β-불포화 카복실산 제조용 촉매의 제조 방법.[8] The method for producing the catalyst for producing α,β-unsaturated carboxylic acid according to [7], wherein 70 mol% or more of molybdenum trioxide is used as the molybdenum raw material.
[9] 상기 α,β-불포화 카복실산 제조용 촉매는, α,β-불포화 알데하이드를 분자상 산소에 의해 기상 접촉 산화시켜 α,β-불포화 카복실산을 제조할 때에 이용되는 촉매로서, 상기 α,β-불포화 알데하이드가 (메트)아크롤레인이고, 또한 상기 α,β-불포화 카복실산이 (메트)아크릴산인, [1] 내지 [8] 중 어느 하나에 기재된 α,β-불포화 카복실산 제조용 촉매의 제조 방법.[9] The catalyst for the production of α,β-unsaturated carboxylic acid is a catalyst used in the gas phase contact oxidation of α,β-unsaturated aldehyde with molecular oxygen to produce α,β-unsaturated carboxylic acid, wherein the α,β- The method for producing a catalyst for producing α,β-unsaturated carboxylic acids according to any one of [1] to [8], wherein the unsaturated aldehyde is (meth)acrolein and the α,β-unsaturated carboxylic acid is (meth)acrylic acid.
[10] [1] 내지 [9] 중 어느 하나에 기재된 방법에 의해 α,β-불포화 카복실산 제조용 촉매를 제조하고, 해당 촉매를 이용하여 α,β-불포화 알데하이드를 분자상 산소에 의해 기상 접촉 산화시켜 α,β-불포화 카복실산을 제조하는 α,β-불포화 카복실산의 제조 방법.[10] A catalyst for the production of α,β-unsaturated carboxylic acid is prepared by the method according to any one of [1] to [9], and the catalyst is used for gas phase contact oxidation of α,β-unsaturated aldehyde with molecular oxygen. Method of producing α,β-unsaturated carboxylic acid to prepare α,β-unsaturated carboxylic acid.
[11] [1] 내지 [9] 중 어느 하나에 기재된 방법에 의해 제조된 α,β-불포화 카복실산 제조용 촉매를 이용하여, α,β-불포화 알데하이드를 분자상 산소에 의해 기상 접촉 산화시켜 α,β-불포화 카복실산을 제조하는 α,β-불포화 카복실산의 제조 방법.[11] α,β-unsaturated aldehyde is catalytically subjected to gas phase contact oxidation with molecular oxygen using α,β-unsaturated carboxylic acid production catalyst prepared by the method according to any one of [1] to [9], α, Method for producing α,β-unsaturated carboxylic acid to produce β-unsaturated carboxylic acid.
[12] [10] 또는 [11]에 기재된 방법에 의해 제조된 α,β-불포화 카복실산을 에스터화하는 α,β-불포화 카복실산 에스터의 제조 방법.[12] A method for producing an α,β-unsaturated carboxylic acid ester to esterify an α,β-unsaturated carboxylic acid produced by the method described in [10] or [11].
[13] [10] 또는 [11]에 기재된 방법에 의해 α,β-불포화 카복실산을 제조하고, 해당 α,β-불포화 카복실산을 에스터화하는 α,β-불포화 카복실산 에스터의 제조 방법.[13] A method for producing an α,β-unsaturated carboxylic acid ester by producing an α,β-unsaturated carboxylic acid by the method described in [10] or [11], and esterifying the α,β-unsaturated carboxylic acid.
본 발명에 의하면, 높은 수율로 α,β-불포화 카복실산을 제조할 수 있는 촉매를 제공할 수 있다.According to the present invention, it is possible to provide a catalyst capable of producing α,β-unsaturated carboxylic acid with high yield.
도 1은 실시예 1∼4 및 비교예 1∼3에 있어서의 삼산화 몰리브데넘의 입자경 분포를 나타내는 도면이다.1 is a view showing the particle size distribution of molybdenum trioxide in Examples 1 to 4 and Comparative Examples 1 to 3.
[α,β-불포화 카복실산 제조용 촉매] [Catalyst for the production of α,β-unsaturated carboxylic acids]
본 발명에 따른 방법에 의해 제조되는 α,β-불포화 카복실산 제조용 촉매는, 적어도 몰리브데넘을 포함하지만, 인 및 몰리브데넘을 포함하는 것이 바람직하고, 하기 식(1)로 표시되는 조성을 갖는 것이 보다 바람직하다. 이에 의해, α,β-불포화 카복실산의 제조에 있어서 고수율로 α,β-불포화 카복실산을 제조할 수 있다. 한편, 촉매의 원소 조성은, 촉매를 암모니아수에 용해시킨 용액을 ICP 발광 분석법으로 분석하는 것에 의해 구한 값으로 한다.The catalyst for preparing an α,β-unsaturated carboxylic acid prepared by the method according to the present invention contains at least molybdenum, but preferably contains phosphorus and molybdenum, and has a composition represented by the following formula (1) It is more preferable. Thereby, in the production of α,β-unsaturated carboxylic acid, α,β-unsaturated carboxylic acid can be produced with high yield. On the other hand, the elemental composition of the catalyst is a value obtained by analyzing a solution in which the catalyst is dissolved in ammonia water by ICP emission spectrometry.
PaMobVcCudAeEfGgOh (1) P a Mo b V c Cu d A e E f G g O h (1)
식(1) 중, P, Mo, V, Cu 및 O는 각각 인, 몰리브데넘, 바나듐, 구리 및 산소를 나타내는 원소 기호이다. A는 안티모니, 비스무트, 비소, 저마늄, 지르코늄, 텔루륨, 은, 셀레늄, 규소, 텅스텐 및 붕소로 이루어지는 군으로부터 선택되는 적어도 1종의 원소를 나타내고, E는 철, 아연, 크로뮴, 마그네슘, 칼슘, 스트론튬, 탄탈럼, 코발트, 니켈, 망가니즈, 바륨, 타이타늄, 주석, 납, 나이오븀, 인듐, 황, 팔라듐, 갈륨, 세륨 및 란타넘으로 이루어지는 군으로부터 선택되는 적어도 1종의 원소를 나타내고, G는 리튬, 나트륨, 칼륨, 루비듐, 세슘 및 탈륨으로 이루어지는 군으로부터 선택되는 적어도 1종의 원소를 나타낸다. a∼h는 각 원소의 원자 비율을 나타내고, b=12일 때, a=0.5∼3, c=0.01∼3, d=0.01∼2, e=0∼3, f=0∼3, g=0.01∼3이며, h는 상기 각 원소의 원자가를 만족하는 데 필요한 산소의 원자 비율이다.In formula (1), P, Mo, V, Cu and O are elemental symbols representing 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, Represents at least one element selected from the group consisting of calcium, strontium, tantalum, cobalt, nickel, manganese, barium, titanium, tin, lead, niobium, indium, sulfur, palladium, gallium, cerium and lanthanum , G represents at least one element selected from the group consisting of lithium, sodium, potassium, rubidium, cesium and thallium. a to h represent the atomic ratio of each element, 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 the atomic ratio of oxygen required to satisfy the valence of each element.
또한, 촉매는 식(1)에 기재가 없는 원소를 소량 포함하고 있어도 된다.In addition, the catalyst may contain a small amount of elements not described in formula (1).
본 발명에 따른 방법에 의해 제조되는 α,β-불포화 카복실산 제조용 촉매는, α,β-불포화 알데하이드를 분자상 산소에 의해 기상 접촉 산화시켜 α,β-불포화 카복실산을 제조할 때에 이용되는 것이 바람직하다. 또한, α,β-불포화 알데하이드가 (메트)아크롤레인이고, 또한 α,β-불포화 카복실산이 (메트)아크릴산인 것이 바람직하다.The catalyst for the production of α,β-unsaturated carboxylic acids produced by the method according to the present invention is preferably used when preparing α,β-unsaturated carboxylic acids by gas phase catalytic oxidation of α,β-unsaturated aldehydes with molecular oxygen. . In addition, it is preferable that α,β-unsaturated aldehyde is (meth)acrolein, and α,β-unsaturated carboxylic acid is (meth)acrylic acid.
[α,β-불포화 카복실산 제조용 촉매의 제조 방법] [Production Method of Catalyst for the Production of α,β-unsaturated carboxylic acids]
본 발명에 따른 α,β-불포화 카복실산 제조용 촉매의 제조 방법에서는, 몰리브데넘 원료로서, 입자경 분포 측정에 의해 얻어지는 빈도 분포 곡선에 있어서, 입자경이 6μm 이하인 입자의 비율이 2∼55체적%인 몰리브데넘 산화물을 사용한다. 한편, 몰리브데넘 산화물의 입자경 분포 측정은, 레이저 회절식 입도 분포 측정 장치 SALD-7000(제품명, 시마즈 제작소사제)을 이용하여, 순수 500g에 대해서 몰리브데넘 산화물 0.02∼0.1g을 분산시키고, 30초간 교반시킨 후에 행해진다. 또한, 본 발명에서는, 입자경이 1000μm 이하인 입자의 적산 체적을 전체 입자 체적으로 해서 빈도 분포 곡선을 구한다.In the method for producing an α,β-unsaturated carboxylic acid production catalyst according to the present invention, as a molybdenum raw material, in a frequency distribution curve obtained by particle size distribution measurement, the proportion of particles having a particle diameter of 6 μm or less is 2 to 55% by volume Ribdenum oxide is used. On the other hand, for the particle size distribution measurement of the molybdenum oxide, 0.02 to 0.1 g of molybdenum oxide was dispersed with respect to 500 g of pure water using a laser diffraction particle size distribution measuring device SALD-7000 (product name, manufactured by Shimadzu Corporation). This is done after stirring for a second. In the present invention, the frequency distribution curve is obtained by making the total volume of particles having a particle diameter of 1000 µm or less as the total particle volume.
본 발명에서는, 전술한 입자경 분포 측정에 의해 얻어지는 빈도 분포 곡선에 있어서, 입자경 1000μm 이하의 입자에 있어서의 입자경이 6μm 이하인 입자의 비율이 2∼55체적%인 몰리브데넘 산화물을 몰리브데넘 원료에 이용하여 α,β-불포화 카복실산 제조용 촉매를 제조한다. 이에 의해, 얻어진 촉매에 적합한 활성점이 형성되고, 촉매 활성이 향상되어, α,β-불포화 카복실산의 수율을 향상시킬 수 있다고 생각된다.In the present invention, in the frequency distribution curve obtained by the particle size distribution measurement described above, the molybdenum oxide having a proportion of 2 to 55% by volume of the particles having a particle diameter of 6 μm or less in the particles having a particle diameter of 1000 μm or less is added to the molybdenum raw material. Using to prepare a catalyst for the production of α,β-unsaturated carboxylic acid. Thereby, it is considered that an active point suitable for the obtained catalyst is formed, the catalytic activity is improved, and the yield of α,β-unsaturated carboxylic acid can be improved.
본 발명에 따른 α,β-불포화 카복실산 제조용 촉매의 제조 방법은, 상기 몰리브데넘 산화물을 몰리브데넘 원료로서 사용하는 것 이외에는 특별히 한정되지 않고, 예를 들면 상기 몰리브데넘 산화물을 포함하는 원료와 물을 혼합하여 수성 슬러리 또는 수용액을 얻는 공정을 가질 수 있다. 그러나, α,β-불포화 카복실산의 수율이 보다 향상되는 관점에서, 상기 방법은 이하의 공정(i) 내지 (iv)를 갖는 것이 바람직하다.The method for producing the catalyst for producing α,β-unsaturated carboxylic acids according to the present invention is not particularly limited except for using the molybdenum oxide as the molybdenum oxide, and for example, the raw material containing the molybdenum oxide and It is possible to have a process of mixing water to obtain an aqueous slurry or aqueous solution. However, from the viewpoint of further improving the yield of the α,β-unsaturated carboxylic acid, the method preferably has the following steps (i) to (iv).
(i) 적어도 몰리브데넘 원료 및 인 원료를 포함하는 촉매 원료와 물을 혼합하여 얻어진 수성 슬러리(I)을, 90∼150℃로 가열하여 헤테로폴리산을 포함하는 수성 슬러리 또는 수용액(II)를 얻는 공정.(i) a process of obtaining an aqueous slurry or aqueous solution (II) containing heteropoly acid by heating the aqueous slurry (I) obtained by mixing water with a catalyst raw material containing at least a molybdenum raw material and a phosphorus raw material at 90 to 150°C. .
(ii) 상기 수성 슬러리 또는 수용액(II)에 금속 양이온 함유 화합물을 첨가하여, 헤테로폴리산염이 석출된 수성 슬러리(III)을 얻는 공정.(ii) A step of adding an aqueous cation-containing compound to the aqueous slurry or aqueous solution (II) to obtain an aqueous slurry (III) in which heteropolyacids have been deposited.
(iii) 상기 수성 슬러리(III)을 건조하여, 촉매 전구체 건조물을 얻는 공정.(iii) A step of drying the aqueous slurry (III) to obtain a catalyst precursor dried product.
(iv) 상기 촉매 전구체 건조물을 열처리하여, 촉매를 얻는 공정.(iv) A step of heat-treating the catalyst precursor dried material to obtain a catalyst.
또한, 본 발명에 따른 α,β-불포화 카복실산 제조용 촉매의 제조 방법은, 후술하는 성형 공정을 추가로 가져도 된다.In addition, the method for producing the catalyst for producing an α,β-unsaturated carboxylic acid according to the present invention may further have a molding process described later.
(공정(i)) (Process (i))
공정(i)에서는, 적어도 몰리브데넘 원료 및 인 원료를 포함하는 촉매 원료와 물을 혼합하여 얻어진 수성 슬러리(I)을, 90∼150℃로 가열하여 헤테로폴리산을 포함하는 수성 슬러리 또는 수용액(II)를 얻는다. 한편, 수성 슬러리(I)을 가열한 후, 수성 슬러리가 되는 경우도 수용액이 되는 경우도 있다. 그 때문에, 이들을 「수성 슬러리 또는 수용액(II)」라고 총칭한다. 또한, 촉매가 상기 식(1)로 표시되는 조성을 갖는 경우, 상기 식(1)로 표시되는 조성에 포함되는 G 이외의 원소를, 상기 촉매 원료로서 물과 혼합하여, 수성 슬러리(I)을 얻는 것이 바람직하다.In the step (i), the aqueous slurry (I) obtained by mixing the catalyst raw material containing at least the molybdenum raw material and the phosphorus raw material with water is heated to 90 to 150° C. to form an aqueous slurry or aqueous solution (II) containing a heteropoly acid. Get On the other hand, after heating the aqueous slurry (I), it may be an aqueous slurry or an aqueous solution. Therefore, these are collectively referred to as "aqueous slurry or aqueous solution (II)". Further, when the catalyst has a composition represented by the formula (1), elements other than G included in the composition represented by the formula (1) are mixed with water as the catalyst raw material to obtain an aqueous slurry (I). It is preferred.
수성 슬러리(I)을 가열하면 몰리브데넘 원료가 물에 용해되지만, 이때의 용해 속도는, 몰리브데넘 원료의 입자경 분포에 의해 변화한다. 이 용해 속도가 얻어지는 촉매의 활성점에 영향을 주고 있다고 추측된다.When the aqueous slurry (I) is heated, the molybdenum raw material is dissolved in water, but the dissolution rate at this time varies depending on the particle size distribution of the molybdenum raw material. It is assumed that this dissolution rate affects the activity point of the catalyst obtained.
몰리브데넘 원료로서는, 입자경 분포 측정에 의해 얻어지는 빈도 분포 곡선에 있어서, 입자경이 6μm 이하인 입자의 비율이 2∼55체적%인 몰리브데넘 산화물을 사용한다. 이에 의해, α,β-불포화 알데하이드의 분자상 산소에 의한 기상 접촉 산화에 적합한 활성점이 형성된다. 해당 비율의 하한은 5체적% 이상이 바람직하고, 10체적% 이상이 보다 바람직하다. 또한, 상한은 35체적% 이하가 바람직하고, 30체적% 이하가 보다 바람직하고, 25체적% 이하가 더 바람직하고, 20체적% 이하가 특히 바람직하며, 15체적% 이하가 가장 바람직하다.As the raw material for molybdenum, molybdenum oxide having a proportion of 2 to 55% by volume of particles having a particle diameter of 6 μm or less is used in a frequency distribution curve obtained by particle size distribution measurement. Thereby, an active point suitable for gas phase catalytic oxidation of α,β-unsaturated aldehydes with molecular oxygen is formed. The lower limit of the ratio is preferably 5% by volume or more, and more preferably 10% by volume or more. Moreover, the upper limit is preferably 35 vol% or less, more preferably 30 vol% or less, more preferably 25 vol% or less, particularly preferably 20 vol% or less, and most preferably 15 vol% or less.
또한, 상기 몰리브데넘 산화물은, 입자경이 30∼200μm인 입자의 비율이 35∼90체적%인 것이 바람직하다. 해당 비율의 하한은 40체적% 이상이 보다 바람직하고, 50체적% 이상이 더 바람직하고, 60체적% 이상이 특히 바람직하며, 70체적% 이상이 가장 바람직하다. 또한, 상한은 85체적% 이하가 보다 바람직하고, 80체적% 이하가 더 바람직하다. 이에 의해, α,β-불포화 알데하이드의 분자상 산소에 의한 기상 접촉 산화에 보다 적합한 활성점이 형성된다.In addition, it is preferable that the proportion of particles having a particle diameter of 30 to 200 µm is 35 to 90% by volume of the molybdenum oxide. The lower limit of the ratio is more preferably 40% by volume or more, more preferably 50% by volume or more, particularly preferably 60% by volume or more, and most preferably 70% by volume or more. The upper limit is more preferably 85% by volume or less, and more preferably 80% by volume or less. Thereby, an active point more suitable for gas phase catalytic oxidation of α,β-unsaturated aldehydes with molecular oxygen is formed.
몰리브데넘 산화물 중의 몰리브데넘과 산소의 원자 비율은 특별히 한정되지 않고, 예를 들면, 몰리브데넘:산소의 원자 비율이 1:2인 이산화 몰리브데넘, 1:3인 삼산화 몰리브데넘 등을 들 수 있다. 단, α,β-불포화 카복실산의 수율이 보다 향상되는 관점에서, 몰리브데넘 원료로서, 입자경이 6μm 이하인 입자의 비율이 2∼55체적%인 삼산화 몰리브데넘을 50질량% 이상 사용하는 것이 바람직하다. 삼산화 몰리브데넘의 비율의 하한은 70질량% 이상이 보다 바람직하고, 90질량% 이상이 더 바람직하다. 몰리브데넘 산화물에는, 예를 들면, 나트륨, 칼륨, 철, 납, 황산근(根), 질산근 및 암모늄근 등의 불순물이 미량 포함되어 있어도 되지만, 이들 불순물의 함유량은 적을수록 바람직하고, 이들 불순물을 포함하지 않는 것이 특히 바람직하다.The atomic ratio of molybdenum and oxygen in the molybdenum oxide is not particularly limited, for example, molybdenum dioxide having an atomic ratio of molybdenum:oxygen of 1:2, molybdenum trioxide having 1:3, etc. Can be heard. However, from the viewpoint of further improving the yield of the α,β-unsaturated carboxylic acid, it is preferable to use 50 mol% or more of molybdenum trioxide having a ratio of 2 to 55% by volume of particles having a particle diameter of 6 μm or less as a molybdenum raw material. Do. The lower limit of the proportion of molybdenum trioxide is more preferably 70% by mass or more, and more preferably 90% by mass or more. The molybdenum oxide may contain, for example, trace amounts of impurities such as sodium, potassium, iron, lead, sulfate sulfate, nitrate and ammonium muscle, but the smaller the content of these impurities, the more preferable. It is particularly preferred that it does not contain impurities.
본 발명에 따른 몰리브데넘 산화물의 제조 방법으로서는, 예를 들면 이하의 방법을 들 수 있다. 몰리브데넘을 포함하는 광석을 배소하여 얻어진 조(粗) 삼산화 몰리브데넘을 순수에 분산시킨 후, 암모니아수에 용해시킨다. 이 용액을 여과 후, 염산을 첨가해서 pH 조정을 행하여 얻어진 침전물을, 순수, 질산 암모늄이나 염화 암모늄 등을 소량 포함하는 수용액으로 분산·세정한다. 그 후, 원심 여과 등에 의해 함수량을 저감하여 전구체 침전물을 얻고, 이것을 건조 후 소성하여, 몰리브데넘 산화물을 얻을 수 있다. 또한, 상기 전구체 침전물에 암모니아수를 첨가해서 용해·정석하여 얻어진 파라몰리브데넘산 암모늄을 소성하는 방법도 들 수 있다. 후자의 방법쪽이, 전자의 방법보다도 얻어지는 몰리브데넘 산화물의 입자경을 작게 할 수 있다. 또, 상기 소성 온도에 의해서도 몰리브데넘 산화물의 입자경을 조정할 수 있다. 소성 온도를 낮게 함으로써 얻어지는 몰리브데넘 산화물의 입자경이 작아지고, 소성 온도를 높게 함으로써 얻어지는 몰리브데넘 산화물의 입자경이 커지는 경향이 있다. 또한, 상기 방법으로 제조한 몰리브데넘 산화물에 대해서, 필요에 따라서, 입자경이 6μm 이하인 입자의 비율이 2∼55체적%, 바람직하게는 2∼35체적%, 보다 바람직하게는 2∼15체적%가 되도록 분쇄 조작이나 분급 조작을 해도 된다. 분쇄 조작으로서는, 볼 밀, 로드 밀, SAG 밀, 자생 분쇄 밀, 페블 밀, 고압 분쇄 롤, 종축 임팩터 밀, 제트 밀 등의 장치를 이용하는 방법을 들 수 있다. 분급 조작으로서는, 체에 의한 방법, 중력이나 원심력을 이용하는 방법(반자유 소용돌이식 분급기, 강제 소용돌이식 분급기) 등을 들 수 있다. 또한, 본 발명에 따른 몰리브데넘 산화물로서, 전술한 방법에 의해 제조된, 상이한 입도 분포를 갖는 복수의 몰리브데넘 산화물을 혼합한 것을 이용해도 된다.As a method for producing the molybdenum oxide according to the present invention, for example, the following methods are mentioned. After dispersing the crude molybdenum trioxide obtained by roasting ore containing molybdenum in pure water, it is dissolved in ammonia water. After filtration of this solution, the precipitate obtained by pH adjustment by adding hydrochloric acid is dispersed and washed with an aqueous solution containing a small amount of pure water, ammonium nitrate or ammonium chloride. Thereafter, the water content is reduced by centrifugal filtration or the like to obtain a precursor precipitate, which is dried and calcined to obtain molybdenum oxide. Also, a method of firing ammonium paramolybdate obtained by adding and dissolving and crystallizing water by adding ammonia water to the precursor precipitate may be mentioned. The latter method can make the particle diameter of the molybdenum oxide obtained smaller than the former method. In addition, the particle diameter of the molybdenum oxide can also be adjusted by the firing temperature. The particle diameter of the molybdenum oxide obtained by lowering the firing temperature becomes small, and the particle diameter of the molybdenum oxide obtained by increasing the firing temperature tends to become large. In addition, with respect to the molybdenum oxide produced by the above method, if necessary, the proportion of particles having a particle diameter of 6 μm or less is 2 to 55% by volume, preferably 2 to 35% by volume, more preferably 2 to 15% by volume. You may perform a grinding operation or classification operation so that Examples of the grinding operation include a method using apparatuses such as a ball mill, a rod mill, a SAG mill, a native grinding mill, a pebble mill, a high pressure grinding roll, a vertical axis impact mill, and a jet mill. Examples of the classification operation include a method using a sieve, a method using gravity or centrifugal force (semi-free vortex classifier, forced vortex classifier) and the like. Further, as the molybdenum oxide according to the present invention, a mixture of a plurality of molybdenum oxides having different particle size distributions prepared by the above-described method may be used.
인 원료로서는, 예를 들면 정인산, 오산화 인, 인산 암모늄, 인산 세슘 등을 들 수 있다. 이들은 1종을 이용해도 되고, 2종 이상을 병용해도 된다.Examples of the phosphorus raw material include phosphoric acid, phosphorus pentoxide, ammonium phosphate, cesium phosphate, and the like. These may use 1 type and may use 2 or more types together.
몰리브데넘 원료 및 인 원료 이외의 촉매 원료의 종류는 특별히 한정되지 않고, 각 원소의 황산염, 질산염, 탄산염, 중탄산염, 아세트산염, 암모늄염, 산화물, 수산화물, 염화물, 할로젠화물, 옥소산, 옥소산염 등을 들 수 있다. 구리 원료로서는, 예를 들면 황산 구리, 질산 구리, 아세트산 구리, 산화 구리, 염화 구리 등을 들 수 있다. 바나듐 원료로서는, 예를 들면 바나드산 암모늄, 메타바나드산 암모늄, 오산화 바나듐, 염화 바나듐 등을 들 수 있다. 이들은 1종을 이용해도 되고, 2종 이상을 병용해도 된다.Kinds of catalyst raw materials other than molybdenum raw materials and phosphorus raw materials are not particularly limited, and sulfates, nitrates, carbonates, bicarbonates, acetates, ammonium salts, oxides, hydroxides, chlorides, halides, oxo acids, and oxoates of each element are not particularly limited. And the like. As a copper raw material, copper sulfate, copper nitrate, copper acetate, copper oxide, copper chloride, etc. are mentioned, for example. Examples of the vanadium raw material include ammonium vanadate, ammonium metavanadate, vanadium pentoxide, and vanadium chloride. These may use 1 type and may use 2 or more types together.
헤테로폴리산을 포함하는 수성 슬러리 또는 수용액(II)의 조제는, 물에 상기 촉매 원료의 일부 또는 전부를 가하여 얻어지는 수성 슬러리(I)을, 가열하면서 교반하는 방법에 의해 행하는 것이 간편하여 바람직하다. 수성 슬러리(I)은, 물에 상기 촉매 원료의 수용액, 수성 슬러리 또는 수성 졸을 첨가하여 얻을 수도 있다. 수성 슬러리(I)을, 90∼150℃로 가열함으로써 수성 슬러리 또는 수용액(II)를 얻는 것이 바람직하다. 가열 온도의 하한은 95℃ 이상, 상한은 130℃ 이하가 보다 바람직하다. 해당 가열 온도를 90℃ 이상으로 함으로써, 상기 촉매 원료로부터 효율적으로 헤테로폴리산이 생성된다. 또한, 해당 가열 온도를 150℃ 이하로 함으로써, 수성 슬러리 또는 수용액 중의 물의 증발을 억제할 수 있다.The preparation of the aqueous slurry or aqueous solution (II) containing a heteropoly acid is preferable because it is easy to carry out the aqueous slurry (I) obtained by adding a part or all of the catalyst raw material to water by stirring while heating. The aqueous slurry (I) can also be obtained by adding an aqueous solution of the catalyst raw material, an aqueous slurry, or an aqueous sol to water. It is preferable to obtain the aqueous slurry or aqueous solution (II) by heating the aqueous slurry (I) to 90 to 150°C. The lower limit of the heating temperature is more preferably 95°C or higher, and the upper limit is 130°C or lower. By setting the heating temperature to 90°C or higher, heteropoly acids are efficiently generated from the catalyst raw materials. Moreover, evaporation of water in an aqueous slurry or aqueous solution can be suppressed by setting the heating temperature to 150°C or lower.
전술한 대로, 몰리브데넘 원료로서, 입자경 분포 측정에 의해 얻어지는 빈도 분포 곡선에 있어서, 입자경이 6μm 이하인 입자의 비율이 2∼55체적%인 몰리브데넘 산화물을 사용한 경우, 상기 수성 슬러리(I)을 가열하여, 상기 몰리브데넘 원료가 물에 용해될 때의 용해 속도가, 얻어지는 촉매의 활성점에 영향을 주고 있다고 추측된다. 이때, 상기 수성 슬러리(I)의 온도가 60℃에 도달하고 나서 90℃에 도달할 때까지의 동안에 상기 몰리브데넘 원료가 물에 용해된다. 그 때문에, 이 시간을 조정함으로써, α,β-불포화 알데하이드의 분자상 산소에 의한 기상 접촉 산화에 보다 적합한 활성점을 형성시킬 수 있다. 상기 수성 슬러리(I)의 온도가 60℃에 도달하고 나서 90℃에 도달할 때까지의 시간은, 바람직하게는 5∼40분, 보다 바람직하게는 7∼30분이다.As described above, when the molybdenum raw material is a molybdenum oxide having a ratio of 2 to 55% by volume of particles having a particle diameter of 6 μm or less in a frequency distribution curve obtained by particle size distribution measurement, the aqueous slurry (I) It is presumed that, by heating, the dissolution rate when the molybdenum raw material is dissolved in water affects the active point of the obtained catalyst. At this time, the molybdenum raw material is dissolved in water while the temperature of the aqueous slurry (I) reaches 60°C and then reaches 90°C. Therefore, by adjusting this time, it is possible to form an active point more suitable for gas phase contact oxidation of α,β-unsaturated aldehydes with molecular oxygen. The time from the temperature of the aqueous slurry (I) to 60° C. until reaching 90° C. is preferably 5 to 40 minutes, more preferably 7 to 30 minutes.
상기 수성 슬러리(I)에 있어서, 온도가 60℃에 도달하고 나서 90℃에 도달할 때까지의 시간은, 승온 속도의 조정 등에 의해 제어할 수 있다. 또한, 상기 수성 슬러리(I)의 온도는 단조 증가시켜도 되고, 승온 속도를 적절히 변화시키면서 제어해도 된다.In the aqueous slurry (I), the time from reaching the temperature of 60°C to reaching 90°C can be controlled by adjusting the rate of temperature increase or the like. In addition, the temperature of the aqueous slurry (I) may be monotonically increased, or may be controlled while appropriately changing the temperature increase rate.
조제되는 수성 슬러리 또는 수용액(II)의 pH는, α,β-불포화 카복실산의 수율 향상의 관점에서 4 이하가 바람직하고, 2 이하가 보다 바람직하다. 수성 슬러리 또는 수용액(II)의 pH가 높은 경우에는, 질산근 등을 많이 포함하도록 각 원료를 선택하는 것이 바람직하다.The pH of the prepared aqueous slurry or aqueous solution (II) is preferably 4 or less, more preferably 2 or less, from the viewpoint of improving the yield of the α,β-unsaturated carboxylic acid. When the pH of the aqueous slurry or aqueous solution (II) is high, it is preferable to select each raw material so as to contain a lot of nitric acid roots and the like.
공정(i)에 있어서 수성 슬러리 또는 수용액(II) 중에 헤테로폴리산이 형성되어 있는지 여부는, NICOLET6700FT-IR(제품명, Thermo electron사제) 등을 이용한 적외 흡수 분석 및 X선 회절 장치 X'Pert PRO MPD(제품명, PANaltical사제) 등을 이용한 X선 회절 분석에 의해 확인할 수 있다.In the step (i), whether or not heteropoly acids are formed in the aqueous slurry or aqueous solution (II), infrared absorption analysis using an NICOLET6700FT-IR (product name, manufactured by Thermo electron), and an X-ray diffraction device X'Pert PRO MPD (product name) , PANaltical).
(공정(ii)) (Process (ii))
공정(ii)에서는, 공정(i)에서 얻어진 수성 슬러리 또는 수용액(II)에 금속 양이온 함유 화합물을 첨가하여, 헤테로폴리산염이 석출된 수성 슬러리(III)을 얻는다. 금속 양이온 함유 화합물로서는, 리튬, 나트륨, 칼륨, 루비듐, 세슘 및 탈륨으로 이루어지는 군으로부터 선택되는 적어도 1종의 원소(상기 식(1)의 G에 상당)를 포함하는 화합물을 이용하는 것이 바람직하다. 또한, 공정(ii)에서는, 금속 양이온 함유 화합물에 더하여, 암모늄 화합물을 첨가하는 것이 바람직하다. 암모늄 화합물을 첨가하는 것에 의해, α,β-불포화 알데하이드의 분자상 산소에 의한 기상 접촉 산화에 적합한 결정 구조가 형성된다. 암모늄 화합물로서는, 탄산수소 암모늄, 탄산 암모늄, 질산 암모늄, 암모니아수 등을 들 수 있다. 이들 암모늄 화합물은 1종을 이용해도 되고, 2종 이상을 병용해도 된다.In step (ii), a metal cation-containing compound is added to the aqueous slurry or aqueous solution (II) obtained in step (i) to obtain an aqueous slurry (III) in which heteropolyacid salts have been deposited. As the metal cation-containing compound, it is preferable to use a compound containing at least one element selected from the group consisting of lithium, sodium, potassium, rubidium, cesium and thallium (corresponding to G in the formula (1)). In addition, in step (ii), it is preferable to add an ammonium compound in addition to the metal cation-containing compound. By adding an ammonium compound, a crystal structure suitable for gas phase catalytic oxidation of α,β-unsaturated aldehydes with molecular oxygen is formed. Examples of the ammonium compound include ammonium hydrogen carbonate, ammonium carbonate, ammonium nitrate, and ammonia water. One of these ammonium compounds may be used, or two or more of them may be used in combination.
금속 양이온 함유 화합물 및 암모늄 화합물은, 용매에 용해 또는 현탁시켜 첨가하는 것이 바람직하다. 용매로서는, 물, 에틸 알코올, 아세톤 등을 들 수 있다. 단, 상기 공정(i)에서 얻어지는 수성 슬러리 또는 수용액(II)와 동일한 물을 용매로서 이용하는 것이 바람직하다. 금속 양이온 함유 화합물 및 필요에 따라서 첨가되는 암모늄 화합물을 첨가한 후의 수성 슬러리 또는 수용액의 교반 시간은, 1∼300분이 바람직하고, 하한은 10분 이상, 상한은 30분 이하가 보다 바람직하다. 또한, 교반 시의 수성 슬러리 또는 수용액의 온도는, 50∼100℃가 바람직하고, 하한은 80℃ 이상이 보다 바람직하다. 교반 시간을 1분 이상, 온도를 50℃ 이상으로 함으로써, 헤테로폴리산의 금속염 및 암모늄염을 충분히 형성시킬 수 있다. 한편, 교반 시간을 300분 이하, 온도를 100℃ 이하로 함으로써, 목적으로 하는 헤테로폴리산의 금속염 및 암모늄염 이외의 화합물의 형성을 억제할 수 있다.It is preferable to add a metal cation-containing compound and an ammonium compound by dissolving or suspending it in a solvent. Examples of the solvent include water, ethyl alcohol, and acetone. However, it is preferable to use the same water as the aqueous slurry or aqueous solution (II) obtained in the step (i) as a solvent. The stirring time of the aqueous slurry or aqueous solution after the addition of the metal cation-containing compound and the ammonium compound added as necessary is preferably 1 to 300 minutes, more preferably 10 minutes or more, and 30 minutes or less for the upper limit. Further, the temperature of the aqueous slurry or aqueous solution during stirring is preferably 50 to 100°C, and the lower limit is more preferably 80°C or more. The metal salt and the ammonium salt of the heteropoly acid can be sufficiently formed by setting the stirring time to 1 minute or more and the temperature to 50°C or more. On the other hand, when the stirring time is 300 minutes or less and the temperature is 100° C. or less, formation of compounds other than the target metal salt and ammonium salt of the heteropoly acid can be suppressed.
석출시키는 헤테로폴리산염(헤테로폴리산의 금속염 및 암모늄염)은, 케긴형 구조를 갖고 있어도, 도슨형 구조 등의 케긴형 이외의 구조를 갖고 있어도 상관없지만, α,β-불포화 카복실산의 수율 향상의 관점에서, 케긴형 구조를 갖는 것이 바람직하다. 케긴형 구조를 갖는 헤테로폴리산염을 석출시키는 방법으로서는, 공정(ii)에 있어서 얻어지는 수성 슬러리(III)의 pH를 3 이하로 조정하는 방법을 들 수 있다. 한편, 석출된 헤테로폴리산염의 구조는, NICOLET6700FT-IR(제품명, Thermo electron사제)을 이용한 적외 흡수 분석 및 X선 회절 장치 X'Pert PRO MPD(제품명, PANaltical사제)를 이용한 X선 회절 분석에 의해 확인할 수 있다.The precipitated heteropoly acid salt (metal salt and ammonium salt of heteropoly acid) may have a Keggin-type structure or a structure other than a Keggin-type structure such as a Dawson-type structure, but from the viewpoint of improving the yield of the α,β-unsaturated carboxylic acid, ke It is preferred to have an elongated structure. As a method of depositing a heteropoly acid salt having a kegin-type structure, a method of adjusting the pH of the aqueous slurry (III) obtained in step (ii) to 3 or less can be given. On the other hand, the structure of the precipitated heteropoly acid salt can be confirmed by infrared absorption analysis using a NICOLET6700FT-IR (product name, manufactured by Thermo electron) and X-ray diffraction analysis using an X-ray diffraction apparatus X'Pert PRO MPD (product name, manufactured by PANaltical). have.
(공정(iii)) (Process (iii))
공정(iii)에서는, 공정(ii)에서 얻어진 수성 슬러리(III)을 건조하여, 촉매 전구체 건조물을 얻는다. 건조 방법으로서는, 예를 들면, 드럼 건조법, 기류 건조법, 증발 건고법, 분무 건조법 등을 들 수 있다. 건조 온도는 120∼500℃가 바람직하고, 하한은 140℃ 이상, 상한은 350℃ 이하가 보다 바람직하다. 건조는 수성 슬러리(III)이 건고될 때까지 행할 수 있다. 촉매 전구체 건조물의 수분 함유율은 0.1∼4.5질량%가 바람직하다. 한편, 이들 조건은 원하는 촉매 전구체 건조물의 형상이나 크기에 따라 적절히 선택할 수 있다.In step (iii), the aqueous slurry (III) obtained in step (ii) is dried to obtain a catalyst precursor dried product. Examples of the drying method include a drum drying method, an air flow drying method, an evaporative drying method, and a spray drying method. The drying temperature is preferably 120 to 500°C, the lower limit is more than 140°C, and the upper limit is more preferably 350°C or less. Drying can be performed until the aqueous slurry (III) is dried. The moisture content of the catalyst precursor dry matter is preferably 0.1 to 4.5% by mass. On the other hand, these conditions can be appropriately selected according to the shape or size of the desired catalyst precursor dried product.
(성형 공정) (Forming process)
성형 공정에서는, 공정(iii)에서 얻어진 촉매 전구체 건조물을 성형할 수 있다. 성형에 이용되는 장치로서는, 타정 성형기, 압출 성형기, 가압 성형기, 전동 조립(造粒)기 등의 분체용 성형기를 들 수 있다. 성형품의 형상으로서는 특별히 제한은 없고, 구형 입상, 링상, 원주형 펠릿상, 별형상, 성형 후에 분쇄 분급한 과립상 등의 임의의 형상을 들 수 있다. 성형할 때에는, 담체에 담지해도 되고, 또한 필요에 따라서 예를 들면 그래파이트, 탤크 등의 공지의 첨가제나 유기물, 무기물 유래의 공지의 바인더를 첨가해도 된다. 본 발명에서는, 공정(iii)에서 얻어진 촉매 전구체 건조물, 및 해당 촉매 전구체 건조물을 성형한 것을 통틀어 촉매 전구체 건조물로 나타낸다.In the molding step, the catalyst precursor dried product obtained in step (iii) can be molded. As a device used for molding, a powder molding machine such as a tableting molding machine, an extrusion molding machine, a pressure molding machine, and an electric granulating machine can be mentioned. The shape of the molded article is not particularly limited, and any shape such as a spherical granular shape, a ring shape, a columnar pellet shape, a star shape, and a granular shape classified by pulverization after molding may be mentioned. When molding, it may be supported on a carrier, and if necessary, known additives such as graphite and talc, or known binders derived from organic or inorganic substances may be added. In the present invention, the catalyst precursor dried product obtained in step (iii) and the catalyst precursor dried product are collectively referred to as a catalyst precursor dried product.
(공정(iv)) (Process (iv))
공정(iv)에서는, 공정(iii) 또는 성형 공정에서 얻어진 촉매 전구체 건조물을 열처리하여, 촉매를 얻는다. 열처리 조건으로서는 특별히 한정은 없지만, 예를 들면 공기 등의 산소 함유 가스 및 불활성 가스 중 적어도 한쪽의 유통하에서 행할 수 있다. 열처리 온도는 200∼500℃인 것이 바람직하고, 하한은 300℃ 이상, 상한은 450℃ 이하인 것이 보다 바람직하다. 열처리 시간은 0.5∼40시간이 바람직하고, 하한은 1시간 이상인 것이 보다 바람직하다. 한편, 공정(iii) 후에 상기 성형 공정을 행하지 않는 경우, 공정(iv)에서 얻어진 열처리 후의 촉매에 대해, 상기 성형 공정을 실시해도 된다.In step (iv), a catalyst precursor dried product obtained in step (iii) or a molding step is heat-treated to obtain a catalyst. Although there is no restriction|limiting in particular as a heat processing condition, For example, it can carry out under flow of at least one of oxygen-containing gas, such as air, and inert gas. The heat treatment temperature is preferably 200 to 500°C, and the lower limit is more preferably 300°C or higher and the upper limit is 450°C or lower. The heat treatment time is preferably 0.5 to 40 hours, and the lower limit is more preferably 1 hour or more. On the other hand, in the case where the forming step is not performed after step (iii), the forming step may be performed on the catalyst after the heat treatment obtained in step (iv).
[α,β-불포화 카복실산의 제조 방법] [Method for producing α,β-unsaturated carboxylic acid]
본 발명에서는, 본 발명에 따른 방법에 의해 α,β-불포화 카복실산 제조용 촉매를 제조하고, 해당 촉매를 이용하여 α,β-불포화 알데하이드를 분자상 산소에 의해 기상 접촉 산화시켜 α,β-불포화 카복실산을 제조한다. 또한, 본 발명에 따른 α,β-불포화 카복실산의 제조 방법은, 본 발명에 따른 방법에 의해 제조된 α,β-불포화 카복실산 제조용 촉매를 이용하여, α,β-불포화 알데하이드를 분자상 산소에 의해 기상 접촉 산화시켜 α,β-불포화 카복실산을 제조하는 방법이다.In the present invention, a catalyst for the production of α,β-unsaturated carboxylic acid is prepared by the method according to the present invention, and α,β-unsaturated carboxylic acid is subjected to gas-phase catalytic oxidation of α,β-unsaturated aldehyde with molecular oxygen using the catalyst. To prepare. In addition, the production method of the α,β-unsaturated carboxylic acid according to the present invention uses the catalyst for the production of the α,β-unsaturated carboxylic acid prepared by the method according to the present invention, and the α,β-unsaturated aldehyde is prepared by molecular oxygen. It is a method of producing α,β-unsaturated carboxylic acid by gas phase contact oxidation.
본 발명에 따른 방법에 있어서, 상기 α,β-불포화 알데하이드로서는, (메트)아크롤레인, 크로톤알데하이드(β-메틸아크롤레인), 신남알데하이드(β-페닐아크롤레인) 등을 들 수 있다. 그 중에서도, 목적 생성물의 수율의 관점에서, (메트)아크롤레인인 것이 바람직하고, 메타크롤레인인 것이 보다 바람직하다. 제조되는 α,β-불포화 카복실산은 α,β-불포화 알데하이드의 알데하이드기가 카복실기로 변화된 α,β-불포화 카복실산이다. 구체적으로는, α,β-불포화 알데하이드가 (메트)아크롤레인인 경우, (메트)아크릴산이 얻어진다. 한편, 「(메트)아크롤레인」은 아크롤레인 및 메타크롤레인을 나타내고, 「(메트)아크릴산」은 아크릴산 및 메타크릴산을 나타낸다.In the method according to the present invention, the α,β-unsaturated aldehydes include (meth)acrolein, crotonaldehyde (β-methylacrolein), cinnamic aldehyde (β-phenylacrolein), and the like. Especially, it is preferable that it is (meth)acrolein from a viewpoint of the yield of a target product, and it is more preferable that it is methacrolein. The α,β-unsaturated carboxylic acid produced is an α,β-unsaturated carboxylic acid in which the aldehyde group of α,β-unsaturated aldehyde is changed to a carboxyl group. Specifically, (meth)acrylic acid is obtained when α,β-unsaturated aldehyde is (meth)acrolein. On the other hand, "(meth)acrolein" represents acrolein and methacrolein, and "(meth)acrylic acid" represents acrylic acid and methacrylic acid.
이하, 대표예로서, 본 발명에 따른 방법에 의해 제조된 메타크릴산 제조용 촉매의 존재하, 메타크롤레인을 분자상 산소에 의해 기상 접촉 산화시켜 메타크릴산을 제조하는 방법에 대하여 설명한다.Hereinafter, as a representative example, a method for preparing methacrylic acid by gas phase contact oxidation of methacrolein with molecular oxygen in the presence of a catalyst for methacrylic acid production by the method according to the present invention will be described.
이 방법에서는, 메타크롤레인 및 분자상 산소를 포함하는 원료 가스와, 본 발명에 따른 촉매를 접촉시킴으로써 메타크릴산을 제조한다. 이 반응에서는, 고정상형 반응기를 사용할 수 있다. 구체적으로는, 반응관 내에 촉매를 충전하고, 해당 반응기로 원료 가스를 공급하는 것에 의해 반응을 행할 수 있다. 촉매층은 1층이어도 되고, 활성이 상이한 복수의 촉매를 각각 복수의 층에 나누어 충전해도 된다. 또한, 활성을 제어하기 위해서, 메타크릴산 제조용 촉매를 불활성 담체에 의해 희석하여 충전해도 된다.In this method, methacrylic acid is produced by contacting a source gas containing methacrolein and molecular oxygen with a catalyst according to the present invention. In this reaction, a fixed bed reactor can be used. Specifically, the reaction can be performed by filling the catalyst in a reaction tube and supplying a raw material gas to the reactor. The catalyst layer may be a single layer, or a plurality of catalysts having different activities may be divided into a plurality of layers and filled. Further, in order to control the activity, the catalyst for producing methacrylic acid may be diluted and filled with an inert carrier.
원료 가스 중의 메타크롤레인의 농도는 특별히 한정되지 않지만, 1∼20용량%가 바람직하고, 하한은 3용량% 이상, 상한은 10용량% 이하가 보다 바람직하다. 원료인 메타크롤레인은, 저급 포화 알데하이드 등의 본 반응에 실질적인 영향을 주지 않는 불순물을 소량 포함하고 있어도 된다.Although the concentration of methacrolein in the raw material gas is not particularly limited, 1 to 20% by volume is preferable, the lower limit is more preferably 3% by volume or more, and the upper limit is more preferably 10% by volume or less. The methacrolein as a raw material may contain a small amount of impurities that do not substantially affect the present reaction, such as lower saturated aldehyde.
원료 가스 중의 분자상 산소의 농도는 메타크롤레인 1몰에 대해서 0.4∼4몰이 바람직하고, 하한은 0.5몰 이상, 상한은 3몰 이하가 보다 바람직하다. 한편, 분자상 산소원으로서는, 경제성의 관점에서 공기가 바람직하다. 필요하면, 공기에 순산소를 가하여 분자상 산소를 부화(富化)한 기체를 이용해도 된다.The concentration of molecular oxygen in the raw material gas is preferably 0.4 to 4 moles per 1 mole of methacrolein, and the lower limit is more preferably 0.5 moles or more and the upper limit is 3 moles or less. On the other hand, as a molecular oxygen source, air is preferable from the viewpoint of economic efficiency. If necessary, a gas in which molecular oxygen is enriched by adding oxygen to the air may be used.
원료 가스는, 메타크롤레인 및 분자상 산소를, 질소, 탄산 가스 등의 불활성 가스로 희석한 것이어도 된다. 추가로, 원료 가스에 수증기를 가해도 된다. 수증기의 존재하에서 반응을 행하는 것에 의해, 메타크릴산을 보다 높은 수율로 얻을 수 있다. 원료 가스 중의 수증기의 농도는 0.1∼50용량%가 바람직하고, 하한은 1용량% 이상, 상한은 40용량% 이하가 보다 바람직하다.The raw material gas may be diluted with methacrolein and molecular oxygen with an inert gas such as nitrogen or carbon dioxide gas. In addition, water vapor may be added to the raw material gas. By reacting 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 or more, and the upper limit is more preferably 40% by volume or less.
원료 가스와 메타크릴산 제조용 촉매의 접촉 시간은 1.5∼15초가 바람직하다. 반응 압력은 0.1∼1MPa(G)가 바람직하다. 단, (G)는 게이지압인 것을 의미한다. 반응 온도는 200∼450℃가 바람직하고, 하한은 250℃ 이상, 상한은 400℃ 이하가 보다 바람직하다.The contact time between the raw material gas and the catalyst for producing methacrylic acid is preferably 1.5 to 15 seconds. The reaction pressure is preferably 0.1 to 1 MPa (G). However, (G) means gauge pressure. The reaction temperature is preferably 200 to 450°C, the lower limit is more preferably 250°C or more, and the upper limit is more preferably 400°C or less.
[α,β-불포화 카복실산 에스터의 제조 방법] [Method for producing α,β-unsaturated carboxylic acid ester]
본 발명에 따른 α,β-불포화 카복실산 에스터의 제조 방법은, 본 발명에 따른 방법에 의해 제조된 α,β-불포화 카복실산을 에스터화하는 방법이다. 또한, 본 발명에 따른 α,β-불포화 카복실산 에스터의 제조 방법은, 본 발명에 따른 방법에 의해 α,β-불포화 카복실산을 제조하고, 해당 α,β-불포화 카복실산을 에스터화하는 방법이다. 이들 방법에 의하면, α,β-불포화 알데하이드의 기상 접촉 산화에 의해 얻어지는 α,β-불포화 카복실산을 이용하여, α,β-불포화 카복실산 에스터를 얻을 수 있다. α,β-불포화 카복실산과 반응시키는 알코올로서는 특별히 한정되지 않고, 예를 들면 메탄올, 에탄올, 아이소프로판올, n-뷰탄올, 아이소뷰탄올 등을 들 수 있다. 얻어지는 α,β-불포화 카복실산 에스터로서는, 예를 들면 (메트)아크릴산 메틸, (메트)아크릴산 에틸, (메트)아크릴산 프로필, (메트)아크릴산 뷰틸 등을 들 수 있다. 반응은 설폰산형 양이온 교환 수지 등의 산성 촉매의 존재하에서 행할 수 있다. 반응 온도는 50∼200℃가 바람직하다.The production method of the α,β-unsaturated carboxylic acid ester according to the present invention is a method of esterifying the α,β-unsaturated carboxylic acid produced by the method according to the present invention. In addition, the production method of the α,β-unsaturated carboxylic acid ester according to the present invention is a method of preparing the α,β-unsaturated carboxylic acid by the method according to the present invention and esterifying the α,β-unsaturated carboxylic acid. According to these methods, an α,β-unsaturated carboxylic acid ester can be obtained using α,β-unsaturated carboxylic acid obtained by vapor phase catalytic oxidation of α,β-unsaturated aldehyde. The alcohol reacted with the α,β-unsaturated carboxylic acid is not particularly limited, and examples thereof include methanol, ethanol, isopropanol, n-butanol, and isobutanol. Examples of the obtained α,β-unsaturated carboxylic acid ester include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and the like. 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.
실시예 Example
이하, 실시예 및 비교예에 의해 본 발명을 상세하게 설명하지만, 본 발명은 이들 실시예로 한정되는 것은 아니다. 실시예 및 비교예 중의 「부」는 질량부를 의미한다. 원료 가스 및 생성물의 분석은 가스 크로마토그래피를 이용하여 행했다. 가스 크로마토그래피의 결과로부터, 메타크릴산 수율을 하기 식으로 구했다.Hereinafter, the present invention will be described in detail by examples and comparative examples, but the present invention is not limited to these examples. "Part" in Examples and Comparative Examples means parts by mass. The raw material gas and the product were analyzed by gas chromatography. From the results of gas chromatography, the methacrylic acid yield was determined by the following formula.
메타크릴산 수율(%)=(B/A)×100 Methacrylic acid yield (%) = (B/A) x 100
식 중, A는 반응기로 공급한 메타크롤레인의 몰수, B는 생성된 메타크릴산의 몰수이다.In the formula, A is the mole number of methacrolein supplied to the reactor, and B is the mole number of methacrylic acid produced.
삼산화 몰리브데넘의 입자경 분포 측정은, 레이저 회절식 입도 분포 측정 장치 SALD-7000(제품명, 시마즈 제작소사제)을 이용하여, 순수 500g에 대해서 삼산화 몰리브데넘 0.02∼0.1g을 분산시키고, 30초간 교반시킨 후에 행했다.To measure the particle size distribution of molybdenum trioxide, 0.02 to 0.1 g of molybdenum trioxide was dispersed in 500 g of pure water using a laser diffraction particle size distribution measuring device SALD-7000 (product name, manufactured by Shimadzu Corporation), and stirred for 30 seconds. It was done after ordered.
(실시예 1) (Example 1)
순수 400부에, 도 1에 있어서 실시예 1로서 나타내는 입자경 분포를 갖는 삼산화 몰리브데넘(입자경이 6μm 이하인 입자의 비율: 2.9체적%) 100부, 메타바나드산 암모늄 3.4부, 85질량% 인산 수용액 9.4부를 순수 6.0부로 희석한 희석물, 및 질산 구리(II) 삼수화물 2.1부를 순수 4.5부에 용해시킨 용해물을 첨가하여, 수성 슬러리(I)을 얻었다. 해당 수성 슬러리(I)을 교반하면서 25℃로부터 95℃로 승온하고, 액온을 95℃로 유지하면서 2시간 교반하여, 헤테로폴리산을 포함하는 수성 슬러리(II)를 얻었다. 이때, 상기 수성 슬러리(I)의 온도가 60℃에 도달하고 나서 90℃에 도달할 때까지의 시간은 15분이었다. 추가로 액온을 95℃로 유지하고 교반하면서, 중탄산 세슘 13.5부를 순수 24부에 용해시킨 용해물과, 탄산 암모늄 9.2부를 순수 26부에 용해시킨 용해물을 적하하고 교반하여, 헤테로폴리산의 세슘염 및 암모늄염을 석출시켰다. 석출된 헤테로폴리산의 세슘염 및 암모늄염은 케긴형 구조를 갖고 있었다. 그 후, 액온을 95℃로 유지하면서 15분간 교반했다. 얻어진 수성 슬러리(III)을 스프레이 드라이어로 건조하여, 촉매 전구체 건조물을 얻었다. 얻어진 촉매 전구체 건조물을 압출 성형함으로써 직경 5.5mm, 높이 5.5mm의 원주상으로 성형하고, 공기 유통하, 380℃에서 10시간 열처리함으로써 촉매를 제조했다. 해당 촉매의 산소 이외의 조성은 P1.4Mo12V0.5Cu0.15Cs1.2였다.400 parts of pure water, 100 parts of molybdenum trioxide having a particle size distribution shown in Example 1 in Fig. 1 (the proportion of particles having a particle diameter of 6 μm or less: 2.9% by volume), 3.4 parts of ammonium metavanadate, 85 parts of phosphoric acid An aqueous slurry (I) was obtained by adding a dilution obtained by diluting 9.4 parts of aqueous solution to 6.0 parts of pure water, and a dissolved solution of 2.1 parts of copper (II) nitrate trihydrate dissolved in 4.5 parts of pure water. The aqueous slurry (I) was heated from 25°C to 95°C while stirring, and stirred for 2 hours while maintaining the liquid temperature at 95°C to obtain an aqueous slurry (II) containing heteropolyacid. At this time, the time from reaching the temperature of the aqueous slurry (I) to 60°C and reaching 90°C was 15 minutes. Further, while maintaining the solution temperature at 95° C. and stirring, the dissolved solution in which 13.5 parts of cesium bicarbonate was dissolved in 24 parts of pure water and the dissolved solution of 9.2 parts of ammonium carbonate in 26 parts of pure water was added dropwise and stirred, and cesium salt and ammonium salt of heteropoly acid Precipitated. The precipitated cesium salt and ammonium salt of the heteropoly acid had a Keggin structure. Then, it stirred for 15 minutes, maintaining liquid temperature at 95 degreeC. The obtained aqueous slurry (III) was dried with a spray dryer to obtain a catalyst precursor dried product. A catalyst was prepared by extruding the obtained catalyst precursor dried into a column shape having a diameter of 5.5 mm and a height of 5.5 mm, and heat-treating at 380° C. for 10 hours under air flow. The catalyst had a composition other than oxygen of P 1.4 Mo 12 V 0.5 Cu 0.15 Cs 1.2 .
상기 촉매를 반응관에 충전하고, 메타크롤레인 5용량%, 산소 10용량%, 수증기 30용량% 및 질소 55용량%의 원료 가스를 반응 온도 310℃, 상기 원료 가스와 상기 촉매의 접촉 시간 7.1초로 통하게 했다. 반응기로부터 얻어지는 생성물을 포집하고, 가스 크로마토그래피로 분석하여 메타크릴산 수율을 산출했다. 결과를 표 1에 나타낸다.The catalyst is charged into the reaction tube, and the raw material gas of 5% by volume of methacrolein, 10% by volume of oxygen, 30% by volume of water vapor and 55% by volume of nitrogen is reacted at a temperature of 310°C, and the contact time between the source gas and the catalyst is 7.1 seconds. Made it work. The product obtained from the reactor was collected and analyzed by gas chromatography to calculate the methacrylic acid yield. Table 1 shows the results.
(실시예 2∼4, 비교예 1∼3) (Examples 2 to 4 and Comparative Examples 1 to 3)
실시예 1에 있어서 이용한 삼산화 몰리브데넘 100부 대신에, 도 1에 있어서 각 실시예, 비교예로서 나타내는 입자경 분포를 갖는 삼산화 몰리브데넘(입자경이 6μm 이하인 입자의 비율은 표 1에 기재) 100부를 이용한 것 이외에는, 실시예 1과 마찬가지로 촉매를 제조하고, 메타크릴산 수율을 산출했다. 결과를 표 1에 나타낸다. 한편, 실시예 2∼4 및 비교예 1∼3에 있어서도, 실시예 1과 마찬가지로, 석출된 헤테로폴리산의 세슘염 및 암모늄염은 케긴형 구조를 갖고 있었다.Instead of 100 parts of molybdenum trioxide used in Example 1, molybdenum trioxide having a particle size distribution shown in each example and comparative example in FIG. 1 (the ratio of particles having a particle diameter of 6 μm or less is shown in Table 1) 100 A catalyst was prepared in the same manner as in Example 1 except that parts were used, and the methacrylic acid yield was calculated. Table 1 shows the results. On the other hand, in Examples 2 to 4 and Comparative Examples 1 to 3, as in Example 1, the precipitated cesium salt and ammonium salt of the heteropoly acid had a Keggin structure.
(실시예 5∼8) (Examples 5 to 8)
실시예 1에 있어서, 수성 슬러리(I)의 온도가 60℃에 도달하고 나서 90℃에 도달할 때까지의 시간을, 각각 표 1에 나타내는 대로 조정한 것 이외에는, 실시예 1과 마찬가지로 촉매를 제조하고, 메타크릴산 수율을 산출했다. 결과를 표 1에 나타낸다. 한편 실시예 5∼8에 있어서도, 실시예 1과 마찬가지로, 석출된 헤테로폴리산의 세슘염 및 암모늄염은 케긴형 구조를 갖고 있었다.In Example 1, the catalyst was prepared in the same manner as in Example 1, except that the time from the temperature of the aqueous slurry (I) to reach 60° C. until reaching 90° C. was adjusted as shown in Table 1, respectively. Then, the methacrylic acid yield was calculated. Table 1 shows the results. On the other hand, in Examples 5 to 8, as in Example 1, the precipitated cesium salt and ammonium salt of the heteropoly acid had a Keggin structure.
표 1에 나타내는 바와 같이, 몰리브데넘 원료로서, 입자경 분포에 있어서의 입자경이 6μm 이하인 입자의 비율이 2∼55체적%인 몰리브데넘 산화물을 사용한 실시예 1∼8에서는, 높은 수율로 메타크릴산이 얻어졌다. 또한 실시예 1∼8 중에서도, 수성 슬러리(I)의 온도가 60℃에 도달하고 나서 90℃에 도달할 때까지의 시간이 5∼40분의 범위 내인 실시예 1∼6은, 보다 메타크릴산 수율이 높고, 7∼30분의 범위 내인 실시예 1∼4는, 특히 메타크릴산 수율이 높았다. 한편, 몰리브데넘 원료로서, 입자경 분포에 있어서의 입자경이 6μm 이하인 입자의 비율이 상기 범위 외인 몰리브데넘 산화물을 사용한 비교예 1∼3에서는, 모두 실시예와 비교해서 메타크릴산 수율이 낮은 것이 되었다.As shown in Table 1, in Examples 1-8 using molybdenum oxide having a ratio of 2 to 55% by volume of particles having a particle diameter of 6 µm or less in the particle diameter distribution as a raw material for molybdenum, methacrylic with high yield Acid was obtained. Further, among Examples 1 to 8, Examples 1 to 6 in which the time from the temperature of the aqueous slurry (I) reached 60°C until reaching 90°C was in the range of 5 to 40 minutes, more methacrylic acid The yields were high, and Examples 1 to 4 in the range of 7 to 30 minutes were particularly high in methacrylic acid yield. On the other hand, as the raw material for molybdenum, in Comparative Examples 1 to 3 in which the proportion of particles having a particle diameter of 6 µm or less in the particle diameter distribution was outside the above range, all of them had a lower methacrylic acid yield compared to Examples. Became.
이 출원은 2017년 10월 20일에 출원된 일본 출원 특원2017-203592를 기초로 하는 우선권을 주장하고, 그 개시의 모두를 여기에 원용한다.This application claims priority based on Japanese Patent Application No. 2017-203592 filed on October 20, 2017, and uses the entirety of the disclosure herein.
이상, 실시형태 및 실시예를 참조하여 본원 발명을 설명했지만, 본원 발명은 상기 실시형태 및 실시예로 한정되는 것은 아니다. 본원 발명의 구성이나 상세는 본원 발명의 범주 내에서 당업자가 이해할 수 있는 다양한 변경을 할 수 있다.The present invention has been described above with reference to embodiments and examples, but the present invention is not limited to the above embodiments and examples. The configuration and details of the present invention can be variously changed by those skilled in the art within the scope of the present invention.
본 발명에 의하면, α,β-불포화 알데하이드로부터 높은 수율로 α,β-불포화 카복실산을 제조할 수 있는 α,β-불포화 카복실산 제조용 촉매를 제공할 수 있어, 공업적으로 유용하다.According to the present invention, it is possible to provide a catalyst for the production of α,β-unsaturated carboxylic acids capable of producing α,β-unsaturated carboxylic acids with high yield from α,β-unsaturated aldehydes, which is industrially useful.
Claims (13)
(i) 적어도 상기 몰리브데넘 원료 및 인 원료를 포함하는 촉매 원료와 물을 혼합하여 얻어진 수성 슬러리(I)을, 90∼150℃로 가열하여 헤테로폴리산을 포함하는 수성 슬러리 또는 수용액(II)를 얻는 공정과,
(ii) 상기 수성 슬러리 또는 수용액(II)에 금속 양이온 함유 화합물을 첨가하여, 헤테로폴리산염이 석출된 수성 슬러리(III)을 얻는 공정과,
(iii) 상기 수성 슬러리(III)을 건조하여, 촉매 전구체 건조물을 얻는 공정과,
(iv) 상기 촉매 전구체 건조물을 열처리하여, 촉매를 얻는 공정
을 갖고, 상기 공정(i)에 있어서, 상기 수성 슬러리(I)의 온도가 60℃에 도달하고 나서 90℃에 도달할 때까지의 시간이 5∼40분인, α,β-불포화 카복실산 제조용 촉매의 제조 방법.According to claim 1,
(i) an aqueous slurry (I) obtained by mixing water and a catalyst raw material containing at least the molybdenum raw material and phosphorus raw material is heated to 90 to 150° C. to obtain an aqueous slurry or aqueous solution (II) containing heteropoly acid. Fairness,
(ii) adding a metal cation-containing compound to the aqueous slurry or aqueous solution (II) to obtain an aqueous slurry (III) in which heteropolyacids are precipitated,
(iii) drying the aqueous slurry (III) to obtain a catalyst precursor dried product,
(iv) Process of heat-treating the dried catalyst precursor to obtain a catalyst
And, in the step (i), the temperature from the temperature of the aqueous slurry (I) reaches 60°C and then reaches 90°C is 5 to 40 minutes. Manufacturing method.
상기 공정(i)에 있어서, 상기 수성 슬러리(I)의 온도가 60℃에 도달하고 나서 90℃에 도달할 때까지의 시간이 7∼30분인, α,β-불포화 카복실산 제조용 촉매의 제조 방법.According to claim 2,
In the step (i), the time until the temperature of the aqueous slurry (I) reaches 60°C and then reaches 90°C is 7 to 30 minutes, the method for producing the α,β-unsaturated carboxylic acid catalyst.
상기 몰리브데넘 원료가, 입자경이 6μm 이하인 입자의 비율이 2∼35체적%인 몰리브데넘 산화물인, α,β-불포화 카복실산 제조용 촉매의 제조 방법.The method according to any one of claims 1 to 3,
The method for producing a catalyst for producing α,β-unsaturated carboxylic acids, wherein the molybdenum raw material is a molybdenum oxide having a particle size of 2 to 35% by volume with a particle size of 6 μm or less.
상기 몰리브데넘 원료가, 입자경이 6μm 이하인 입자의 비율이 2∼15체적%인 몰리브데넘 산화물인, α,β-불포화 카복실산 제조용 촉매의 제조 방법.The method of claim 4,
The method for producing a catalyst for the production of α,β-unsaturated carboxylic acids, wherein the molybdenum raw material is molybdenum oxide having a particle diameter of 6 μm or less and a proportion of 2 to 15% by volume.
상기 α,β-불포화 카복실산 제조용 촉매가, 하기 식(1)로 표시되는 조성을 갖는, α,β-불포화 카복실산 제조용 촉매의 제조 방법.
PaMobVcCudAeEfGgOh (1)
(식(1) 중, P, Mo, V, Cu 및 O는 각각 인, 몰리브데넘, 바나듐, 구리 및 산소를 나타내는 원소 기호이다. A는 안티모니, 비스무트, 비소, 저마늄, 지르코늄, 텔루륨, 은, 셀레늄, 규소, 텅스텐 및 붕소로 이루어지는 군으로부터 선택되는 적어도 1종의 원소를 나타내고, E는 철, 아연, 크로뮴, 마그네슘, 칼슘, 스트론튬, 탄탈럼, 코발트, 니켈, 망가니즈, 바륨, 타이타늄, 주석, 납, 나이오븀, 인듐, 황, 팔라듐, 갈륨, 세륨 및 란타넘으로 이루어지는 군으로부터 선택되는 적어도 1종의 원소를 나타내고, G는 리튬, 나트륨, 칼륨, 루비듐, 세슘 및 탈륨으로 이루어지는 군으로부터 선택되는 적어도 1종의 원소를 나타낸다. a∼h는 각 원소의 원자 비율을 나타내고, b=12일 때, a=0.5∼3, c=0.01∼3, d=0.01∼2, e=0∼3, f=0∼3, g=0.01∼3이며, h는 상기 각 원소의 원자가를 만족하는 데 필요한 산소의 원자 비율이다.)The method according to any one of claims 1 to 5,
The method for producing a catalyst for producing α,β-unsaturated carboxylic acid, wherein the catalyst for producing α,β-unsaturated carboxylic acid has a composition represented by the following formula (1).
P a Mo b V c Cu d A e E f G g O h (1)
(In formula (1), P, Mo, V, Cu, and O are elemental symbols representing phosphorus, molybdenum, vanadium, copper, and oxygen, respectively. A is antimony, bismuth, arsenic, germanium, zirconium, and tellurium. Represents at least one element selected from the group consisting of rulium, silver, selenium, silicon, tungsten and boron, E is iron, zinc, chromium, magnesium, calcium, strontium, tantalum, cobalt, nickel, manganese, barium , Titanium, tin, lead, niobium, indium, sulfur, palladium, gallium, cerium, and at least one element selected from the group consisting of lanthanum, G is lithium, sodium, potassium, rubidium, cesium and thallium Represents at least one element selected from the group consisting of: a to h represent the atomic ratio of each element, 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 the atomic ratio of oxygen required to satisfy the valence of each element.)
상기 몰리브데넘 원료로서 삼산화 몰리브데넘을 50질량% 이상 사용하는, α,β-불포화 카복실산 제조용 촉매의 제조 방법.The method according to any one of claims 1 to 6,
Method for producing a catalyst for the production of α,β-unsaturated carboxylic acid, wherein 50 mol% or more of molybdenum trioxide is used as the molybdenum raw material.
상기 몰리브데넘 원료로서 삼산화 몰리브데넘을 70질량% 이상 사용하는, α,β-불포화 카복실산 제조용 촉매의 제조 방법.The method of claim 7,
Method for producing a catalyst for the production of α,β-unsaturated carboxylic acid, using 70 mol% or more of molybdenum trioxide as the molybdenum raw material.
상기 α,β-불포화 카복실산 제조용 촉매는, α,β-불포화 알데하이드를 분자상 산소에 의해 기상 접촉 산화시켜 α,β-불포화 카복실산을 제조할 때에 이용되는 촉매로서, 상기 α,β-불포화 알데하이드가 (메트)아크롤레인이고, 또한 상기 α,β-불포화 카복실산이 (메트)아크릴산인, α,β-불포화 카복실산 제조용 촉매의 제조 방법.The method according to any one of claims 1 to 8,
The α,β-unsaturated carboxylic acid production catalyst is a catalyst used when preparing α,β-unsaturated carboxylic acid by gas phase catalytic oxidation of α,β-unsaturated aldehyde with molecular oxygen, wherein the α,β-unsaturated aldehyde is Method for producing a catalyst for production of α,β-unsaturated carboxylic acid, wherein the (meth)acrolein is, and the α,β-unsaturated carboxylic acid is (meth)acrylic acid.
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