CN115155630A - Method for producing catalyst for methacrylic acid production, method for producing methacrylic acid, and method for producing methacrylic acid ester - Google Patents
Method for producing catalyst for methacrylic acid production, method for producing methacrylic acid, and method for producing methacrylic acid ester Download PDFInfo
- Publication number
- CN115155630A CN115155630A CN202210741113.1A CN202210741113A CN115155630A CN 115155630 A CN115155630 A CN 115155630A CN 202210741113 A CN202210741113 A CN 202210741113A CN 115155630 A CN115155630 A CN 115155630A
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- China
- Prior art keywords
- catalyst
- liquid
- raw material
- methacrylic acid
- material liquid
- 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.)
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- 239000003054 catalyst Substances 0.000 title claims abstract description 326
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 title claims abstract description 154
- 238000004519 manufacturing process Methods 0.000 title claims description 134
- 125000005397 methacrylic acid ester group Chemical group 0.000 title claims description 10
- 239000007788 liquid Substances 0.000 claims abstract description 357
- 239000002994 raw material Substances 0.000 claims abstract description 232
- 238000000034 method Methods 0.000 claims abstract description 41
- 239000011964 heteropoly acid Substances 0.000 claims abstract description 39
- 150000003839 salts Chemical class 0.000 claims abstract description 36
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 18
- 125000002091 cationic group Chemical group 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims description 28
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 21
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 19
- 229910052698 phosphorus Inorganic materials 0.000 claims description 19
- 229910001882 dioxygen Inorganic materials 0.000 claims description 18
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 17
- 150000001768 cations Chemical class 0.000 claims description 17
- 229910052750 molybdenum Inorganic materials 0.000 claims description 17
- 239000011733 molybdenum Substances 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 17
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 16
- 239000012018 catalyst precursor Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 239000011574 phosphorus Substances 0.000 claims description 16
- 239000010949 copper Substances 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 13
- 230000003197 catalytic effect Effects 0.000 claims description 11
- 230000003647 oxidation Effects 0.000 claims description 11
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 8
- 150000001340 alkali metals Chemical class 0.000 claims description 7
- 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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 229910052792 caesium Inorganic materials 0.000 claims description 4
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 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
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052712 strontium Inorganic materials 0.000 claims description 4
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-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
- 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 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
- 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
- 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
- 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 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
- 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
- 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
- 239000011133 lead 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
- 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
- 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 compound [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
- 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
- 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
- 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
- 230000001590 oxidative effect Effects 0.000 claims description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims 3
- 239000002002 slurry Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 12
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 12
- -1 alkali metal salt Chemical class 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- 239000012071 phase Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 8
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000007858 starting material Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 4
- 150000001342 alkaline earth metals Chemical class 0.000 description 4
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000010953 base metal Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 2
- 239000004254 Ammonium phosphate Substances 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 2
- 235000019289 ammonium phosphates Nutrition 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-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
- 238000010304 firing Methods 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound 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
- 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
- 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
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- XUFUCDNVOXXQQC-UHFFFAOYSA-L azane;hydroxy-(hydroxy(dioxo)molybdenio)oxy-dioxomolybdenum Chemical compound N.N.O[Mo](=O)(=O)O[Mo](O)(=O)=O XUFUCDNVOXXQQC-UHFFFAOYSA-L 0.000 description 1
- ZMCUDHNSHCRDBT-UHFFFAOYSA-M caesium bicarbonate Chemical compound [Cs+].OC([O-])=O ZMCUDHNSHCRDBT-UHFFFAOYSA-M 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- 229910000431 copper oxide Inorganic materials 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
- 238000007865 diluting Methods 0.000 description 1
- 238000002036 drum drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004993 emission spectroscopy Methods 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
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000004715 keto acids Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- OGUCKKLSDGRKSH-UHFFFAOYSA-N oxalic acid oxovanadium Chemical compound [V].[O].C(C(=O)O)(=O)O OGUCKKLSDGRKSH-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 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
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- SEACXNRNJAXIBM-UHFFFAOYSA-N triethyl(methyl)azanium Chemical compound CC[N+](C)(CC)CC SEACXNRNJAXIBM-UHFFFAOYSA-N 0.000 description 1
- 239000012808 vapor phase Substances 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
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
- B01J27/198—Vanadium
- B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
- C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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
- C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
- C07C51/252—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
- C07C57/02—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
- C07C57/03—Monocarboxylic acids
- C07C57/04—Acrylic acid; Methacrylic acid
-
- 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)
- 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 producing methacrylic acid with high methacrylic acid yield. The invention provides a method for preparing a catalyst for methacrylic acid productionThe method comprises the following steps: the method comprises (1) a step of preparing a catalyst raw material liquid A containing Mo, P and V, (2) a step of preparing a catalyst raw material liquid B containing a cationic raw material, (3) a step of adding and mixing another liquid to either one of the catalyst raw material liquid A and the catalyst raw material liquid B to prepare a liquid containing a heteropoly acid having a Keggin type structure or a salt thereof, wherein in the step (3), the formulas (i) and (ii) are satisfied. 3.0. Ltoreq. T/() 3 V) is less than or equal to 13.0 (i); 0.01. Ltoreq. U1. Ltoreq.1.0 (ii). In the formulae (i) and (ii), V represents the volume [ m ] of the catalyst raw material liquid A 3 ]T represents the number of addition ports to which another liquid is added, u1 represents the volume flow rate [ L/min ] of the other liquid added]. When T is 2 or more, u1 represents an average value.
Description
The present application is a divisional application of an invention patent application having a chinese application No. 201780050136.5 (the name of the invention of the original application is "method for producing a catalyst for methacrylic acid production, method for producing methacrylic acid, and method for producing methacrylic acid ester", and the date of application of the original application is 2017, 8, 17).
Technical Field
The present invention relates to a method for producing a catalyst for methacrylic acid production, a method for producing methacrylic acid, and a method for producing methacrylic acid ester.
Background
As a catalyst for methacrylic acid production used in the production of methacrylic acid by vapor-phase catalytic oxidation of methacrolein with molecular oxygen, a heteropolyacid catalyst containing molybdenum and phosphorus is known. As such a heteropoly acid catalyst, there are 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. As the heteropolyacid salt, an alkali metal salt in which the cation is an alkali metal ion and an ammonium salt in which the cation is an ammonium ion (hereinafter, a proton-type heteropolyacid is also simply referred to as "heteropolyacid", and at least 1 selected from the proton-type heteropolyacid and a heteropolyacid salt is also simply referred to as "heteropolyacid (salt)") are known as the cation.
As a method for producing a catalyst for methacrylic acid production, for example, patent document 1 discloses a method for producing a catalyst for methacrylic acid production containing a predetermined atom at a predetermined atomic ratio, which is a method for producing a catalyst for producing methacrylic acid by gas-phase catalytic oxidation of methacrolein with molecular oxygen, comprising the steps of: (I) a step of preparing a solution or slurry (I liquid) containing at least molybdenum (Mo), phosphorus (P) and vanadium (V), (II) a step of preparing a solution or slurry (II liquid) containing ammonium groups, (iii) a step of charging at least one liquid (PR liquid) of the I liquid or the II liquid into a tank (a tank), and charging the other liquid (LA liquid) into a continuous liquid surface region having an area of 0.01 to 10% with respect to the total area of the liquid surface of the PR liquid charged into the a tank to prepare a liquid I liquid/II liquid mixed liquid, and (iv) a step of drying and firing the solution or slurry containing the catalyst precursor containing all the catalyst components.
Documents of the prior art
Patent document
Patent document 1: international publication No. 2005/039760
Disclosure of Invention
However, when the catalyst for methacrylic acid production produced by the method disclosed in patent document 1 is used for methacrylic acid production, the yield of methacrylic acid is insufficient, and further improvement is desired. The purpose of the present invention is to provide a catalyst for methacrylic acid production, which has a high methacrylic acid yield.
The present invention is [1] to [18] below.
[1] A method for producing a catalyst for methacrylic acid production, which is used for producing methacrylic acid by catalytically oxidizing methacrolein in a gas phase with molecular oxygen, comprising the steps of:
(1) A step of preparing a catalyst raw material liquid A containing at least molybdenum, phosphorus and vanadium,
(2) A step of preparing a catalyst material liquid B containing a cationic material,
(3) A step of adding and mixing another liquid to either one of the catalyst raw material liquid a and the catalyst raw material liquid B to prepare a liquid containing a heteropoly acid having a Keggin-type structure or a salt thereof;
in the step (3), the following formulae (i) and (ii) are satisfied.
0.01≤u1≤1.0 (ii)
(formula (i)And (ii) in which V represents the volume [ m ] of the catalyst raw material liquid A 3 ]T represents the number of addition ports for adding another liquid, and u1 represents the volume flow rate [ L/min ] of the added another liquid]. When T is 2 or more, u1 represents an average value of the volume flow rates of the other liquid added from the respective addition ports. )
[2] A method for producing a catalyst for methacrylic acid production, which is used for producing methacrylic acid by gas-phase catalytic oxidation of methacrolein with molecular oxygen, comprising the steps of:
(1) A step of preparing a catalyst raw material liquid A containing at least molybdenum, phosphorus and vanadium,
(2) A step of preparing a catalyst raw material liquid B containing a cation raw material,
(3) Adding and mixing the catalyst raw material liquid B to the catalyst raw material liquid a to prepare a liquid containing a heteropoly acid having a Keggin-type structure or a salt thereof;
in the step (3), the following formulae (i) and (iii) are satisfied.
0.01≤u2≤8 (iii)
(in the formulae (i) and (iii), V represents the volume [ m ] of the catalyst raw material liquid A 3 ]T represents the number of addition ports for adding the catalyst raw material liquid B, and u2 represents the volume flow rate [ mol/min ] of the cation raw material of the catalyst raw material liquid B]. When T is 2 or more, u2 represents an average value of the flow rates of the cationic raw materials of the catalyst raw material liquid B added from the respective addition ports. )
[3] The process for producing a catalyst for methacrylic acid production according to [1] or [2], wherein T is 2 or more in the formula (i).
[4] The method for producing a catalyst for methacrylic acid production according to [1], wherein in the step (3), the other liquid is added and mixed in a container containing either the catalyst raw material liquid A or the catalyst raw material liquid B and satisfying the following formula (iv).
0.1≤S 3 /W 2 ≤50 (iv)
(in the formula (iv), S represents the surface area [ m ] of the liquid surface of the liquid in the container 2 ]W represents the volume [ m ] of liquid in the container 3 ]。)
[5] The method for producing a catalyst for methacrylic acid production according to [2], wherein the catalyst raw material liquid B is added and mixed in the step (3) in a vessel containing the catalyst raw material liquid A and satisfying the following formula (iv).
0.1≤S 3 /W 2 ≤50 (iv)
(in the formula (iv), S represents the surface area of the liquid surface of the liquid in the container [ m ] 2 ]W represents the volume [ m ] of liquid in the container 3 ]。)
[6] The method for producing a catalyst for methacrylic acid production according to [4] or [5], wherein in the step (3), the addition port is disposed above a liquid surface of the liquid in the container.
[7] The method for producing a catalyst for methacrylic acid production according to [6], wherein the following formula (v) is satisfied in the step (3).
2≤T/S≤100 (v)
(in the formula (v), T has the same meaning as in the formula (i) and S has the same meaning as in the formula (iv))
[8]According to [6]Or [7]In the process for producing a catalyst for methacrylic acid production, in the step (3), a T-bar straight line is drawn from the center of the liquid surface of the liquid in the container to be substantially parallel to the liquid surface so that the central angle is 360 °/T toward the wall surface of the container, and the regions of the liquid surface divided by the T-bar straight line are each Y 1 ～Y T At each Y 1 ～Y T Respectively, 1 of the addition ports are disposed in the upper part of the container.
[9] The method for producing a catalyst for methacrylic acid production according to any one of [6] to [8], wherein in the step (3), the addition port is not present in an upper portion within a circular region drawn with a radius Rm around a center of a liquid surface of the liquid in the container, and the radius R is calculated by the following formula (vi).
(in the formula (vi), S has the same meaning as that of the formula (iv))
[10] The method for producing a catalyst for methacrylic acid production according to [1], wherein the catalyst raw material liquid B is added to and mixed with the container containing the catalyst raw material liquid A in the step (3).
[11]According to [1]～[10]The method for producing a catalyst for methacrylic acid production according to any one of the above processes, wherein the total volume of the catalyst raw material liquid A prepared in the step (1) and the catalyst raw material liquid B prepared in the step (2) is 0.2m 3 As described above.
[12] The method for producing a catalyst for methacrylic acid production according to any one of [1] to [11], wherein the cationic raw material is at least 1 selected from an alkali metal-containing compound and an ammonium ion-containing compound.
[13] The method for producing a catalyst for methacrylic acid production according to any one of [1] to [12], further comprising: and drying the liquid containing the heteropoly acid with the Keggin type structure or the salt thereof to obtain the catalyst precursor.
[14] The method for producing a catalyst for methacrylic acid production according to [13], further comprising a step of heat-treating the catalyst precursor.
[15] The method for producing a catalyst for methacrylic acid production according to any one of [1] to [14], wherein the catalyst for methacrylic acid production has an element composition represented by the following formula (vii).
Mo a P b V c Cu d A e E f G g O h (vii)
( In formula (vii), mo, P, V, cu and O are symbols of elements representing molybdenum, phosphorus, vanadium, copper 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, lead, niobium, indium, sulfur, palladium, gallium, cerium and lanthanum. G represents at least 1 element selected from the group consisting of lithium, sodium, potassium, rubidium, cesium and thallium. a. b, c, d, e, f, g and h represent atomic ratios of the respective elements, and when a =12, b =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 represents an atomic ratio of oxygen necessary to satisfy the atomic valence of the respective elements. )
[16] A process for producing methacrylic acid, which comprises subjecting methacrolein to gas phase catalytic oxidation with molecular oxygen in the presence of the catalyst for producing methacrylic acid produced by the process according to any one of [1] to [15 ].
[17] A process for producing methacrylic acid, which comprises producing a catalyst for methacrylic acid production by the process according to any one of [1] to [15], and subjecting methacrolein to gas phase catalytic oxidation with molecular oxygen in the presence of the catalyst for methacrylic acid production.
[18] A method for producing a methacrylic acid ester, comprising esterifying methacrylic acid produced by the method for producing a methacrylic acid according to [16] or [17 ].
According to the present invention, a catalyst for methacrylic acid production having a high methacrylic acid yield can be provided.
Detailed Description
[ method for producing catalyst for methacrylic acid production ]
The method for producing a catalyst for methacrylic acid production of the present invention is a method for producing a catalyst for methacrylic acid production used for producing methacrylic acid by gas-phase catalytic oxidation of methacrolein with molecular oxygen. The first embodiment of the method includes the following steps (1) to (3).
(1) A step of preparing a catalyst raw material liquid A containing at least molybdenum, phosphorus and vanadium.
(2) A step of preparing a catalyst material liquid B containing a cationic material.
(3) And a step of adding and mixing another liquid to either one of the catalyst raw material liquid a and the catalyst raw material liquid B to prepare a liquid containing a heteropoly acid having a Keggin-type structure or a salt thereof.
In the step (3), the following formulae (i) and (ii) are satisfied.
0.01≤u1≤1.0 (ii)
In the formulae (i) and (ii), V represents the volume [ m ] of the catalyst raw material liquid A 3 ]T represents the number of addition ports for adding another liquid, and u1 represents the volumetric flow rate [ L/min ] of the added another liquid]. When T is 2 or more, u1 represents an average value of the volumetric flow rates of the other liquid added from the respective addition ports.
The second embodiment of the above method includes the following steps (1) to (3).
(1) A step of preparing a catalyst raw material liquid A containing at least molybdenum, phosphorus and vanadium.
(2) A step of preparing a catalyst material liquid B containing a cationic material.
(3) And a step of adding and mixing the catalyst raw material liquid B to the catalyst raw material liquid a to prepare a liquid containing a heteropoly acid having a Keggin-type structure or a salt thereof.
In the step (3), the following formulae (i) and (iii) are satisfied.
0.01≤u2≤8 (iii)
In the formulae (i) and (iii), V represents the volume [ m ] of the catalyst raw material liquid A 3 ]T represents the number of addition ports for adding the catalyst raw material liquid B, and u2 represents the flow rate [ mol/min ] of the cation raw material of the catalyst raw material liquid B]. In addition to this, the present invention is,when T is 2 or more, u2 represents an average value of flow rates of the cation raw materials of the catalyst raw material liquid B added from the respective addition ports.
In the first and second embodiments of the method of the present invention, the above steps (1) to (3) are included, and the above formula (i) and (ii) are satisfied or the above formula (i) and (iii) are satisfied in the above step (3), whereby a catalyst for methacrylic acid production which can produce methacrylic acid in a high yield can be produced. The detailed mechanism thereof is not necessarily clear, but it is assumed that catalyst particles effective for improving the yield of methacrylic acid are easily produced.
The catalyst for methacrylic acid production produced by the method of the present invention contains at least molybdenum, phosphorus and vanadium, but may further contain other elements such as copper in addition to these elements. From the viewpoint of being able to produce methacrylic acid in a high yield, the catalyst preferably has an elemental composition represented by the following formula (vii).
Mo a P b V c Cu d A e E f G g O h (vii)
In formula (vii), mo, P, V, cu and O are symbols of elements representing molybdenum, phosphorus, vanadium, copper 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, lead, niobium, indium, sulfur, palladium, gallium, cerium and lanthanum. G represents at least 1 element selected from the group consisting of lithium, sodium, potassium, rubidium, cesium and thallium. a. b, c, d, e, f, g, and h represent atomic ratios of the respective elements, and when a =12, b =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 represents an atomic ratio of oxygen necessary to satisfy the valence of the respective elements. The elemental composition is a value calculated by analyzing a component obtained by dissolving a catalyst in ammonia water by an ICP emission analysis method.
(step (1))
In the step (1), a catalyst raw material liquid a containing at least molybdenum, phosphorus and vanadium is prepared. For example, a catalyst raw material liquid a can be obtained by dissolving or suspending a raw material compound of a catalyst component containing molybdenum, phosphorus, and vanadium in a solvent using a preparation vessel. The catalyst raw material liquid a contains at least molybdenum, phosphorus, and vanadium, and thus a catalyst for methacrylic acid production with a higher methacrylic acid yield can be produced.
The starting compound of the catalyst component is not particularly limited, and 2 or more of the following components may be used alone or in combination: nitrates, carbonates, acetates, ammonium salts, oxides, halides, oxyacids, oxyacid salts, and the like of the respective constituent elements of the catalyst. Examples of the raw material compound of molybdenum include molybdenum oxide such as molybdenum trioxide, ammonium molybdate such as ammonium paramolybdate and ammonium dimolybdate, and the like. Examples of the phosphorus raw material compound include phosphoric acid, phosphorus pentoxide, and ammonium phosphate. Examples of the raw material compound of vanadium include ammonium metavanadate, vanadium pentoxide, vanadyl oxalate, and the like. Examples of the raw material compound of copper include copper nitrate, copper oxide, copper carbonate, and copper acetate. The raw material compound of the catalyst component may be used in 1 kind or in combination of 2 or more kinds with respect to each element constituting the catalyst component.
Examples of the solvent include water, ethanol, and acetone. These may be used in 1 kind, or 2 or more kinds may be used in combination. Among these, water is preferably used.
The catalyst raw material liquid a is preferably prepared by using a preparation vessel, adding a raw material compound of the catalyst component to a solvent, and stirring the mixture while heating. The heating temperature is preferably 80 to 130 ℃ and the lower limit is more preferably 90 ℃ or higher. The pH of the catalyst starting material liquid a is preferably 3.0 or less, and more preferably 2.5 or less. As a method for adjusting the pH of the catalyst raw material liquid a to 3.0 or less, for example, a method of using molybdenum trioxide as a molybdenum raw material and selecting a raw material compound of a catalyst component so as to contain a large amount of nitrate ions can be given. The concentration of the raw material compound of the catalyst component in the catalyst raw material liquid a is not particularly limited, and may be, for example, 5 to 90 mass%.
(step (2))
In the step (2), a catalyst raw material liquid B containing a cationic raw material is prepared. For example, the catalyst raw material liquid B can be obtained by dissolving or suspending the cation raw material in a solvent using a preparation vessel.
Here, the "cation raw material" represents at least 1 selected from the group consisting of an alkali metal-containing compound, an alkaline earth metal-containing compound, a transition metal-containing compound, a base metal-containing compound, and a nitrogen-containing compound (ammonia, an ammonium ion-or alkylammonium ion-containing compound, or a nitrogen-containing heterocyclic compound). Examples of the alkali metal include lithium, sodium, potassium, rubidium, and cesium. Examples of the alkaline earth metal include magnesium, calcium, strontium, and barium. Examples of the alkali metal-containing compound, alkaline earth metal-containing compound, transition metal-containing compound, and base metal-containing compound include alkali metal, alkaline earth metal, transition metal, and base metal nitrate, carbonate, bicarbonate, acetate, sulfate, ammonium salt, oxide, hydroxide, halide, oxo acid, and oxo acid salt. Examples of the compound containing an ammonium ion include ammonium hydrogen carbonate, ammonium nitrate, ammonium phosphate, and ammonium vanadate. Examples of the compound containing an alkylammonium ion include halides and hydroxides such as tetramethylammonium, tetraethylammonium, tetra-n-propylammonium, tetra-n-butylammonium, and triethylmethylammonium. Examples of the nitrogen-containing heterocyclic compound include pyridine, piperidine, piperazine, pyrimidine, quinoline, isoquinoline, and alkyl derivatives thereof. One kind of them may be used, or two or more kinds may be used in combination. Among these, the cationic raw material is preferably at least 1 selected from the group consisting of alkali metal-containing compounds and ammonium ion-containing compounds, from the viewpoint of obtaining a methacrylic acid production catalyst having a higher methacrylic acid yield.
Examples of the solvent include water, ethanol, and acetone. These may be used in 1 kind, or 2 or more kinds may be used in combination. Among these, water is preferably used.
When a plurality of types of cationic raw materials are used, a plurality of preparation vessels may be used to prepare a plurality of catalyst raw material liquids B in the form of catalyst raw material liquids B1, B2, \8230aby dissolving or suspending each cationic raw material in a solvent. When the catalyst starting material liquid B is added to the catalyst starting material liquid a, the catalyst starting material liquids B1, B2 and/or 8230can be added to the catalyst starting material liquid a out of order, or simultaneously. In the first embodiment, when the catalyst raw material liquid a is added to the catalyst raw material liquid B, the catalyst raw material liquid a may be added to any one of the catalyst raw material liquids B and the obtained liquid may be mixed with another catalyst raw material liquid B, or the obtained liquids may be mixed after being divided into a plurality of catalyst raw material liquids a and added to the catalyst raw material liquid B as in the catalyst raw material liquids A1, A2, and 8230a. The concentration of the cationic material in the catalyst material liquid B is not particularly limited, and may be, for example, 5 to 90 mass%.
In addition, when the catalyst raw material liquids a and B are prepared in the steps (1) and (2), if industrial production is considered, the total volume of the catalyst raw material liquid a prepared in the step (1) and the catalyst raw material liquid B prepared in the step (2) is preferably 0.2m in terms of production cost 3 Above, more preferably 0.8m 3 Above, more preferably 1.5m 3 As described above. The upper limit of the volume range is not particularly limited, and may be, for example, 5m 3 The following.
(step (3))
In the first embodiment, in the step (3), a liquid containing a heteropoly acid having a Keggin-type structure or a salt thereof is prepared by adding and mixing another liquid to either of the catalyst raw material liquid a and the catalyst raw material liquid B. That is, the catalyst raw material liquid B is added to and mixed with the catalyst raw material liquid a, or the catalyst raw material liquid a is added to and mixed with the catalyst raw material liquid B. In the former, the catalyst raw material liquid B corresponds to "another liquid", and in the latter, the catalyst raw material liquid a corresponds to "another liquid". Hereinafter, "another liquid" is also referred to as an additive liquid. In the second embodiment, in the step (3), the catalyst raw material liquid B is added to and mixed with the catalyst raw material liquid a to prepare a liquid containing a heteropoly acid having a Keggin-type structure or a salt thereof. In the first embodiment, in the step (3), the conditions of the following formulae (i) and (ii) need to be satisfied at the same time. In the second embodiment, in the step (3), it is necessary to satisfy both the conditions of the following formulae (i) and (iii).
0.01≤u1≤1.0 (ii)
0.01≤u2≤8 (iii)
In the formulae (i), (ii) and (iii), V represents the volume [ m ] of the catalyst raw material liquid A 3 ]T represents the number of addition ports for adding another liquid (the above catalyst raw material liquid B), and u1 represents the volume flow rate [ L/min ] of the other liquid added]U2 represents the flow rate [ mol/min ] of the cation raw material in the catalyst raw material liquid B]. The "addition port" is an outlet of the other liquid (catalyst raw material liquid B) provided for adding the other liquid (catalyst raw material liquid B) to either one of the catalyst raw material liquid a and the catalyst raw material liquid B (catalyst raw material liquid a). When T is 2 or more, u1 and u2 represent the average value of the volumetric flow rate of the other liquid added from each addition port and the average value of the flow rate of the cation material of the catalyst material liquid B added from each addition port, respectively. In addition, when there are a plurality of additive solutions, it is necessary to satisfy the above conditions. That is, when the catalyst raw material liquids B1, B2, and \ 8230are present as the addition liquids, it is necessary that the addition of the respective liquids all satisfy the conditions of the formulae (i) and (ii) or satisfy the conditions of the formulae (i) and (iii). In the first embodiment, in the presence of the catalyst raw material liquids A1, A2, and/or' \ 8230, the conditions of the formulae (i) and (ii) must be satisfied simultaneously for all the liquids to be added, similarly.
By mixing the catalyst raw material liquid a and the catalyst raw material liquid B, a liquid containing a heteropoly acid (salt) having a Keggin-type structure is obtained. In the above-mentioned formula (i),
the number T of addition ports is a value obtained by dividing the cubic root of the volume V of the catalyst raw material liquid a, and affects the contact state of the respective liquids when the catalyst raw material liquid a and the catalyst raw material liquid B are mixed. Thus, the deviceIt is presumed that the compound is obtained by reacting the compound represented by the above formula (i)
Within the specific range, a heteropoly acid (salt) effective for increasing the yield of methacrylic acid among heteropoly acids (salts) is easily produced. The total amount of the obtained heteropoly acid (salt) is related to the amount of the catalyst component contained in the catalyst raw material liquid a.
Has a value of
The lower limit is preferably 4.0 or more, more preferably 5.0 or more, and further preferably 6.0 or more. The upper limit is preferably 12.0 or less, more preferably 11.0 or less, and further preferably 9.0 or less.
From the viewpoint of obtaining a catalyst for methacrylic acid production with a higher methacrylic acid yield, the value of T is preferably 2 or more, more preferably 4 or more, and further preferably 8 or more. The upper limit of the range of the value of T is not particularly limited, and may be, for example, 20 or less. Examples of a method for setting the value of T to 2 or more include using a pipe having a plurality of holes and using a multi-nozzle having a plurality of discharge ports. The diameter of the addition port is preferably 0.5 to 30mm, the lower limit is more preferably 1mm or more, and the upper limit is more preferably 10mm or less.
In the formula (ii), the volume flow rate u1 of the addition liquid affects the contact speed of the catalyst raw material liquid a and the catalyst raw material liquid B when the two liquids are mixed. Therefore, it is presumed that by adding another liquid to either one of the catalyst raw material liquid a and the catalyst raw material liquid B so as to satisfy the above formula (ii), catalyst particles effective for improving the yield of methacrylic acid are easily produced. The value of u1 preferably satisfies 0.01. Ltoreq. U1. Ltoreq.1.0, and the lower limit is preferably 0.05 or more, more preferably 0.1 or more. The upper limit is preferably 0.5 or less, more preferably 0.4 or less, and still more preferably 0.3 or less.
In the formula (iii), the flow rate u2 of the cationic material of the catalyst material liquid B to be added affects the contact rate of the catalyst material liquid a and the catalyst material liquid B when the two liquids are mixed. Therefore, it is presumed that by adding the catalyst raw material liquid B to the catalyst raw material liquid a so as to satisfy the above formula (iii), catalyst particles effective for improving the yield of methacrylic acid are easily produced. The value of u2 satisfies 0.01. Ltoreq. U2. Ltoreq.8, and the lower limit is preferably 0.1 or more, more preferably 0.5 or more. The upper limit is preferably 5 or less, more preferably 4 or less, and still more preferably 2 or less.
In the first embodiment, in the step (3), it is preferable to add and mix another liquid in a container containing either one of the catalyst raw material liquid a and the catalyst raw material liquid B and satisfying the following formula (iv). In the second embodiment, in the step (3), it is preferable to add and mix the catalyst raw material liquid B in a container containing the catalyst raw material liquid a and satisfying the following formula (iv).
0.1≤S 3 /W 2 ≤50 (iv)
In the formula (iv), S represents the surface area [ m ] of the liquid surface of the liquid in the container 2 ]W represents the volume [ m ] of liquid in the container 3 ]. Here, the "in-container liquid" indicates the catalyst raw material liquid a or the catalyst raw material liquid B charged in the container.
S 3 /W 2 The value is related to the shape of the container in which the catalyst raw material liquid a and the catalyst raw material liquid B are mixed. By adjusting the shape of the vessel in which the catalyst raw material liquid a and the catalyst raw material liquid B are mixed so as to satisfy the above formula (iv), the surface area of the liquid surface with respect to the volume of the liquid in the vessel is in a preferred range, and a stable stirring state can be maintained. S 3 /W 2 The lower limit of the value (b) is more preferably 0.5 or more, and still more preferably 0.8 or more.
In the case where the catalyst raw material liquid a and the catalyst raw material liquid B are prepared separately using a preparation vessel in the steps (1) and (2), either one of the catalyst raw material liquid a and the catalyst raw material liquid B (catalyst raw material liquid a) may be directly charged into the preparation vessel, and then the other liquid (catalyst raw material liquid B) may be added. In addition, a plurality of containers may be used, and the additive liquid may be added to the liquid in each container so as to satisfy the above formula (iv).
The value of S is not particularly limited, but is preferably 0.01m 2 ≤S≤3m 2 The lower limit is more preferably 0.05m 2 Above, the upper limit is more preferably 2m 2 The following. The value of W is not particularly limited, but is preferably 0.1m 3 ≤W≤4.5m 3 The lower limit is more preferably 0.5m 3 Above, the upper limit is more preferably 3.0m 3 The following.
In the step (3), the addition port is preferably disposed above the liquid surface of the liquid in the container. The value of T/S preferably satisfies the following formula (v).
2≤T/S≤100 (v)
In the formula (v), T has the same meaning as in the formula (i) and S has the same meaning as in the formula (iv). T/S represents the number of addition ports per unit surface area of the liquid surface of the liquid in the container, and by adjusting the addition ports so as to satisfy the above formula (v), a stable stirring state can be maintained. The lower limit of the value of T/S is more preferably 3 or more, and still more preferably 4 or more. The upper limit is more preferably 80 or less, and still more preferably 60 or less.
Furthermore, T straight lines are drawn from the center of the liquid surface of the liquid in the container to the wall surface of the container in parallel with the liquid surface so that the central angle is 360 DEG/T, and the regions of the liquid surface divided by the T straight lines are respectively set as Y 1 ～Y T When it is used, it is more preferable that each Y is 1 ～Y T 1 of the addition ports are disposed respectively in the upper portions of the respective substrates. By disposing the addition ports in this manner, when the catalyst raw material liquid a and the catalyst raw material liquid B are mixed, the contact surface between the two liquids becomes more uniform, and the mixed state is stable, whereby catalyst particles effective for improving the yield of methacrylic acid can be stably produced. The "center of the liquid surface of the liquid in the container" means the center of gravity of the liquid surface of the liquid in the container, and may be, for example, the center of a circle when the liquid surface is circular, or may be the intersection of diagonal lines when the liquid surface is rectangular. In addition, "substantially parallel" means parallel within a range of ± 5 °. Especially when it will be present in Y 1 The upper adding port of (1) droopsThe tangent point of the vertical line to the liquid level of the liquid in the container is set as Z 1 In this case, it is preferable that all the addition ports are located such that Z is located around the center of the liquid surface of the liquid in the container 1 Upper part of each 360 °/T rotation position.
In the step (3), the addition port is preferably not present in an upper portion of a circular region which is drawn by a radius R [ m ] around the center of the liquid surface of the liquid in the container, the radius R being calculated by the following formula (vi). That is, the addition port is preferably entirely present in the upper portion outside the range of the circular region.
In the formula (vi), S is as defined above for the formula (iv). When the liquid level of the liquid in the vessel is circular, R in the following formula (vi) is 1/3 of the radius of the liquid level of the liquid in the vessel. By disposing the addition port in this manner, when the catalyst raw material liquid a and the catalyst raw material liquid B are mixed, the contact surface between the two liquids becomes more uniform, and the mixed state is stabilized, whereby catalyst particles effective for improving the yield of methacrylic acid can be stably produced.
In the first embodiment, in the step (3), it is preferable to add and mix the catalyst raw material liquid B in a container containing the catalyst raw material liquid a. It is presumed that by mixing a catalyst raw material liquid containing a cationic raw material as an additive liquid, catalyst particles more effective for improving the yield of methacrylic acid are easily produced.
The liquid obtained in step (3) contains a heteropoly acid having a Keggin-type structure or a salt thereof. When the liquid contains a heteropolyacid having a Keggin-type structure or a salt thereof, the produced catalyst particles can be stably present without change, and therefore, a catalyst having a high methacrylic acid yield can be obtained. Further, the case where the liquid contains a heteropoly acid having a Keggin-type structure or a salt thereof can be confirmed by measuring a substance obtained by drying the liquid by infrared absorption analysis. In the case of containing a heteropoly acid having a Keggin type structure or a salt thereof, the obtained infrared absorptionThe spectrum is 1060, 960, 870, 780cm －1 With characteristic peaks in the vicinity.
The pH of the liquid obtained in step (3) is preferably 3.0 or less, and more preferably 2.5 or less. When the pH is 3.0 or less, a liquid containing a heteropoly acid having a Keggin-type structure or a salt thereof can be easily obtained. As a method for adjusting the pH to 3.0 or less, a method of adjusting the pH of the catalyst raw material liquid a to be low in advance may be mentioned.
(drying Process)
The method of the present invention preferably includes a step of drying the liquid containing the heteropoly acid having a Keggin-type structure or a salt thereof obtained in the step (3) to obtain a catalyst precursor. The conditions such as the drying method and the drying temperature of the liquid are not particularly limited, and may be appropriately selected according to the shape and size of the desired dried product. Examples of the drying method include a drying method using a box dryer, a drum drying method, an air flow drying method, an evaporation drying method, and a spray drying method. The drying temperature may be, for example, 120 to 500 ℃ with the lower limit of 140 ℃ or higher and the upper limit of 400 ℃ or lower. The drying may be carried out until the liquid is dried.
(Molding Process)
The method of the present invention may further comprise a step of molding the catalyst precursor obtained in the drying step, before the heat treatment step described later. The molding method is not particularly limited, and a known dry or wet molding method can be applied. Examples thereof include tablet forming, press forming, extrusion forming, and granulation forming. The shape of the molded article is not particularly limited, and examples thereof include a cylindrical shape, a ring shape, and a spherical shape. In addition, the catalyst precursor is preferably molded alone without adding a carrier, a binder, or the like to the catalyst precursor at the time of molding, and a known additive such as graphite or talc, or a known binder derived from an organic material or an inorganic material may be added as necessary. Hereinafter, the catalyst precursor obtained in the drying step and the molded product of the catalyst precursor obtained in the molding step are collectively shown as the catalyst precursor.
(Heat treatment Process)
The method of the present invention preferably includes a step of heat-treating the catalyst precursor. For example, the catalyst precursor may be heat-treated by passing at least one of air and an inert gas therethrough. The heat treatment is preferably performed by flowing an oxygen-containing gas such as air. The "inert gas" means a gas that does not reduce the activity of the catalyst, and examples thereof include nitrogen, carbon dioxide, helium, argon, and the like. One kind of them may be used, or two or more kinds of them may be used in combination. The shape of the heat treatment vessel is not particularly limited, and a tubular heat treatment vessel having a cross-sectional area of 2 cm or more and 100 cm or less is preferably used. The heat treatment temperature is preferably 300 ℃ to 700 ℃, the lower limit is preferably 320 ℃ or higher, and the upper limit is more preferably 450 ℃ or lower.
The catalyst for methacrylic acid production thus obtained preferably contains a heteropolyacid having a Keggin-type structure or a salt thereof, from the viewpoint of higher methacrylic acid yield. The presence of a heteropoly acid having a Keggin-type structure or a salt thereof can be confirmed by measurement using infrared absorption analysis as described above.
[ method for producing methacrylic acid ]
In the method for producing methacrylic acid of the present invention, methacrolein is catalytically oxidized in the gas phase with molecular oxygen in the presence of the catalyst for producing methacrylic acid produced by the method of the present invention to produce methacrylic acid. In the method for producing methacrylic acid of the present invention, a catalyst for producing methacrylic acid is produced by the method of the present invention, and methacrolein is subjected to gas phase catalytic oxidation with molecular oxygen in the presence of the catalyst for producing methacrylic acid to produce methacrylic acid. According to these methods, methacrylic acid can be produced in a high yield. Specifically, methacrylic acid can be produced by bringing a raw material gas containing methacrolein and molecular oxygen into contact with the catalyst for methacrylic acid production of the present invention. The reaction can be carried out using a fixed bed. The catalyst layer may be 1 layer or 2 or more layers. The catalyst for methacrylic acid production may be supported on a carrier, and may contain other additives. The concentration of methacrolein in the raw material gas is not particularly limited, but is preferably 1 to 20% by volume, with the lower limit more preferably 3% by volume or more and the upper limit more preferably 10% by volume or less. The methacrolein may contain a small amount of impurities such as lower saturated aldehydes, which do not substantially affect the main reaction. The concentration of molecular oxygen in the raw material gas is preferably 0.4 to 4mol based on 1mol of methacrolein, and the lower limit is more preferably 0.5 mol or more and the upper limit is more preferably 3mol or less. Although air is preferred as the molecular oxygen source from the viewpoint of economy, a gas obtained by enriching the molecular oxygen-containing substance by adding pure oxygen to air may be used as necessary. 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, steam 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 or more, 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 5 seconds or less. The reaction pressure is preferably from 0.1MPa (G) to 1.0MPa (G), and (G) is a gauge pressure. The reaction temperature is preferably 200 to 450 ℃ with the lower limit of 250 ℃ or higher and the upper limit of 400 ℃ or lower.
[ method for producing methacrylic acid ester ]
The method for producing a methacrylic acid ester of the present invention esterifies methacrylic acid produced by the method of the present invention. According to this method, methacrylic acid ester can be obtained using methacrylic acid obtained by gas-phase catalytic oxidation of methacrolein. Examples of the alcohol to be reacted with methacrylic acid include methanol, ethanol, isopropanol, n-butanol, 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 to 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 mean parts by mass. The molar ratio of the element composition of the catalyst was calculated by analyzing the components obtained by dissolving the catalyst in ammonia water by ICP emission spectrometry. The raw material gas and the product were analyzed by gas chromatography. From the results of the gas chromatography, the conversion of methacrolein, the selectivity of methacrylic acid produced and the single stream yield of methacrylic acid were determined from the following formulae.
Methacrolein conversion (%) = (B/a) × 100
Methacrylic acid selectivity (%) = (C/B) × 100
Methacrylic acid single stream yield = (C/a) × 100
In the formula, A represents the number of carbon atoms of methacrolein to be supplied, B represents the number of carbon atoms of methacrolein to be reacted, and C represents the number of carbon atoms of methacrylic acid to be produced.
Further, u2 is calculated as the product of the molar concentration [ mol/L ] of the catalyst raw material liquid B and u 1.
[ example 1]
100 parts of molybdenum trioxide, 7.5 parts of ammonium metavanadate, 11.4 parts of 85 mass% aqueous phosphoric acid solution, and 7.0 parts of copper (II) nitrate 3 hydrate were dissolved in 400 parts of pure water. The temperature was raised to 95 ℃ while stirring the solution, and the solution was stirred for 2 hours while keeping the solution temperature at 95 ℃ to obtain a catalyst raw material solution A. The pH of the catalyst raw material liquid A was 2.1. On the other hand, 15.7 parts of cesium bicarbonate was dissolved in 20 parts of pure water to obtain a catalyst raw material liquid B1. Further, 20.0 parts of ammonium hydrogencarbonate was dissolved in 20 parts of pure water to obtain catalyst raw material liquid B2. The total volume of the catalyst raw material liquid A, the catalyst raw material liquid B1 and the catalyst raw material liquid B2 was 2.1m 3 。
While stirring the catalyst raw material liquid a with a rotary blade stirrer in a state in which the liquid temperature of the catalyst raw material liquid a in the vessel was kept at 95 ℃, the catalyst raw material liquid B1 was added and stirred for 15 minutes. Then, the catalyst raw material liquid B2 was added and stirred for 15 minutes. In addition, when the catalyst raw material liquids B1 and B2 are added, T = T10，S＝1.54m 2 ，V＝1.9m 3 ，S 3 /W 2 ＝1.01，
T/S =6.5, u1= 0.20L/min. In this case, u2 was 0.62 mol/min for the catalyst raw material liquid B1 and 1.40 mol/min for the catalyst raw material liquid B2. In addition, the radius of the addition ports with the diameter of 2mm is configured with equal intervals
The annular pipe is arranged in the region Y so that the center of the annular pipe is positioned above the center of the liquid surface of the liquid in the container 1 ～Y 10 The upper portions of the respective chambers are arranged so that 1 addition port is arranged. Catalyst raw material liquids B1 and B2 were sequentially added from the addition port of the annular pipe. The obtained slurry contains a heteropoly acid or a salt thereof having a Keggin-type structure. Then, the slurry was spray-dried to obtain a catalyst precursor.
The catalyst precursor was molded and placed in a cylindrical quartz glass firing vessel having an inner diameter of 3 cm. The temperature was raised at 10 ℃ per hour under air circulation, and heat treatment was performed at 380 ℃ for 2 hours, thereby preparing a catalyst for methacrylic acid production. The obtained catalyst for methacrylic acid production has a Keggin-type structure. Further, the catalyst for methacrylic acid production obtained had an element composition of Mo other than oxygen 12 P 1.7 V 1.1 Cu 0.5 Cs 1.4 。
The reaction tube was filled with the above-mentioned catalyst for methacrylic acid production, and a raw material gas composed of methacrolein 5% by volume, oxygen 10% by volume, water vapor 30% by volume, and nitrogen 55% by volume was passed through the tube to carry out a reaction at a reaction temperature of 300 ℃. 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]
Catalyzing the catalyst raw material liquid AThe total volume of the agent raw material liquid B1 and the catalyst raw material liquid B2 was changed to 0.10m 3 And is changed to T =4, s =0.196m 2 ，V＝0.088m 3 ，S 3 /W 2 ＝0.97，
T/S =20.4, u1= 0.03L/min, to be in region Y 1 ～Y 4 The upper part of (2) is provided with 1 addition port respectively, and the radius of the addition ports with the diameter of 2mm is arranged at equal intervals
The annular pipe of (2). In addition, u2 at this time was 0.09 mol/min for the catalyst raw material liquid B1 and 0.21 mol/min for the catalyst raw material liquid B2. Except for these, a slurry was obtained in the same manner as in example 1. The obtained slurry contains a heteropoly acid or a salt thereof having a Keggin-type structure. Then, a catalyst for methacrylic acid production was prepared in the same manner as in example 1. The obtained catalyst for methacrylic acid production has a Keggin-type structure. Further, the catalyst for methacrylic acid production obtained had an element composition of Mo other than oxygen 12 P 1.7 V 1.1 Cu 0.5 Cs 1.4 . Methacrylic acid was produced in the same manner as in example 1, except that this methacrylic acid production catalyst was used. The results are shown in Table 1.
[ example 3]
Change to T =13,s =1.54m 2 ，V＝1.9m 3 ，S 3 /W 2 ＝1.01，
T/S =8.4, u1= 0.26L/min, and all the addition ports are arranged in the region Y 1 Radius from the center of the liquid level of the liquid in the container
The aboveUpper part of the region (a). In addition, u2 at this time was 0.80 mol/min for the catalyst raw material liquid B1 and 1.83 mol/min for the catalyst raw material liquid B2. Except for these, a slurry was obtained in the same manner as in example 1. The obtained slurry contains a heteropoly acid or a salt thereof having a Keggin-type structure. Then, a catalyst for methacrylic acid production was prepared in the same manner as in example 1. The obtained catalyst for methacrylic acid production has a Keggin-type structure. The obtained catalyst for methacrylic acid production had an elemental composition of Mo other than oxygen 12 P 1.7 V 1.1 Cu 0.5 Cs 1.4 . Methacrylic acid was produced in the same manner as in example 1, except that this methacrylic acid production catalyst was used. The results are shown in Table 1.
Comparative example 1
The total volume of the catalyst raw material liquid A, the catalyst raw material liquid B1 and the catalyst raw material liquid B2 was changed to 0.0014m 3 And to T =1, s =0.0177m 2 ，V＝0.0013m 3 ，S 3 /W 2 ＝3.28，
T/S =56.5, u1= 1.41L/min, starting from the center of the liquid surface of the liquid in the container
The addition port is disposed above the position of (1). Further, u2 in this case was 4.35 mol/min for the catalyst raw material liquid B1 and 9.90 mol/min for the catalyst raw material liquid B2. Except for these, a slurry was obtained in the same manner as in example 1. The obtained slurry contains a heteropoly acid or a salt thereof having a Keggin-type structure. Then, a catalyst for methacrylic acid production was prepared in the same manner as in example 1. The obtained catalyst for methacrylic acid production has a Keggin-type structure. Further, the catalyst for methacrylic acid production obtained had an element composition of Mo other than oxygen 12 P 1.7 V 1.1 Cu 0.5 Cs 1.4 . Methacrylic acid was produced in the same manner as in example 1, except that this methacrylic acid production catalyst was used. Will knotThe results are shown in Table 1.
Comparative example 2
The total volume of the catalyst raw material liquid A, the catalyst raw material liquid B1 and the catalyst raw material liquid B2 was changed to 0.00048m 3 And to T =1, s =0.00785m 2 ，V＝0.00043m 3 ，S 3 /W 2 ＝2.62，
T/S =127.4, u1= 0.07L/min, starting from the center of the liquid surface of the liquid in the container
An addition port is disposed above the position of (1). In addition, u2 at this time was 0.22 mol/min for the catalyst raw material liquid B1 and 0.49 mol/min for the catalyst raw material liquid B2. Except for these, a slurry was obtained in the same manner as in example 1. The obtained slurry contains a heteropoly acid or a salt thereof having a Keggin-type structure. Then, a catalyst for methacrylic acid production was prepared in the same manner as in example 1. The obtained catalyst for methacrylic acid production has a Keggin-type structure. Further, the catalyst for methacrylic acid production obtained had an element composition of Mo other than oxygen 12 P 1.7 V 1.1 Cu 0.5 Cs 1.4 . Methacrylic acid was produced in the same manner as in example 1, except that the catalyst for methacrylic acid production was used. The results are shown in Table 1.
Comparative example 3
100 parts of molybdenum trioxide, 7.5 parts of ammonium metavanadate and 11.4 parts of an 85 mass% phosphoric acid aqueous solution were dissolved in 400 parts of pure water. The temperature was raised to 95 ℃ while stirring the solution, and the solution was stirred for 2 hours while keeping the solution temperature at 95 ℃ to obtain a catalyst raw material solution a. The pH of the catalyst raw material liquid a was 6.9. On the other hand, 15.8 parts of cesium nitrate was dissolved in 20 parts of pure water to prepare a catalyst raw material liquid B1. Further, 40.0 parts of 30 mass% ammonia water was dissolved in 20 parts of pure water to prepare a catalyst raw material solution B2. Further, 7.0 parts of copper (II) nitrate 3 hydrate was dissolved in 40 parts of pure water to obtain a catalyst raw material liquid B3. The catalyst raw material liquid A and the procatalystThe total volume of the feed liquids B1 to B3 was 2.3m 3 。
The liquid temperature of the catalyst raw material liquid a in the vessel was cooled to 50 ℃ and maintained, and in this state, the catalyst raw material liquid B1 was added while stirring the catalyst raw material liquid a with a rotary blade stirrer and stirred for 15 minutes. Then, the catalyst raw material liquid B2 was added and stirred for 15 minutes. Further, the catalyst raw material liquid B3 was added. The catalyst raw materials B1 to B3 were added in the same manner as in example 3. In addition, u2 at this time was 0.80 mol/min for the catalyst raw material liquid B1, 2.87 mol/min for the catalyst raw material liquid B2, and 0.18 mol/min for the catalyst raw material liquid B3. The obtained slurry contains a heteropoly acid having a Dawson-type structure or a salt thereof.
Then, a catalyst for methacrylic acid production was prepared in the same manner as in example 1. The obtained catalyst for methacrylic acid production had a Dawson type structure. The obtained catalyst for methacrylic acid production had an elemental composition of Mo other than oxygen 12 P 1.7 V 1.1 Cu 0.5 Cs 1.4 . Methacrylic acid was produced in the same manner as in example 1, except that this methacrylic acid production catalyst was used. The results are shown in Table 1.
Comparative example 4
Catalyst raw material liquids a and B1 to B3 were prepared in the same manner as in comparative example 3. The liquid temperature of the catalyst raw material liquid a in the vessel was cooled to 50 ℃ and maintained, and in this state, the catalyst raw material liquid B1 was added and stirred for 15 minutes while the catalyst raw material liquid a was stirred by a rotary blade stirrer. Then, the catalyst raw material liquid B2 was added and stirred for 15 minutes. Further, the catalyst raw material liquid B3 was added. The catalyst raw materials B1 to B3 were added in the same manner as in example 1. In addition, u2 at this time was 0.62 mol/min for the catalyst raw material liquid B1, 2.21 mol/min for the catalyst raw material liquid B2, and 0.14 mol/min for the catalyst raw material liquid B3. The obtained slurry contains a heteropoly acid having a Dawson-type structure or a salt thereof.
Then, a catalyst for methacrylic acid production was prepared in the same manner as in example 1. The obtained catalyst for methacrylic acid production had a Dawson-type structure. In addition, the resultant nailThe catalyst for producing methacrylic acid has Mo as an element composition other than oxygen 12 P 1.7 V 1.1 Cu 0.5 Cs 1.4 . Methacrylic acid was produced in the same manner as in example 1, except that this methacrylic acid production catalyst was used. The results are shown in Table 1.
[ TABLE 1]
In the examples 1, 2 and 3,
the values of (3) and (u 1) and (u 2) are within the range of the present invention, and it was confirmed that the yield was high. In example 3, the addition port was disposed only above the region Y1, and the yield was slightly lower than in examples 1 and 2. In comparative example 1, u1 and u2 of the catalyst raw material liquid B2 are out of the range of the present invention, and in comparative example 2,
is outside the range of the present invention, and therefore, the yield is low as compared with the examples. In comparative examples 3 and 4, since the obtained slurries did not contain heteropolyacids having a Keggin-type structure or salts thereof, the yields were low as compared with the examples. Further, a methacrylate ester can be obtained by esterifying the methacrylic acid obtained in the present example.
This application claims priority based on japanese application 2016-161888, filed on 8/22/2016, the disclosure of which is incorporated herein in its entirety.
The present invention has been described above with reference to the embodiments and examples, but the present invention is not limited to the embodiments and examples. Various modifications that can be understood by those skilled in the art can be made to the structure and details of the invention of the present application within the scope of the invention of the present application.
Industrial applicability
The catalyst for methacrylic acid production obtained by the method of the present invention is industrially useful because methacrylic acid can be produced in a high yield.
Claims (15)
1. A method for producing a catalyst for methacrylic acid production, which is used for producing methacrylic acid by gas-phase catalytic oxidation of methacrolein with molecular oxygen, comprising the steps of:
(1) A step of preparing a catalyst raw material liquid A containing at least molybdenum, phosphorus and vanadium,
(2) A step of preparing a catalyst raw material liquid B containing a cation raw material,
(3) A step of adding and mixing another liquid to either one of the catalyst raw material liquid a and the catalyst raw material liquid B to prepare a liquid containing a heteropolyacid having a Keggin-type structure or a salt thereof;
in the step (3), the pH of the obtained liquid is 3.0 or less and satisfies the following formulas (i) and (ii),
0.01≤u1≤0.5 (ii)
in the formulae (i) and (ii), V represents the volume of the catalyst raw material liquid A and is expressed in m 3 T represents the number of addition ports of 2 or more for adding another liquid, u1 represents the volumetric flow rate of the other liquid added in L/min, and further, u1 represents the average value of the volumetric flow rates of the other liquids added from the respective addition ports,
the total volume of the catalyst raw material liquid A prepared in the step (1) and the catalyst raw material liquid B prepared in the step (2) is 0.2m 3 In the above-mentioned manner,
in the step (3), the other liquid is added to and mixed with a container containing either the catalyst raw material liquid A or the catalyst raw material liquid B and satisfying the following formula (iv),
0.1≤S 3 /W 2 ≤50 (iv)
in the formula (iv), S represents the surface area of the liquid surface of the liquid in the container and has a unit of m 2 W represents the volume of liquid in the container and is expressed in m 3 。
2. A method for producing a catalyst for methacrylic acid production, which is used for producing methacrylic acid by catalytically oxidizing methacrolein in a gas phase with molecular oxygen, comprising the steps of:
(1) A step of preparing a catalyst raw material liquid A containing at least molybdenum, phosphorus and vanadium,
(2) A step of preparing a catalyst material liquid B containing a cationic material,
(3) Adding and mixing the catalyst raw material liquid B to the catalyst raw material liquid a to prepare a liquid containing a heteropoly acid having a Keggin-type structure or a salt thereof;
in the step (3), the pH of the obtained liquid is 3.0 or less and the following formulas (i) and (iii) are satisfied,
0.01≤u2≤5 (iii)
in the formulae (i) and (iii), V represents the volume of the catalyst raw material liquid A and is expressed in the unit of m 3 Wherein T represents the number of addition ports of 2 or more for adding the catalyst raw material liquid B, u2 represents the flow rate of the cation raw material of the catalyst raw material liquid B in mol/min, and u2 represents the average value of the flow rates of the cation raw materials of the catalyst raw material liquid B added from the respective addition ports,
the total volume of the catalyst raw material liquid A prepared in the step (1) and the catalyst raw material liquid B prepared in the step (2) is 0.2m 3 In the above-mentioned manner,
in the step (3), the catalyst raw material liquid B is added and mixed in a vessel containing the catalyst raw material liquid A and satisfying the following formula (iv),
0.1≤S 3 /W 2 ≤50 (iv)
in the formula (iv), S represents the surface area of the liquid surface of the liquid in the container and has a unit of m 2 W represents the volume of liquid in the container and is expressed in m 3 。
3. The method for producing a catalyst for methacrylic acid production according to claim 1, wherein in the step (3), the addition port is disposed above a liquid level of the liquid in the container.
4. The method for producing a catalyst for methacrylic acid production according to claim 2, wherein in the step (3), the addition port is disposed above a liquid level of the liquid in the container.
5. The method of producing a catalyst for methacrylic acid production according to claim 1, wherein in the step (3), the catalyst raw material liquid B is added to and mixed with a container containing the catalyst raw material liquid A.
6. The method for producing a catalyst for methacrylic acid production according to claim 3 or 4, wherein in the step (3), the following formula (v) is satisfied,
2≤T/S≤100 (v)
in the formula (v), T has the same meaning as that of the formula (i), and S has the same meaning as that of the formula (iv).
7. The method for producing a catalyst for methacrylic acid production according to claim 3 or 4, wherein in the step (3), a T-shaped straight line is drawn from the center of the liquid surface of the liquid in the container to the wall surface of the container substantially in parallel with the liquid surface so that the central angle is 360 °/T, and Y represents each of the regions of the liquid surface divided by the T-shaped straight line 1 ～Y T At each Y 1 ～Y T Respectively, 1 of the addition ports are disposed in the upper part of the container.
8. The method for producing a catalyst for methacrylic acid production according to claim 3 or 4, wherein in the step (3), the addition port is not present in an upper portion of a circular region which is drawn by a radius R calculated from the following formula (vi) and has a unit of m around a center of a liquid surface of the liquid in the vessel,
in the formula (vi), S has the same meaning as that of the formula (iv).
9. The method for producing a catalyst for methacrylic acid production according to any one of claims 1 to 5, wherein the cation raw material is at least 1 selected from an alkali metal-containing compound and an ammonium ion-containing compound.
10. The method for producing a catalyst for methacrylic acid production according to any one of claims 1 to 5, further comprising: drying the liquid containing the heteropoly acid with the Keggin type structure or the salt thereof to obtain the catalyst precursor.
11. The method of producing a catalyst for use in production of methacrylic acid according to claim 10, further comprising a step of heat-treating the catalyst precursor.
12. The method for producing a catalyst for methacrylic acid production according to any one of claims 1 to 5, wherein the catalyst for methacrylic acid production has an elemental composition represented by the following formula (vii),
Mo a P b V c Cu d A e E f G g O h (vii)
in formula (vii), mo, P, V, cu, and O are symbol elements respectively representing molybdenum, phosphorus, vanadium, copper, and oxygen, 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, lead, niobium, indium, sulfur, palladium, gallium, cerium, and lanthanum, G represents at least 1 element selected from lithium, sodium, potassium, rubidium, cesium, and thallium, a, b, c, d, E, f, G, and h represent atomic ratios of the respective elements, and when a =12, b =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, h is an atomic ratio satisfying the valence of the respective elements.
13. A process for producing methacrylic acid, which comprises subjecting methacrolein to gas phase catalytic oxidation with molecular oxygen in the presence of the catalyst for producing methacrylic acid produced by the process according to any one of claims 1 to 5.
14. A process for producing methacrylic acid, wherein a catalyst for producing methacrylic acid is produced by the process according to any one of claims 1 to 5, and methacrolein is subjected to gas phase catalytic oxidation with molecular oxygen in the presence of the catalyst for producing methacrylic acid.
15. A method for producing a methacrylic acid ester, comprising esterifying methacrylic acid produced by the method for producing a methacrylic acid according to claim 13.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016161888 | 2016-08-22 | ||
| JP2016-161888 | 2016-08-22 | ||
| CN201780050136.5A CN109641202A (en) | 2016-08-22 | 2017-08-17 | The manufacturing method of the manufacturing method of methacrylic acid catalyst for producing, the manufacturing method of methacrylic acid and methacrylate |
| PCT/JP2017/029556 WO2018037998A1 (en) | 2016-08-22 | 2017-08-17 | Method for producing catalyst for methacrylic acid production, method for producing methacrylic acid and method for producing methacrylic acid ester |
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| CN201780050136.5A Division CN109641202A (en) | 2016-08-22 | 2017-08-17 | The manufacturing method of the manufacturing method of methacrylic acid catalyst for producing, the manufacturing method of methacrylic acid and methacrylate |
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| CN202210741113.1A Pending CN115155630A (en) | 2016-08-22 | 2017-08-17 | Method for producing catalyst for methacrylic acid production, method for producing methacrylic acid, and method for producing methacrylic acid ester |
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| KR20220098013A (en) | 2020-01-08 | 2022-07-08 | 미쯔비시 케미컬 주식회사 | A method for producing a catalyst for methacrylic acid production, a method for producing methacrylic acid and a method for producing a methacrylic acid ester, and an apparatus for producing a catalyst for producing methacrylic acid |
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| KR20190039262A (en) | 2019-04-10 |
| SG11201900018RA (en) | 2019-02-27 |
| SA519400951B1 (en) | 2024-01-23 |
| JP2019195807A (en) | 2019-11-14 |
| CN109641202A (en) | 2019-04-16 |
| MY190344A (en) | 2022-04-15 |
| WO2018037998A1 (en) | 2018-03-01 |
| KR102228713B1 (en) | 2021-03-16 |
| JP7003974B2 (en) | 2022-02-04 |
| JPWO2018037998A1 (en) | 2018-08-23 |
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