WO2020184616A1 - 触媒、触媒の製造方法、並びに不飽和カルボン酸及び/又は不飽和カルボン酸エステルの製造方法 - Google Patents
触媒、触媒の製造方法、並びに不飽和カルボン酸及び/又は不飽和カルボン酸エステルの製造方法 Download PDFInfo
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- WO2020184616A1 WO2020184616A1 PCT/JP2020/010570 JP2020010570W WO2020184616A1 WO 2020184616 A1 WO2020184616 A1 WO 2020184616A1 JP 2020010570 W JP2020010570 W JP 2020010570W WO 2020184616 A1 WO2020184616 A1 WO 2020184616A1
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- metal element
- catalyst
- carrier
- carboxylic acid
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- 239000003054 catalyst Substances 0.000 title claims abstract description 133
- 150000001732 carboxylic acid derivatives Chemical class 0.000 title claims description 31
- 238000004519 manufacturing process Methods 0.000 title claims description 28
- 150000001733 carboxylic acid esters Chemical class 0.000 title claims description 26
- 238000000034 method Methods 0.000 title description 46
- 229910052751 metal Inorganic materials 0.000 claims abstract description 84
- 239000002184 metal Substances 0.000 claims abstract description 80
- 239000002245 particle Substances 0.000 claims abstract description 61
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 53
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 40
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 28
- 125000005372 silanol group Chemical group 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052796 boron Inorganic materials 0.000 claims abstract description 10
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 9
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011777 magnesium Substances 0.000 claims abstract description 9
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims description 37
- 239000007787 solid Substances 0.000 claims description 31
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 30
- -1 alkali metal salt Chemical class 0.000 claims description 27
- 239000006185 dispersion Substances 0.000 claims description 24
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 23
- 229910052792 caesium Inorganic materials 0.000 claims description 22
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical group [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 96
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 54
- 239000000243 solution Substances 0.000 description 33
- 238000006243 chemical reaction Methods 0.000 description 32
- 239000000047 product Substances 0.000 description 29
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 28
- 239000011148 porous material Substances 0.000 description 23
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 18
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 17
- 229910000024 caesium carbonate Inorganic materials 0.000 description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 15
- 150000003755 zirconium compounds Chemical class 0.000 description 15
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 11
- 230000007423 decrease Effects 0.000 description 11
- 229940017219 methyl propionate Drugs 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 235000010724 Wisteria floribunda Nutrition 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 7
- 239000005977 Ethylene Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000011049 filling Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 230000006866 deterioration Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 238000005810 carbonylation reaction Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229910052701 rubidium Inorganic materials 0.000 description 3
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 229910008051 Si-OH Inorganic materials 0.000 description 2
- 229910006358 Si—OH Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000005882 aldol condensation reaction Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 2
- FLJPGEWQYJVDPF-UHFFFAOYSA-L caesium sulfate Chemical compound [Cs+].[Cs+].[O-]S([O-])(=O)=O FLJPGEWQYJVDPF-UHFFFAOYSA-L 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- MIUYJIDYPIERRC-UHFFFAOYSA-J Cl(=O)(=O)(=O)[O-].[Hf+4].Cl(=O)(=O)(=O)[O-].Cl(=O)(=O)(=O)[O-].Cl(=O)(=O)(=O)[O-] Chemical compound Cl(=O)(=O)(=O)[O-].[Hf+4].Cl(=O)(=O)(=O)[O-].Cl(=O)(=O)(=O)[O-].Cl(=O)(=O)(=O)[O-] MIUYJIDYPIERRC-UHFFFAOYSA-J 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- ZMCUDHNSHCRDBT-UHFFFAOYSA-M caesium bicarbonate Chemical compound [Cs+].OC([O-])=O ZMCUDHNSHCRDBT-UHFFFAOYSA-M 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- NXKAMHRHVYEHER-UHFFFAOYSA-J hafnium(4+);disulfate Chemical compound [Hf+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O NXKAMHRHVYEHER-UHFFFAOYSA-J 0.000 description 1
- ZFMIEZYJPABXSU-UHFFFAOYSA-J hafnium(4+);tetraacetate Chemical compound [Hf+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O ZFMIEZYJPABXSU-UHFFFAOYSA-J 0.000 description 1
- TZNXTUDMYCRCAP-UHFFFAOYSA-N hafnium(4+);tetranitrate Chemical compound [Hf+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O TZNXTUDMYCRCAP-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 235000007686 potassium Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 description 1
- 229910000026 rubidium carbonate Inorganic materials 0.000 description 1
- RTHYXYOJKHGZJT-UHFFFAOYSA-N rubidium nitrate Inorganic materials [Rb+].[O-][N+]([O-])=O RTHYXYOJKHGZJT-UHFFFAOYSA-N 0.000 description 1
- 229910000344 rubidium sulfate Inorganic materials 0.000 description 1
- GANPIEKBSASAOC-UHFFFAOYSA-L rubidium(1+);sulfate Chemical compound [Rb+].[Rb+].[O-]S([O-])(=O)=O GANPIEKBSASAOC-UHFFFAOYSA-L 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 235000015424 sodium Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- KHAUBYTYGDOYRU-IRXASZMISA-N trospectomycin Chemical compound CN[C@H]([C@H]1O2)[C@@H](O)[C@@H](NC)[C@H](O)[C@H]1O[C@H]1[C@]2(O)C(=O)C[C@@H](CCCC)O1 KHAUBYTYGDOYRU-IRXASZMISA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- MQGNWZLWQBTZJR-UHFFFAOYSA-J zirconium(4+) tetraperchlorate Chemical compound [Zr+4].[O-][Cl](=O)(=O)=O.[O-][Cl](=O)(=O)=O.[O-][Cl](=O)(=O)=O.[O-][Cl](=O)(=O)=O MQGNWZLWQBTZJR-UHFFFAOYSA-J 0.000 description 1
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical compound [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
- B01J23/04—Alkali metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
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- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
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- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C67/347—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to unsaturated carbon-to-carbon bonds
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of rare earths
Definitions
- the present invention relates to a catalyst, a method for producing a catalyst, and a method for producing an unsaturated carboxylic acid and / or an unsaturated carboxylic acid ester.
- Methyl methacrylate is used for various purposes. Many production methods for methyl methacrylate, such as the ACH method and the direct oxidation method using a C4 raw material, have been studied, but in recent years, a production method called the alpha method has attracted attention.
- the alpha method is a method for producing methyl propionate from ethylene as a raw material as a first-stage reaction, and then performing an aldol condensation reaction of the methyl propionate as a second-stage reaction to produce methyl methacrylate, particularly in the latter stage.
- Various catalysts have been investigated to improve the selectivity and yield of methyl methacrylate in the reaction.
- Patent Document 1 describes a compound of at least one modifier element selected from boron, magnesium, aluminum, zirconium and hafnium, which contains 1 to 10% by mass of an alkali metal as a catalyst for the subsequent reaction in the alpha method. It has been proposed to use a catalyst containing a specific amount of porous high surface silica.
- the present invention has been made in view of the above circumstances, and the present inventors have found that the above problems can be solved by using a specific catalyst, and have achieved the present invention.
- the gist of the present invention is as follows.
- a catalyst composed of a carrier having a silanol group on which at least one first metal element selected from boron, magnesium, zirconium and hafnium and an alkali metal element are supported.
- the average particle size of the compound of the first metal element is 0.4 nm or more and 50 nm or less.
- the molar ratio of the alkali metal element to the first metal element was X
- the BET specific surface area of the catalyst was Y (m 2 / g)
- the number of silanol groups per unit area of the catalyst (pieces / nm 2 ) was Z.
- a catalyst satisfying the following formula (1) a catalyst satisfying the following formula (1).
- the first solid content is impregnated with a solution or dispersion containing an alkali metal salt to obtain a second solid content.
- the average particle size of the inorganic salt of the first metal element is 0.4 nm or more and 50 nm or less.
- the molar ratio of the alkali metal element to the first metal element is X', the BET specific surface area of the carrier is Y'(m 2 / g), and the number of silanol groups per unit area of the carrier Z'(pieces / nm). 2 ), a method for producing a catalyst that satisfies the following formula (2).
- a catalyst capable of producing an unsaturated carboxylic acid and / or an unsaturated carboxylic acid ester with a high selectivity in a reaction between a carboxylic acid and / or a carboxylic acid ester and formaldehyde and a method for producing the catalyst.
- an unsaturated carboxylic acid and / or an unsaturated carboxylic acid ester is produced by an aldol condensation reaction between a carboxylic acid and / or a carboxylic acid ester and formaldehyde in the presence of a catalyst. The method of doing so will be described.
- the catalyst according to the present embodiment has a structure in which at least one first metal element selected from boron, magnesium, zirconium and hafnium and an alkali metal element are supported on a carrier having a silanol group.
- the average particle size of the compound containing the first metal element is 0.4 nm or more and 50 nm or less, the molar ratio of the alkali metal element to the first metal element is X, and the BET specific surface area (m 2 / g) of the catalyst. ) Is Y, and the number of silanol groups (pieces / nm 2 ) per unit area of the catalyst is Z, the following formula (1) is satisfied.
- the number of moles of the alkali metal element used in the above formula (1) means the number of moles of all the alkali metal elements contained in the catalyst. That is, when two or more kinds of alkali metal elements are used, it means the total number of moles of two or more kinds of alkali metal elements.
- the number of moles of the first metal element shall mean the total number of moles of two or more kinds of first metal elements when two or more kinds of first metal elements are used.
- the molar ratio of the alkali metal element to the first metal element, the number of silanol groups on the carrier surface, and the BET specific surface area can be calculated by the methods described in Examples described later. it can.
- the mechanism by which unsaturated carboxylic acid and / or unsaturated carboxylic acid ester can be produced with high selectivity in the reaction of carboxylic acid and / or carboxylic acid ester with formaldehyde is not clear.
- the first metal element and the alkali metal element are appropriately highly dispersed on the surface of the catalyst. Therefore, due to the high dispersion, the unsaturated carboxylic acid and / or the unsaturated It is considered that the selectivity of the carboxylic acid ester can be improved.
- the alkali metal element which is a catalyst component, is not particularly limited, but lithium, sodium, potassium, cesium or rubidium is preferable, and potassium, rubidium or cesium is more preferable, and cesium is particularly preferable. preferable.
- the alkali metal element may be one kind or two or more kinds.
- the first metal element is selected from boron, magnesium, zirconium and hafnium, and among them, boron or zirconium is preferable, and zirconium is particularly preferable.
- these metal elements may be one kind or two or more kinds.
- the value of X / (Y ⁇ Z) is more preferably 1.0 ⁇ 10-21 (g / piece) or more in order to improve the yield of the target product. It is particularly preferably .5 ⁇ 10-21 (g / piece) or more, while it is further preferably 10.7 ⁇ 10-21 (g / piece) or less in order to suppress a decrease in the yield of the target product. It is preferably 10.5 ⁇ 10 -21 (g / piece) or less, and is particularly preferable.
- the average particle size of the compound containing the first metal element constituting the catalyst is preferably 0.5 nm or more, particularly preferably 0.8 nm or more, and on the other hand, 30 nm or less. It is more preferably 20 nm or less, further preferably 10 nm or less, further preferably 8 nm or less, further preferably 6 nm or less, further preferably 5 nm or less, and further preferably 4 nm or less. Is particularly preferable, and 3 nm or less is particularly preferable.
- the molar ratio X of the alkali metal element to the first metal element is preferably 1.3 or more in order to improve the yield of the target product. It is more preferably .5 or more, further preferably 1.7 or more, particularly preferably 1.9 or more, while it is 6.0 or less in order to suppress a decrease in the yield of the target product. It is preferably present, more preferably 5.5 or less, and particularly preferably 5.0 or less.
- the amount of alkali metal element with respect to the total mass of the catalyst component and the carrier is not particularly limited as long as the above formula (1) is satisfied, but is preferably 4% by mass or more in order to improve the yield of the target product. It is more preferably 7% by mass or more, particularly preferably 9% by mass or more, and on the other hand, it is preferably 25% by mass or less, and 18% by mass or less in order to suppress a decrease in the yield of the target product. It is more preferably present, and particularly preferably 14% by mass or less.
- the amount of the first metal element with respect to the total mass of the catalyst component and the carrier is not particularly limited as long as the above formula (1) is satisfied, but is 0.3% by mass or more in order to improve the yield of the target product. It is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, and on the other hand, it is 10% by mass or less in order to suppress a decrease in the yield of the target product. Is more preferable, and it is more preferably 6% by mass or less, further preferably 5% by mass or less, and particularly preferably 4% by mass or less.
- the catalyst component supported on the carrier may contain a metal element other than the above.
- a metal element for example, aluminum, titanium, iron and the like can be mentioned.
- the ratio of the element to the total mass of the catalyst component supported on the carrier is preferably 1.0% by mass or less, preferably 0.5% by mass or less, in order to suppress a decrease in the yield of the target product. Is more preferable, and 0.2% by mass or less is particularly preferable.
- the catalyst component supported on the carrier may be composed of other elements in addition to the above metal elements.
- it may be composed of an element derived from the production of the catalyst component.
- the carrier can carry a catalyst component and is not particularly limited as long as it has a silanol group on the surface, but specifically, it is preferably a porous inorganic compound carrier containing silicon oxide. ..
- the material constituting the carrier is not particularly limited, but preferably, silica, silica alumina, zeolite, titania containing silica, or zirconia containing silica can be mentioned. Of these, silica is preferred.
- a commercially available product can be used as the carrier. For example, trade name: CARiACT (manufactured by Fuji Silysia Chemical Ltd.) and the like can be mentioned.
- the number Z of silanol groups per unit area of the catalyst is not particularly limited as long as the above formula (1) is satisfied, but it should be 0.5 elements / nm 2 or more in order to improve the yield of the target product. It is more preferably 0.8 pieces / nm 2 or more, further preferably 2.5 pieces / nm 2 or more, particularly preferably 4 pieces / nm 2 or more, while the target product. In order to suppress the decrease in yield, the number is preferably 20 pieces / nm 2 or less, more preferably 17 pieces / nm 2 or less, further preferably 15 pieces / nm 2 or less, and 13 pieces / nm. It is particularly preferably nm 2 or less.
- the BET specific surface area Y of the catalyst is not particularly limited as long as the above formula (1) is satisfied, but is preferably 50 m 2 / g or more, preferably 70 m 2 / g or more, in order to improve the yield of the target product. It is more preferably 90 m 2 / g or more, particularly preferably 100 m 2 / g or more, while it is preferably 600 m 2 / g or less, and 500 m 2 / g or less. It is more preferably present, and particularly preferably 350 m 2 / g or less.
- the shape of the carrier is not particularly limited, and examples thereof include powder, granular, pellet, and tablet.
- the average particle size of the carrier is not particularly limited, but is preferably 500 ⁇ m or more, more preferably 1 mm or more, and more preferably 1.5 mm in order to suppress pressure loss and by-products during the reaction.
- the above is particularly preferable, while the amount is preferably 10 mm or less, more preferably 6 mm or less, and particularly preferably 5 mm or less in order to suppress by-products.
- the average pore size of the carrier is not particularly limited, but is preferably 3 nm or more, more preferably 5 nm or more, and particularly preferably 10 nm or more in order to suppress by-products. In order to secure the specific surface area, it is preferably 200 nm or less, more preferably 150 nm or less, and particularly preferably 100 nm or less.
- the shape of the catalyst is not particularly limited, and examples thereof include a spherical shape, a columnar shape, and a ring shape.
- the average volume of the catalyst is not particularly limited, but is preferably 0.06 mm 3 or more and 550 mm 3 or less.
- the method for producing the catalyst is not particularly limited, and the catalyst can be produced by supporting a metal element on the carrier. However, from the viewpoint of preventing deterioration of the catalyst, there is a step of impregnating the carrier with at least an average particle size of the inorganic salt of the first metal element in the solution or dispersion of 0.4 nm or more and 50 nm or less.
- the catalyst is preferably produced.
- an example in which the catalyst is produced by the following first to fourth steps will be shown.
- First step A step of dissolving or dispersing an inorganic salt of a first metal element in a first solvent to obtain a solution or a dispersion.
- Second step A step of impregnating a carrier with the solution or dispersion obtained in the first step to obtain a first solid content.
- Third step A step of dissolving or dispersing an alkali metal salt in a second solvent to obtain a solution or a dispersion.
- Fourth step A step of mixing the first solid content obtained in the second step with the solution or dispersion obtained in the third step to obtain a second solid content.
- Examples of the first metal element constituting the inorganic salt of the first metal element include the above-mentioned first metal element.
- the inorganic salt of the first metal element is an inorganic compound containing no hydrocarbon and is not particularly limited.
- the halides can be used alone or in combination.
- the first metal element is zirconium, zirconium oxynitrate, zirconium sulfate, zirconium carbonate, zirconium perchlorate, zirconium acetate and the like can be mentioned.
- the first metal element is boron, boron oxide and the like can be mentioned.
- the first metal element is magnesium
- examples thereof include magnesium nitrate, magnesium sulfate, magnesium carbonate and magnesium acetate.
- examples thereof include hafnium nitrate, hafnium sulfate, hafnium perchlorate, and hafnium acetate.
- the first solvent is not particularly limited, and examples thereof include water and organic solvents. Of these, alcohol is more preferable as the organic solvent in order to improve the dispersibility of the inorganic salt of the first metal element. As the alcohol, an alcohol having 1 to 6 carbon atoms is preferable, and methanol is particularly preferable.
- the amount of the inorganic salt of the first metal element with respect to 100 ml of the solvent is not particularly limited, but is preferably 2 mmol or more, more preferably 5 mmol or more in order to support the desired first metal element. It is particularly preferably 10 mmol or more, while it is preferably 60 mmol or less, more preferably 50 mmol or less, and particularly preferably 40 mmol or less in order to suppress the amount of support.
- the first solvent may be stirred.
- the obtained solution or dispersion is allowed to stand.
- the standing time is not particularly limited, but if the standing time is long, the average particle size of the inorganic salt of the first metal element in the solution or dispersion tends to be small.
- the carrier is impregnated with the solution or the dispersion liquid in the second step, it is preferable to have a specific average particle size, so that the desired particle size is set. It is preferable to leave it to stand until it is obtained.
- the standing time is preferably 30 minutes or more, more preferably 2 hours or more, further preferably 4 hours or more, and particularly preferably 16 hours or more. On the other hand, it is preferably 100 hours or less, more preferably 80 hours or less, and particularly preferably 50 hours or less.
- the above-mentioned carrier can be used.
- the method of impregnating the carrier with the first solvent is not particularly limited and can be used by a known method.
- a pore filling method using a first solvent that fills the pore volume of the carrier there is a pore filling method using a first solvent that fills the pore volume of the carrier, a dipping method in which the carrier is immersed in the first solvent, and the like.
- the amount of the carrier with respect to the first solvent is not particularly limited, but the ratio of the first solvent to the carrier is 0.9 times the pore volume of the carrier in order to uniformly support the first metal element.
- the above is preferable, while the pore volume of the carrier is preferably 10 times or less, and particularly preferably 5 times or less in order to reduce the amount of the solvent used.
- the average particle size of the inorganic salt of the first metal element is 50 nm as described above in order to obtain good catalytic properties. It is preferably less than or equal to, more preferably 30 nm or less, further preferably 20 nm or less, further preferably 10 nm or less, further preferably 5 nm or less, further preferably 3 nm or less, and particularly preferably 2 nm or less. preferable.
- the average particle size of the inorganic salt of the first metal element is preferably 0.4 nm or more, more preferably 0.5 nm or more, and more preferably 0.8 nm or more. Especially preferable.
- the average particle size of the inorganic salt is a value obtained by measuring a 0.1 mol / l inorganic salt solution using a laser beam having a wavelength of 633 nm by a dynamic light scattering method and calculating the volume distribution.
- the impregnation time of the carrier is not particularly limited, but it is preferably 15 minutes or more and 50 hours or less in order to support the first metal element.
- the first solvent When obtaining the first solid content, it is preferable to remove the first solvent.
- the removal of the first solvent can be carried out by a known method.
- a rotary evaporator can be used to remove the first solvent.
- the first solvent can be removed by separating the solid substance and the first solvent by filtration.
- the obtained first solid content is preferably dried or fired, but it is not always necessary.
- the first solvent remaining in the first solid content can be removed by drying or firing.
- These heating temperatures are preferably 50 ° C. or higher, more preferably 70 ° C. or higher, further preferably 120 ° C. or higher, particularly preferably 400 ° C. or higher, while preferably 800 ° C. or lower, more preferably 700 ° C. or lower, and 600 ° C. or lower. Is particularly preferable.
- the heating time is not particularly limited, but among the above, when the heating temperature is 400 ° C. or higher and 800 ° C. or lower, it is preferably 15 minutes or longer, more preferably 30 minutes or longer, and 1 hour or longer. On the other hand, it is preferably 100 hours or less, and particularly preferably 50 hours or less.
- the first metal element exists in the state of a compound, but the average particle size of the compound composed of the first metal element is 50 nm or less in order to obtain good catalytic properties. It is more preferably 30 nm or less, further preferably 20 nm or less, further preferably 10 nm or less, further preferably 8 nm or less, further preferably 6 nm or less, and further preferably 5 nm. It is more preferably less than or equal to, further preferably 4 nm or less, and particularly preferably 3 nm or less.
- the average particle size of the compound composed of the first metal element is more preferably 0.4 nm or more, further preferably 0.5 nm or more, and further preferably 0.8 nm or more. Is particularly preferable.
- the average particle size of the compound composed of the first metal element can be calculated from an image obtained by observing flakes with a solid content of 300 nm or less using a transmission electron microscope.
- the specific composition of the compound composed of the first metal element is not clear, the inorganic salt of the first metal element, the oxide of the first metal element, and the composite of the carrier and the first metal element Oxides and the like can be considered.
- the first metal element has high dispersibility on the carrier. It is thought that it is to have.
- the molar ratio of the alkali metal element to the first metal element is set to X', and in the second step, the solution obtained by the first step or
- the BET specific surface area of the carrier when impregnating the dispersion with the carrier is Y'(m 2 / g) and the number of silanol groups per unit area of the carrier is Z'(pieces / nm 2 )
- the following formula is used. It is preferable to satisfy (2).
- the molar ratio of the alkali metal element to the first metal element used in the catalyst production is usually X', which is the same value as X in the above formula (1).
- the value of X'/ (Y'xZ') may be 2.0 x 10-21 (g / piece) or more in order to improve the yield of the target product. More preferably, it is 2.3 ⁇ 10-21 (g / piece) or more, while it is 15.0 ⁇ 10-21 (g / piece) or less in order to suppress a decrease in the yield of the target product. It is more preferable that the amount is 10.0 ⁇ 10-21 (g / piece) or less.
- the BET specific surface area Y'(m 2 / g) of the carrier of the carrier when the carrier is impregnated with the solution or dispersion containing the first metal element is not particularly limited as long as the above formula (1) is satisfied. but because of the improved yield of the desired product, it is preferably 50 m 2 / g or more, more preferably 60 m 2 / g or more, more preferably 70m 2 / g or more, 90m 2 / It is more preferably g or more, particularly preferably 100 m 2 / g or more, while it is preferably 600 m 2 / g or less, further preferably 500 m 2 / g or less, and 350 m 2 / g. It is more preferably 300 m 2 / g or less, and particularly preferably 300 m 2 / g or less.
- the number Z'(pieces / nm 2 ) of silanol groups per unit area of the carrier surface of the carrier when the carrier is impregnated with the solution or dispersion containing the first metal element is as long as the above formula (2) is satisfied.
- it is preferably 0.5 pieces / nm 2 or more, more preferably 0.8 pieces / nm 2 or more, and 2.5 pieces / nm.
- nm 2 is preferably pieces / nm 2 or more, particularly preferably 4 or / nm 2 or more, whereas, for a yield of suppressing reduction of the target compound, is preferably 15 / nm 2 or less, 13 further preferably pieces / nm 2 or less, and particularly preferably 11 / nm 2 or less.
- Examples of the alkali metal element include the above-mentioned alkali metal elements.
- alkali metal salt and carbonates, nitrates, sulfates, acetates, ammonium salts, oxides, halides, etc., which are alkali metal elements, can be used alone or in combination.
- alkali metal element cesium, cesium carbonate, cesium bicarbonate, cesium nitrate, cesium sulfate and the like can be mentioned.
- the alkali metal element is lithium, examples thereof include lithium carbonate and lithium nitrate.
- the alkali metal element is sodium, sodium carbonate, sodium nitrate, sodium sulfate and the like can be mentioned.
- the alkali metal element is potassium, potassium carbonate, potassium nitrate, potassium sulfate and the like can be mentioned.
- the alkali metal element is rubidium, examples thereof include rubidium carbonate, rubidium nitrate, and rubidium sulfate.
- the second solvent is not particularly limited, and examples thereof include water and organic solvents. Of these, alcohol is preferable as the organic solvent in order to improve the dispersibility of the alkali metal salt. As the alcohol, an alcohol having 1 to 6 carbon atoms is preferable, and methanol is particularly preferable.
- the amount of the alkali metal salt with respect to 100 ml of the solvent is not particularly limited, but is preferably 6 mmol or more, more preferably 14 mmol or more, and particularly preferably 25 mmol or more in order to improve the yield of the target product. On the other hand, 60 mmol or less is preferable, 50 mmol or less is more preferable, and 40 mmol or less is particularly preferable, in order to suppress a decrease in the yield of the target product.
- the second solvent when dissolving or dispersing the alkali metal salt in the second solvent, the second solvent may be agitated. Moreover, it is preferable that the obtained solution or dispersion is allowed to stand.
- the standing time is not particularly limited, but if the standing time is long, the average particle size of the alkali metal salt in the solution or dispersion tends to be small. Specifically, the standing time is preferably 15 minutes or more, and preferably 50 hours or less.
- the third step may be performed before the second step or after the second step.
- the mixing method of the first solid content obtained in the second step and the solution or dispersion obtained in the third step is not particularly limited, but the first solid content obtained in the second step is not particularly limited. Is preferably impregnated in the solution or dispersion obtained in the third step.
- the method of impregnating the carrier with the second solvent is not particularly limited and can be used by a known method.
- a pore filling method using a second solvent that fills the pore volume of the carrier there is a pore filling method using a second solvent that fills the pore volume of the carrier, a dipping method in which the carrier is immersed in the second solvent, and the like.
- the amount of the first solid content with respect to the solution or dispersion is not particularly limited, but the ratio of the solution or dispersion to the first solid content is the pore volume of the carrier in order to uniformly support the alkali metal. It is preferably 0.9 times or more, and on the other hand, in order to reduce the amount of the solvent used, it is preferably 10 times or less, and particularly preferably 5 times or less, the pore volume of the carrier.
- the impregnation time is not particularly limited, but is preferably 15 minutes or more for supporting the alkali metal, more preferably 1 hour or more, while 50 hours for improving the productivity of the catalyst. It is preferably less than or equal to, and more preferably 30 hours or less.
- the second solvent When obtaining the second solid content, it is preferable to remove the second solvent.
- the removal of the second solvent can be performed by a known method. For example, a rotary evaporator can be used to remove the second solvent. Further, for example, the second solvent can be removed by filtration.
- the obtained second solid content is preferably dried or calcined.
- the second solvent remaining in the second solid content can be removed by drying or firing.
- These heating temperatures are preferably 50 ° C. or higher, more preferably 70 ° C. or higher, further preferably 120 ° C. or higher, particularly preferably 400 ° C. or higher, while preferably 800 ° C. or lower, more preferably 700 ° C. or lower, and 600 ° C. or lower. Is particularly preferable.
- the heating temperature is 400 ° C. or higher and 800 ° C. or lower, it is preferably 15 minutes or longer, more preferably 30 minutes or longer, particularly preferably 1 hour or longer, while 100. It is preferably less than an hour, and particularly preferably less than 50 hours.
- the second solid content thus produced can be used as a catalyst.
- Carriers generally tend to be highly hygroscopic. Therefore, it is preferable that the carrier is fired to remove water before supporting the catalyst component.
- the pre-baked carrier is preferably stored in an environment from which water has been removed. That is, the carrier is preferably stored in a desiccator, dry air, or a dry inert gas, but these techniques need not necessarily be used.
- the molar ratio of the alkali metal element and the first metal element supported on the carrier may be adjusted by adjusting the charging amount.
- the method of adjusting the number of silanol groups per unit area of the carrier surface There are no particular restrictions on the method of adjusting the number of silanol groups per unit area of the carrier surface. For example, if the silicon oxide content in the carrier is increased, the number of silanol groups on the surface of the carrier tends to increase, and if the silicon oxide content in the carrier is decreased, the number of silanol groups on the surface of the carrier tends to decrease.
- the method for adjusting the BET specific surface area of the carrier is not particularly limited, but the BET specific surface area of the carrier tends to increase as the pore ratio of the carrier increases, and the carrier tends to increase as the pore ratio of the carrier decreases. BET specific surface area tends to be small. Therefore, a carrier having pores so as to obtain a desired BET specific surface area may be used.
- the molar ratio of the alkali metal element to the first metal element, the number of silanol groups per unit area of the carrier surface, and the BET of the carrier may be adjusted.
- Unsaturated carboxylic acid and / or unsaturated carboxylic acid ester can be produced by reacting carboxylic acid and / or carboxylic acid ester with formaldehyde in the presence of the catalyst produced according to this embodiment. That is, unsaturated carboxylic acid and / or unsaturated carboxylic acid ester corresponding to these carboxylic acid and / or carboxylic acid ester can be produced from carboxylic acid and / or carboxylic acid ester as a raw material.
- the unsaturated carboxylic acid and / or unsaturated carboxylic acid ester is preferably represented by the following formula.
- R 1 and R 2 each independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.
- the catalyst according to the present embodiment is particularly effective in a method for producing methacrylic acid and / methyl methacrylate by the reaction of methyl propionate with formaldehyde.
- the molar ratio of carboxylic acid and / or carboxylic acid ester to the total number of moles of carboxylic acid and carboxylic acid ester used in the reaction with formaldehyde is not particularly limited, but in order to improve the yield of the target product. , 0.05 or more and 20 or less is preferable, and more preferably 0.2 or more and 15 or less.
- reaction is preferably carried out in the presence of alcohol in order to suppress the hydrolysis of the ester.
- the molar ratio of alcohol to the total number of moles of carboxylic acid and / or carboxylic acid ester is not particularly limited, but is preferably in the range of 0.05 or more and 20 or less, preferably 0.1. The range of 10 or more is more preferable.
- a compound other than the above may be contained as long as the effect of the present invention is not significantly impaired.
- it may contain water.
- the reaction temperature in the above reaction is not particularly limited, but is preferably 100 ° C. or higher, more preferably 200 ° C. or higher, and more preferably 250 ° C. or higher in order to improve the yield of the target product.
- the temperature is preferably 400 ° C. or lower, more preferably 370 ° C. or lower, and particularly preferably 360 ° C. or lower.
- the contact time in the above reaction is not particularly limited, but is preferably 0.1 second or more, more preferably 1 second or more, and 2 seconds or more in order to improve the yield of the target product. On the other hand, in order to suppress by-products, it is preferably 100 seconds or less, more preferably 50 seconds or less, and particularly preferably 30 seconds or less.
- the method for producing the carboxylic acid and / or the alkanoic acid ester which is the raw material for the above reaction is not particularly limited, and can be produced by a known method.
- methyl propionate it is preferably produced by a carbonylation reaction of ethylene.
- the reaction by carbonylation of ethylene will be described.
- the reaction is a method for producing methyl propionate by reacting ethylene with carbon monoxide in the presence of a catalyst.
- the amount of ethylene with respect to carbon monoxide is not particularly limited, but is preferably 0.01 mol% or more, more preferably 0.1 mol% or more, and on the other hand, 100 mol% or less. It is preferably 10 mol% or less, and more preferably 10 mol% or less.
- the reaction temperature is not particularly limited, but is preferably 20 ° C. or higher, more preferably 40 ° C. or higher, particularly preferably 70 ° C. or higher, and preferably 250 ° C. or lower. It is more preferably 150 ° C. or lower, and particularly preferably 120 ° C. or lower.
- the reaction time is not particularly limited, but is preferably 0.1 hour or more and 100 hours or less.
- the catalyst is not particularly limited as long as it is a catalyst capable of the carbonylation reaction of ethylene, and a known catalyst can be used.
- a palladium catalyst having a phosphine-based ligand and the like can be mentioned.
- Specific examples of such a catalyst include the catalysts described in JP-A No. 10-511304.
- such a catalyst can be produced by a known method.
- reaction is preferably carried out in the presence of alcohol.
- the alcohol is not particularly limited, and examples thereof include methanol, ethanol, propanol, 2-propanol, 2-butanol or t-butyl alcohol, and among them, methanol or ethanol is preferable.
- the alcohol one type may be used alone, or two or more types of alcohol may be used in combination.
- the amount of ethylene with respect to alcohol is not particularly limited, but is preferably 0.01 mol% or more, more preferably 0.1 mol% or more, and preferably 100 mol% or less. It is more preferably 10 mol% or less.
- Carbon monoxide may be supplied in combination with an inert gas in the reaction.
- an inert gas include hydrogen, nitrogen, carbon dioxide, argon and the like.
- Methyl methacrylate can be produced by the method described above, but the produced methyl methacrylate usually contains impurities. Therefore, in order to remove impurities, it is preferable to purify the obtained methyl methacrylate by a known method such as distillation. The conditions for purification may be appropriately adjusted so that methyl methacrylate having a desired purity can be obtained.
- the BET specific surface area of the carrier and the catalyst is a value calculated by the BET 1-point method using a nitrogen adsorption measuring device (manufactured by Mountech, trade name: Macsorb), and the number of silanol groups in the unit area of the carrier and the catalyst.
- D (Si-OH)) uses a thermal weight differential thermal analyzer (manufactured by Rigaku Co., Ltd., model number: TG8120) to reduce the weight from 180 ° C. to 950 ° C. under the condition of a heating rate of 10 ° C./min under air flow. It was calculated from the value of the following formula (3).
- N A Avogadro constant (6.02 ⁇ 10 23 (mol -1 ) ⁇ wt: Weight loss rate (%) from 180 ° C to 950 ° C SA: BET specific surface area (m 2 / g).
- the molar ratio of the alkali metal element to the first metal element was calculated from the contents of the first metal element and the alkali metal element measured by fluorescent X-ray analysis.
- a deterioration test of the catalyst was performed. Specifically, nitrogen was passed through a water saturated device heated to 92 ° C. at a flow rate of 20 ml / min, and further passed through a tube heated to 385 ° C. filled with 1 g of catalyst, and 7 days after the test. The BET specific surface area of the catalyst was measured after 28 days, and the BET specific surface area reduction rate of the carrier was calculated by the following formula (4).
- the examples and comparative examples in which the results of the catalyst deterioration test in Table 1 are described are the targets for which the catalyst deterioration test was performed.
- Example 1 4.5 g of zirconium oxynitrate dihydrate (Kishida chemistry, special grade) was dissolved in 135 ml of methanol (Nacalai Tesque, special grade) and allowed to stand for 24 hours. 60 g of CARiACT Q-10 (trade name, Fuji Silysia Chemical Ltd., particle size 1.7-4 mm, average pore diameter 10 nm) used as a carrier is immersed in this solution, allowed to stand for 3.5 hours, and rotary. The solvent was distilled off using an evaporator. The average particle size of zirconium oxynitrate in methanol when the carrier was immersed was 0.8 nm.
- 30 g was immersed in a solution of 4.8 g of cesium carbonate (Wako Pure Chemical Substances, 1st grade) in 65 ml of methanol for 3.5 hours, and filtered to obtain the second solid content.
- the solution was separated.
- a catalyst was obtained by drying the second solid content at 120 ° C. for 14 hours.
- the particle size of the zirconium compound of the catalyst was 0.8 nm to 5 nm.
- the reactor was filled with about 3 g of the obtained catalyst. Then, under normal pressure, the reaction solution having a molar ratio of methyl propionate, methanol, formaldehyde and water of 1: 1.40: 0.19: 0.5 was evaporated at 300 ° C. at a flow rate of 0.034 ml / min. It was circulated in a vessel and circulated in a reactor at 330 ° C. for 16 hours. Then, under normal pressure, a reaction raw material solution having a molar ratio of methyl propionate, methanol, formaldehyde, and water of 1: 0.64: 0.27: 0.01 was passed through an evaporator at 300 ° C. to 330 ° C. It was supplied to the reactor.
- the reaction raw material liquid was recovered by changing the flow rate of the liquid feed at 5 points between 0.034 and 0.35 ml / min, and cooling and condensing the vapor at the outlet of the reactor at each liquid feed flow rate.
- the obtained reaction solution was analyzed by gas chromatography (Shimadzu Corporation, trade name: GC-2010) to determine the yield and selectivity of methacrylic acid and methyl methacrylate at a flow rate of 0.16 ml / min. , Calculated by the following formulas (5) and (6), respectively. The results obtained are shown in Table 1.
- Examples 2 to 7> By the same method as in Example 1 except that a catalyst produced by adjusting the amounts of zirconium oxynitrate dihydrate and cesium carbonate so that the amounts of zirconium and cesium after support are as shown in Table 1 was used. Methacrylic acid and methyl methacrylate were produced, and the selectivity and yield of methacrylic acid and methyl methacrylate were calculated. The average particle size of zirconium oxynitrate in methanol when the carrier was immersed was 0.8 nm. The particle size of the zirconium compound after the catalyst was produced was 0.8 nm to 5 nm. The results obtained are shown in Table 1.
- Example 8 Example 1 except that the amount of cesium carbonate used was changed to 4.6 g and a catalyst produced by distilling off the solvent using a rotary evaporator was used instead of separating the second solid content and the liquid by filtration. Methacrylic acid and methyl methacrylate were produced by the same method as in the above, and the selectivity and yield of methacrylic acid and methyl methacrylate were calculated.
- the average particle size of zirconium oxynitrate in methanol when the carrier was immersed was 0.8 nm.
- the particle size of the zirconium compound after the catalyst was produced was 0.8 nm to 5 nm. The results obtained are shown in Table 1.
- Examples 9 to 15> By the same method as in Example 8 except that a catalyst produced by adjusting the amounts of zirconium oxynitrate dihydrate and cesium carbonate so that the amounts of zirconium and cesium after support are as shown in Table 1 was used. Methacrylic acid and methyl methacrylate were produced, and the selectivity and yield of methacrylic acid and methyl methacrylate were calculated. The average particle size of zirconium oxynitrate in methanol when the carrier was immersed was 0.8 nm. The particle size of the zirconium compound after the catalyst was produced was 0.8 nm to 5 nm. The results obtained are shown in Table 1.
- Example 16 7.3 g of zirconium oxynitrate dihydrate (Kishida Chemistry, special grade) was dissolved in 57 ml of methanol (Nacalai Tesque, special grade) and allowed to stand for 24 hours. This solution was impregnated with 60 g of CARiACT Q-10 (trade name, Fuji Silysia Chemical Ltd., particle size 1.7-4 mm, average pore diameter 10 nm) by a pore filling method. The average particle size of zirconium oxynitrate in methanol when the carrier was impregnated was 0.8 nm. Then, it dried at 120 degreeC for 14 hours, and the first solid content was obtained.
- CARiACT Q-10 trade name, Fuji Silysia Chemical Ltd., particle size 1.7-4 mm, average pore diameter 10 nm
- Examples 17 to 21 CARiACT Q15 (trade name, Fuji Silicia Chemical Co., Ltd., particle size 1.7 mm-4 mm, average pore diameter 15 nm) was used instead of CARiACT Q-10 as the carrier, and the amounts of zirconium and cesium after support are shown in the table.
- Methyl methacrylate and methyl methacrylate were produced by the same method as in Example 1 except that a catalyst produced by adjusting the amounts of zirconium oxynitrate dihydrate and cesium carbonate so as to have the values shown in 1 was used. The selectivity and yield of methacrylic acid and methyl methacrylate were calculated.
- the average particle size of zirconium oxynitrate in methanol when the carrier was immersed was 0.8 nm.
- the particle size of the zirconium compound after the catalyst was produced was 0.8 nm to 5 nm. The results obtained are shown in Table 1.
- Methyl methacrylate and methyl methacrylate were produced by the same method as in Example 1 except that a catalyst produced by adjusting the amounts of zirconium oxynitrate dihydrate and cesium carbonate so as to have values was used. And the selectivity and yield of methyl methacrylate were calculated.
- the average particle size of zirconium oxynitrate in methanol when the carrier was immersed was 0.8 nm.
- the average particle size of the zirconium compound after the catalyst was produced was 0.8 nm to 5 nm. The results obtained are shown in Table 1.
- Examples 28 to 32> CARiACT Q30 (trade name, Fuji Silicia Chemical Co., Ltd., particle size 1.7-4 mm, average pore diameter 30 nm) was used instead of CARiACT Q-10 as a carrier, and the amounts of zirconium and cesium after support are shown in Table 1.
- Methyl methacrylate and methyl methacrylate were produced by the same method as in Example 1 except that a catalyst produced by adjusting the amounts of zirconium oxynitrate dihydrate and cesium carbonate so as to have values was used. And the selectivity and yield of methyl methacrylate were calculated.
- the average particle size of zirconium oxynitrate in methanol when the carrier was immersed was 0.8 nm.
- the particle size of the zirconium compound after the catalyst was produced was 0.8 nm to 5 nm. The results obtained are shown in Table 1.
- Examples 33 to 39> CARiACT Q30C (trade name, Fuji Silicia Chemical Co., Ltd., particle size 1.7-4 mm, average pore diameter 30 nm) was used instead of CARiACT Q-10 as a carrier, and the amounts of zirconium and cesium after support are shown in Table 1.
- Methyl methacrylate and methyl methacrylate were produced by the same method as in Example 1 except that a catalyst produced by adjusting the amounts of zirconium oxynitrate dihydrate and cesium carbonate so as to have values was used. And the selectivity and yield of methyl methacrylate were calculated.
- the average particle size of zirconium oxynitrate in methanol when the carrier was immersed was 0.8 nm.
- the particle size of the zirconium compound after the catalyst was produced was 0.8 nm to 5 nm. The results obtained are shown in Table 1.
- ⁇ Comparative example 1> By the same method as in Example 1 except that a catalyst produced by adjusting the amounts of zirconium oxynitrate dihydrate and cesium carbonate so that the amounts of zirconium and cesium after support are as shown in Table 1 was used. Methacrylic acid and methyl methacrylate were produced, and the selectivity and yield of methacrylic acid and methyl methacrylate were calculated. The average particle size of zirconium oxynitrate in methanol when the carrier was immersed was 0.8 nm. The particle size of the zirconium compound after the catalyst was produced was 0.8 nm to 5 nm. The results obtained are shown in Table 1.
- ⁇ Comparative example 2> By the same method as in Example 26, except that a catalyst produced by adjusting the amounts of zirconium oxynitrate dihydrate and cesium carbonate so that the amounts of zirconium and cesium after support are as shown in Table 1 was used. Methacrylic acid and methyl methacrylate were produced, and the selectivity and yield of methacrylic acid and methyl methacrylate were calculated. The average particle size of zirconium oxynitrate in methanol when the carrier was immersed was 0.8 nm. The particle size of the zirconium compound after the catalyst was produced was 0.8 nm to 5 nm. The results obtained are shown in Table 1.
- ⁇ Comparative example 3> By the same method as in Example 39, except that a catalyst produced by adjusting the amounts of zirconium oxynitrate dihydrate and cesium carbonate so that the amounts of zirconium and cesium after support are as shown in Table 1 was used. Methacrylic acid and methyl methacrylate were produced, and the selectivity and yield of methacrylic acid and methyl methacrylate were calculated. The average particle size of zirconium oxynitrate in methanol when the carrier was immersed was 0.8 nm. The particle size of the zirconium compound after the catalyst was produced was 0.8 nm to 5 nm. The results obtained are shown in Table 1.
- Example 40 5.4 g of zirconium oxynitrate dihydrate (Kishida chemistry, special grade) was dissolved in 125 ml of methanol (Nacalai Tesque, special grade) and allowed to stand for 24 hours. 130 g of CARiACT Q-10 (trade name, Fuji Silysia Chemical Ltd., particle size 1.7-4 mm, average pore diameter 10 nm) was impregnated with this solution by the pore filling method. The average particle size of zirconium oxynitrate in methanol when the carrier was impregnated was 0.8 nm. Then, it dried at 120 degreeC for 14 hours, and the first solid content was obtained.
- CARiACT Q-10 trade name, Fuji Silysia Chemical Ltd., particle size 1.7-4 mm, average pore diameter 10 nm
- the catalyst was obtained by drying at 120 ° C. for 14 hours and then calcining at 600 ° C. for 3 hours.
- the particle size of the zirconium compound after the catalyst was produced was 0.8 nm to 5 nm.
- the reactor was filled with about 3 g of the obtained catalyst. Then, under normal pressure, the reaction solution having a molar ratio of methyl propionate, methanol, formaldehyde and water of 1: 1.40: 0.19: 0.5 was evaporated at 300 ° C. at a flow rate of 0.034 ml / min. It was circulated in a vessel and circulated in a reactor at 350 ° C. for 16 hours. Then, under normal pressure, a reaction raw material solution having a molar ratio of methyl propionate, methanol, formaldehyde, and water of 1: 1.40: 0.19: 0.5 was passed through an evaporator at 300 ° C. to 350 ° C. It was supplied to the reactor.
- the reaction raw material liquid was recovered by changing the flow rate of the liquid feed at 5 points between 0.35 and 0.034 ml / min, and cooling and condensing the vapor at the outlet of the reactor at each liquid feed flow rate.
- the obtained reaction solution was analyzed by gas chromatography (Shimadzu Corporation, trade name: GC-2010) to determine the yield and selectivity of methacrylic acid and methyl methacrylate at a flow rate of 0.16 ml / min. Each was calculated. The results obtained are shown in Table 1.
- Example 41-42> By the same method as in Example 40, except that a catalyst produced by adjusting the amounts of zirconium oxynitrate dihydrate and cesium carbonate so that the amounts of zirconium and cesium after support are as shown in Table 1 was used. Methacrylic acid and methyl methacrylate were produced, and the selectivity and yield of methacrylic acid and methyl methacrylate were calculated. The average particle size of zirconium oxynitrate in methanol when the carrier was immersed was 0.8 nm. The particle size of the zirconium compound after the catalyst was produced was 0.8 nm to 5 nm. The results obtained are shown in Table 1.
- Example 43-45> Water was used as the solvent instead of methanol, and a catalyst produced by adjusting the amounts of zirconium oxynitrate dihydrate and cesium carbonate so that the amounts of zirconium and cesium after support were as shown in Table 1 was used. Except for the above, methacrylic acid and methyl methacrylate were produced by the same method as in Example 40, and the selectivity and yield of methacrylic acid and methyl methacrylate were calculated. The average particle size of zirconium oxynitrate in methanol when the carrier was immersed was 0.8 nm. The particle size of the zirconium compound after the catalyst was produced was 0.8 nm to 5 nm. The results obtained are shown in Table 1.
- Example 46-49> The time for allowing zirconium oxynitrate to stand in methanol was changed from 24 hours to 15 minutes, and zirconium oxynitrate dihydrate and cesium carbonate so that the amounts of zirconium and cesium after support were as shown in Table 1.
- Methyl methacrylate and methyl methacrylate were produced by the same method as in Example 42 except that the catalyst produced by adjusting the amount of the above was used, and the selectivity and yield of the methacrylate and methyl methacrylate were calculated.
- the average particle size of zirconium oxynitrate in methanol when the carrier was immersed was 10 to 50 nm. The results obtained are shown in Table 1.
- Cs (wt%) represents the content of cesium with respect to the total mass of the catalyst component and the carrier
- Zr (wt%) represents the content of zirconium with respect to the total mass of the catalyst component and the carrier
- the / Zr molar ratio X represents the molar ratio of cesium to zirconia in the catalyst component.
- the MMA + MAA yield (%) and the MMA + MAA selectivity (%) represent the yield and selectivity of methyl methacrylate and methacrylic acid, respectively.
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Abstract
Description
[1]シラノール基を有する担体に、ホウ素、マグネシウム、ジルコニウム及びハフニウムから選択される少なくとも1種の第1の金属元素と、アルカリ金属元素と、が担持して構成される触媒であって、
前記第1の金属元素の化合物の平均粒子径が0.4nm以上50nm以下であり、
前記第1の金属元素に対する前記アルカリ金属元素のモル比をX、触媒のBET比表面積をY(m2/g)、触媒が有する単位面積当たりのシラノール基数(個/nm2)をZとした場合、下記式(1)を満たす触媒。
0.9×10-21(g/個)≦X/(Y×Z)<10.8×10-21(g/個) ・・・式(1)
[2]前記第1の金属元素に対する前記アルカリ金属元素のモル比Xが、1.3以上6.0以下である[1]に記載の触媒。
[3]前記アルカリ金属元素がセシウムである、[1]又は[2]に記載の触媒。
[4]前記第1の金属元素がジルコニウムである、[1]~[3]のいずれか1項に記載の触媒。
[5]不飽和カルボン酸及び/又は不飽和カルボン酸エステルの製造用触媒であ[1]~[4]のいずれか1項に記載の触媒。
[6][1]~[5]のいずれか1項に記載の触媒の存在下で、カルボン酸及び/又はカルボン酸エステルと、ホルムアルデヒドと、を反応させて、不飽和カルボン酸及び/又は不飽和カルボン酸エステルを製造する方法。
[7]担体に、ホウ素、マグネシウム、ジルコニウム及びハフニウムから選択される少なくとも一種の第1の金属元素と、アルカリ金属元素と、が担持された触媒の製造方法であって、
担体に、前記第1の金属元素の無機塩を含む溶液又は分散液を含浸させて第1の固形分を得る工程と、
該第1の固形分に、アルカリ金属塩を含む溶液又は分散液を含浸させて第2の固形分を得る工程を有し、
前記第1の金属元素の無機塩の平均粒子径が0.4nm以上50nm以下であり、
前記第1の金属元素に対する前記アルカリ金属元素のモル比をX’、前記担体のBET比表面積をY’(m2/g)、前記担体が有する単位面積あたりのシラノール基数Z’(個/nm2)とした場合、下記式(2)を満たす触媒の製造方法。
1.5×10-21 (g/個)≦X’/(Y’×Z’)≦17.0×10-21(g/個)・・・(2)
[8]前記記第1の金属元素の無機塩を含む溶液又は分散液の溶媒が、アルコールを含有する、[7]に記載の製造方法。
[9]前記第1の金属元素がジルコニウムである、[7]又は[8]に記載の製造方法。
[10]前記アルカリ金属元素がセシウムである、[7]~[9]のいずれか1項に記載の製造方法。
本実施形態に係る触媒は、シラノール基を有する担体に、ホウ素、マグネシウム、ジルコニウム及びハフニウムから選択される少なくとも1種の第1の金属元素と、アルカリ金属元素とが担持した構成を有し、該第1の金属元素を含む化合物の平均粒子径が0.4nm以上50nm以下であり、該第1の金属元素に対する前記アルカリ金属元素のモル比をX、前記触媒のBET比表面積(m2/g)をY、前記触媒が有する単位面積当たりのシラノール基数(個/nm2)をZとした場合、下記式(1)を満たす。
第1の金属元素の無機塩を構成する第1の金属元素は、上述した第1の金属元素が挙げられる。
担体は、上述の担体を使用することができる。
アルカリ金属元素は上述のアルカリ金属元素が挙げられる。
第2の工程により得た第1の固形分と、第3の工程により得た溶液又は分散液と、の混合方法は特段の制限はないが、第2の工程により得た第1の固形分を第3の工程により得た溶液又は分散液に含浸させることが好ましい。
・・・式(3)
Δwt: 180℃から950℃における重量減少割合(%)
SA: BET比表面積(m2/g)。
オキシ硝酸ジルコニウム2水和物(キシダ化学、特級)4.5gをメタノール(ナカライテスク、特級)135mlに溶解し、24時間静置した。この溶液に、担体として使用するCARiACT Q-10(商品名、富士シリシア化学(株)、粒径1.7-4mm、平均細孔径10nm)60gを浸漬し、3.5時間静置し、ロータリーエパポレーターを用いて溶媒を留去した。なお、担体を浸漬した際のメタノール中のオキシ硝酸ジルコニウムの平均粒子径は0.8nmであった。その後、120℃で14時間乾燥を行い、第1の固形分を得た。得られた第1の固形分のうち、30gを、炭酸セシウム(和光純薬、1級)4.8gをメタノール65mlに溶解した溶液に3.5時間浸漬し、濾過により第2の固形分と溶液を分離した。第2の固形分を120℃で14時間乾燥することにより触媒を得た。なお、当該触媒のジルコニウム化合物の粒子径は0.8nm~5nmであった。
担持後のジルコニウム及びセシウム量が表1に示す値となるようにオキシ硝酸ジルコニウム2水和物と炭酸セシウムの量を調整して製造した触媒を使用した以外は、実施例1と同様の方法によりメタクリル酸及びメタクリル酸メチルを製造してメタクリル酸及びメタクリル酸メチルの選択率及び収率を算出した。なお、担体を浸漬した際のメタノール中のオキシ硝酸ジルコニウムの平均粒子径はいずれも0.8nmであった。また、触媒製造後のジルコニウム化合物の粒子径は0.8nm~5nmであった。得られた結果を表1に示す。
炭酸セシウムの使用量を4.6gに変更し、濾過により第2の固形分と液体を分離する代わりにロータリーエバポレーターを用いて溶媒を留去して製造した触媒を使用した以外は、実施例1と同様の方法によりメタクリル酸及びメタクリル酸メチルを製造してメタクリル酸及びメタクリル酸メチルの選択率及び収率を算出した。なお、担体を浸漬した際のメタノール中のオキシ硝酸ジルコニウムの平均粒子径は0.8nmであった。また、触媒製造後のジルコニウム化合物の粒子径は0.8nm~5nmであった。得られた結果を表1に示す。
担持後のジルコニウム及びセシウム量が表1に示す値となるようにオキシ硝酸ジルコニウム2水和物と炭酸セシウムの量を調整して製造した触媒を使用した以外は、実施例8と同様の方法によりメタクリル酸及びメタクリル酸メチルを製造してメタクリル酸及びメタクリル酸メチルの選択率及び収率を算出した。なお、担体を浸漬した際のメタノール中のオキシ硝酸ジルコニウムの平均粒子径はいずれも0.8nmであった。また、触媒製造後のジルコニウム化合物の粒子径は0.8nm~5nmであった。得られた結果を表1に示す。
オキシ硝酸ジルコニウム2水和物(キシダ化学、特級)7.3gをメタノール(ナカライテスク、特級)57mlに溶解し、24時間静置した。この溶液を、CARiACT Q-10(商品名、富士シリシア化学(株)、粒径1.7-4mm、平均細孔径10nm)60gをポアフィリング法により含浸した。なお、担体を含浸した際のメタノール中のオキシ硝酸ジルコニウムの平均粒子径は0.8nmであった。その後、120℃で14時間乾燥を行い、第1の固形分を得た。得られた第1の固形分のうちの30gに対し、炭酸セシウム7.0gをメタノール29mlに溶解した溶液をポアフィリング法を用いて含浸した。その後、120℃で14時間乾燥することにより触媒を得た。なお、触媒製造後のジルコニウム化合物の粒子径は0.8nm~5nmであった。その後、実施例1と同様の方法によりメタクリル酸及びメタクリル酸メチルを製造してメタクリル酸及びメタクリル酸メチルの選択率及び収率を算出した。得られた結果を表1に示す。
担体としてCARiACT Q-10の代わりに、CARiACT Q15(商品名、富士シリシア化学(株)、粒径1.7mm-4mm、平均細孔径15nm)を用い、さらに、担持後のジルコニウム及びセシウム量が表1に示す値となるようにオキシ硝酸ジルコニウム2水和物と炭酸セシウムの量を調整して製造した触媒を使用した以外は、実施例1と同様の方法によりメタクリル酸及びメタクリル酸メチルを製造してメタクリル酸及びメタクリル酸メチルの選択率及び収率を算出した。なお、担体を浸漬した際のメタノール中のオキシ硝酸ジルコニウムの平均粒子径はいずれも0.8nmであった。また、触媒製造後のジルコニウム化合物の粒子径は0.8nm~5nmであった。得られた結果を表1に示す。
担体としてCARiACT Q-10の代わりにCARiACT Q15C(商品名、富士シリシア化学(株)、粒径1.7-4mm、平均細孔径15nm)を用い、担持後のジルコニウム及びセシウム量が表1に示す値となるようにオキシ硝酸ジルコニウム2水和物と炭酸セシウムの量を調整して製造した触媒を使用した以外は、実施例1と同様の方法によりメタクリル酸及びメタクリル酸メチルを製造してメタクリル酸及びメタクリル酸メチルの選択率及び収率を算出した。なお、担体を浸漬した際のメタノール中のオキシ硝酸ジルコニウムの平均粒子径はいずれも0.8nmであった。また、触媒製造後のジルコニウム化合物の平均粒子径は0.8nm~5nmであった。得られた結果を表1に示す。
担体としてCARiACT Q-10の代わりにCARiACT Q30(商品名、富士シリシア化学(株)、粒径1.7-4mm、平均細孔径30nm)を用い、担持後のジルコニウム及びセシウム量が表1に示す値となるようにオキシ硝酸ジルコニウム2水和物と炭酸セシウムの量を調整して製造した触媒を使用した以外は、実施例1と同様の方法によりメタクリル酸及びメタクリル酸メチルを製造してメタクリル酸及びメタクリル酸メチルの選択率及び収率を算出した。なお、担体を浸漬した際のメタノール中のオキシ硝酸ジルコニウムの平均粒子径はいずれも0.8nmであった。また、触媒製造後のジルコニウム化合物の粒子径は0.8nm~5nmであった。得られた結果を表1に示す。
担体としてCARiACT Q-10の代わりにCARiACT Q30C(商品名、富士シリシア化学(株)、粒径1.7-4mm、平均細孔径30nm)を用い、担持後のジルコニウム及びセシウム量が表1に示す値となるようにオキシ硝酸ジルコニウム2水和物と炭酸セシウムの量を調整して製造した触媒を使用した以外は、実施例1と同様の方法によりメタクリル酸及びメタクリル酸メチルを製造してメタクリル酸及びメタクリル酸メチルの選択率及び収率を算出した。なお、担体を浸漬した際のメタノール中のオキシ硝酸ジルコニウムの平均粒子径はいずれも0.8nmであった。また、触媒製造後のジルコニウム化合物の粒子径は0.8nm~5nmであった。得られた結果を表1に示す。
担持後のジルコニウム及びセシウム量が表1に示す値となるようにオキシ硝酸ジルコニウム2水和物と炭酸セシウムの量を調整して製造した触媒を使用した以外は、実施例1と同様の方法によりメタクリル酸及びメタクリル酸メチルを製造してメタクリル酸及びメタクリル酸メチルの選択率及び収率を算出した。なお、担体を浸漬した際のメタノール中のオキシ硝酸ジルコニウムの平均粒子径はいずれも0.8nmであった。また、触媒製造後のジルコニウム化合物の粒子径は0.8nm~5nmであった。得られた結果を表1に示す。
担持後のジルコニウム及びセシウム量が表1に示す値となるようにオキシ硝酸ジルコニウム2水和物と炭酸セシウムの量を調整して製造した触媒を使用した以外は、実施例26と同様の方法によりメタクリル酸及びメタクリル酸メチルを製造してメタクリル酸及びメタクリル酸メチルの選択率及び収率を算出した。なお、担体を浸漬した際のメタノール中のオキシ硝酸ジルコニウムの平均粒子径はいずれも0.8nmであった。また、触媒製造後のジルコニウム化合物の粒子径は0.8nm~5nmであった。得られた結果を表1に示す。
担持後のジルコニウム及びセシウム量が表1に示す値となるようにオキシ硝酸ジルコニウム2水和物と炭酸セシウムの量を調整して製造した触媒を使用した以外は、実施例39と同様の方法によりメタクリル酸及びメタクリル酸メチルを製造してメタクリル酸及びメタクリル酸メチルの選択率及び収率を算出した。なお、担体を浸漬した際のメタノール中のオキシ硝酸ジルコニウムの平均粒子径はいずれも0.8nmであった。また、触媒製造後のジルコニウム化合物の粒子径は0.8nm~5nmであった。得られた結果を表1に示す。
オキシ硝酸ジルコニウム2水和物(キシダ化学、特級)5.4gをメタノール(ナカライテスク、特級)125mlに溶解し、24時間静置した。この溶液を、CARiACT Q-10(商品名、富士シリシア化学(株)、粒径1.7-4mm、平均細孔径10nm)130gにポアフィリング法により含浸した。なお、担体に含浸した際のメタノール中のオキシ硝酸ジルコニウムの平均粒子径は0.8nmであった。その後、120℃で14時間乾燥を行い、第1の固形分を得た。得られた第1の固形分のうち、30gに対し、炭酸セシウム(和光純薬、1級)1.9gをメタノール29mlに溶解した溶液をポアフィリング法を用いて含浸した。その後、120℃で14時間乾燥を行った後、600℃で3時間焼成を行うことにより触媒を得た。なお、触媒製造後のジルコニウム化合物の粒子径は0.8nm~5nmであった。
担持後のジルコニウム及びセシウム量が表1に示す値となるようにオキシ硝酸ジルコニウム2水和物と炭酸セシウムの量を調整して製造した触媒を使用した以外は、実施例40と同様の方法によりメタクリル酸及びメタクリル酸メチルを製造してメタクリル酸及びメタクリル酸メチルの選択率及び収率を算出した。なお、担体を浸漬した際のメタノール中のオキシ硝酸ジルコニウムの平均粒子径はいずれも0.8nmであった。また、触媒製造後のジルコニウム化合物の粒子径は0.8nm~5nmであった。得られた結果を表1に示す。
溶媒としてメタノールの代わりに水を用い、さらに、担持後のジルコニウム及びセシウム量が表1に示す値となるようにオキシ硝酸ジルコニウム2水和物と炭酸セシウムの量を調整して製造した触媒を使用した以外は、実施例40と同様の方法によりメタクリル酸及びメタクリル酸メチルを製造してメタクリル酸及びメタクリル酸メチルの選択率及び収率を算出した。なお、担体を浸漬した際のメタノール中のオキシ硝酸ジルコニウムの平均粒子径はいずれも0.8nmであった。また、触媒製造後のジルコニウム化合物の粒子径は0.8nm~5nmであった。得られた結果を表1に示す。
オキシ硝酸ジルコニウムをメタノール中で静置させる時間を24時間から15分に変更し、さらに、担持後のジルコニウム及びセシウム量が表1に示す値となるようにオキシ硝酸ジルコニウム2水和物と炭酸セシウムの量を調整して製造した触媒を使用した以外は、実施例42と同様の方法によりメタクリル酸及びメタクリル酸メチルを製造してメタクリル酸及びメタクリル酸メチルの選択率及び収率を算出した。なお、担体を浸漬した際のメタノール中のオキシ硝酸ジルコニウムの平均粒子径はいずれも10~50nmであった。得られた結果を表1に示す。
Claims (10)
- シラノール基を有する担体に、ホウ素、マグネシウム、ジルコニウム及びハフニウムから選択される少なくとも1種の第1の金属元素と、アルカリ金属元素と、が担持して構成される触媒であって、
前記第1の金属元素の化合物の平均粒子径が0.4nm以上50nm以下であり、
前記第1の金属元素に対する前記アルカリ金属元素のモル比をX、触媒のBET比表面積をY(m2/g)、触媒が有する単位面積当たりのシラノール基数(個/nm2)をZとした場合、下記式(1)を満たす触媒。
0.90×10-21(g/個)≦X/(Y×Z)<10.8×10-21(g/個) ・・・式(1) - 前記第1の金属元素に対する前記アルカリ金属元素のモル比Xが、1.3以上6.0以下である請求項1に記載の触媒。
- 前記アルカリ金属元素がセシウムである、請求項1又は2に記載の触媒。
- 前記第1の金属元素がジルコニウムである、請求項1~3のいずれか1項に記載の触媒。
- 不飽和カルボン酸及び/又は不飽和カルボン酸エステルの製造用触媒である請求項1~4のいずれか1項に記載の触媒。
- 請求項1~5のいずれか1項に記載の触媒の存在下で、カルボン酸及び/又はカルボン酸エステルと、ホルムアルデヒドと、を反応させて、不飽和カルボン酸及び/又は不飽和カルボン酸エステルを製造する方法。
- 担体に、ホウ素、マグネシウム、ジルコニウム及びハフニウムから選択される少なくとも一種の第1の金属元素と、アルカリ金属元素と、が担持された触媒の製造方法であって、
担体に、前記第1の金属元素の無機塩を含む溶液又は分散液を含浸させて第1の固形分を得る工程と、
該第1の固形分に、アルカリ金属塩を含む溶液又は分散液を含浸させて第2の固形分を得る工程を有し、
前記第1の金属元素の無機塩の平均粒子径が0.4nm以上50nm以下であり、
前記第1の金属元素に対する前記アルカリ金属元素のモル比をX’、前記担体のBET比表面積をY’(m2/g)、前記担体が有する単位面積あたりのシラノール基数Z’(個/nm2)とした場合、下記式(2)を満たす触媒の製造方法。
1.5×10-21 (g/個)≦X’/(Y’×Z’)≦17.0×10-21(g/個)・・・(2) - 前記記第1の金属元素の無機塩を含む溶液又は分散液の溶媒が、アルコールを含有する、請求項7に記載の製造方法。
- 前記第1の金属元素がジルコニウムである、請求項7又は8に記載の製造方法。
- 前記アルカリ金属元素がセシウムである、請求項7~9のいずれか1項に記載の製造方法。
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JP2015205842A (ja) * | 2014-04-22 | 2015-11-19 | 住友化学株式会社 | アセチレン結合を有する化合物及び/又はジエンの製造方法 |
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WO2022255368A1 (ja) * | 2021-06-01 | 2022-12-08 | 三菱ケミカル株式会社 | 触媒、触媒の製造方法、並びに不飽和カルボン酸及び/又は不飽和カルボン酸エステルの製造方法 |
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SG11202109990XA (en) | 2021-10-28 |
US20210387165A1 (en) | 2021-12-16 |
CA3130565C (en) | 2023-09-05 |
TW202045251A (zh) | 2020-12-16 |
CN113557086A (zh) | 2021-10-26 |
EP3939698A4 (en) | 2022-06-08 |
KR20210133296A (ko) | 2021-11-05 |
CN113557086B (zh) | 2023-10-27 |
CA3130565A1 (en) | 2020-09-17 |
JP7136321B2 (ja) | 2022-09-13 |
BR112021016346A2 (pt) | 2021-10-26 |
JPWO2020184616A1 (ja) | 2021-11-11 |
MX2021010976A (es) | 2021-10-13 |
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