WO2022201533A1 - カルボン酸エステル製造用触媒、カルボン酸エステルの製造方法及びカルボン酸エステル製造用触媒の製造方法 - Google Patents
カルボン酸エステル製造用触媒、カルボン酸エステルの製造方法及びカルボン酸エステル製造用触媒の製造方法 Download PDFInfo
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- WO2022201533A1 WO2022201533A1 PCT/JP2021/013068 JP2021013068W WO2022201533A1 WO 2022201533 A1 WO2022201533 A1 WO 2022201533A1 JP 2021013068 W JP2021013068 W JP 2021013068W WO 2022201533 A1 WO2022201533 A1 WO 2022201533A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- carboxylic acid
- acid ester
- producing
- nickel
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 221
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 86
- 125000003262 carboxylic acid ester group Chemical class [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 title abstract 6
- 239000002245 particle Substances 0.000 claims abstract description 104
- 238000009826 distribution Methods 0.000 claims abstract description 49
- 239000002923 metal particle Substances 0.000 claims abstract description 16
- 230000001186 cumulative effect Effects 0.000 claims abstract description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 311
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 169
- 229910052759 nickel Inorganic materials 0.000 claims description 145
- 229910017052 cobalt Inorganic materials 0.000 claims description 94
- 239000010941 cobalt Substances 0.000 claims description 94
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 94
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 88
- 239000011246 composite particle Substances 0.000 claims description 88
- 239000010931 gold Substances 0.000 claims description 60
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 57
- 229910052737 gold Inorganic materials 0.000 claims description 56
- 239000000203 mixture Substances 0.000 claims description 54
- 239000000377 silicon dioxide Substances 0.000 claims description 41
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 29
- 150000001299 aldehydes Chemical class 0.000 claims description 27
- 230000003197 catalytic effect Effects 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 21
- 229910052760 oxygen Inorganic materials 0.000 claims description 21
- 239000001301 oxygen Substances 0.000 claims description 21
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 18
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical group C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims description 14
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 14
- 229910052709 silver Inorganic materials 0.000 claims description 14
- 239000004332 silver Substances 0.000 claims description 14
- 230000008093 supporting effect Effects 0.000 claims description 14
- 239000010949 copper Substances 0.000 claims description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 12
- 150000001298 alcohols Chemical class 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 12
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 11
- 229910052763 palladium Inorganic materials 0.000 claims description 11
- 229910052707 ruthenium Inorganic materials 0.000 claims description 11
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052697 platinum Inorganic materials 0.000 claims description 9
- 239000011133 lead Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 description 93
- 230000000694 effects Effects 0.000 description 42
- 229910052751 metal Inorganic materials 0.000 description 38
- 229910052782 aluminium Inorganic materials 0.000 description 36
- 239000011148 porous material Substances 0.000 description 36
- 239000000126 substance Substances 0.000 description 36
- 239000002184 metal Substances 0.000 description 34
- 229910052783 alkali metal Inorganic materials 0.000 description 30
- 150000001340 alkali metals Chemical class 0.000 description 30
- 238000000034 method Methods 0.000 description 30
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 29
- 150000001342 alkaline earth metals Chemical class 0.000 description 29
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 29
- 229910000480 nickel oxide Inorganic materials 0.000 description 29
- -1 Ni 2 O Chemical compound 0.000 description 28
- 229910052761 rare earth metal Inorganic materials 0.000 description 27
- 150000002910 rare earth metals Chemical class 0.000 description 27
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical group [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 26
- 239000002994 raw material Substances 0.000 description 23
- 239000002131 composite material Substances 0.000 description 22
- 238000005259 measurement Methods 0.000 description 21
- 239000000523 sample Substances 0.000 description 21
- 238000004458 analytical method Methods 0.000 description 17
- 229910001038 basic metal oxide Inorganic materials 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 239000007864 aqueous solution Substances 0.000 description 16
- 229910052728 basic metal Inorganic materials 0.000 description 16
- 239000011268 mixed slurry Substances 0.000 description 16
- 239000002105 nanoparticle Substances 0.000 description 16
- 239000002002 slurry Substances 0.000 description 14
- 150000003818 basic metals Chemical class 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- 238000001228 spectrum Methods 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 230000008859 change Effects 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- 230000002378 acidificating effect Effects 0.000 description 10
- 229910000428 cobalt oxide Inorganic materials 0.000 description 10
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical group [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 10
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 10
- 230000005540 biological transmission Effects 0.000 description 9
- 239000013078 crystal Substances 0.000 description 9
- 230000007423 decrease Effects 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 238000010304 firing Methods 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 8
- 230000000704 physical effect Effects 0.000 description 8
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 7
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 7
- 239000000969 carrier Substances 0.000 description 7
- 238000005755 formation reaction Methods 0.000 description 7
- 229910052749 magnesium Inorganic materials 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 7
- 239000007921 spray Substances 0.000 description 7
- 238000001694 spray drying Methods 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 125000001931 aliphatic group Chemical group 0.000 description 6
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 6
- 230000007774 longterm Effects 0.000 description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 238000000790 scattering method Methods 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 230000032683 aging Effects 0.000 description 5
- 239000000470 constituent Substances 0.000 description 5
- 238000010828 elution Methods 0.000 description 5
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- 238000007561 laser diffraction method Methods 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 239000000395 magnesium oxide Substances 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000006104 solid solution Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 4
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 4
- 150000004706 metal oxides Chemical group 0.000 description 4
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- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
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- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 3
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- 229910052744 lithium Inorganic materials 0.000 description 3
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- 229910052712 strontium Inorganic materials 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
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- 229910018557 Si O Inorganic materials 0.000 description 2
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- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
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- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
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- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 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 description 1
- 230000007246 mechanism Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- QCAWEPFNJXQPAN-UHFFFAOYSA-N methoxyfenozide Chemical compound COC1=CC=CC(C(=O)NN(C(=O)C=2C=C(C)C=C(C)C=2)C(C)(C)C)=C1C QCAWEPFNJXQPAN-UHFFFAOYSA-N 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 1
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- GKYQBMNOFTZZSX-UHFFFAOYSA-K n-ethylethanamine;trichlorogold Chemical compound Cl[Au](Cl)Cl.CCNCC GKYQBMNOFTZZSX-UHFFFAOYSA-K 0.000 description 1
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- DWYJHMSKXMHOAP-UHFFFAOYSA-N oxetan-2-ol Chemical class OC1CCO1 DWYJHMSKXMHOAP-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 230000010412 perfusion Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- JTJMJGYZQZDUJJ-UHFFFAOYSA-N phencyclidine Chemical class C1CCCCN1C1(C=2C=CC=CC=2)CCCCC1 JTJMJGYZQZDUJJ-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N propiophenone Chemical compound CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 150000002909 rare earth metal compounds Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000013074 reference sample Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- CQRYARSYNCAZFO-UHFFFAOYSA-N salicyl alcohol Chemical compound OCC1=CC=CC=C1O CQRYARSYNCAZFO-UHFFFAOYSA-N 0.000 description 1
- 238000000851 scanning transmission electron micrograph Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/12—Silica and alumina
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8946—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali or alkaline earth metals
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- B01J35/391—Physical properties of the active metal ingredient
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- B01J35/397—Egg shell like
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
- B01J35/53—Spheres with a core-shell structure
-
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- B01J35/615—100-500 m2/g
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0045—Drying a slurry, e.g. spray drying
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- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/39—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
- B01J2235/30—Scanning electron microscopy; Transmission electron microscopy
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Definitions
- the present invention relates to a catalyst for producing a carboxylic acid ester, a method for producing a carboxylic acid ester, and a method for producing a catalyst for producing a carboxylic acid ester.
- Nickel or nickel compounds are widely used as catalysts for chemical synthesis such as oxidation reactions, reduction reactions, and hydrogenation reactions. has been realized. However, in the chemical industry, nickel and nickel compounds are used not only in the oxidation reaction of alcohol, but also in various reactions such as various oxidation reactions, reduction reactions, and hydrogenation reactions, as well as catalysts for purifying automobile exhaust gases and photocatalysts. It is known to be widely effective.
- Patent Document 1 nickel in an oxidized state and X (X is at least one selected from the group consisting of nickel, palladium, platinum, ruthenium, gold, silver and copper and a carrier that supports the composite particles, wherein the composite particles have a support layer in which the composite particles are localized. It has been proposed for use as a catalyst. Such a catalyst is said to be able to maintain high reactivity over a long period of time.
- Patent Document 2 a spherical silica containing aluminum and magnesium, in which the specific surface area, pore volume, pore distribution, bulk density, wear resistance, average particle size, aluminum content and magnesium content are set to predetermined ranges Particles are described. According to the document, it is possible to use in a wide range of applications including catalyst carriers, and it is possible to provide spherical silica-based particles with high mechanical strength, large specific surface area, and good fluidity. .
- the present invention has been made in view of the above-mentioned problems of the prior art, and an object of the present invention is to provide a catalyst for producing carboxylic acid esters that exhibits high activity while suppressing outflow of the catalyst.
- the present inventors found that the above problems can be solved by setting the bulk density and particle size distribution (D 10 /D 50 , D 90 /D 50 , and W/D 50 ) within predetermined ranges, and have completed the present invention. completed.
- a catalyst for producing a carboxylic acid ester comprising catalytic metal particles and a carrier supporting the catalytic metal particles
- the bulk density of the carboxylic acid ester production catalyst is 0.50 g/cm 3 or more and 1.50 g/cm 3 or less
- D x is the particle diameter at which the cumulative frequency is x % in the volume-based particle diameter distribution of the catalyst for producing a carboxylic acid ester
- D 10 /D 50 ⁇ 0.2 and D 90 /D 50 ⁇ 2. is 5
- a catalyst for producing a carboxylic acid ester wherein W/D 50 ⁇ 1.5, where W is the half width of the particle size distribution.
- [2] The catalyst for producing a carboxylic acid ester according to [1], wherein the W is 100 ⁇ m or less.
- [3] The carboxylic acid according to [1] or [2], wherein the catalytic metal particles contain at least one element selected from the group consisting of nickel, cobalt, palladium, platinum, ruthenium, lead and gold, silver and copper. Catalyst for ester production.
- the catalytic metal particles are nickel and/or cobalt in an oxidized state; and X (X represents at least one element selected from the group consisting of nickel, palladium, platinum, ruthenium, gold, silver and copper);
- the equivalent diameter is 200 ⁇ m or less, and the support layer in which the composite particles are localized exists in a region from the surface of the carboxylic acid ester-producing catalyst to 30% of the equivalent diameter of the carboxylic acid ester-producing catalyst.
- an outer layer substantially free of composite particles is provided, and the outer layer is formed with a thickness of 0.01 to 15 ⁇ m, [4] to [9]
- a step of reacting (a) an aldehyde and an alcohol, or (b) one or more alcohols in the presence of the catalyst for producing a carboxylic acid ester according to any one of [1] to [13] and oxygen.
- a method for producing a carboxylic acid ester comprising: [15] The method for producing a carboxylic acid ester according to [14], wherein the aldehyde is acrolein and/or methacrolein. [16] The method for producing a carboxylic acid ester according to [14] or [15], wherein the aldehyde is acrolein and/or methacrolein, and the alcohol is methanol.
- the catalyst for producing a carboxylic acid ester of the present embodiment is a catalyst for producing a carboxylic acid ester containing catalytic metal particles and a carrier supporting the catalytic metal particles, wherein the bulk density of the catalyst for producing a carboxylic acid ester is It is 0.5 g/cm 3 or more and 1.5 g/cm 3 or less, the half width of the volume-based particle size distribution of the carboxylic acid ester-producing catalyst is 100 ⁇ m or less, and the volume-based catalyst for carboxylic acid ester production is When the particle diameter at which the cumulative frequency becomes x% in the particle size distribution of is D x , D 10 /D 50 ⁇ 0.2 and D 90 /D 50 ⁇ 2.5, and the volume-based particle size Where W is the half width of the distribution, W/D 50 ⁇ 1.5. Because of this configuration, the catalyst for producing a carboxylic acid ester of the present embodiment exhibits high activity while suppressing outflow of the catalyst
- the bulk density of the carboxylic acid ester production catalyst is 0.50 g/cm 3 or more and 1.50 g/cm 3 or less.
- the bulk density is considered to have little relevance to the problem of reduced catalytic activity, but by adjusting the bulk density to the above range, the catalyst can easily diffuse in the reactor, and the conversion rate of the raw material is increased. expected to increase. That is, if the bulk density is less than the above lower limit, the catalyst flows out of the reactor during long-term operation and the amount of catalyst decreases, resulting in lower activity. It is thought that the low cyclability of the material reduces the chance of contact with the raw material, resulting in low activity.
- the bulk density of the catalyst for producing carboxylic acid ester is preferably 0.70 g/cm 3 or more and 1.30 g/cm 3 or less, more preferably 0.90 g/cm 3 or more and 1.20 g. / cm 3 or less.
- the bulk density can be measured by the method described in Examples below. The bulk density can be adjusted within the range described above, for example, by adopting preferable manufacturing conditions described later.
- D 10 /D 50 is 0.2 or more, where D x is the particle diameter at which the cumulative frequency is x % in the volume-based particle diameter distribution of the catalyst for producing a carboxylic acid ester.
- D 10 /D 50 is an index showing how many particles with a small particle size are present relative to the average particle size as a catalyst for producing a carboxylic acid ester. It means that the distribution of is sharp.
- D 10 /D 50 is 0.2 or more, the fluidity of the carboxylic acid ester production catalyst is increased, and high activity is exhibited. From the same point of view, D 10 /D 50 is preferably 0.3 to 0.8.
- D 10 /D 50 can be measured by a laser diffraction/scattering method, and more specifically by the method described in Examples below.
- D 10 /D 50 can be adjusted within the range described above, for example, by adopting the preferable manufacturing conditions described later.
- D90 / D50 is 2.5 or more. It is an index showing how much large particles are present in the catalyst for carboxylic acid ester production with respect to the average particle size. The closer this value is to 1.0, the sharper the distribution of large particles. represents that In the present embodiment, when D 90 /D 50 is 2.5 or more, the fluidity of the carboxylic acid ester production catalyst is increased, and high activity is exhibited. From the same point of view, D 90 /D 50 is preferably 1.4 to 2.3. D 90 /D 50 can be measured by a laser diffraction/scattering method, and more specifically by the method described in Examples below. D 90 /D 50 can be adjusted within the range described above, for example, by adopting the preferable manufacturing conditions described later.
- W/ D50 is 1.5 or less, where W is the half width of the volume-based particle size distribution of the carboxylic acid ester production catalyst.
- W/ D50 is an index showing how much the peak half-value width in the particle size distribution spreads with respect to the average particle size, and the smaller the value, the sharper the distribution.
- W/D 50 is 1.5 or less, the fluidity of the carboxylic acid ester production catalyst is increased while suppressing the outflow of the catalyst, and high activity is exhibited while suppressing the outflow of the catalyst. be done.
- W for the highest peak shall satisfy the above relationship.
- W/D 50 is preferably 0.6 to 1.3.
- W/D 50 can be measured by a laser diffraction/scattering method, and more specifically, by the method described in Examples below. W/D 50 can be adjusted within the range described above, for example, by adopting the preferred manufacturing conditions described later.
- W is preferably 100 ⁇ m or less. Setting the value of W to 100 ⁇ m or less tends to further suppress outflow of the catalyst. Not only the bulk density described above, but also the above-mentioned half-value width is considered to have a weak relationship with the problem related to the decrease in catalytic activity, but by adjusting the half-value width to the above range, the catalyst outflow from the reactor is prevented, and the conversion rate of the raw material tends to increase accordingly. It should be noted that, depending on the particle size distribution of the catalyst, the outflow of the catalyst from the reactor to the extent that it affects the conversion rate of the raw material is not known and is a novel finding.
- W is more preferably 5 ⁇ m or more and 95 ⁇ m or less, still more preferably 10 ⁇ m or more and 90 ⁇ m or less.
- W can be measured by a laser diffraction/scattering method, and more specifically by the method described in the examples below. W can be adjusted to the range described above, for example, by adopting the preferable manufacturing conditions described later.
- D 50 in the present embodiment is preferably 10 ⁇ m or more and 200 ⁇ m or less, more preferably 20 ⁇ m or more and 150 ⁇ m or less, further preferably 40 ⁇ m or more and 100 ⁇ m or less, and even more preferably 40 ⁇ m or more and 80 ⁇ m or less. preferable.
- D 50 can be measured by a laser diffraction/scattering method, and more specifically by the method described in Examples below.
- D50 can be adjusted within the range described above, for example, by adopting the preferable manufacturing conditions described later.
- the particle size distribution of the catalyst preferably has a single peak.
- a particle size distribution having a single peak means that the volume-based particle size distribution does not have a peak other than the highest peak that is 1/5 or more of the highest peak.
- the catalyst metal particles are not particularly limited as long as they have the function of catalyzing the reaction for producing the carboxylic acid ester. , lead and gold, silver and copper.
- the catalytic metal particles include nickel and/or cobalt in an oxidized state and X (X is selected from the group consisting of nickel, palladium, platinum, ruthenium, gold, silver and copper. It is more preferred that the composite particles contain nickel or cobalt in an oxidized state and gold.
- the carboxylic acid ester production catalyst preferably has a carrier layer in which the composite particles are localized.
- the term “supporting layer in which composite particles are localized” refers to a region in a support where composite particles are concentratedly supported.
- the composite particles are preferably selectively supported in a certain region rather than randomly supported in the carrier. It is referred to as the "existing carrier layer".
- the composite particles are concentrated in a certain region compared to other parts, that region is a “support layer in which the composite particles are localized”, so which region is the “composite Whether or not it is a “support layer in which particles are localized” can be determined by the X-ray microprobe analysis method described later or a secondary electron reflected image of a high-resolution scanning electron microscope. It is preferable that the support layer in which the composite particles are localized exists in a region extending from the surface of the carboxylic acid ester-producing catalyst to 40% of the equivalent diameter of the carboxylic acid ester-producing catalyst. When the support layer in which the composite particles are localized is present in the above region, the influence of the diffusion speed of the reactants inside the support is reduced, and the reaction activity tends to be improved.
- the catalyst for carboxylic acid ester production of the present embodiment can have a substantial thickness or particle size of various sizes on the order of ⁇ m to cm, and various shapes.
- Specific examples of the shape of the catalyst for producing a carboxylic acid ester include, but are not limited to, various shapes such as spherical, elliptical, cylindrical, tablet-like, hollow cylindrical, plate-like, rod-like, sheet-like, and honeycomb-like. is mentioned.
- Such a shape can be appropriately changed depending on the reaction mode, and is not limited to the following. For example, in a fixed bed reaction, a hollow columnar shape or a honeycomb shape with little pressure loss is selected. A spherical shape is selected for
- equivalent diameter means the diameter of a spherical particle or, in the case of an irregularly shaped particle, the diameter of a sphere of equal volume or surface area equal to that of the particle. show.
- the equivalent diameter is measured by using a laser diffraction/scattering particle size distribution analyzer to measure D50 , which is taken as the equivalent diameter.
- the optimum range is selected according to the thickness of the support, particle size, type of reaction, and reaction mode. Since the "equivalent diameter of the catalyst for producing a carboxylic acid ester" is usually the same as the “equivalent diameter of the support", the “equivalent diameter of the catalyst for producing a carboxylic acid ester” can be determined by the equivalent diameter of the support. .
- the composite particles can be supported on a region of up to 30% of the equivalent diameter of the catalyst for producing a carboxylic acid ester from the surface of the catalyst for producing a carboxylic acid ester. preferable.
- the reaction rate and the pore diffusion rate of reactants inside the carrier are affected.
- a highly active catalyst for producing a carboxylic acid ester can be obtained without reducing the particle size of the support.
- the catalyst for carboxylic acid ester production may have an external layer substantially free of composite particles outside the support layer in which the composite particles are localized.
- the outer layer is preferably formed with a thickness of 0.01 to 15 ⁇ m from the outer surface of the carrier.
- the thickness of the outer layer substantially free of composite particles is selected in an optimum range depending on the reaction characteristics, the physical properties of the support, the amount of composite particles supported, etc., preferably 0.01 to 15 ⁇ m, more preferably 0.1 to 0.1 ⁇ m. 10 ⁇ m, more preferably 0.2 to 5 ⁇ m.
- the thickness of the outer layer exceeds 15 ⁇ m, the effect of improving the life of the catalyst does not change when the composite particles are used as a catalyst, but the catalytic activity may be lowered.
- the thickness of the outer layer is less than 0.01 ⁇ m, the composite particles tend to fall off due to abrasion.
- the term "substantially free of composite particles” means that the relative intensity of 10% or more in the X-ray microprobe analysis method described later or the secondary electron reflection image of a high-resolution scanning electron microscope.
- a peak indicating the distribution of nickel and/or cobalt in an oxidized state and X is substantially It means it doesn't exist.
- Nickel in an oxidized state that can constitute the composite particles in the present embodiment is preferably a nickel oxide produced by combining nickel with oxygen (e.g., Ni 2 O, NiO, NiO 2 , Ni 3 O 4 , Ni 2 O 3 ), or a composite oxide containing nickel, such as a nickel oxide compound or solid solution formed by combining nickel with X and/or one or more other metal elements and oxygen, or a mixture thereof. .
- nickel oxide produced by combining nickel with oxygen (e.g., Ni 2 O, NiO, NiO 2 , Ni 3 O 4 , Ni 2 O 3 )
- a composite oxide containing nickel such as a nickel oxide compound or solid solution formed by combining nickel with X and/or one or more other metal elements and oxygen, or a mixture thereof.
- the oxidized cobalt that can constitute the composite particles in the present embodiment is preferably a cobalt oxide (e.g., CoO, Co 2 O 3 , Co 3 O 4 ) produced by combining cobalt with oxygen, Alternatively, it is a cobalt-containing composite oxide such as a cobalt oxide compound or solid solution produced by combining cobalt with X and/or one or more other metal elements with oxygen, or a mixture thereof.
- a cobalt oxide e.g., CoO, Co 2 O 3 , Co 3 O 4
- it is a cobalt-containing composite oxide such as a cobalt oxide compound or solid solution produced by combining cobalt with X and/or one or more other metal elements with oxygen, or a mixture thereof.
- nickel oxide refers to a compound containing nickel and oxygen.
- Nickel oxides include Ni 2 O, NiO, NiO 2 , Ni 3 O 4 , Ni 2 O 3 or hydrates thereof, hydroperoxides of nickel containing OOH groups, or nickel containing O 2 groups. of peroxides or mixtures thereof.
- composite oxide used herein represents an oxide containing two or more metals.
- a “composite oxide” is an oxide in which two or more kinds of metal oxides form a compound. oxides), but it is a broader concept than composite oxides, and includes all oxides in which two or more metals are composited. An oxide in which two or more kinds of metal oxides form a solid solution is also included in the category of composite oxides.
- nickel oxide and/or cobalt oxide and X when nickel oxide and/or cobalt oxide and X are combined as described above, nickel oxide and/or cobalt oxide having oxidative esterification activity
- the original catalytic performance tends to be drawn out, and a remarkably high catalytic performance that has not been achieved with catalysts composed of each single component tends to appear.
- This is a unique effect expressed by combining nickel oxide and/or cobalt oxide with X. Due to the dual functional effect or the generation of new active species between the two metal components, each single This is thought to be due to the creation of a new catalytic action completely different from that of a single component.
- Such a catalyst for producing carboxylic acid esters has higher selectivity for carboxylic acid esters than a catalyst in which nickel oxide or gold is supported alone on a carrier, and the activity is greatly improved at a specific Ni/Au composition ratio. There is a tendency.
- the catalytic activity per metal atom is higher than that of each single-component supported particle, and the expression of the catalytic function by the composite strongly depends on the supported composition of nickel and gold. This is presumed to be due to the presence of an optimum ratio for forming the optimum oxidation state of nickel for the reaction.
- TEM/STEM transmission electron microscope/scanning transmission electron microscope
- the nickel component alone is supported on the carrier. Furthermore, the existence state of the metal can be confirmed by subjecting it to X-ray photoelectron spectroscopy (XPS) and powder X-ray diffraction (powder XRD).
- XPS X-ray photoelectron spectroscopy
- Powder XRD powder X-ray diffraction
- gold exists as a crystalline metal
- Nickel is observed to exist as an amorphous oxide with a valence of two.
- UV-Vis ultraviolet-visible spectroscopy
- surface plasmons derived from gold nanoparticles typically observed in gold nanoparticles of a single metal species It is observed that the absorption peak (about 530 nm) disappears due to the compositing of nickel oxide and gold. Such disappearance of the surface plasmon absorption peak is due to other metal oxide species other than nickel oxide (for example, chromium oxide, manganese oxide, iron oxide, cobalt oxide, copper oxide, zinc oxide, etc.) that had no effect on the reaction. metal oxides) and gold.
- nickel oxide for example, chromium oxide, manganese oxide, iron oxide, cobalt oxide, copper oxide, zinc oxide, etc.
- This disappearance of the surface plasmon absorption peak is considered to be the result of the hybridization of the electronic states through the contact interface between the oxidized nickel and gold, that is, the hybridization of the two metal species.
- the conversion to highly oxidized nickel oxide can be confirmed by the color tone change of the catalyst and ultraviolet-visible spectroscopy (UV-Vis).
- UV-Vis ultraviolet-visible spectroscopy
- the addition of gold to nickel oxide causes the nickel oxide to change color from grayish green to brownish brown, and the UV spectrum exhibits absorption over almost the entire visible region.
- the shape of its UV spectrum and the color of the catalyst are similar to highly oxidized nickel peroxide (NiO 2 ) measured as a reference sample.
- NiO 2 highly oxidized nickel peroxide
- the structure of the composite particles when gold is selected as X is a form in which gold particles are used as nuclei and the surfaces are coated with nickel oxide in a highly oxidized state. Gold atoms are thought to be absent.
- the composite particles are preferably carried on the carrier in a highly dispersed state.
- the composite particles are more preferably dispersed and supported in the form of fine particles or thin films, and the average particle diameter is preferably 2 to 10 nm, more preferably 2 to 8 nm, and even more preferably 2 to 6 nm.
- the average particle diameter of the composite particles is within the above range, a specific active species structure composed of nickel and/or cobalt and X tends to be formed, and reaction activity tends to be improved.
- the average particle size of the composite particles in the present embodiment means the number average particle size measured with a transmission electron microscope (TEM). Specifically, in the image observed with the transmission electron microscope, the black contrast portion is the composite particle, and the diameter of each particle can be measured and the number average calculated.
- TEM transmission electron microscope
- the composition of nickel or cobalt and X in the composite particles is preferably in the range of 0.1 to 10, more preferably 0.2 to 8.0, More preferably, it is in the range of 0.3 to 6.0.
- Ni/X atomic ratio or the Co/X atomic ratio is within the above range, a specific active species structure composed of nickel and/or cobalt and X and an oxidation state of nickel and/or cobalt optimum for the reaction are formed. As a result, the activity and selectivity tend to be higher than those outside the above range.
- the form of the composite particles is not particularly limited as long as both components of nickel and/or cobalt and X are contained, but preferably both components coexist in the particles, and the phase structure, for example, the chemical species are randomly distributed at the crystal sites.
- core-shell structure with concentric spherical separation of each chemical species, anisotropic phase-separated structure with anisotropic phase separation, and heterobondophilic structure with both chemical species existing next to each other on the particle surface It is preferably in the form having a structure of More preferably, it has a nucleus composed of X, and the surface of the nucleus is coated with nickel and/or cobalt in an oxidized state.
- the shape of the composite particles is not particularly limited as long as both components are included, and may be spherical or hemispherical.
- the composite particles in the present embodiment contain nickel and/or cobalt and X in any particle, and the surface of X is coated with nickel and/or cobalt. confirmed to have.
- the atomic ratio of nickel and/or cobalt to X varies depending on the position of the composition analysis point in the particle, and more nickel and/or cobalt is detected at the edge of the particle than at the center of the particle. . Therefore, even individual particles have a range in the atomic ratio of nickel or cobalt to X depending on the position of the analysis point, and the range is included in the Ni/X atomic ratio or Co/X atomic ratio range described above. .
- UV-Vis ultraviolet-visible spectroscopy
- Single nanoparticles of gold, silver, and copper exhibit surface plasmon absorption due to the coupling of the optical field in the visible to near-infrared region with the surface free electrons of the metal.
- an absorption spectrum based on plasmon resonance derived from gold particles is observed at a wavelength of about 530 nm.
- the surface plasmon absorption disappears, so it is conceivable that gold does not exist on the surface of the composite particles in the present embodiment. can.
- the solid form of nickel is not particularly limited as long as a predetermined activity can be obtained, but it is preferably amorphous in which no diffraction peak is observed in X-ray diffraction. With such a form, it is estimated that when used as a catalyst for an oxidation reaction, the interaction with oxygen increases, and furthermore, the bonding interface between nickel and X in the oxidized state increases, so it is more excellent. activity tends to be obtained.
- X is at least one element selected from the group consisting of nickel, palladium, platinum, ruthenium, gold, silver and copper. More preferably, it is selected from nickel, palladium, ruthenium, gold and silver.
- the chemical state of X may be a metal, an oxide, a hydroxide, a complex compound containing X and nickel, cobalt or one or more other metal elements, or a mixture thereof, but the preferred chemical state is metal Alternatively, it is an oxide, more preferably a metal.
- the solid form of X is not particularly limited as long as it can obtain a predetermined activity, and may be in either crystalline or amorphous form.
- other metal elements refers to the constituent elements of the carrier, nickel and/or cobalt in an oxidized state, and X, as well as the third component contained in the catalyst for producing a carboxylic acid ester.
- elements or metal components such as alkali metals, alkaline earth metals and rare earth metals.
- the catalyst for carboxylic acid ester production of the present embodiment supports nickel and/or cobalt in an oxidized state and X on a support as described above, and provides composite particles composed of nickel and/or cobalt in an oxidized state and X. Excellent effect is exhibited by forming.
- composite particles refers to particles containing different bimetallic species in one particle.
- Other bimetallic species include bimetallic particles in which both nickel and/or cobalt and X are metals, and metal particles forming an alloy or intermetallic compound of nickel and/or cobalt and X.
- these tend to have lower selectivity and catalytic activity for the target product than the catalyst for producing carboxylic acid esters of the present embodiment.
- the catalyst for carboxylic acid ester production of the present embodiment contains oxidized nickel and/or cobalt alone on a support, in addition to composite particles composed of oxidized nickel and/or cobalt and X. is preferred.
- the presence of nickel and/or cobalt in an oxidized state that is not combined with X further enhances the structural stability of the catalyst for producing a carboxylic acid ester, resulting in an increase in pore diameter due to a long-term reaction and accompanying particle growth of the composite particles. is suppressed. This effect becomes remarkable when an aluminum-containing silica-based composition containing silica and alumina is used as a carrier, as will be described later.
- the structural stability of the catalyst for carboxylic acid ester production is enhanced by allowing nickel and/or cobalt in an oxidized state to exist alone on the support, and the pore diameter increases due to long-term reaction, and the particles of the composite particles accompany this. The effect of suppressing growth will be described.
- an alkali metal or alkaline earth metal compound is added to the reaction system, and the pH of the reaction system is adjusted to 6 to 9, preferably under neutral conditions (e.g., pH 6 .5 to 7.5), that is, by maintaining the pH at around 7 as much as possible, by-products such as acetal due to acidic substances typified by methacrylic acid or acrylic acid, which are by-products unique to the production reaction of carboxylic acid esters. can be suppressed.
- neutral conditions e.g., pH 6 .5 to 7.5
- a long-term reaction was carried out by the above-described reaction operation using a gold particle-supported material in which single-component gold particles were supported on a support made of an aluminum-containing silica-based composition containing silica and alumina.
- the structure of the gold particle-supported material tends to change, albeit gradually.
- This phenomenon is caused by repeated local exposure of the support particles to acids and bases due to the reaction operation, dissolution and deposition of part of the Al in the support, and rearrangement of the silica-alumina crosslinked structure. , is considered to be caused by the enlargement of the pore size of the support particles.
- sintering of the gold particles occurs as the pore diameter increases, and the surface area decreases, which tends to decrease the catalytic activity.
- the structural stability of the support particles due to the above reaction operation is enhanced, and the expansion of the pore size and the growth of the composite particles are suppressed.
- nickel and/or cobalt in an oxidized state react with the constituent elements of the carrier to produce a composite oxide containing nickel and/or cobalt, such as an oxide compound or solid solution of nickel and/or cobalt. It is believed that such a nickel compound acted to stabilize the silica-alumina crosslinked structure, and as a result, the structural change of the support particles was greatly improved.
- the present inventors presume that the appearance of such a structure-stabilizing effect of the support is due to nickel and/or cobalt in an oxidized state present in the support. Therefore, when the oxidized nickel and/or cobalt contained in the composite particles are in contact with the support, this effect can of course be obtained, and the oxidized nickel and/or cobalt alone does not exist on the support. It is thought that a greater stabilizing effect can be obtained when the
- the carrier of the carboxylic acid ester production catalyst of the present embodiment is not particularly limited as long as it can support nickel and/or cobalt in an oxidized state and X, and a catalyst carrier used for conventional chemical synthesis may be used. can be done.
- Examples of carriers include activated carbon, silica, alumina, silica-alumina, titania, silica-titania, zirconia, magnesia, silica-magnesia, silica-alumina-magnesia, calcium carbonate, zinc oxide, zeolite, crystalline metallosilicate, and the like.
- Various carriers can be mentioned.
- Preferred are activated carbon, silica, alumina, silica-alumina, silica-magnesia, silica-alumina-magnesia, titania, silica-titania and zirconia, more preferred are silica-alumina and silica-alumina-magnesia.
- the carrier is selected from alkali metals (Li, Na, K, Rb, Cs), alkaline earth metals (Be, Mg, Ca, Sr, Ba), and rare earth metals (La, Ce, Pr) alone or in multiple Some metal components may also be included.
- alkali metals Li, Na, K, Rb, Cs
- alkaline earth metals Be, Mg, Ca, Sr, Ba
- rare earth metals La, Ce, Pr
- the metal component to be supported for example, nitrates, acetates, and the like, which are converted to oxides by calcination, are preferable.
- a carrier made of an aluminum-containing silica-based composition containing silica and aluminum is preferably used. That is, it is preferred that the carrier contains silica and alumina.
- the carrier has higher water resistance than silica and higher acid resistance than alumina.
- it has superior physical properties compared to conventional supports, such as being harder and having higher mechanical strength than activated carbon, and it stabilizes nickel and/or cobalt in an oxidized state, which are active ingredients, and X. can be carried.
- the catalyst for carboxylic acid ester production can maintain high reactivity over a long period of time.
- a catalyst for producing a carboxylic acid ester having a specific atomic ratio between nickel and/or cobalt in an oxidized state and X, and having an aluminum-containing silica-based composition as a carrier when used as a catalyst for chemical synthesis, a catalyst carrier While having a high surface area suitable for use as a catalyst, it has high mechanical strength, is physically stable, and satisfies the corrosion resistance to the reaction-specific liquid properties.
- the following describes the characteristics of the carrier made of the alumina-containing silica-based composition containing silica and alumina of the present embodiment, which made it possible to significantly improve the catalyst life.
- the reason why the mechanical strength and chemical stability of the carrier could be greatly improved is presumed as follows.
- Si—O—Al—O—Si bonds are newly formed by adding aluminum (Al) to uncrosslinked silica (Si—O) chains of silica gel, resulting in Si—
- the Si—O bond is strengthened by forming an Al crosslinked structure without losing the original stability of the O chain to acidic substances, and the hydrolysis resistance stability (hereinafter simply referred to as “water resistance”) is remarkably improved. It is considered to be improving.
- water resistance hydrolysis resistance stability
- the formation of the Si--O--Al--O--Si crosslinked structure reduces the number of uncrosslinked Si--O chains and increases the mechanical strength as compared with the case of silica gel alone. That is, it is presumed that there is a correlation between the amount of Si--O--Al--O--Si structure formed and the improvement in mechanical strength and water resistance of the resulting silica gel.
- the support has high mechanical strength and high chemical stability, as described above. It is to be provided with improved physical properties as compared with conventional generally used carriers. As a result, nickel and/or cobalt, which are the active ingredients, are less likely to separate from X, and it is believed that they can be stably supported over a long period of time.
- nickel oxide or cobalt oxide is an acid-soluble compound, when it is used as a catalyst for synthesizing carboxylic acid esters, it is eluted by acidic substances typified by methacrylic acid or acrylic acid, which are by-products unique to this reaction. presumed to be
- nickel and/or cobalt in the catalyst for producing carboxylic acid esters of the present embodiment is a single compound. Not only nickel oxide and/or cobalt oxide, but also nickel and/or cobalt oxide compounds or solid solutions of nickel and/or cobalt produced by combining nickel oxide and/or cobalt oxide with constituent elements of the carrier, or mixtures thereof. Alternatively, it is presumed that a composite oxide containing cobalt is produced.
- Double-crystal high-resolution X-ray fluorescence spectroscopy has extremely high energy resolution, and the chemical state can be analyzed from the energy position (chemical shift) and shape of the obtained spectrum.
- the chemical state can be analyzed in detail.
- the catalyst for carboxylic acid ester production of the present embodiment a change appeared in the NiK ⁇ spectrum, and a chemical state of nickel different from nickel oxide, which is a single compound, was confirmed.
- nickel aluminate which is produced from nickel oxide and alumina, is a compound that is insoluble in acids. It is presumed that the elution of the nickel component was greatly improved as a result of the formation of such a nickel compound on the carrier.
- a preferred elemental composition of the support made of an aluminum-containing silica-based composition containing silica and alumina is that the amount of aluminum is 1 to 30 mol%, preferably 5 to 30 mol%, more preferably 5 to 30 mol%, relative to the total molar amount of silicon and aluminum. It is preferably in the range of 5 to 25 mol %. When the amount of aluminum is within the above range, acid resistance and mechanical strength tend to be good.
- the carrier in the catalyst for producing a carboxylic acid ester of the present embodiment further contains at least one basic metal oxide selected from alkali metals, alkaline earth metals and rare earth metals. is preferable from the viewpoint of further improving mechanical strength and chemical stability.
- Li, Na, K, Rb, and Cs as alkali metals of the basic metal component, Be, Mg, Ca, Sr, Ba, etc. as alkaline earth metals, and La, Ce, Pr as rare earth metals. is mentioned.
- Mg is preferred as the alkaline earth metal
- the carrier contains silica, alumina and magnesia.
- the elemental composition of the support containing silica, alumina, and oxides of at least one basic metal selected from alkali metals, alkaline earth metals and rare earth metals is such that the amount of aluminum is 1 to 1 with respect to the total molar amount of silicon and aluminum. It is in the range of 30 mol %, preferably 5 to 30 mol %, more preferably 5 to 25 mol %.
- the composition ratio of the basic metal oxide and alumina is (alkali metal + 1/2 ⁇ alkaline earth metal + 1/3 ⁇ rare earth metal) / Al atomic ratio, preferably 0.5 to 10, more preferably 0 0.5 to 5.0, more preferably 0.5 to 2.0.
- a preferred method for preparing a carrier will be described using an example of using an aluminum-containing silica-based composition containing silica and alumina, but the method for preparing the carrier is not limited to the following. Specifically, a silica sol and an aluminum compound solution are reacted to prepare an aluminum-containing silica-based composition, thereby preparing a carrier.
- silica sol is used as the silica source.
- a silica sol and an aluminum compound are mixed to obtain a mixture sol containing the silica sol and the aluminum compound, subjected to multistage hydrothermal reaction at 20 to 100° C. for 1 to 48 hours, and then dried to form a gel. It is preferable to obtain and calcine under the temperature, time, and atmosphere conditions described later, or add an alkaline aqueous solution to the above mixture sol to coprecipitate silica and an aluminum compound, dry, and then calcine under the conditions described later.
- a carrier made of an aluminum-containing silica-based composition having a desired particle size can be obtained by a process such as pulverizing the mixture sol as it is using a spray dryer or drying the mixture sol to granulate a gel. is also possible.
- a method for preparing a carrier comprising silica, alumina, and an oxide of at least one basic metal selected from alkali metals, alkaline earth metals and rare earth metals includes a carrier comprising an aluminum-containing silica-based composition comprising silica and alumina described above. Dry a slurry obtained by mixing an alkali metal compound, an alkaline earth metal compound and/or a rare earth metal compound with silica and aluminum components according to the preparation method of No., and then calcine under the conditions described later.
- alkali metals alkali metals, alkaline earth metals, and rare earth metals
- compounds that are generally commercially available can be used in the same manner as aluminum raw materials.
- Preferred are water-soluble compounds, more preferred are hydroxides, carbonates, nitrates and acetates.
- a method of adsorbing a basic metal component selected from alkali metals, alkaline earth metals and rare earth metals onto a carrier made of an aluminum-containing silica-based composition can be used.
- a method using an immersion method such as adding a carrier to a solution in which a basic metal compound is dissolved and then performing a drying treatment, or an impregnation method, in which a basic compound equivalent to the pore capacity of the carrier is impregnated and then dried.
- an impregnation method in which a basic compound equivalent to the pore capacity of the carrier is impregnated and then dried.
- it is necessary to take care such as carrying out the liquid drying treatment under moderate conditions in order to highly disperse the basic metal component on the carrier.
- inorganic substances and organic substances to the mixed slurry of the various raw materials described above in order to control the slurry properties, finely adjust the characteristics such as the pore structure of the product, and the physical properties of the resulting carrier.
- inorganic substances used include mineral acids such as nitric acid, hydrochloric acid and sulfuric acid, alkali metals such as Li, Na, K, Rb and Cs, and metal salts such as alkaline earth metals such as Mg, Ca, Sr and Ba. and water-soluble compounds such as ammonia and ammonium nitrate, as well as clay minerals that disperse in water to form suspensions.
- organic substances include polymers such as polyethylene glycol, methyl cellulose, polyvinyl alcohol, polyacrylic acid, and polyacrylamide.
- the effects of adding inorganic substances and organic substances vary, but the main effects are the formation of spherical carriers and the control of pore diameter and pore volume. is an important factor.
- the viscosity and solid content concentration with an inorganic substance or an organic substance, the liquid quality can be changed so that a spherical carrier can be easily obtained.
- the pore diameter and pore volume can be controlled by a multistage hydrothermal synthesis process of a mixed slurry, which will be described later. It is also preferable to appropriately select and use an optimum organic compound that remains inside the carrier during the molding step and that can be removed by baking and washing operations after molding.
- the method for producing the catalyst for producing a carboxylic acid ester is not particularly limited, but according to the following method, it is easy to obtain a catalyst for producing a carboxylic acid ester having a predetermined range of bulk density and a predetermined particle size distribution according to the present embodiment. Become.
- a preferred method for producing the catalyst for producing a carboxylic acid ester according to the present embodiment includes Step I of spray-drying the mixed slurry in a dryer using a rotating disc system, and Step II of calcining the resulting spray-dried product to obtain a carrier. and a step III of supporting catalytic metal particles on the carrier. Furthermore, in the method for producing a catalyst for producing a carboxylic acid ester according to the present embodiment, in the step I, the feed amount of the mixed slurry to be sprayed with respect to the lateral radius of the spray dryer is 5 ⁇ 10 ⁇ 3 m 2 /Hr or more.
- the catalyst for producing a carboxylic acid ester according to the present embodiment can easily obtain a bulk density and a particle size distribution within a predetermined range, suppressing outflow of the catalyst, and exhibiting high activity. A production catalyst is obtained.
- the raw material mixed liquid can be stirred while appropriately adjusting the heating conditions.
- the carrier in this embodiment can be produced by spray-drying a mixed slurry containing the various raw materials and additives described above, as in Steps I to II.
- a known spraying device such as a rotary disk system, a two-fluid nozzle system, a pressurized nozzle system, or the like can be used.
- the liquid (mixed slurry) to be sprayed is preferably used in a well-mixed state (a state in which each component is well dispersed).
- a good mixed state tends to reduce adverse effects on the performance of the carrier, such as deterioration in durability due to uneven distribution of each component.
- the viscosity of the slurry may increase and gelation (condensation of colloid) may occur in some cases, and there is concern about the formation of non-uniform particles. Therefore, in addition to consideration such as gradually mixing the raw materials under stirring, it may be preferable to control the silica sol to a metastable region around pH 2, for example, by adding an acid or alkali. .
- the liquid (mixed slurry) to be sprayed preferably has a certain degree of viscosity and solid content concentration.
- the viscosity and solid content concentration are above a certain level, the porous body obtained by spray drying tends to be prevented from becoming a depressed sphere rather than a true sphere.
- the viscosity and solid content concentration are below a certain level, the dispersibility between the porous bodies can be ensured, and there is a tendency to contribute to the stable formation of droplets.
- the change in viscosity (final ⁇ viscosity) from 1 hour before the start of spray drying (raw material mixture state) to spraying (mixed slurry state) affects the particle size distribution and bulk density obtained by spray drying.
- the final ⁇ viscosity is preferably less than 10 mPa ⁇ s/Hr, more preferably 7 mPa ⁇ s/Hr or less, and even more preferably 5 mPa ⁇ s/Hr or less.
- the lower limit of the final ⁇ viscosity is not particularly limited, it is, for example, 0 mPa ⁇ s/Hr or more.
- the final ⁇ viscosity can be measured based on the method described in Examples below.
- the solid content concentration is preferably in the range of 10 to 50% by mass in terms of shape, bulk density and particle size.
- the tip speed of the stirring blade when stirring the raw material mixture is not particularly limited, but from the viewpoint of controlling the final ⁇ viscosity, it is preferably 3 m / s or more and 9 m / s or less, more preferably 4 m / s or more and 8 m / s. or less, more preferably 5 m/s or more and 7 m/s or less.
- a rotating disk type dryer includes, for example, a disk such as an atomizer.
- the disk can be used to spray the mixed slurry and adjust the bulk density and particle size distribution of the dried product.
- the feed amount of the liquid to be sprayed with respect to the lateral radius of the spray dryer is preferably 5 ⁇ 10 ⁇ 3 m 2 /Hr or more and 70 ⁇ 10 ⁇ 3 m 2 /Hr or less, and is preferably 10 ⁇ 10 ⁇ 3 m 2 .
- the peripheral speed of the disk is preferably 10 m/s to 120 m/s, more preferably 20 m/s to 100 m/s, and even more preferably 30 m/s to 90 m/s.
- the sintering temperature of the carrier is generally selected from the range of 200-800°C. Firing at a temperature exceeding 800° C. is not preferable because the specific surface area tends to decrease significantly. Also, the firing atmosphere is not particularly limited, but the firing is generally performed in air or nitrogen. The firing time can be determined according to the specific surface area after firing, but is generally 1 to 48 hours. Since the physical properties of the support such as porosity change depending on the firing conditions, it is necessary to select appropriate temperature conditions and temperature rising conditions. If the firing temperature is too low, it tends to be difficult to maintain the durability of the composite oxide, and if it is too high, the pore volume may decrease. Moreover, it is preferable that the temperature is gradually increased by using a program temperature increase or the like.
- the inorganic and organic substances are violently gasified or burned, and exposed to a temperature higher than the set temperature, which causes pulverization, which is not preferable.
- the particle size distribution can also be controlled by adding a classification step after calcination or after supporting the catalyst.
- Classifiers include sieves, vibrating sieves, inertial classifiers, forced vortex centrifugal classifiers, free vortex classifiers such as cyclones, and the like.
- the specific surface area of the carrier is preferably 10 m 2 /g or more as measured by the BET nitrogen adsorption method, from the viewpoints of ease of supporting the composite particles, reaction activity when used as a catalyst, difficulty in detachment, and reaction activity. 2 /g or more is more preferable, and 50 m 2 /g or more is even more preferable. From the viewpoint of activity, there is no particular limitation, but from the viewpoint of mechanical strength and water resistance, it is preferably 700 m 2 /g or less, more preferably 350 m 2 /g or less, and even more preferably 300 m 2 /g or less.
- the pore diameter of the support is smaller than 3 nm, the peeling property of the supported metal tends to be good.
- the pore diameter is preferably 3 nm or more.
- the pore size of the carrier is preferably 3 nm to 50 nm, more preferably 3 nm to 30 nm.
- the pore volume is necessary because there are pores that support the composite nanoparticles. However, when the pore volume increases, the strength tends to decrease rapidly.
- the pore volume is preferably in the range of 0.1 to 1.0 mL/g, more preferably in the range of 0.1 to 0.5 mL/g, from the viewpoint of strength and supporting properties.
- the carrier of the present embodiment preferably has a pore diameter and a pore volume that satisfy the above ranges.
- a hollow columnar or honeycomb shape with a structure with little pressure loss is selected for a fixed bed.
- the form used is selected by selecting the particle size.
- a particle size of 10 to 200 ⁇ m is preferable, more preferably 20 to 150 ⁇ m, and still more preferably 30 to 150 ⁇ m in terms of balance with reaction characteristics.
- a particle size is selected.
- small particles of 0.1 to 20 ⁇ m or less are preferred because they are more reactive. It can be used as a catalyst for chemical synthesis by changing the type and form in accordance with such purpose of use.
- the amount of oxidized nickel or cobalt supported on the carrier is not particularly limited, but is usually 0.01 to 20% by mass, preferably 0.1 to 10% by mass, more preferably 0.1 to 10% by mass, as nickel or cobalt relative to the mass of the carrier. 0.2 to 5% by mass, more preferably 0.5 to 2% by mass.
- the amount of X supported on the carrier is usually 0.01 to 10% by mass, preferably 0.1 to 5% by mass, more preferably 0.2 to 2% by mass, more preferably 0% by mass, as a metal, relative to the mass of the carrier. .3 to 1.5% by weight, particularly preferably 0.5 to 1.0% by weight.
- the composition ratio of nickel or cobalt and alumina in the catalyst is the Ni / Al atomic ratio or the Co / Al atomic ratio, preferably 0.01 to 1.0, more preferably 0.02 to 0.8, still more preferably 0.04 to 0.6.
- the composition ratio of nickel or cobalt and alumina in the support is Ni/
- the Al atomic ratio or Co/Al atomic ratio is preferably 0.01 to 1.0, more preferably 0.02 to 0.8, still more preferably 0.04 to 0.6, and nickel or cobalt and the composition ratio of the basic metal component is Ni / (alkali metal + alkaline earth metal + rare earth metal) atomic ratio or Co / (alkali metal + alkaline earth metal + rare earth metal) atomic ratio, preferably 0.01 ⁇ 1.2, more preferably 0.02 to 1.0, still more preferably 0.04 to 0.6.
- the catalyst for carboxylic acid ester production of the present embodiment may contain a third component element in addition to nickel and/or cobalt in an oxidized state and X as active components.
- the third component element include titanium, vanadium, chromium, manganese, iron, zinc, gallium, zirconium, niobium, molybdenum, rhodium, cadmium, indium, tin, antimony, tellurium, hafnium, tantalum, tungsten, rhenium, and osnium. , iridium, mercury, thallium, lead, bismuth, aluminum, boron, silicon, phosphorous.
- the content of these third component elements is preferably 0.01 to 20% by mass, more preferably 0.05 to 10% by mass, in the supported material.
- the carboxylic acid ester production catalyst may contain at least one metal component selected from alkali metals, alkaline earth metals and rare earth metals. The contents of alkali metals, alkaline earth metals and rare earth metals are preferably selected from the range of 15 mass % or less in the support.
- These third component elements or alkali metals, alkaline earth metals and rare earth metals may be contained in the carrier during the production or reaction of the catalyst for producing carboxylic acid ester, or may be incorporated in the carrier in advance. You can also use the method of keeping
- the specific surface area of the catalyst for producing a carboxylic acid ester of the present embodiment is preferably 20 to 350 m 2 /g, more preferably 20 to 350 m 2 /g, as measured by the BET nitrogen adsorption method, from the viewpoint of reaction activity and difficulty in releasing active components. is in the range of 50-300 m 2 /g, more preferably 100-250 m 2 /g.
- the pore diameter of the carboxylic acid ester production catalyst is derived from the pore structure of the carrier.
- the pore diameter is preferably 3 nm or more from the viewpoint of maintaining high reaction activity without excessively increasing the diffusion resistance in the pores so as not to make the diffusion process of the reaction substrate rate-limiting.
- it is preferably 50 nm or less from the viewpoint of the difficulty of breaking the supported material and the difficulty of peeling off the supported composite particles. Therefore, the pore size of the catalyst for producing carboxylic acid ester is preferably 3 nm to 50 nm, more preferably 3 nm to 30 nm, and still more preferably 3 nm to 10 nm.
- the pore volume is preferably in the range of 0.1 to 1.0 mL/g, more preferably 0.1 to 0.5 mL/g, still more preferably 0.1 to 0.5 mL/g, from the viewpoint of supporting characteristics and reaction characteristics. 3 mL/g range.
- the carboxylic acid ester production catalyst of the present embodiment preferably has a pore diameter and a pore volume that satisfy the above ranges.
- the method for producing the catalyst for producing a carboxylic acid ester of the present embodiment is not particularly limited, but may include the following preferred steps. Each step will be described below.
- the temperature is adjusted so that the temperature of the mixture of both liquids is 60° C. or higher.
- a precursor of a catalyst for producing a carboxylic acid ester is produced in which nickel and/or cobalt and the X component are deposited on a carrier.
- the precursor obtained in the first step is washed with water as necessary, dried, and then heat-treated to obtain a catalyst for producing a carboxylic acid ester.
- a carrier carrying an oxide of at least one basic metal selected from the group consisting of alkali metals, alkaline earth metals and rare earth metals is aged in water. It is preferred to carry out the steps.
- a sharper distribution layer of the composite particles can be obtained.
- the aging temperature of the carrier can be room temperature, but it is preferably selected from the range of 60 to 150° C., which is higher than room temperature, because the change in pore structure is slow.
- the range of 60 to 100°C is preferable.
- the aging treatment time varies depending on the temperature conditions. For example, at 90° C., it is preferably 1 minute to 5 hours, more preferably 1 to 60 minutes, and even more preferably 1 to 30 minutes.
- the carrier can be dried and calcined once before use. It is preferable to contact with an acidic aqueous solution to immobilize nickel and/or cobalt and the X component on the carrier insoluble.
- Examples of soluble metal salts containing nickel used for catalyst preparation include nickel nitrate, nickel acetate, and nickel chloride.
- As the soluble metal salt containing X for example, when palladium is selected as X, palladium chloride, palladium acetate, etc. are selected, and when ruthenium is selected, ruthenium chloride, ruthenium nitrate, etc. are selected, and gold is selected. Examples thereof include chloroauric acid, sodium chloride, potassium dicyanoaurate, diethylamine gold trichloride, gold cyanide, and the like, and when silver is selected, silver chloride, silver nitrate, and the like.
- Each concentration of the aqueous solution containing nickel and/or cobalt and X is usually 0.0001 to 1.0 mol/L, preferably 0.001 to 0.5 mol/L, more preferably 0.005 to 0.2 mol/L. L range.
- the ratio of nickel or cobalt and X in the aqueous solution is preferably in the range of 0.1 to 10, more preferably 0.2 to 5.0, further preferably 0 as Ni/X atomic ratio or Co/X atomic ratio. 0.5 to 3.0.
- the temperature at which the support is brought into contact with an acidic aqueous solution of a soluble metal salt containing nickel and/or cobalt and X is one of the important factors controlling the distribution of the composite particles.
- the temperature is too low, the reaction tends to slow down and the distribution of the composite particles tends to widen, although this varies depending on the amount of at least one basic metal oxide selected from the group consisting of alkaline earth metals and rare earth metals.
- the temperature when contacting nickel and/or cobalt with an acidic aqueous solution of a soluble metal salt containing X is high.
- the temperature is such that a reaction rate can be obtained, preferably 60° C. or higher, more preferably 70° C. or higher, still more preferably 80° C. or higher, and particularly preferably 90° C. or higher. Since the mixture of the acidic aqueous solution and the aqueous slurry should be mixed so that the temperature of the mixture is 60° C. or higher, the aqueous slurry may be heated to such an extent that the mixed solution exceeds 60° C. even if the acidic aqueous solution is added. Alternatively, only the acidic aqueous solution may be heated. Of course, both the acidic aqueous solution and the water slurry may be heated to 60° C. or higher.
- the reaction can be carried out under pressure at a temperature above the boiling point of the solution, but for ease of operation, it is usually preferred to carry out at a temperature below the boiling point.
- the time for immobilizing nickel and/or cobalt and the X component is not particularly limited, and varies depending on conditions such as the carrier species, the amount of nickel and/or cobalt and X supported, the ratio, etc., but is usually from 1 minute to. 5 hours, preferably 5 minutes to 3 hours, more preferably 5 minutes to 1 hour.
- the method for producing a catalyst for producing a carboxylic acid ester of the present embodiment includes at least one basic metal oxide selected from the group consisting of alkali metals, alkaline earth metals and rare earth metals pre-supported on a carrier, and nickel and/or is based on the principle of immobilizing nickel and/or cobalt and the X component insoluble by chemical reaction between the cobalt and the soluble metal salt containing X. In order to make the composite of nickel and/or cobalt and the X component more satisfactory, it is preferable to simultaneously immobilize both components from a mixed aqueous solution.
- the aqueous slurry containing a carrier carrying an oxide of at least one basic metal selected from the group consisting of alkali metals, alkaline earth metals and rare earth metals contains an alkali metal, It preferably contains at least one basic metal salt selected from the group consisting of alkaline earth metals and rare earth metals.
- the generation of metal black of X can be suppressed, the formation of a composite of nickel and/or cobalt with X can be promoted, and the distribution of composite particles can be controlled more precisely.
- Such an effect can be obtained by adding at least one metal salt selected from the group consisting of alkali metals, alkaline earth metals and rare earth metals to the aqueous solution, and the basic metal oxide preliminarily carried on the carrier. This is presumed to be caused by controlling the rate of chemical reaction between nickel and/or cobalt and a soluble metal salt containing X.
- At least one basic metal salt selected from the group consisting of alkali metals, alkaline earth metals and rare earth metals is selected from water-soluble salts such as inorganic salts such as organic acid salts, nitrates and chlorides of these metals. One or more can be used.
- the amount of at least one basic metal salt selected from the group consisting of alkali metals, alkaline earth metals and rare earth metals varies depending on the amounts and ratios of nickel and/or cobalt and the X component. It is determined by the amount of basic metal oxide allowed to react. Generally, it is 0.001 to 2 mol, preferably 0.005 to 1 mol, with respect to the amounts of nickel and/or cobalt and X component in the aqueous solution.
- the aqueous slurry containing the carrier supporting at least one basic metal oxide selected from the group consisting of alkali metals, alkaline earth metals and rare earth metals contains a soluble aluminum salt.
- Aluminum chloride and aluminum nitrate can be used as soluble aluminum salts.
- a soluble aluminum salt By adding a soluble aluminum salt to the water slurry, it is possible to form an external layer substantially free of composite particles outside the carrier layer in which the composite particles are localized. This is also based on the insoluble immobilization principle described above.
- a soluble salt such as aluminum chloride or aluminum nitrate is used, and aluminum is reacted on the outer surface of the carrier by a chemical reaction with a basic metal oxide pre-loaded on the carrier to produce nickel and/or The reaction field of cobalt and X is consumed, and the basic metal oxide, nickel and/or cobalt and the X component inside are fixed by reaction.
- the amount of the aluminum component varies depending on how many ⁇ m the thickness of the layer that does not support nickel and/or cobalt and the X component is set, and is determined by the amount of the basic metal oxide previously supported on the carrier. . Usually, it is 0.001 to 2 mol, preferably 0.005 to 1 mol, relative to the amount of the basic metal oxide supported on the carrier.
- the first precursor Prior to the heat treatment in the second step, the first precursor is washed with water and dried as necessary.
- the heating temperature of the first precursor is usually 40 to 900°C, preferably 80 to 800°C, more preferably 200 to 700°C, still more preferably 300 to 600°C.
- the atmosphere for heat treatment can be in the air (or in the air), in an oxidizing atmosphere (oxygen, ozone, nitrogen oxides, carbon dioxide, hydrogen peroxide, hypochlorous acid, inorganic or organic peroxides, etc.), or inert It is carried out in a gas atmosphere (helium, argon, nitrogen, etc.).
- the heating time may be appropriately selected according to the heating temperature and the amount of the first precursor.
- the heat treatment can be performed under normal pressure, increased pressure, or reduced pressure.
- reduction treatment can be performed in a reducing atmosphere (hydrogen, hydrazine, formalin, formic acid, etc.) as necessary.
- a treatment method is selected that does not completely reduce the oxidized nickel and/or cobalt to the metallic state.
- the temperature and time for the reduction treatment may be appropriately selected according to the type of reducing agent, the type of X, and the amount of catalyst.
- oxidizing atmosphere oxygen, ozone, nitrogen oxides, carbon dioxide, hydrogen peroxide, hypochlorous acid, inorganic / organic It can also be oxidized with a peroxide, etc.
- the temperature and time in that case are appropriately selected according to the type of oxidizing agent, the type of X and the amount of catalyst.
- a third component element other than nickel and/or cobalt and X can be added during preparation of the support or under reaction conditions.
- Alkali metals, alkaline earth metals and rare earth metals can also be added during catalyst preparation or to the reaction system.
- raw materials for the third component element, alkali metal, alkaline earth metal and rare earth metal are selected from organic acid salts, inorganic acid salts, hydroxides and the like.
- the catalyst for carboxylic acid ester production of the present embodiment can be widely used as a catalyst for chemical synthesis.
- it can be used for a carboxylic acid ester production reaction between an aldehyde and an alcohol, and a carboxylic acid ester production reaction from alcohols.
- the method for producing a carboxylic acid ester of the present embodiment comprises (a) an aldehyde and an alcohol, or (b) one or more alcohols in the presence of the catalyst for producing a carboxylic acid ester of the present embodiment and oxygen. and the step of reacting.
- the catalyst for producing a carboxylic acid ester of the present embodiment exhibits excellent effects particularly when used as a catalyst for an oxidation reaction.
- reaction substrates used in the present embodiment various reaction substrates such as alkanes, olefins, alcohols, and ketones can be used in addition to the aldehydes and alcohols used in the carboxylic acid ester formation reaction shown in the examples. , aldehydes, ethers, aromatic compounds, phenols, sulfur compounds, phosphorus compounds, oxygen-containing nitrogen compounds, amines, carbon monoxide, water and the like.
- These reaction substrates can be used singly or as a mixture of two or more. From these reaction substrates, various industrially useful oxidation products such as oxygen-containing compounds, oxidative adducts and oxidative dehydrogenates can be obtained.
- reaction substrates include alkanes such as methane, ethane, propane, n-butane, isobutane, n-pentane, n-hexane, 2-methylpentane, and 3-methylpentane.
- alkanes such as methane, ethane, propane, n-butane, isobutane, n-pentane, n-hexane, 2-methylpentane, and 3-methylpentane.
- Alkane alkane
- alicyclic alkanes such as cyclopentane, cyclohexane, cycloheptane, cyclooctane, and the like.
- olefins examples include aliphatic olefins such as ethylene, propylene, butene, pentene, hexene, heptene, octene, decene, 3-methyl-1-butene, 2,3-dimethyl-1-butene, and allyl chloride; , cyclohexene, cycloheptene, cyclooctene, and cyclodecene; and aromatic substituted olefins such as styrene and ⁇ -methylstyrene.
- aliphatic olefins such as ethylene, propylene, butene, pentene, hexene, heptene, octene, decene, 3-methyl-1-butene, 2,3-dimethyl-1-butene, and allyl chloride
- alcohols include saturated alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, s-butanol, t-butanol, n-pentanol, n-hexanol, n-heptanol, allyl alcohol and crotyl alcohol.
- saturated and unsaturated aliphatic alcohols such as cyclopentanol, cyclohexanol, cycloheptanol, methylcyclohexanol, cyclohexen-1-ol; ethylene glycol, propylene glycol, trimethylene glycol, 1, Aliphatic and alicyclic polyhydric alcohols such as 3-butanediol, 1,2-cyclohexanediol and 1,4-cyclohexanediol; and aromatic alcohols such as benzyl alcohol, salicyl alcohol and benzhydrol.
- Aldehydes include, for example, aliphatic saturated aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, isobutyraldehyde and glyoxal; aliphatic ⁇ , ⁇ -unsaturated aldehydes such as acrolein, methacrolein and crotonaldehyde; benzaldehyde, tolylaldehyde and benzyl Aromatic aldehydes such as aldehydes and phthalaldehydes, and derivatives of these aldehydes are included.
- aliphatic saturated aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, isobutyraldehyde and glyoxal
- aliphatic ⁇ , ⁇ -unsaturated aldehydes such as acrolein, methacrolein and crotonaldehyde
- ketones include aliphatic ketones such as acetone, methyl ethyl ketone, diethyl ketone, dipropyl ketone and methyl propyl ketone; aromatic ketones such as acetophenone, propiophenone and benzophenone;
- aromatic compounds include benzene, toluene, xylene, naphthalene, anthracene, and derivatives thereof substituted with alkyl groups, aryl groups, halogens, sulfone groups, and the like.
- Phenols include phenol, cresol, xylenol, naphthol, anthol (hydroxyanthracene), and derivatives thereof (hydrogen atoms of aromatic rings substituted with alkyl groups, aryl groups, halogen atoms, sulfonic acid groups, etc.). be done.
- Sulfur compounds include mercaptans such as methyl mercaptan, ethyl mercaptan, propyl mercaptan, benzyl mercaptan, and thiophenol.
- amines include methylamine, ethylamine, propylamine, isopropylamine, butylamine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, allylamine, diallylamine, and the like.
- reaction substrates can be used singly or as a mixture of two or more. Moreover, it does not necessarily need to be purified, and may be a mixture with other organic compounds.
- a method for producing a carboxylic acid ester from an aldehyde and an alcohol by an oxidative esterification reaction in the presence of oxygen using the catalyst for producing a carboxylic acid ester of the present embodiment will be described below as an example.
- aldehydes used as raw materials include C 1 -C 10 aliphatic saturated aldehydes such as formaldehyde , acetaldehyde, propionaldehyde, isobutyraldehyde and glyoxal ; ⁇ -unsaturated aldehydes; C 6 -C 20 aromatic aldehydes such as benzaldehyde, tolylaldehyde, benzaldehyde, phthalaldehyde; and derivatives of these aldehydes. These aldehydes can be used singly or as a mixture of any two or more. In this embodiment the aldehyde is preferably selected from acrolein, methacrolein or mixtures thereof.
- Alcohols include, for example, C 1 -C 10 aliphatic saturated alcohols such as methanol, ethanol, isopropanol, butanol, 2-ethylhexanol and octanol; C 5 -C 10 alicyclic alcohols such as cyclopentanol and cyclohexanol; C 2 -C 10 diols such as ethylene glycol, propylene glycol, butanediol; C 3 -C 10 aliphatic unsaturated alcohols such as allyl alcohol, methallyl alcohol; C 6 -C 20 aromatic alcohols such as benzyl alcohol; Hydroxyoxetanes such as 3-alkyl-3-hydroxymethyloxetane can be mentioned. These alcohols can be used singly or as a mixture of any two or more. In this embodiment, it is preferred that the aldehyde is acrolein and/or methacrolein and the alcohol is methanol.
- the amount ratio of aldehyde and alcohol is not particularly limited, and can be carried out in a wide range such as aldehyde/alcohol molar ratio of 10 to 1/1,000. It is implemented in the range of 2 to 1/50.
- the amount of catalyst used is not particularly limited, and can be greatly changed depending on the type of reaction raw material, catalyst composition and preparation method, reaction conditions, reaction mode, etc. However, when the catalyst is reacted in a slurry state,
- the solid content concentration is preferably within the range of 1 to 50% by mass/volume, more preferably 3 to 30% by mass/volume, and still more preferably 10 to 25% by mass/volume.
- carboxylic acid ester In the production of carboxylic acid ester, it can be carried out by any method such as gas phase reaction, liquid phase reaction, perfusion reaction, etc., either batchwise or continuously.
- reaction can be carried out without a solvent, it can also be carried out using a solvent that is inert to the reaction components, such as hexane, decane, benzene, dioxane, and the like.
- a solvent that is inert to the reaction components such as hexane, decane, benzene, dioxane, and the like.
- the reaction system can also be based on conventionally known systems such as a fixed bed system, a fluidized bed system, and a stirring tank system.
- a reactor type such as a bubble column reactor, a draft tube reactor, a stirred tank reactor, or the like can be used.
- the oxygen used in the production of the carboxylic acid ester may be in the form of molecular oxygen, that is, oxygen gas itself or a mixed gas obtained by diluting oxygen gas with a diluent inert to the reaction, such as nitrogen or carbon dioxide gas.
- Air is preferably used as the oxygen source from the viewpoints of operability, economy, and the like.
- the oxygen partial pressure varies depending on the reaction raw materials such as aldehyde species and alcohol species, reaction conditions, reactor type, etc., but practically, the oxygen partial pressure at the reactor outlet is in a range where the concentration is below the lower limit of the explosive range. and, for example, it is preferable to control it to 20 to 80 kPa.
- the reaction pressure can be any wide pressure range from reduced pressure to increased pressure, it is usually carried out at a pressure in the range of 0.05 to 2 MPa. From the viewpoint of safety, it is preferable to set the total pressure so that the oxygen concentration of the reactor effluent gas does not exceed the explosion limit (for example, the oxygen concentration is 8%).
- an alkali metal or alkaline earth metal compound e.g., oxide, hydroxide, carbonate, carboxylate
- alkali metal or alkaline earth metal compounds can be used alone or in combination of two or more.
- the reaction temperature for producing the carboxylic acid ester may be a high temperature of 200°C or higher, but is preferably 30 to 200°C, more preferably 40 to 150°C, and still more preferably 60 to 120°C.
- the reaction time is not particularly limited and cannot be unequivocally determined because it varies depending on the set conditions, but is usually 1 to 20 hours.
- Ni and X supported amounts and Ni/X atomic ratio The concentrations of nickel and X in the composite particles were quantified using an IRIS Intrepid II XDL type ICP emission spectrometer (ICP-AES, MS) manufactured by Thermo Fisher Scientific. The sample was prepared by weighing the support into a Teflon decomposition container, adding nitric acid and hydrogen fluoride, heating and decomposing it with an ETHOS TC microwave decomposition apparatus manufactured by Milestone General, and then evaporating it to dryness on a heater. Next, nitric acid and hydrochloric acid were added to the precipitated residue, and the residue was decomposed under pressure in a microwave decomposing device. Quantitative determination was carried out by the internal standard method in ICP-AES, and the nickel and X contents in the catalyst were obtained by subtracting the blank value of the operation performed at the same time, and the supported amount and atomic ratio were calculated.
- ICP-AES IRIS Intrepid II XDL type ICP emission spectrometer
- filter paper was used as an absorber for the standard sample, and the counting time for the support sample was selected for each sample, and the peak intensity of the K ⁇ spectrum was measured to be 3,000 cps or less and 10,000 counts or more. Measurements were repeated five times for each sample, and the metal samples were measured before and after each repeated measurement. After smoothing the measured spectrum (SG method 7 points - 5 times), the peak position, half width (FWHM), and asymmetry factor (AI) are calculated. The peak position is the metal sample measured before and after the sample measurement. was treated as a chemical shift ( ⁇ E).
- TEM/STEM transmission electron microscope/scanning transmission electron microscope
- EDX energy dispersive X-ray detector
- Data analysis software is TEM image, STEM image analysis (length measurement, Fourier transform analysis): DigitalMicrographTM Ver. 1.70.16, Gatan, EDS data analysis (mapping image processing, composition quantitative calculation): NORAN System SIX ver. 2.0, Thermo Fisher Scientific was used.
- a measurement sample was obtained by crushing the composite particle-supported material in a mortar, dispersing it in ethanol, ultrasonically cleaning it for about 1 minute, dropping it on a Mo microgrit and blowing it, and obtaining a TEM/STEM observation sample.
- UV-visible spectrum of composite particles Using a UV-visible spectrophotometer (UV-Vis) model V-550 manufactured by JASCO Corporation [integrating sphere unit, powder sample holder included], the measurement range was 800-200 nm, and the scanning speed was 400 nm/min. As a measurement sample, the composite particle-supported material was ground in an agate mortar, placed in a powder sample holder, and subjected to UV-Vis measurement.
- UV-Vis UV-visible spectrophotometer
- the specific surface area was measured by the BET method using Quadrasorb from Quantachrome.
- the residual catalyst amount was the catalyst mass obtained by drying the carboxylic acid ester production catalyst at 130° C. for 10 hours after producing the carboxylic acid ester for 500 hours. That is, a catalyst with a high outflow rate tends to flow out of the reactor and is unlikely to remain in the reactor, and less catalyst is used for the reaction during long-term operation, resulting in a deterioration in the conversion rate.
- the raw material mixed liquid was stirred for 30 hours at a stirring blade tip speed of 5.5 m/s to obtain a mixed slurry having a final ⁇ viscosity of 0.5 mPa ⁇ s/Hr.
- spray drying is performed under the conditions of a disk (atomizer) peripheral speed of 80 m/s to solidify the slurry. got stuff
- the SD radius means the lateral radius of the rotating disk type spray dryer used in this example.
- the obtained solid was filled in a stainless steel container with an open top to a thickness of about 1 cm, heated from room temperature to 300° C.
- the obtained carrier contained 83.3 mol %, 8.3 mol % and 8.3 mol % of silicon, aluminum and magnesium, respectively, based on the total molar amount of silicon, aluminum and magnesium. Further, observation with a scanning electron microscope (SEM) revealed that the shape of the carrier was almost spherical.
- 300 g of the carrier obtained as described above was dispersed in 1.0 L of water heated to 90° C. and stirred at 90° C. for 15 minutes.
- an aqueous solution containing 16.35 g of nickel nitrate hexahydrate and 12 mL of a 1.3 mol/L chloroauric acid aqueous solution was prepared, heated to 90°C, added to the carrier slurry, and heated at 90°C for another 30 minutes. Stirring was continued to immobilize the nickel and gold components on the carrier insoluble. Then, the mixture was allowed to stand, the supernatant was removed, washed several times with distilled water, and then filtered.
- the carrier has an outer layer substantially free of nickel and gold in a region 0.5 ⁇ m deep from the outermost surface, and nickel and gold are supported in a region up to 10 ⁇ m deep from the surface. , it was confirmed that no composite particles were present inside the carrier.
- TEM/STEM transmission electron microscope
- spherical nanoparticles having a maximum distribution (number average particle size: 3.0 nm) at 2 to 3 nm were found to be the support. It was confirmed that the When the nanoparticles were further magnified and observed, lattice fringes corresponding to the interplanar spacing of Au(111) were observed in the nanoparticles.
- the individual nanoparticles were analyzed by STEM-EDS, nickel and gold were detected in all particles.
- the average nickel/gold atomic ratio of the nanoparticles (calculated number: 50) was 1.05.
- the Ni/Au atomic ratio at the center of the particles was 0.90 and the edge of the particles was 2.56. Only a very small amount of nickel was detected in the part other than the particles. As a result of performing similar measurements at 50 points, a large amount of nickel was detected around the edges of all particles. From EDS elemental mapping, it was observed that the nickel and gold distributions were nearly identical.
- the distribution of nickel was one size larger than the distribution of gold in any scanning direction.
- NiK ⁇ spectrum of the catalyst obtained from the measured spectrum had a half width (FWHM) of 3.470 and a chemical shift ( ⁇ E) of 0.335.
- NiK ⁇ spectrum of nickel oxide measured as a standard substance had a half width (FWHM) of 3.249 and a chemical shift ( ⁇ E) of 0.344.
- the specific surface area of the obtained catalyst for producing carboxylic acid ester was determined to be 141 m 2 /g.
- the particle size distribution half width W is 50 ⁇ m
- the D 50 and W/D 50 values were 60 ⁇ m, 0.7, 1.5 and 0.8, respectively.
- the particle size distribution was single peaked. Also, when the bulk density was measured, it was 1.05 g/cm 3 .
- reaction product was continuously withdrawn from the reactor outlet by overflow and analyzed by gas chromatography to examine reactivity. After 500 hours from the start of the reaction, the conversion of methacrolein was 72% and the selectivity of methyl methacrylate was 95%. Also, the outflow rate of the catalyst was 2%.
- Examples 2 to 7 and Comparative Examples 1 to 7 A catalyst for producing a carboxylic acid ester was produced in the same manner as in Example 1, except that the conditions for preparing the mixed slurry and the conditions for spray drying during the production of the carrier were changed as shown in Table 1. That is, (i) the amount of solid content is adjusted by increasing or decreasing the amount of pure water for dissolving aluminum nitrate nonahydrate and magnesium nitrate in the raw material mixture, and (ii) the amount of 60% by mass nitric acid is increased or decreased to adjust the pH. were adjusted to the values shown in Table 1, respectively.
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Abstract
Description
[1]
触媒金属粒子と、前記触媒金属粒子を担持する担体と、を含むカルボン酸エステル製造用触媒であって、
前記カルボン酸エステル製造用触媒の嵩密度が0.50g/cm3以上1.50g/cm3以下であり、
前記カルボン酸エステル製造用触媒の体積基準の粒径分布にて頻度累計がx%となる粒子径をDxとするとき、D10/D50≧0.2かつD90/D50≦2.5であり、
前記粒径分布の半値幅をWとするとき、W/D50≦1.5である、カルボン酸エステル製造用触媒。
[2]
前記Wが100μm以下である、[1]に記載のカルボン酸エステル製造用触媒。
[3]
前記触媒金属粒子が、ニッケル、コバルト、パラジウム、白金、ルテニウム、鉛及び金、銀及び銅からなる群から選択される少なくとも1種の元素を含む、[1]又は[2]に記載のカルボン酸エステル製造用触媒。
[4]
前記触媒金属粒子が、酸化状態のニッケル及び/又はコバルトと、X(Xはニッケル、パラジウム、白金、ルテニウム、金、銀及び銅からなる群から選択される少なくとも1種の元素を示す)と、を含む複合粒子である、[1]~[3]のいずれかに記載のカルボン酸エステル製造用触媒。
[5]
前記複合粒子におけるニッケル又はコバルトとXの組成比は、Ni/X原子比又はCo/X原子比で0.1~10である、[4]に記載のカルボン酸エステル製造用触媒。
[6]
前記複合粒子が、酸化状態のニッケル又はコバルトと、金と、を含む、[4]又は[5]に記載のカルボン酸エステル製造用触媒。
[7]
前記複合粒子の平均粒子径が2~10nmである、[4]~[6]のいずれかに記載のカルボン酸エステル製造用触媒。
[8]
前記複合粒子が局在した担持層が、前記カルボン酸エステル製造用触媒の表面から前記カルボン酸エステル製造用触媒の相当直径の40%までの領域に存在する、[4]~[7]のいずれかに記載のカルボン酸エステル製造用触媒。
[9]
前記相当直径が200μm以下であり、前記複合粒子が局在した担持層が、前記カルボン酸エステル製造用触媒の表面から前記カルボン酸エステル製造用触媒の相当直径の30%までの領域に存在する、[4]~[8]のいずれかに記載のカルボン酸エステル製造用触媒。
[10]
前記複合粒子が局在した担持層の外側に、実質的に複合粒子を含まない外部層を有し、外部層は0.01~15μmの厚みで形成されている、[4]~[9]のいずれかに記載のカルボン酸エステル製造用触媒。
[11]
前記複合粒子がXからなる核を有し、前記核が酸化状態のニッケル又はコバルトで被覆されている、[4]~[10]のいずれかに記載のカルボン酸エステル製造用触媒。
[12]
前記担体が、シリカ及びアルミナを含む、[1]~[11]のいずれかに記載のカルボン酸エステル製造用触媒。
[13]
前記D50が、10μm以上200μm以下である、[1]~[12]のいずれかに記載のカルボン酸エステル製造用触媒。
[14]
[1]~[13]のいずれかに記載のカルボン酸エステル製造用触媒及び酸素の存在下、(a)アルデヒドとアルコール、又は、(b)1種もしくは2種以上のアルコール、を反応させる工程を含む、カルボン酸エステルの製造方法。
[15]
前記アルデヒドは、アクロレイン及び/又はメタクロレインである、[14]に記載のカルボン酸エステルの製造方法。
[16]
前記アルデヒドは、アクロレイン及び/又はメタクロレインであり、前記アルコールは、メタノールである、[14]又は[15]に記載のカルボン酸エステルの製造方法。
本実施形態のカルボン酸エステル製造用触媒は、触媒金属粒子と、前記触媒金属粒子を担持する担体と、を含むカルボン酸エステル製造用触媒であって、前記カルボン酸エステル製造用触媒の嵩密度が0.5g/cm3以上1.5g/cm3以下であり、前記カルボン酸エステル製造用触媒の体積基準の粒径分布の半値幅が100μm以下であり、前記カルボン酸エステル製造用触媒の体積基準の粒径分布にて頻度累計がx%となる粒子径をDxとするとき、D10/D50≧0.2かつ、D90/D50≦2.5であり、体積基準の粒径分布の半値幅をWとするとき、W/D50≦1.5である。このように構成されているため、本実施形態のカルボン酸エステル製造用触媒は、触媒の流出を抑制しつつ、高い活性を示す。
上記嵩密度は後述する実施例に記載の方法により測定することができる。
上記嵩密度は、例えば、後述する好ましい製造条件を採用すること等により、上述した範囲に調整することができる。
D10/D50は、レーザー回折・散乱法により測定でき、より具体的には、後述する実施例に記載の方法により測定することができる。
D10/D50は、例えば、後述する好ましい製造条件を採用すること等により、上述した範囲に調整することができる。
D90/D50は、レーザー回折・散乱法により測定でき、より具体的には、後述する実施例に記載の方法により測定することができる。
D90/D50は、例えば、後述する好ましい製造条件を採用すること等により、上述した範囲に調整することができる。
W/D50は、レーザー回折・散乱法により測定でき、より具体的には、後述する実施例に記載の方法により測定することができる。
W/D50は、例えば、後述する好ましい製造条件を採用すること等により、上述した範囲に調整することができる。
Wは、同様の観点から、5μm以上95μm以下であることがより好ましく、さらに好ましくは10μm以上90μm以下である。
Wは、レーザー回折・散乱法により測定でき、より具体的には、後述する実施例に記載の方法により測定することができる。
Wは、例えば、後述する好ましい製造条件を採用すること等により、上述した範囲に調整することができる。
D50は、レーザー回折・散乱法により測定でき、より具体的には、後述する実施例に記載の方法により測定することができる。
D50は、例えば、後述する好ましい製造条件を採用すること等により、上述した範囲に調整することができる。
また、本実施形態における複合粒子を構成し得る酸化状態のコバルトとしては、好ましくはコバルトと酸素とが結合して生成するコバルト酸化物(例えば、CoO,Co2O3,Co3O4)、或いはコバルトとX及び/又は1種以上の他の金属元素と酸素とが結合して生成するコバルトの酸化化合物若しくは固溶体又はこれらの混合物等のコバルトが含まれる複合酸化物である。
また、エネルギー分散型X線分光(EDS)によるナノ粒子の元素分析に供する場合、典型的には、いずれの粒子にもニッケルと金が共存しており、金ナノ粒子の表面にニッケルが被覆した形態であることが観察され、ニッケルと金が含まれるナノ粒子以外にも担体上にニッケル成分が単体で担持されていることも観察される。
さらに、X線光電子分光法(XPS)及び粉末X線回折(粉末XRD)に供することにより金属の存在状態を確認することができ、典型的には、金は結晶性の金属として存在する一方、ニッケルは2価の価数を有する非晶質状の酸化物として存在していることが観測される。
さらにまた、電子の励起状態の変化を観測できる紫外可視分光法(UV-Vis)に供すれば、典型的には、単一金属種の金ナノ粒子では観測された金ナノ粒子由来の表面プラズモン吸収ピーク(約530nm)が酸化ニッケルと金との複合化により消失することが観測される。このような表面プラズモン吸収ピークの消失現象は、反応に効果が見られなかった酸化ニッケル以外の他の金属酸化物種(例えば、酸化クロム、酸化マンガン、酸化鉄、酸化コバルト、酸化銅及び酸化亜鉛等の金属酸化物)と金との組み合わせからなる触媒では認められていない。この表面プラズモン吸収ピークの消失は、酸化状態のニッケルと金の接触界面を介した電子状態の混成が生じた結果、つまり2種類の金属化学種のハイブリット化によるものと考えられる。
なお、高酸化型のニッケル酸化物への変換は、触媒の色調変化と紫外可視分光法(UV-Vis)により確認できる。酸化ニッケルへの金の添加により、酸化ニッケルは灰緑色から茶褐色に変色し、UVスペクトルは可視光領域がほぼ全体にわたって吸収を示す。そのUVスペクトルの形状と触媒の色は、参照試料として測定した高酸化型の過酸化ニッケル(NiO2)と類似する。このように、酸化ニッケルは金の添加により、高酸化状態のニッケル酸化物に変換されていることが推察される。
以上の結果から、Xとして金を選択した場合の複合粒子の構造については、金粒子を核とし、その表面が高酸化状態のニッケル酸化物で被覆された形態であり、複合粒子の表面には金原子は存在しないと考えられる。
複合粒子の平均粒子径が上記範囲内であると、ニッケル及び/又はコバルトとXとからなる特定の活性種構造が形成され、反応活性が向上する傾向にある。ここで、本実施形態における複合粒子の平均粒子径は、透過型電子顕微鏡(TEM)により測定された数平均粒子径を意味する。具体的には、透過型電子顕微鏡で観察される画像において、黒いコントラストの部分が複合粒子であり、各粒子の直径を全て測定してその数平均を算出することができる。
カルボン酸エステル製造用触媒の製造方法は、特に限定されないが、下記の方法によると、本実施形態に係る所定の範囲の嵩密度及び所定の粒径分布を有するカルボン酸エステル製造用触媒を得やすくなる。
上述の方法によれば、本実施形態に係るカルボン酸エステル製造用触媒における、所定範囲の嵩密度と粒径分布を得やすくなり、触媒の流出を抑制しつつ、高い活性を示す、カルボン酸エステル製造用触媒が得られる。
上述した観点から、最終Δ粘度としては10mPa・s/Hr未満であることが好ましく、より好ましくは7mPa・s/Hr以下、さらに好ましくは5mPa・s/Hr以下である。最終Δ粘度は、その下限値は特に限定されないが、例えば0mPa・s/Hr以上である。最終Δ粘度は、後述する実施例に記載の方法に基づいて測定することができる。
また、固形分濃度は10~50質量%の範囲内にあることが形状や嵩密度、粒子径から好ましい。
さらに、原料混合液を攪拌する際の攪拌翼先端速度は特に限定されないが、最終Δ粘度の制御の観点から、3m/s以上9m/s以下が好ましく、より好ましくは4m/s以上8m/s以下であり、更に好ましくは5m/s以上7m/s以下である。
具体的には噴霧乾燥機の横方向の半径に対する噴霧する液のフィード量は5×10-3m2/Hr以上70×10-3m2/Hr以下が好ましく、10×10-3m2/Hr以上50×10-3m2/Hr以下がより好ましく、20×10-3m2/Hr以上40×10-3m2/Hr以下がさらに好ましい。
また、円盤の周速度は10m/s以上120m/s以下であることが好ましく、20m/s以上100m/s以下であることがより好ましく、30m/s以上90m/s以下がさらに好ましい。
なお、焼成後又は触媒担持後に分級工程を追加することでも粒径分布を制御できる。分級装置としては、ふるいや振動ふるい機、慣性分級機、強制渦遠心式分級機、サイクロン等の自由渦式分級機等が挙げられる。
本実施形態のカルボン酸エステル製造用触媒の製造方法としては、特に限定されないが、次の好ましい工程を含むものとすることができる。以下、各工程について説明する。
第2工程の加熱処理に先立ち、第1の前駆体を必要に応じて水洗、乾燥する。第1の前駆体の加熱温度は、通常40~900℃、好ましくは80~800℃、より好ましくは200~700℃、さらに好ましくは300~600℃である。
本実施形態のカルボン酸エステル製造用触媒は、広く化学合成用の触媒として使用することができる。例えば、アルデヒドとアルコールとの間のカルボン酸エステル生成反応、アルコール類からのカルボン酸エステル生成反応のために利用することができる。すなわち、本実施形態のカルボン酸エステルの製造方法は、本実施形態のカルボン酸エステル製造用触媒及び酸素の存在下、(a)アルデヒドとアルコール、又は、(b)1種もしくは2種以上のアルコール、を反応させる工程を含むものとすることができる。
混合スラリーの攪拌開始から毎時間、下記の条件で室温にて粘度を測定した。
粘度計:ブルックデジタル粘度計「LVDV1M」
スピンドル:LV-1
回転数:100rpm
温度:室温(25℃)
スプレードライヤー装置でのFeed開始直前の粘度とFeed開始1時間前の粘度の差を最終Δ粘度とした。
複合粒子中のニッケル及びXの濃度は、サーモフィッシャーサイエンティフィック社製 IRIS Intrepid II XDL型ICP発光分析装置(ICP-AES,MS)を用いて定量した。
試料の調製は、担持物をテフロン製分解容器に秤取り、硝酸及びフッ化水素を加えて、マイルストーンゼネラル社製ETHOS TC型マイクロウェーブ分解装置にて加熱分解後、ヒーター上で蒸発乾固し、次いで析出した残留物に硝酸及び塩酸を加えてマイクロウェーブ分解装置にて加圧分解し、得られた分解液を純粋で一定容したものを検液とした。
定量方法はICP-AESにて内標準法で定量を行い、同時に実施した操作ブランク値を差し引いて触媒中のニッケル及びX含有量を求め、担持量と原子比を算出した。
リガク社製Rint2500型粉末X線回折装置(XRD)を用い、X線源Cu管球(40kV,200mA)、測定範囲5~65deg(0.02deg/step)、測定速度0.2deg/min、スリット幅(散乱、発散、受光)1deg,1deg,0.15mmの条件で行った。
試料は、無反射試料板上に均一散布し、ネオプレンゴムで固定する手法を採用した。
サーモエレクトロン社製ESCALAB250型X線光電子分光装置(XPS)を用い、励起源AlKα15kV×10mA、分析面積 約1mm(形状:楕円)取込領域:サーベイスキャン0~1,100eV、ナロースキャンNi2pの条件で行った。
測定試料は、複合粒子担持物をメノウ乳鉢ですりつぶし、粉体専用試料台にて採取してXPS測定に供した。
NiKαスペクトルをTechnos社製XFRA190型二結晶型高分解能蛍光X線分析装置(HRXRF)で測定し、得られた各種パラメーターを標準物質(ニッケル金属、酸化ニッケル)のそれらと比較し、担持物中ニッケルの価数等の化学状態を推測した。
測定試料はそのままの状態で測定に供した。NiのKαスペクトルの測定は、部分スペクトルモードで行った。この際、分光結晶にはGe(220)、スリットは縦発散角1°のものを使用し、励起電圧と電流はそれぞれ35kVと80mAに設定した。その上で、標準試料ではアブソーバとしてろ紙を使用し、担持物試料では計数時間を試料毎に選択してKαスペクトルのピーク強度が3,000cps以下、10,000counts以上になるように測定した。それぞれの試料で5回測定を繰り返し、その繰り返し測定前後に金属試料の測定を行った。実測スペクトルを平滑化処理(S-G法7点-5回)後、ピーク位置、半値幅(FWHM)、非対称性係数(AI)を算出し、ピーク位置は試料の測定前後に測定した金属試料の測定値からのズレ、化学シフト(ΔE)として取り扱った。
JEOL社製3100FEF型透過型電子顕微鏡/走査透過電子顕微鏡装置(TEM/STEM)[加速電圧300kV,エネルギー分散型X線検出器(EDX)付属]を用いて、TEM明視野像、STEM暗視野像、STEM-EDS組成分析(点分析、マッピング、ライン分析)を測定した。
データ解析ソフトは、TEM像、STEM像解析(長さ測定、フーリエ変換解析):DigitalMicrographTM Ver.1.70.16,Gatan、EDSデータ解析(マッピング画像処理、組成定量計算):NORAN System SIX ver.2.0,Thermo Fisher Scientificを用いた。
測定試料は、複合粒子担持物を乳鉢で破砕後、エタノールに分散させ、超音波洗浄を約1分間行った後、Mo製マイクログリット上に滴下・風間し、TEM/STEM観察用試料とした。
日本分光社製V-550型紫外可視分光光度計(UV-Vis)[積分球ユニット、粉末試料用ホルダ付属]を用い、測定範囲800-200nm、走査速度400nm/minで行った。
測定試料は、複合粒子担持物をメノウ乳鉢ですりつぶし、粉末試料用ホルダに設置してUV-Vis測定に供した。
日立製作所社製X-650走査型電子顕微鏡装置(SEM)を用いて、担体及びカルボン酸エステル製造用触媒を観察した。
触媒を0.2gビーカーに取り、精製水を16mL添加し、その後、SONIC&MATERIALS.INC.製VCX130型超音波分散器を用いて1分間分散処理して測定用サンプルを調製した。この測定用サンプルを、ベックマン・コールター社製LS230型レーザー回折・散乱法粒度分布測定装置を用いて、カルボン酸エステル製造用触媒の体積基準の粒径分布にて頻度累計がx%となる粒子径Dx(D10、D50、及びD90)及び粒径分布(体積基準)の半値幅Wを測定した。
Quantachrome社のQuadrasorbを使用し、BET法により比表面積を測定した。
前処理として、カルボン酸エステル製造用触媒をステンレス製のるつぼに約120g採取し、150℃のマッフル炉で6時間乾燥を行った。焼成後、デシケータ(シリカゲル入り)に入れ室温まで冷却する。次いで、前処理したカルボン酸エステル製造用触媒を100.0g採取し、250mLのメスシリンダーに移し、メスシリンダーを振とう器で15分間タッピング充填した。その後、メスシリンダーにおける試料表面を平らにし、充填容積を読み取った。嵩密度は、カルボン酸エステル製造用触媒の質量を充填容積で割った値とした。
後述するカルボン酸エステルの製造に使用した触媒の全量と、カルボン酸エステルの製造を500時間実施した後の残存触媒量に基づき、以下の式にて流出率を算出した。
流出率={1-(残存触媒量/反応に用いた触媒量)}×100〔%〕
ここで、残存触媒量は、カルボン酸エステルの製造を500時間実施した後のカルボン酸エステル製造用触媒を130℃で10時間乾燥させた触媒質量とした。
すなわち、流出率が高い触媒は、反応器から流出しやすいため反応器内に残存しにくく、長期間の運転において反応に供する触媒が少なくなるため、結果として転化率が悪化する傾向にある。
(カルボン酸エステル製造用触媒の製造)
硝酸アルミニウム9水和物3.75kg、硝酸マグネシウム2.56kg、60質量%硝酸540gを純水5.0Lに溶解した水溶液を15℃に保持した攪拌状態のコロイド粒子径10~20nmのシリカゾル溶液(SiO2含有量30質量%)20.0kg中へ徐々に滴下し、pH=1.8となるようにpHを調整した。このようにして得られたシリカゾル、硝酸アルミニウム及び硝酸マグネシウムを含む原料混合液(固形分25質量%)を55℃に昇温した。その後、原料混合液を攪拌翼先端速度5.5m/sにて30時間攪拌し、最終Δ粘度0.5mPa・s/Hrの混合スラリーが得られた。
その後、スプレードライヤー装置にてFeed量/SD半径が25×10-3[m2]となるようにスラリーをフィードしながら、円盤(アトマイザ)周速度80m/sの条件で噴霧乾燥を行い、固形物を得た。なお、SD半径は本実施例で使用した回転円盤方式の噴霧乾燥機における横方向の半径を意味する。
次いで、得られた固形物を上部が開放したステンレス製容器に厚さ約1cm程充填し、電気炉で室温から300℃まで2時間かけ昇温後3時間保持した。さらに600℃まで2時間で昇温後3時間保持した後徐冷し、担体を得た。得られた担体は、ケイ素、アルミニウム及びマグネシウムの合計モル量に対し、ケイ素、アルミニウム及びマグネシウムをそれぞれ83.3モル%、8.3モル%、8.3モル%含んでいた。また、走査型電子顕微鏡(SEM)による観察から、担体の形状はほぼ球状であった。
次いで、静置して上澄みを除去し、蒸留水で数回洗浄した後、濾過した。これを乾燥機により105℃で10時間乾燥した後、マッフル炉で空気中450℃で5時間焼成することにより、ニッケル1.05質量%、金0.91質量%担持したカルボン酸エステル製造用触媒(NiOAu/SiO2-Al2O3-MgOの複合粒子担持物)を得た。得られたカルボン酸エステル製造用触媒のNi/Au原子比は4.0であった。
得られた複合粒子担持物を樹脂に包埋して研磨して得た試料をX線マイクロプローブ(EPMA)を用い、粒子断面の線分析に付した。その結果、担体の最外表面から0.5μmの深さの領域にはニッケル及び金を実質的に含まない外部層を有し、表面から10μmまでの深さの領域にニッケル及び金が担持され、担体内部には複合粒子は存在していないことが確認された。
次に、上記複合粒子担持物の形態を透過型電子顕微鏡(TEM/STEM)で観察したところ、粒子2~3nmに極大分布(数平均粒子径:3.0nm)を持つ球状のナノ粒子が担体に担持されていることが確認された。ナノ粒子をさらに拡大して観察すると、ナノ粒子にはAu(111)の面間隔と対応する格子縞が観察された。個々のナノ粒子に対してSTEM-EDSによる組成点分析を行ったところ、いずれの粒子にもニッケルと金が検出された。そのナノ粒子のニッケル/金原子比の平均値(算出個数:50)は1.05であった。さらに観察された粒子のナノ領域分析を行ったところ、粒子中央部のNi/Au原子比は0.90、粒子エッジ部が2.56であった。粒子以外の部分ではニッケルのみが微量に検出された。同様の測定を50点行った結果、いずれの粒子もエッジ部周辺においてニッケルが多く検出された。EDS元素マッピングからは、ニッケルと金の分布はほぼ一致していることが観察された。また、組成のラインプロファイルからは、いずれの走査方向においても、金の分布より一回り大きくニッケルが分布していた。
粉末X線回折(XRD)の結果から、ニッケルに由来する回折パターンは観測されず、非晶質の状態で存在していることが確認された。一方、明瞭なピークとは言えないものの、金の結晶に相当するブロードなピークが存在した。粉末X線回折の検出限界(2nm)に近い値ではあるものの、その平均結晶子径をScherrerの式より算出すると3nm程度であった。ニッケルの化学状態については、X線光電子分光法(XPS)の結果から、ニッケルは2価であることが確認された。
二結晶型高分解能蛍光X線分析法(HRXRF)の結果から、ニッケルの化学状態は、ニッケルのハイスピン2価と推測され、NiKαスペクトルの相違から単一化合物である酸化ニッケルとは異なる化学状態であることが判明した。実測スペクトルから得られた触媒のNiKαスペクトルの半値幅(FWHM)は3.470、化学シフト(ΔE)は0.335であった。標準物質として測定した酸化ニッケルのNiKαスペクトルの半値幅(FWHM)は3.249、化学シフト(ΔE)は0.344であった。
また、この複合粒子担持物の電子励起状態の変化を紫外可視分光法(UV-Vis)で調べた結果、530nm近傍の金ナノ粒子に由来する表面プラズモン吸収ピークは現れず、200~800nm波長域にNiO2起因のブロードな吸収が認められた。
以上の結果から、複合粒子の微細構造は、金ナノ粒子の表面が酸化状態のニッケルで覆われた形態を有していることが推測される。
得られたカルボン酸エステル製造用触媒の比表面積を求めたところ、141m2/gであった。また、カルボン酸エステル製造用触媒のレーザー・散乱法粒度分布測定による結果から粒径分布を得た結果、粒径分布半値幅Wは50μmであり、D50、D10/D50、D90/D50、W/D50の値は、それぞれ、60μm、0.7、1.5、0.8であった。粒径分布は、単一ピークであった。また嵩密度を測定したところ、1.05g/cm3であった。
得られたカルボン酸エステル製造用触媒240gを、触媒分離器を備え、液相部が1.2リットルの攪拌型ステンレス製反応器に仕込み、攪拌羽の先端速度4m/sの速度で内容物を攪拌しながら、アルデヒドとアルコールからの酸化的カルボン酸エステルの生成反応を実施した。すなわち、36.7質量%のメタクロレイン/メタノール溶液を0.6リットル/hr、1~4質量%のNaOH/メタノール溶液を0.06リットル/hrで連続的に反応器に供給し、反応温度80℃、反応圧力0.5MPaで出口酸素濃度が8.0容量%となるように空気を吹き込み、反応系のpHが7となるように反応器に供給するNaOH濃度をコントロールした。反応生成物は、反応器出口からオーバーフローにより連続的に抜き出し、ガスクロマトグラフィーで分析して反応性を調べた。
反応開始から500時間のメタクロレイン転化率は72%、メタクリル酸メチルの選択率は95%であった。また、触媒の流出率は2%であった。
担体製造時の混合スラリーの調製条件及び噴霧乾燥条件を表1に示すように変更したことを除き、実施例1と同様にカルボン酸エステル製造用触媒を製造した。すなわち、(i)原料混合液中の硝酸アルミニウム9水和物及び硝酸マグネシウムを溶解させる純水の量を増減することで固形分量を、(ii)60質量%硝酸の量を増減することでpHを、それぞれ表1の値となるように調整した。かかるカルボン酸エステル製造用触媒の物性を、実施例1と同様に評価し、さらに、これを用いて実施例1と同様にカルボン酸エステルを製造し、反応成績及び触媒の流出率を算出した。なお、実施例2~7の触媒の体積基準の粒径分布は、単一ピークであった。これらの結果を表1に示す。
Claims (16)
- 触媒金属粒子と、前記触媒金属粒子を担持する担体と、を含むカルボン酸エステル製造用触媒であって、
前記カルボン酸エステル製造用触媒の嵩密度が0.50g/cm3以上1.50g/cm3以下であり、
前記カルボン酸エステル製造用触媒の体積基準の粒径分布にて頻度累計がx%となる粒子径をDxとするとき、D10/D50≧0.2かつD90/D50≦2.5であり、
前記粒径分布の半値幅をWとするとき、W/D50≦1.5である、カルボン酸エステル製造用触媒。 - 前記Wが100μm以下である、請求項1に記載のカルボン酸エステル製造用触媒。
- 前記触媒金属粒子が、ニッケル、コバルト、パラジウム、白金、ルテニウム、鉛及び金、銀及び銅からなる群から選択される少なくとも1種の元素を含む、請求項1又は2に記載のカルボン酸エステル製造用触媒。
- 前記触媒金属粒子が、酸化状態のニッケル及び/又はコバルトと、X(Xはニッケル、パラジウム、白金、ルテニウム、金、銀及び銅からなる群から選択される少なくとも1種の元素を示す)と、を含む複合粒子である、請求項1~3のいずれか1項に記載のカルボン酸エステル製造用触媒。
- 前記複合粒子におけるニッケル又はコバルトとXの組成比は、Ni/X原子比又はCo/X原子比で0.1~10である、請求項4に記載のカルボン酸エステル製造用触媒。
- 前記複合粒子が、酸化状態のニッケル又はコバルトと、金と、を含む、請求項4又は5に記載のカルボン酸エステル製造用触媒。
- 前記複合粒子の平均粒子径が2~10nmである、請求項4~6のいずれか1項に記載のカルボン酸エステル製造用触媒。
- 前記複合粒子が局在した担持層が、前記カルボン酸エステル製造用触媒の表面から前記カルボン酸エステル製造用触媒の相当直径の40%までの領域に存在する、請求項4~7のいずれか1項に記載のカルボン酸エステル製造用触媒。
- 前記相当直径が200μm以下であり、前記複合粒子が局在した担持層が、前記カルボン酸エステル製造用触媒の表面から前記カルボン酸エステル製造用触媒の相当直径の30%までの領域に存在する、請求項4~8のいずれか1項に記載のカルボン酸エステル製造用触媒。
- 前記複合粒子が局在した担持層の外側に、実質的に複合粒子を含まない外部層を有し、外部層は0.01~15μmの厚みで形成されている、請求項4~9のいずれか1項に記載のカルボン酸エステル製造用触媒。
- 前記複合粒子がXからなる核を有し、前記核が酸化状態のニッケル又はコバルトで被覆されている、請求項4~10のいずれか1項に記載のカルボン酸エステル製造用触媒。
- 前記担体が、シリカ及びアルミナを含む、請求項1~11のいずれか1項に記載のカルボン酸エステル製造用触媒。
- 前記D50が、10μm以上200μm以下である、請求項1~12のいずれか1項に記載のカルボン酸エステル製造用触媒。
- 請求項1~13のいずれか1項に記載のカルボン酸エステル製造用触媒及び酸素の存在下、(a)アルデヒドとアルコール、又は、(b)1種もしくは2種以上のアルコール、を反応させる工程を含む、カルボン酸エステルの製造方法。
- 前記アルデヒドは、アクロレイン及び/又はメタクロレインである、請求項14に記載のカルボン酸エステルの製造方法。
- 前記アルデヒドは、アクロレイン及び/又はメタクロレインであり、前記アルコールは、メタノールである、請求項14又は15に記載のカルボン酸エステルの製造方法。
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EP21933136.0A EP4316656A4 (en) | 2021-03-26 | 2021-03-26 | CATALYST FOR PRODUCING CARBOXYLIC ACID ESTER, METHOD FOR PRODUCING CARBOXYLIC ACID ESTER AND METHOD FOR PRODUCING A CATALYST FOR PRODUCING CARBOXYLIC ACID ESTER |
US18/283,912 US20240157345A1 (en) | 2021-03-26 | 2021-03-26 | Catalyst for production of carboxylic acid ester, method for producing carboxylic acid ester, and method for producing catalyst for production of carboxylic acid ester |
KR1020237032422A KR20230146651A (ko) | 2021-03-26 | 2021-03-26 | 카르복실산에스테르 제조용 촉매, 카르복실산에스테르의 제조 방법 및 카르복실산에스테르 제조용 촉매의 제조 방법 |
CN202180096355.3A CN117083123A (zh) | 2021-03-26 | 2021-03-26 | 羧酸酯制造用催化剂、羧酸酯的制造方法和羧酸酯制造用催化剂的制造方法 |
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2021
- 2021-03-26 CN CN202180096355.3A patent/CN117083123A/zh active Pending
- 2021-03-26 US US18/283,912 patent/US20240157345A1/en active Pending
- 2021-03-26 EP EP21933136.0A patent/EP4316656A4/en active Pending
- 2021-03-26 WO PCT/JP2021/013068 patent/WO2022201533A1/ja active Application Filing
- 2021-03-26 KR KR1020237032422A patent/KR20230146651A/ko unknown
- 2021-03-26 JP JP2023508403A patent/JPWO2022201533A1/ja active Pending
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EP4316656A4 (en) | 2024-05-22 |
EP4316656A1 (en) | 2024-02-07 |
KR20230146651A (ko) | 2023-10-19 |
JPWO2022201533A1 (ja) | 2022-09-29 |
US20240157345A1 (en) | 2024-05-16 |
CN117083123A (zh) | 2023-11-17 |
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