JP6533621B2 - グリセリン脱水反応用触媒、その製造方法および前記触媒を利用したアクロレインの製造方法 - Google Patents
グリセリン脱水反応用触媒、その製造方法および前記触媒を利用したアクロレインの製造方法 Download PDFInfo
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- JP6533621B2 JP6533621B2 JP2018505020A JP2018505020A JP6533621B2 JP 6533621 B2 JP6533621 B2 JP 6533621B2 JP 2018505020 A JP2018505020 A JP 2018505020A JP 2018505020 A JP2018505020 A JP 2018505020A JP 6533621 B2 JP6533621 B2 JP 6533621B2
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- catalyst
- precursor
- glycerin
- dehydration reaction
- reaction
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 title claims description 271
- 239000003054 catalyst Substances 0.000 title claims description 148
- 235000011187 glycerol Nutrition 0.000 title claims description 115
- 238000006297 dehydration reaction Methods 0.000 title claims description 81
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 title claims description 76
- 238000004519 manufacturing process Methods 0.000 title claims description 60
- 239000002243 precursor Substances 0.000 claims description 92
- 239000007864 aqueous solution Substances 0.000 claims description 43
- 238000000034 method Methods 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 150000001875 compounds Chemical class 0.000 claims description 22
- 230000008569 process Effects 0.000 claims description 22
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 21
- 239000012688 phosphorus precursor Substances 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 229910052726 zirconium Inorganic materials 0.000 claims description 17
- 229910052725 zinc Inorganic materials 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 15
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 15
- 229910052721 tungsten Inorganic materials 0.000 claims description 15
- 239000010937 tungsten Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 229910052720 vanadium Inorganic materials 0.000 claims description 14
- 230000018044 dehydration Effects 0.000 claims description 10
- 229910052758 niobium Inorganic materials 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 239000012018 catalyst precursor Substances 0.000 claims description 3
- 239000011701 zinc Substances 0.000 description 41
- 238000006243 chemical reaction Methods 0.000 description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 27
- 229910052799 carbon Inorganic materials 0.000 description 27
- 239000000047 product Substances 0.000 description 27
- 238000002360 preparation method Methods 0.000 description 25
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 20
- 239000007789 gas Substances 0.000 description 19
- 239000007791 liquid phase Substances 0.000 description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 15
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 14
- 230000003197 catalytic effect Effects 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 13
- 239000012153 distilled water Substances 0.000 description 13
- 239000012071 phase Substances 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- 239000012692 Fe precursor Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 239000010955 niobium Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 239000003377 acid catalyst Substances 0.000 description 6
- -1 aldehyde compound Chemical class 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 239000007809 chemical reaction catalyst Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000009849 deactivation Effects 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910000608 Fe(NO3)3.9H2O Inorganic materials 0.000 description 2
- 241000282326 Felis catus Species 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 229910021550 Vanadium Chloride Inorganic materials 0.000 description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003225 biodiesel Substances 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- XLSMFKSTNGKWQX-UHFFFAOYSA-N hydroxyacetone Chemical compound CC(=O)CO XLSMFKSTNGKWQX-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 2
- ZDYUUBIMAGBMPY-UHFFFAOYSA-N oxalic acid;hydrate Chemical compound O.OC(=O)C(O)=O ZDYUUBIMAGBMPY-UHFFFAOYSA-N 0.000 description 2
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 2
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- VLOPEOIIELCUML-UHFFFAOYSA-L vanadium(2+);sulfate Chemical compound [V+2].[O-]S([O-])(=O)=O VLOPEOIIELCUML-UHFFFAOYSA-L 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 2
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 1
- HSRJKNPTNIJEKV-UHFFFAOYSA-N Guaifenesin Chemical compound COC1=CC=CC=C1OCC(O)CO HSRJKNPTNIJEKV-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 description 1
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 238000010960 commercial process Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 1
- 238000005235 decoking Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 235000015872 dietary supplement Nutrition 0.000 description 1
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N dimethylmethane Natural products CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000006052 feed supplement Substances 0.000 description 1
- 238000000769 gas chromatography-flame ionisation detection Methods 0.000 description 1
- 238000001165 gas chromatography-thermal conductivity detection Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- ALTWGIIQPLQAAM-UHFFFAOYSA-N metavanadate Chemical compound [O-][V](=O)=O ALTWGIIQPLQAAM-UHFFFAOYSA-N 0.000 description 1
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1808—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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Description
本出願は、2015年12月22日付の韓国特許出願第10−2015−0184168号および2016年10月7日付の韓国特許出願第10−2016−0129986号に基づく優先権の利益を主張し、当該韓国特許出願の文献に開示された全ての内容は本明細書の一部として含まれる。
このような問題を解決するために考案された前記化学式1で表される触媒はブレンステッド酸点を有する触媒であるが、グリセリンの脱水反応中に容易に不活性化しない特徴がある。また、前記化学式1の触媒はブレンステッド酸点を持って触媒活性に優れたものとして知られたジルコニウムホスフェートよりもっと優れたアクロレインの収率と触媒活性を示すことができる。
製造例1:グリセリン脱水反応用触媒の製造
蒸留水150mLにジルコニウム前駆体としてZrOCl2 12.208gを添加して水溶液を製造した。前記水溶液にジンク前駆体としてZn(NO3)2・6H2Oを0.225g、タングステン前駆体としてH26N6O40W12を0.933g入れて約30分ないし1時間攪拌した。そして、蒸留水150mLにリン前駆体化合物としてNH4H2PO4を8.714g添加して水溶液を製造し、上記で製造したジルコニウム水溶液にリン前駆体水溶液を添加して製造された水溶液を約95℃の温度で一晩攪拌した。
以降、前記水溶液から沈殿された沈殿物をエタノールで洗浄し100度温度で12時間乾燥させた後に、700度の温度で6時間焼成してグリセリン脱水反応用触媒ZrZn0.02W0.1P2HxOyを得た。
蒸留水150mLにジルコニウム前駆体としてZrOCl2 10.986gを添加して水溶液を製造した。前記水溶液に鉄前駆体としてFe(NO3)3・9H2Oを1.54g、タングステン前駆体としてH26N6O40W12を0.933g入れて約30分ないし1時間攪拌した。そして、蒸留水150mLにリン前駆体化合物としてNH4H2PO4を8.714g添加して水溶液を製造し、上記で製造したジルコニウム水溶液にリン前駆体水溶液を添加して製造された水溶液を約95℃の温度で一晩攪拌した。
この後の工程は製造例1と同様な方法でグリセリン脱水反応用触媒Zr0.9Fe0.1W0.1P2HxOyを得た。
前記製造例2で鉄前駆体の代わりにバナジウム前駆体としてNH4VO3を0.448gの含有量で使ったことを除いて、製造例2と同様な方法でグリセリン脱水反応用触媒Zr0.9V0.1W0.1P2HxOyを得た。
前記製造例2でニオブ前駆体としてアンモニウムナイオベート(V)オキサレートハイドレート(C4H4NNbO9・xH2O、Ammonium niobate(V) oxalate hydrate)を0.230gの含有量でさらに添加したことを除いて、製造例2と同様な方法でグリセリン脱水反応用触媒Zr0.9Nb0.02Fe0.1W0.1P2HxOyを得た。
前記製造例2でジンク前駆体としてZn(NO3)2・6H2Oを0.225gの含有量でさらに添加したことを除いて、製造例2と同様な方法でグリセリン脱水反応用触媒Zr0.9Zn0.02Fe0.1W0.1P2HxOyを得た。
前記製造例3でジンク前駆体としてZn(NO3)2・6H2Oを0.225gの含有量でさらに添加したことを除いて、製造例3と同様な方法でグリセリン脱水反応用触媒Zr0.9Zn0.02V0.1W0.1P2HxOyを得た。
蒸留水150mLにジルコニウム前駆体としてZrOCl2 9.766gを添加して水溶液を製造した。前記水溶液にジンク前駆体としてZn(NO3)2・6H2Oを0.225g、鉄前駆体としてFe(NO3)3・9H2Oを1.54g、バナジウム前駆体としてNH4VO3を0.448g、タングステン前駆体としてH26N6O40W12を0.933g入れて約30分ないし1時間攪拌した。そして、蒸留水150mLにリン前駆体化合物としてNH4H2PO4を8.714gを添加して水溶液を製造し、上記で製造したジルコニウム水溶液にリン前駆体水溶液を添加して製造された水溶液を約95℃の温度で一晩攪拌した。
蒸留水150mLにジルコニウム前駆体としてZrOCl2 9.766gを添加して水溶液を製造した。前記水溶液にジンク前駆体としてZn(NO3)2・6H2Oを0.225g、鉄前駆体としてFe(NO3)3・9H2Oを3.08g、タングステン前駆体としてH26N6O40W12を0.933g入れて約30分ないし1時間攪拌した。そして、蒸留水150mLにリン前駆体化合物としてNH4H2PO4を8.714g添加して水溶液を製造し、上記で製造したジルコニウム水溶液にリン前駆体水溶液を添加して製造された水溶液を約95℃の温度で一晩攪拌した。
前記製造例8で鉄前駆体の代わりにバナジウム前駆体としてNH4VO3を0.896gの含有量で使ったことを除いて、製造例1と同様な方法でグリセリン脱水反応用触媒Zr0.8Zn0.02V0.2W0.1P2HxOyを得た。
蒸留水150mLにジルコニウム前駆体としてZrOCl2 12.208gを添加して水溶液を製造した。前記水溶液にジンク前駆体としてZn(NO3)2・6H2Oを0.225g、タングステン前駆体としてH26N6O40W12を0.933g入れて約30分ないし1時間攪拌した。そして、蒸留水150mLにリン前駆体化合物としてNH4H2PO4を8.714g添加して水溶液を製造し、上記で製造したジルコニウム水溶液にリン前駆体水溶液を添加して製造された水溶液を約95℃の温度で一晩攪拌した。
前記製造例10で鉄前駆体のFe(NO3)3・9H2Oを1.54gの含有量でさらに添加したことを除いて、製造例10と同様な方法でグリセリン脱水反応用成形組立触媒Zr0.9Zn0.02Fe0.1W0.1P2HxOyを得た。
前記製造例10で鉄前駆体の代わりにバナジウム前駆体としてNH4VO3を0.448gの含有量で使ったことを除いて、製造例10と同様な方法でグリセリン脱水反応用成形組立触媒Zr0.9Zn0.02V0.1W0.1P2HxOyを得た。
前記製造例10で鉄前駆体の代わりにバナジウム前駆体としてNH4VO3を0.224gの含有量で使ったことを除いて、製造例10と同様な方法でグリセリン脱水反応用成形組立触媒Zr0.95Zn0.02V0.05W0.1P2HxOyを得た。
蒸留水150mLにジルコニウム前駆体としてZrOCl2 12.208gを添加して水溶液を製造した。そして、蒸留水150mLにリン前駆体化合物としてNH4H2PO4を8.714gを添加して水溶液を製造し、上記で製造したジルコニウム水溶液にリン前駆体水溶液を添加して製造された水溶液を約95℃の温度で一晩攪拌した。
蒸留水150mLにボロン酸H3BO3 3.12gの含有量で水溶液を製造し60度以上の温度を維持して蒸留水50mLにリン前駆体燐酸H3PO4 5.88gの含有量で製造し、前記ボロン水溶液にリン前駆体水溶液を添加して製造された水溶液を担体として用いたSiO2に担持し100度温度で12時間乾燥させた後、500度温度で6時間焼成してグリセリン脱水反応用触媒として11.08wt%BPO4/SiO2を得た。
図1に示したような反応装置を利用して、製造例1ないし13および比較製造例1ないし2により製造された触媒を使ってグリセリンの脱水反応を行った。
Claims (11)
- 下記化学式1で表される、グリセリン脱水反応用触媒:
M1およびM2は互いに同一でも異なっていてもよく、それぞれV、Fe、Nb、Zn、またはこれらの組み合わせであり、
a、b、c、d、およびeは各原子の組成比率を示し、aは0.5ないし1であり、bは0.01ないし0.3であり、cは0.01ないし0.3であり、dは0.01ないし0.3であり、eは1ないし5であり、
xおよびyは結晶水(crystallization water)の結合状態により決定される値であり、0ないし10である。 - aは0.8ないし1であり、bは0.02ないし0.2であり、cは0.02ないし0.2であり、dは0.01ないし0.1であり、eは1ないし2である、請求項1に記載のグリセリン脱水反応用触媒。
- 前記触媒はZrZn0.02W0.1P2HxOy、Zr0.9Fe0.1W0.1P2HxOy、Zr0.9V0.1W0.1P2HxOy、Zr0.9Nb0.02Fe0.1W0.1P2HxOy、Zr0.9Zn0.02Fe0.1W0.1P2HxOy、Zr0.9Zn0.02V0.1W0.1P2Hx O y 、Zr 0.8 Zn0.02(FeV)0.1W0.1P2HxOy、Zr0.8Zn0.02Fe0.2W0.1P2HxOy 、Zr0.8Zn0.02V0.2W0.1P2HxOy、またはZr0.95Zn0.02V0.05W0.1P2HxOyであり、前記xは2ないし6であり、yは1ないし3である、請求項1に記載のグリセリン脱水反応用触媒。
- V、Fe、Nb、およびZnの前駆体からなる群より選択された1種以上の前駆体、ジルコニウム前駆体、リン前駆体、およびタングステン前駆体の水溶液を混合した後に乾燥および焼成工程を経て下記化学式1で表される触媒を生成させる段階を含む、グリセリン脱水反応用触媒の製造方法:
M1およびM2は互いに同一でも異なっていてもよく、それぞれV、Fe、Nb、Zn、またはこれらの組み合わせであり、
a、b、c、d、およびeは各原子の組成比率を示し、aは0.5ないし1であり、bは0.01ないし0.3であり、cは0.01ないし0.3であり、dは0.01ないし0.3であり、eは1ないし5であり、
xおよびyは結晶水(crystallization water)の結合状態により決定される値であり、0ないし10である。 - 前記乾燥工程は25ないし200℃の温度で行うことである、請求項4に記載のグリセリン脱水反応用触媒の製造方法。
- 前記乾燥工程は3ないし48時間行うことである、請求項4または5に記載のグリセリン脱水反応用触媒の製造方法。
- 前記焼成工程は250ないし750℃の温度で行うことである、請求項4ないし6のいずれかに記載のグリセリン脱水反応用触媒の製造方法。
- 前記焼成工程は3ないし48時間行うことである、請求項4ないし7のいずれかに記載のグリセリン脱水反応用触媒の製造方法。
- 前記混合物を3ないし48時間攪拌する、請求項4ないし8のいずれかに記載のグリセリン脱水反応用触媒の製造方法。
- 前記混合水溶液から前記化学式1で表される触媒の前駆体化合物を沈殿させ、沈殿された触媒前駆体化合物をろ過し水またはアルコールで洗浄した後に乾燥および焼成工程を行う、請求項4ないし9のいずれかに記載のグリセリン脱水反応用触媒の製造方法。
- 請求項1ないし3のいずれかに記載のグリセリン脱水反応用触媒下で、グリセリンを脱水反応させる段階を含む、アクロレインの製造方法。
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US10569259B2 (en) | 2020-02-25 |
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EP3315194B1 (en) | 2020-04-01 |
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