JP2010535686A - 制御しやすい微孔質・メソ多孔質構造のチタニア又はその前躯体を速やかに調製する方法 - Google Patents
制御しやすい微孔質・メソ多孔質構造のチタニア又はその前躯体を速やかに調製する方法 Download PDFInfo
- Publication number
- JP2010535686A JP2010535686A JP2010519322A JP2010519322A JP2010535686A JP 2010535686 A JP2010535686 A JP 2010535686A JP 2010519322 A JP2010519322 A JP 2010519322A JP 2010519322 A JP2010519322 A JP 2010519322A JP 2010535686 A JP2010535686 A JP 2010535686A
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- Prior art keywords
- titania
- potassium
- acid solution
- acid
- sodium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 238000000034 method Methods 0.000 title claims abstract description 34
- 239000002243 precursor Substances 0.000 title claims abstract description 17
- 239000011148 porous material Substances 0.000 claims abstract description 43
- 239000002994 raw material Substances 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 239000012298 atmosphere Substances 0.000 claims abstract description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 6
- -1 alkali metal titanate Chemical class 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 18
- 229910052700 potassium Inorganic materials 0.000 claims description 18
- 239000011591 potassium Substances 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 claims description 12
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 8
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 8
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 8
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 235000011187 glycerol Nutrition 0.000 claims description 5
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 claims description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 4
- 229930006000 Sucrose Natural products 0.000 claims description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- 239000005720 sucrose Substances 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical group [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 3
- GROMGGTZECPEKN-UHFFFAOYSA-N sodium metatitanate Chemical compound [Na+].[Na+].[O-][Ti](=O)O[Ti](=O)O[Ti]([O-])=O GROMGGTZECPEKN-UHFFFAOYSA-N 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 229910001615 alkaline earth metal halide Inorganic materials 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- 235000011148 calcium chloride Nutrition 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 235000011147 magnesium chloride Nutrition 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 239000011698 potassium fluoride Substances 0.000 claims description 2
- 235000003270 potassium fluoride Nutrition 0.000 claims description 2
- 239000004323 potassium nitrate Substances 0.000 claims description 2
- 235000010333 potassium nitrate Nutrition 0.000 claims description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- 235000011151 potassium sulphates Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 235000002639 sodium chloride Nutrition 0.000 claims description 2
- 239000011775 sodium fluoride Substances 0.000 claims description 2
- 235000013024 sodium fluoride Nutrition 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- 150000001298 alcohols Chemical class 0.000 claims 1
- 239000011777 magnesium Substances 0.000 claims 1
- 229910052749 magnesium Inorganic materials 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 9
- 239000013078 crystal Substances 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 4
- 230000035484 reaction time Effects 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 description 15
- 239000003795 chemical substances by application Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 2
- 229910002113 barium titanate Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000003112 potassium compounds Chemical class 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 150000003609 titanium compounds Chemical class 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- AEDZKIACDBYJLQ-UHFFFAOYSA-N ethane-1,2-diol;hydrate Chemical compound O.OCCO AEDZKIACDBYJLQ-UHFFFAOYSA-N 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- MJMDTFNVECGTEM-UHFFFAOYSA-L magnesium dichloride monohydrate Chemical compound O.[Mg+2].[Cl-].[Cl-] MJMDTFNVECGTEM-UHFFFAOYSA-L 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- CMDGQTVYVAKDNA-UHFFFAOYSA-N propane-1,2,3-triol;hydrate Chemical compound O.OCC(O)CO CMDGQTVYVAKDNA-UHFFFAOYSA-N 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
-
- 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
- B01J21/063—Titanium; 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/643—Pore diameter less than 2 nm
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
- C01G23/005—Alkali titanates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/06—Washing
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
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Abstract
Description
2.調製条件とプロセスが簡単で制御しやすく、原料の由来が広く、量産に有利である。
3.温度、湿度、反応時間などの条件を制御することにより、生成物のチタニア又はその前躯体の孔径を微孔質とメソ多孔質の範囲内に調節することができるとともに、細孔容積と比表面積を調節・制御することができ、異なる反応における触媒剤への要求を満たすことが可能である。
チタンの非晶質化合物とカリウム含有化合物を反応させて調製された四チタン酸カリウムを原料として、温度200℃、湿度15%のグリセリン−水蒸気雰囲気で6時間反応した後、水で洗浄し、さらに空気焼成を行って得られた微孔質・メソ多孔質チタニアは、最確孔径3nm、比表面積85m2/g、細孔容積0.1cm3/gで、結晶形としては四チタン酸、アナタース相チタニアとTiO2(B)相チタニアの混合物である。その他の実施例を表1に示す。
1.原料の欄に、2TiKは二チタン酸カリウム、8TiKは八チタン酸カリウム、1TiNaはチタン酸ナトリウム、3TiNaは三チタン酸ナトリウム、4TiKは四チタン酸カリウムであることをそれぞれ示す。
2.結晶形の欄に、8TiHは八チタン酸、2TiHは二チタン酸、3TiHは三チタン酸、4TiHは四チタン酸、3TiH・1.5H2Oは1.5結晶水含有三チタン酸、アモルファスはアモルファスチタン酸、TiO2(B)はTiO2(B)相チタニア、アナタースはアナタース相チタニア、ルチルはルチル相チタニアであることをそれぞれ示す。
文献に従って、二チタン酸カリウムを原料として、少量の液体水に常温で72時間浸漬した後、塩酸で洗浄し、さらに空気焼成を行って得られたチタニアは、最確孔径10nmであるが調節することができず、比表面積30m2/g、細孔容積0.04cm3/gで、結晶形としてはアモルファスチタン酸とアナタース相チタニアの混合物である。
四チタン酸カリウムを原料として、温度280℃、湿度1%のエチレングリコール−水蒸気雰囲気で84時間反応した後、水で洗浄し、さらにグリセリンで処理して得られたチタニアは、微孔質もメソ多孔質もなく、比表面積18m2/g、細孔容積0.01cm3/gで、結晶形としては2結晶水含有八チタン酸とTiO2(B)相チタニアの混合物である。
三チタン酸ナトリウムと四チタン酸カリウムの混合物を原料として、温度200℃、湿度30%の塩化マグネシウム−水蒸気雰囲気で10分間反応した後、シュウ酸で洗浄し、さらに空気焼成を行って得られたチタニアは、少量の細孔しか存在しておらず、最確孔径32nm、比表面積15m2/g、細孔容積0.015cm3/gで、結晶形としてはアナタース相チタニアとルチル相チタニアの混合物である。
チタン酸バリウムを原料とし、反応条件を実施例6と同様にして得られた生成物は、いずれの孔路構造もなく、比表面積8m2/g、細孔容積0cm3/gで、結晶形としてはやはりチタン酸バリウムである。
Claims (9)
- 制御しやすい微孔質・メソ多孔質構造のチタニア又はその前躯体を速やかに調製する方法において、アルカリ金属チタン酸塩を原料として、温度20〜250℃、湿度2〜100%の湿気雰囲気で0.5〜72時間反応した後、水又は酸溶液で洗浄し、さらに空気焼成又は溶媒熱処理を行って得られたチタニア又はその前躯体は、最確孔径が1〜20nm、細孔容積が0.05〜0.4cm3/g、比表面積が30m2/gより大きいことを特徴とする方法。
- 前記チタニアは、アナタース相チタニア、TiO2(B)相チタニア、又はルチル相チタニアの中の少なくとも一つであることを特徴とする請求項1に記載の方法。
- 前記チタニア前躯体は、二チタン酸、三チタン酸、四チタン酸、六チタン酸、八チタン酸、又はアモルファスチタン酸の中の少なくとも一つであることを特徴とする請求項1に記載の方法。
- アルカリ金属チタン酸塩は、チタン酸ナトリウム、三チタン酸ナトリウム、二チタン酸カリウム、四チタン酸カリウム、又は八チタン酸カリウムの中の少なくとも一つであることを特徴とする請求項1に記載の方法。
- 前記湿気雰囲気は、通常の水蒸気、アルコール類有機物−水蒸気、又は可溶性無機塩−水蒸気の中の少なくとも一つにより生成されてもよいことを特徴とする請求項1に記載の方法。
- 前記アルコール類有機物は、メタノール、エタノール、エチレングリコール、1−プロパノール、2−プロパノール、1,2−プロピレングリコール、1,3−プロピレングリコール、グリセリン、n−ブタノール、i−ブタノール、t−ブタノール、アセトン、フルフリルアルコール、グルコース、又はショ糖の中の少なくとも一つであり、前記可溶性無機塩はアルカリ金属、アルカリ土類金属のハライド、炭酸塩、硝酸塩、又は硫酸塩の中の少なくとも一つであることを特徴とする請求項5に記載の方法。
- 前記可溶性無機塩は、フッ素化ナトリウム、フッ素化カリウム、塩化ナトリウム、塩化カリウム、塩化マグネシウム、塩化カルシウム、炭酸ナトリウム、炭酸カリウム、硝酸ナトリウム、硝酸カリウム、硝酸マグネシウム、硝酸カルシウム、硫酸ナトリウム、硫酸カリウム又は硫酸マグネシウムであることを特徴とする請求項6に記載の方法。
- 前記酸溶液は、塩酸溶液、硫酸溶液、硝酸溶液、蟻酸溶液、酢酸溶液、又はシュウ酸溶液の中の少なくとも一つの溶液であることを特徴とする請求項1に記載の方法。
- 前記溶媒熱処理は、水、メタノール、エタノール、エチレングリコール、1−プロパノール、2−プロパノール、1,2−プロピレングリコール、1,3−プロピレングリコール、グリセリン、n−ブタノール、i−ブタノール、t−ブタノール、アセトン、フルフリルアルコール、グルコース、又はショ糖の中の少なくとも一つの溶液において行われることを特徴とする請求項1に記載の方法。
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Families Citing this family (12)
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---|---|---|---|---|
KR101218979B1 (ko) * | 2010-12-10 | 2013-01-04 | 삼성전기주식회사 | 페롭스카이트 분말의 제조방법, 그 방법으로 제조한 페롭스카이트 분말 및 적층 세라믹 전자부품 |
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS553372A (en) * | 1978-06-23 | 1980-01-11 | Natl Inst For Res In Inorg Mater | Production of titania hydrate and amorphous titania |
JPH0967124A (ja) * | 1995-08-29 | 1997-03-11 | Natl Inst For Res In Inorg Mater | 薄片状酸化チタンおよびその集合体である多孔体とそれらの製造方法 |
JP2000107599A (ja) * | 1998-09-30 | 2000-04-18 | Otsuka Chem Co Ltd | 二酸化チタン系光触媒 |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2721705B2 (ja) * | 1989-06-23 | 1998-03-04 | チタン工業株式会社 | 六チタン酸ナトリウム微細粒子粉末及びその製造方法 |
US6268307B1 (en) * | 1995-10-20 | 2001-07-31 | Alliedsignal Inc. | Titania bound sodium titanate ion exchanger |
US6086844A (en) * | 1996-12-26 | 2000-07-11 | Sumitomo Chemical Company, Ltd. | Titania fiber, method for producing the fiber and method for using the fiber |
JP3356437B2 (ja) * | 1997-04-01 | 2002-12-16 | 大塚化学株式会社 | 光触媒、その製造法及び多機能部材 |
US6827922B2 (en) * | 2000-03-31 | 2004-12-07 | Sumitomo Chemical Company, Limited | Process for producing titanium oxide |
JP4689020B2 (ja) * | 2000-09-28 | 2011-05-25 | 独立行政法人 日本原子力研究開発機構 | 結晶性酸化チタン単分子膜の作製法 |
CN1206025C (zh) * | 2003-09-22 | 2005-06-15 | 南京工业大学 | 一种高比表面积的氧化钛合成方法 |
MXPA04004265A (es) * | 2004-05-04 | 2005-11-09 | Mexicano Inst Petrol | Material de oxido de titanio nanoestructurado y procedimiento para su obtencion. |
CN1607182A (zh) * | 2003-10-14 | 2005-04-20 | 河南大学 | 一种纳米管钛酸及其制备方法和应用 |
CN1740408A (zh) * | 2004-08-26 | 2006-03-01 | 上海捷晔复合材料有限公司 | 钛酸钾晶须系列产品的生产方法 |
JP4654410B2 (ja) * | 2004-12-27 | 2011-03-23 | 独立行政法人産業技術総合研究所 | 酸化チタンナノワイヤ構造体の製造方法及びその方法で得られる酸化チタンナノワイヤ構造体 |
CN100436329C (zh) * | 2006-03-03 | 2008-11-26 | 厦门大学 | 纳米介孔二氧化钛的低温制备方法 |
CN100421783C (zh) * | 2006-03-15 | 2008-10-01 | 南京工业大学 | 一种介孔氧化钛晶须成型材料的制备方法 |
-
2007
- 2007-08-07 JP JP2010519322A patent/JP5342555B2/ja active Active
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Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS553372A (en) * | 1978-06-23 | 1980-01-11 | Natl Inst For Res In Inorg Mater | Production of titania hydrate and amorphous titania |
JPH0967124A (ja) * | 1995-08-29 | 1997-03-11 | Natl Inst For Res In Inorg Mater | 薄片状酸化チタンおよびその集合体である多孔体とそれらの製造方法 |
JP2000107599A (ja) * | 1998-09-30 | 2000-04-18 | Otsuka Chem Co Ltd | 二酸化チタン系光触媒 |
Non-Patent Citations (2)
Title |
---|
JPN6013011249; Ming HE et al.: 'A simple approach to mesoporous fibrous titania from potassium dititanate' CHEM. COMM. Vol.19, 20041007, p.2202-2203 * |
JPN6013011252; Ming HE et al.: 'Large-Scale Hydrothermal Synthesis of Twinned Rutile Titania' J. Am. Ceram. Soc. Vol.90, No.1, 200701, p.319-321 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2013503094A (ja) * | 2009-08-28 | 2013-01-31 | 南京工▲業▼大学 | メソ多孔性複合酸化チタン及びその調製方法 |
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