JP2004043282A - Method of manufacturing titanium oxide - Google Patents
Method of manufacturing titanium oxide Download PDFInfo
- Publication number
- JP2004043282A JP2004043282A JP2003006748A JP2003006748A JP2004043282A JP 2004043282 A JP2004043282 A JP 2004043282A JP 2003006748 A JP2003006748 A JP 2003006748A JP 2003006748 A JP2003006748 A JP 2003006748A JP 2004043282 A JP2004043282 A JP 2004043282A
- Authority
- JP
- Japan
- Prior art keywords
- group
- titanium
- titanium oxide
- elements
- compound
- 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.)
- Pending
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 55
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 30
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 4
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910021472 group 8 element Inorganic materials 0.000 claims abstract description 4
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 4
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052747 lanthanoid Inorganic materials 0.000 claims abstract description 4
- 150000002602 lanthanoids Chemical class 0.000 claims abstract description 4
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 4
- 239000010703 silicon Substances 0.000 claims abstract description 4
- 229910052718 tin Inorganic materials 0.000 claims abstract description 4
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 28
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 26
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 10
- 239000011701 zinc Substances 0.000 claims description 9
- 239000010955 niobium Substances 0.000 claims description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052758 niobium Inorganic materials 0.000 claims description 7
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052733 gallium Inorganic materials 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 2
- XFVGXQSSXWIWIO-UHFFFAOYSA-N chloro hypochlorite;titanium Chemical compound [Ti].ClOCl XFVGXQSSXWIWIO-UHFFFAOYSA-N 0.000 claims description 2
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 18
- 238000010304 firing Methods 0.000 abstract description 4
- -1 group Ib elements Inorganic materials 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 3
- 239000004615 ingredient Substances 0.000 abstract 2
- 229910001849 group 12 element Inorganic materials 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 description 31
- 239000000047 product Substances 0.000 description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 21
- 235000011114 ammonium hydroxide Nutrition 0.000 description 21
- 239000007788 liquid Substances 0.000 description 21
- 239000002002 slurry Substances 0.000 description 21
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 18
- 238000003756 stirring Methods 0.000 description 13
- 239000000126 substance Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 10
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 10
- 239000001569 carbon dioxide Substances 0.000 description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 description 9
- 230000032683 aging Effects 0.000 description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 7
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- 238000001816 cooling Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- DNUARHPNFXVKEI-UHFFFAOYSA-K gallium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ga+3] DNUARHPNFXVKEI-UHFFFAOYSA-K 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- IGUXCTSQIGAGSV-UHFFFAOYSA-K indium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[In+3] IGUXCTSQIGAGSV-UHFFFAOYSA-K 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 3
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 3
- 229940007718 zinc hydroxide Drugs 0.000 description 3
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- FLTRNWIFKITPIO-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe] FLTRNWIFKITPIO-UHFFFAOYSA-N 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000003507 refrigerant Substances 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- AXIFGFAGYFPNFC-UHFFFAOYSA-I 2-hydroxy-2-oxoacetate;niobium(5+) Chemical compound [Nb+5].OC(=O)C([O-])=O.OC(=O)C([O-])=O.OC(=O)C([O-])=O.OC(=O)C([O-])=O.OC(=O)C([O-])=O AXIFGFAGYFPNFC-UHFFFAOYSA-I 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- LLQPHQFNMLZJMP-UHFFFAOYSA-N Fentrazamide Chemical compound N1=NN(C=2C(=CC=CC=2)Cl)C(=O)N1C(=O)N(CC)C1CCCCC1 LLQPHQFNMLZJMP-UHFFFAOYSA-N 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 229910021513 gallium hydroxide Inorganic materials 0.000 description 1
- 229940044658 gallium nitrate Drugs 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- HVDZMISZAKTZFP-UHFFFAOYSA-N indium(3+) trinitrate trihydrate Chemical compound O.O.O.[In+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HVDZMISZAKTZFP-UHFFFAOYSA-N 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 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
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- WPCMRGJTLPITMF-UHFFFAOYSA-I niobium(5+);pentahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[Nb+5] WPCMRGJTLPITMF-UHFFFAOYSA-I 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-M oxalate(1-) Chemical compound OC(=O)C([O-])=O MUBZPKHOEPUJKR-UHFFFAOYSA-M 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 239000002994 raw material Substances 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
- 230000005070 ripening Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 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
- 229910052713 technetium Inorganic materials 0.000 description 1
- GKLVYJBZJHMRIY-UHFFFAOYSA-N technetium atom Chemical compound [Tc] GKLVYJBZJHMRIY-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
- 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
- 238000003828 vacuum filtration 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
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- RZLVQBNCHSJZPX-UHFFFAOYSA-L zinc sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Zn+2].[O-]S([O-])(=O)=O RZLVQBNCHSJZPX-UHFFFAOYSA-L 0.000 description 1
- UXRMCZYAVOHQNB-UHFFFAOYSA-J zirconium(4+);disulfate;hydrate Chemical compound O.[Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O UXRMCZYAVOHQNB-UHFFFAOYSA-J 0.000 description 1
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Abstract
Description
【0001】
【発明の属する技術分野】
本発明は酸化チタンの製造方法に関するものであり、詳細には、光触媒用途に好適な酸化チタンの製造方法に関するものである。
【0002】
【従来の技術】
従来より、光触媒作用を利用して、大気中の悪臭物質を除去したり、また窓ガラスや道路壁に自己清浄作用を付与することが検討されている(特許文献1参照)。
【0003】
【特許文献1】
特開平9−57912号公報
【0004】
近年、可視光線の照射に対して光触媒活性を示す酸化チタンからなる光触媒体が開発され、紫外光線を照射できる光源が必要でなくなったことから、広範囲に適用できるようになった。例えば、以前は適用困難であったトンネル内などの屋内への用途開発が進められている。
【0005】
一方こうした屋内用途では、蛍光灯、ナトリウムランプのような照明装置からの光線をそのまま光触媒に照射するため、光触媒作用を得るのに必ずしも十分な光量が得られないことがあった。したがって、少ない光量でも高い光触媒活性が得られるように、素材である酸化チタンについて更なる活性向上が要望されている。
【0006】
【発明が解決しようとする課題】
本発明では、従来のものに比べてより高い光触媒活性を示す酸化チタンを製造できる方法を提供することを目的とする。
【0007】
【課題を解決するための手段】
本発明者等は、酸化チタンの光触媒活性を向上させるため、その製造方法について種々検討を行った結果、本発明を完成するに至った。
【0008】
すなわち本発明は、チタン化合物と、IIa族元素、IIIa族元素、Va族元素、VIa族元素、VIIa族元素、VIII族元素、Ib族元素、IIb族元素、IIIb族元素、ランタノイド、ケイ素、ゲルマニウム、錫、鉛、アンチモン、ビスマス、ジルコニウムおよびハフニウムから選ばれる元素またはその化合物からなる第二成分と、溶媒とを混合し、この混合物に塩基を該第二成分を構成する該元素の水酸化物の溶解度が10−4g/L以下となる条件で反応させ、得られた固体を焼成することを特徴とする酸化チタンの製造方法を提供するものである。
【0009】
【発明の実施の形態】
以下、本発明を詳細に説明する。本発明の製造方法では、最初に、チタン化合物と、チタン化合物以外の成分と、溶媒とを混合する。ここで用いるチタン化合物は、水の存在下で塩基との反応により水酸化チタンを生成するものであればよく、例えば、三塩化チタン〔TiCl3〕、四塩化チタン〔TiCl4〕、硫酸チタン〔Ti(SO4)2・mH2O、0≦m≦20〕、オキシ塩化チタン〔TiOCl2〕、オキシ硫酸チタン〔TiOSO4・nH2O、0≦n≦20〕が挙げられ、中でも、オキシ硫酸チタンの適用が好ましい。
【0010】
チタン化合物以外の成分としては、例えば、ベリリウム、マグネシウム、カルシウム、ストロンチウム、バリウムのようなIIa族元素、スカンジウム、イットリウムのようなIIIa族元素、ジルコニウム、ハフニウムのようなIVa族元素、バナジウム、ニオブ、タンタルのようなVa族元素、クロム、モリブデン、タングステンのようなVIa族元素、マンガン、テクネチウム、レニウムのようなVIIa族元素、鉄、ルテニウム、オスミウム、コバルト、ロジウム、イリジウム、ニッケル、パラジウム、白金のようなVIII族元素、銅、銀、金のようなIb族元素、亜鉛、カドミウムのようなIIb族元素、ホウ素、アルミニウム、ガリウム、インジウム、タリウムのようなIIIb族元素、ケイ素、ゲルマニウム、錫、鉛のようなIVb族元素、アンチモン、ビスマスのようなVb族元素、ランタン、セリウム、プラセオジウム、ネオジウム、サマリウム、ユウロピウム、ガドリニウムのようなランタノイドが挙げられ、好ましくは、亜鉛、ジルコニウム、ガリウム、インジウム、鉄、ニオブがあり、さらに好ましくは亜鉛、ニオブがある。チタン化合物以外の成分は、これらの1種であってもよいし、2種以上組み合わせたものであってもよい。チタン化合物以外の成分は、通常、化合物の状態でチタン化合物と混合されるが、溶媒中に均一に分散できる程度であれば、元素単体でチタン化合物と混合してもよい。チタン以外の元素の化合物としては、前記元素の各種の無機化合物や有機化合物が挙げられ、無機化合物としては、例えば、これら元素の硫酸塩、硝酸塩、塩化物などがあり、有機化合物としては、これら元素の蓚酸塩、蓚酸水素塩、酢酸塩などがある。チタン化合物以外の成分は、用いる溶媒に溶解するもの、またはその溶媒中でコロイド粒子として存在できるものが好ましい。チタン化合物以外の成分の量は、これを構成する前記元素を基準として、チタン化合物のチタンに対して0.00001mol倍以上、好ましくは0.0001mol倍以上、さらには0.001mol倍以上、また0.1mol倍以下、さらには0.05mol倍以下であることが好ましい。
【0011】
溶媒は、チタン化合物を溶解するものであればよく、通常、水、過酸化水素水が使用される。
【0012】
本発明では、ついで、チタン化合物とチタン化合物以外の成分と溶媒との混合物に塩基を反応させる。ここで用いる塩基としては、例えば、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸カリウム、アンモニア、ヒドラジン、ヒドロキシルアミン、モノエタノールアミン、非環式アミン化合物、環式脂肪族アミン化合物などが挙げられる。中でもアンモニアの適用が好ましい。混合物との反応に際して、塩基を、その塩基が可溶な溶媒と混合してから用いるとき、この塩基の濃度は通常0.05重量%以上、50重量%以下である。
【0013】
上記の混合物と塩基の反応は、チタン化合物以外の成分について、その成分を構成する元素の水酸化物の溶解度が10−4g/L以下、好ましくは10−6g/L以下となる条件で行う。また、チタン化合物と混合される成分が2種以上のときには、これら成分を構成する元素の水酸化物の溶解度のいずれもが10−4g/L以下となる条件で反応を行うことが好ましい。反応を前記溶解度より低い条件で行うことによって、高い光触媒活性を示す酸化チタンが得られる理由は定かではないが、チタン化合物とチタン化合物以外の成分と溶媒との混合物に塩基を反応させたとき、この成分を構成する元素の水酸化物が溶媒中に溶解して残ることが少なく、生成する水酸化チタン中に均一に取り込まれることが影響していると考えられる。
【0014】
反応は、前記水酸化物の溶解度が10−4g/L以下となる条件であれば、溶媒を適宜選定したうえ、pHや温度などを調節することで行うことができる。溶媒として水を使用し、pHにて溶解度を調節する場合について、元素ごとにその水酸化物の溶解度が10−4g/L以下となるpHを以下に示す。このときのpHは、図1〜5に示すように、pH−金属水酸化物溶解度の相関図から求めることができ、亜鉛水酸化物〔Zn(OH)2〕では、図1に示すようにpH7.4〜12.5である。亜鉛以外の元素として、例えば、ガリウム水酸化物〔Ga(OH)3〕では、図2に示すようにpHは3.5〜10.5であり、インジウム水酸化物〔In(OH)3〕では、図3に示すようにpHは4.2〜11.8であり、ジルコニウム水酸化物〔Zr(OH)2・2H2O〕では、図4に示すようにpHは2.5以上であり、鉄水酸化物〔Fe(OH)3〕では、図5に示すようにpHは3.2以上である。また、元素ごとにその水酸化物の溶解度が10−6g/L以下となるpHについて、同様に示す。亜鉛水酸化物〔Zn(OH)2〕では、pH8.4〜10.6(図1)、ガリウム水酸化物〔Ga(OH)3〕では、pHは5.7〜9.2(図2)、インジウム水酸化物〔In(OH)3〕では、pHは5.2〜9.8(図3)、ジルコニウム水酸化物〔Zr(OH)2・2H2O〕では、pHは3.5〜12.5(図4)、鉄水酸化物〔Fe(OH)3〕では、pHは4.2以上(図5)である。
【0015】
また、ニオブ水酸化物〔Nb(OH)5〕のように、広範囲のpH(概ね1〜13)において溶解度が10−4g/L以下であるものについては、この範囲内のいずれのpHでも反応を行うことができる。この場合、反応のpHは、チタン化合物とチタン化合物以外の成分と溶媒との混合物、およびこれと塩基の反応生成物の取扱い易さなどを考慮して決めることが好ましく、例えば、チタン化合物以外の成分を構成する元素がニオブのときの好適なpHは3〜5である。
【0016】
反応は、90℃以下で行われることが好ましい。反応温度が90℃より高いと、得られる酸化チタンの光触媒活性が低下することがある。反応温度は低いほど、より高い光触媒活性を示す酸化チタンが得られるので好ましく、例えば、60℃以下、さらには40℃以下が好ましい。一方、反応温度を低く維持するには、冷媒が多く必要となるなど冷却コストが高くなるので、1℃以上が適当である。このときの反応率は、通常、90%以上である。反応率は、溶媒の種類を選定または温度、時間、攪拌条件などを変えることにより調節することができる。なお、この反応率は、チタン化合物が塩基との反応により加水分解されて水酸化チタンに変化した割合を示す。
【0017】
反応は、具体的には、冷却ジャケット付き容器内に水を入れた後、この容器に、攪拌下、液温を所定の範囲に保ちながら、チタン化合物とチタン化合物以外の成分と水との混合物を供給するとともに、所定のpHとなるように塩基を供給する方法、または反応温度を制御できる冷却ジャケット付き管内に、チタン化合物とチタン化合物以外の成分と水との混合物および塩基を、所定のpHとなるように各々の量を調節しながら、連続供給する方法などで行うことができる。
【0018】
反応により得られる生成物には、熟成を施してもよい。熟成は、生成物を含むスラリーを、塩基存在下、一定温度に保持する方法などで行うことができる。熟成は、例えば、反応後の混合物から、反応により生じた塩(硫酸アンモニウムなど)を含む溶液を固液分離した後、得られた固体に塩基を添加し、一定温度に保持する方法で行うこともできる。この熟成を施すことにより、生成物を焼成して得られる酸化チタンは、可視光線の照射に対し優れた活性を示すものとなる。熟成に用いる塩基としては、例えば、アンモニア水などが挙げられ、その濃度は、通常0.05重量%以上、50重量%以下である。熟成温度は0℃以上、さらには10℃以上、また110℃以下、さらには80℃以下が好ましい。熟成時間は、塩基濃度、熟成温度により異なり一義的ではないが、通常0.01時間以上、好ましくは0.5時間以上であり、また60時間以内、好ましくは24時間以内である。熟成に用いる塩基と、上述した反応に用いる塩基は、同種でかつ同濃度、同種で異なる濃度、または異種のいずれであってもよい。
【0019】
上で述べた反応と、任意に行われる熟成に用いる塩基の合計量は、水の存在下でチタン化合物を水酸化チタンに変えるのに必要な塩基の化学量論量を超える量であることが好ましく、例えば、その化学量論量の1.1倍以上であることが好ましい。用いる塩基の量が多いほど最終的に得られる酸化チタンの光触媒活性が高くなる傾向にあるので、1.3倍以上がさらに好ましい。一方、塩基の量をあまり多くしても、量に見合う光触媒活性の向上効果が得られないので、20倍以下、さらには10倍以下が適当である。
【0020】
反応後のスラリーまたは熟成後の生成物を含むスラリーには、通常、固体を分離する操作を施す。分離は、加圧濾過、真空濾過、遠心分離、デカンテーションなどで行うことができ、またスラリーを噴霧乾燥機などを用いて液体を蒸発させる方法で行うこともできる。分離された固体は、必要に応じて洗浄、乾燥した後、焼成する。焼成は、300℃以上、好ましくは350℃以上、また600℃以下、好ましくは500℃以下、さらに好ましくは450℃以下の温度で行う。焼成温度があまり高くなると、十分な光触媒活性を示す酸化チタンを得ることが困難になる。焼成は、例えば、静置炉、トンネル炉、回転炉などで行うことができる。ここでは、スラリー中の固体を分離した後、この固体を焼成する方法について示したが、生成物またはこれを熟成したものを含むスラリーをフラッシュジェットドライヤーのような気流乾燥機を用いて、生成物を含むスラリーに固液分離操作を予め施すことなく、生成物の焼成を行ってもよい。
【0021】
上述した本発明の製造方法により得られる酸化チタンは、通常、結晶構造がアナターゼ型であり、可視光線の照射に対して高い光触媒活性を示すものである。またこの酸化チタンは紫外光線の照射に対しても光触媒活性を示す。
【0022】
【実施例】
以下、実施例により本発明をさらに詳細に説明するが、本発明は本実施例に限定されるものではない。
実施例1
〔酸化チタンの調製〕
オキシ硫酸チタン水和物(添川理化学製)102gを水408gに溶解して、pH約1のオキシ硫酸チタン水溶液を調製した。このオキシ硫酸チタン水溶液に硫酸亜鉛七水和物(試薬特級、和光純薬工業製)1.21gを添加し、溶解させて、混合水溶液を得た。この混合水溶液中の亜鉛の量は、チタンに対して0.01mol倍であった。
【0023】
pH電極と、このpH電極に接続され、25重量%アンモニア水(試薬特級、和光純薬工業製)を供給してpHを一定に調節する機構を有するpHコントローラーとを備え、かつ冷媒を使用した冷却機構を有する1Lフラスコに水300gを入れた後、フラスコを冷却した。pHコントローラーのpH設定値を9とし、水のpHを設定値に調節した。このフラスコ内に、400rpmで攪拌しながら、上で得られた混合水溶液511.21gを5ml/minで添加し、pHコントローラーによりフラスコ内に供給されるアンモニア水と反応させた。この間、フラスコ内に供給された25重量%アンモニア水の量は82.54gであった。
【0024】
フラスコ内の液のpHは、混合水溶液の添加を開始してから12分間はpH9.0〜9.8であり、添加開始12分後から添加終了まではpH8.9〜9.2であった。その間、フラスコ内の液温は1.1〜6.2℃であった。供給されたアンモニア水の合計量は、オキシ硫酸チタンを水酸化チタンに変えるのに必要な塩基の化学量論量の1.4倍であった。
【0025】
得られたスラリーを濾過、洗浄、乾燥し、この乾燥物を400℃の空気中で1時間焼成して、粒子状酸化チタンを得た。この酸化チタンについて、X線回折装置(商品名“RAD−IIA”、理学電機製)により分析した結果、その結晶構造はアナターゼ型であった。
【0026】
〔酸化チタンの活性評価〕
直径8cm、高さ10cm、容量約0.5Lの密閉式ガラス製反応容器内に、直径5cmのガラス製シャーレを置き、そのシャーレに、上で得られた粒子状アナターゼ型酸化チタン0.3gを入れた。反応容器内を酸素と窒素の体積比が1:4である混合ガスで満たし、アセトアルデヒドを13.4μmol封入した後、反応容器の外から可視光線を照射した。可視光線の照射には、500Wキセノンランプ(商品名“ランフ゜UXL−500SX”、ウシオ電機製)を取り付けた光源装置(商品名“オフ゜ティカルモシ゛ュレックスSX−UI500XQ”、ウシオ電機製)に、波長約430nm以下の紫外線をカットするフィルター(商品名“Y−45”、旭テクノガラス製)と波長約830nm以上の赤外線をカットするフィルター(商品名“スーハ゜ーコ゛ールト゛フィルター”、ウシオ電機製)とを装着したものを光源として用いた。可視光線の照射によりアセトアルデヒドが分解すると、二酸化炭素が発生するので、二酸化炭素の濃度を光音響マルチガスモニタ(型番“1312型”、INNOVA製)で経時的に測定し、濃度変化より算出した二酸化炭素の生成速度により、酸化チタンのアセトアルデヒドに対する光触媒作用を評価した。この例における二酸化炭素の生成速度は酸化チタン1gあたり31.2μmol/hであった。
【0027】
実施例2
1Lフラスコ内で、実施例1で用いたのと同じオキシ硫酸チタン水和物102gを水408gに溶解し、pH約1のオキシ硫酸チタン水溶液を調製した。このオキシ硫酸チタン水溶液に蓚酸水素ニオブ(三津和化学薬品製、Nb2O5として15重量%)0.39gを添加し、溶解させて、混合水溶液を調製した。この混合水溶液中のニオブの量は、チタンに対して0.001mol倍であった。
【0028】
実施例1の〔酸化チタンの調製〕で使用したと同じ1Lフラスコに水300gを入れた後、フラスコを冷却した。pHコントローラーのpH設定値を4とし、水のpHを設定値に調節した。このフラスコ内に、400rpmで攪拌しながら、上で得られた混合水溶液510.39gを5ml/minで添加し、pHコントローラーによりフラスコ内に供給されるアンモニア水と反応させた。
【0029】
フラスコ内の液のpHは、混合水溶液の添加を開始してから5分間はpH3.2〜4.9であり、添加開始5分後から添加終了まではpH3.8〜4.3であった。添加開始時のフラスコ内の液温は24℃であり、添加終了時の液温は26℃であった。
【0030】
得られたスラリーを、攪拌しながら1時間保持し、ついで25重量%アンモニア水(試薬特級、和光純薬工業製)を供給した後、さらに1時間攪拌して、生成物を熟成した。この間、スラリーの温度は24℃で一定であった。フラスコ内に供給されたアンモニア水の合計量は116gであり、オキシ硫酸チタンを水酸化チタンに変えるのに必要な塩基の化学量論量の2倍であった。
【0031】
熟成後の生成物を含むスラリーを濾過、洗浄、乾燥し、この乾燥物を400℃の空気中で1時間焼成した後、この焼成物を洗浄、乾燥して、粒子状アナターゼ型酸化チタンを得た。
【0032】
この酸化チタンについて、実施例1の〔酸化チタンの活性評価〕と同条件で評価した。この例における二酸化炭素の生成速度は酸化チタン1gあたり27.6μmol/hであった。
【0033】
実施例3
1Lフラスコ内で、実施例1で用いたのと同じオキシ硫酸チタン水和物102gを水238gに溶解し、pH約1のオキシ硫酸チタン水溶液を調製した。このオキシ硫酸チタン水溶液に硝酸インジウム三水和物(キシダ化学製)0.15gを添加し、溶解させ、ついで31%過酸化水素水46.43gを添加して、赤紫色の混合水溶液を得た。この混合水溶液中のインジウムの量は、チタンに対して0.001mol倍であった。
【0034】
実施例1の〔酸化チタンの調製〕で使用したと同じ1Lフラスコに水300gを入れた後、フラスコを冷却した。pHコントローラーのpH設定値を6とし、水のpHを設定値に調節した。このフラスコ内に、内容物を400rpmで攪拌しながら、上で得られた混合水溶液386.58gを5ml/minで添加し、pHコントローラーによりフラスコ内に供給されるアンモニア水と反応させた。
【0035】
フラスコ内の液のpHは、混合水溶液の添加を開始してから20分間はpH5.4〜6.9であり、添加開始20分後から添加終了まではpH5.9〜6.1であった。添加開始時のフラスコ内の液温は24℃であり、添加終了時の液温は30℃であった。
【0036】
得られたスラリーを、攪拌しながら1時間10分保持し、ついで25重量%アンモニア水(試薬特級、和光純薬工業製)を供給した後、さらに1時間攪拌して、生成物を熟成した。この間、スラリーの温度は27℃で一定であった。フラスコ内に供給されたアンモニア水の合計量は115gであり、オキシ硫酸チタンを水酸化チタンに変えるのに必要な塩基の化学量論量の2倍であった。
【0037】
熟成後の生成物を含むスラリーを濾過、洗浄、乾燥し、この乾燥物を400℃の空気中で1時間焼成した後、この焼成物を洗浄、乾燥して、粒子状アナターゼ型酸化チタンを得た。
【0038】
この酸化チタンについて、実施例1の〔酸化チタンの活性評価〕と同条件で評価した。この例における二酸化炭素の生成速度は酸化チタン1gあたり20.1μmol/hであった。
【0039】
実施例4
1Lフラスコ内で、実施例1で用いたのと同じオキシ硫酸チタン水和物102gを水158gに溶解し、pH約1のオキシ硫酸チタン水溶液を調製した。このオキシ硫酸チタン水溶液に硫酸ジルコニウム水和物(和光純薬工業製)0.15gを添加し、溶解させ、ついで31%過酸化水素水81.36gを添加して、赤紫色の混合水溶液を得た。この混合水溶液中のジルコニウムの量は、チタンに対して0.001mol倍であった。
【0040】
実施例1の〔酸化チタンの調製〕で使用したと同じ1Lフラスコに水300gを入れた後、フラスコを冷却した。pHコントローラーのpH設定値を7とし、水のpHを設定値に調節した。このフラスコ内に、内容物を400rpmで攪拌しながら、上で得られた混合水溶液341.51gを5ml/minで添加し、pHコントローラーによりフラスコ内に供給されるアンモニア水と反応させた。
【0041】
フラスコ内の液のpHは、混合水溶液の添加を開始してから17分間はpH6.1〜8.2であり、添加開始17分後から添加終了まではpH6.9〜7.0であった。添加開始時のフラスコ内の液温は23℃であり、添加終了時の液温は32℃であった。
【0042】
得られたスラリーを、攪拌しながら1時間保持し、ついで25重量%アンモニア水(試薬特級、和光純薬工業製)を供給した後、さらに1時間攪拌して、生成物を熟成した。この間、スラリーの温度は28℃で一定であった。フラスコ内に供給されたアンモニア水の合計量は115gであり、オキシ硫酸チタンを水酸化チタンに変えるのに必要な塩基の化学量論量の2倍であった。
【0043】
熟成後の生成物を含むスラリーを濾過、洗浄、乾燥し、この乾燥物を400℃の空気中で1時間焼成した後、この焼成物を洗浄、乾燥して、粒子状アナターゼ型酸化チタンを得た。
【0044】
この酸化チタンについて、実施例1の〔酸化チタンの活性評価〕と同条件で評価した。この例における二酸化炭素の生成速度は酸化チタン1gあたり22.6μmol/hであった。
【0045】
実施例5
1Lフラスコ内で、実施例1で用いたのと同じオキシ硫酸チタン水和物102gを水238gに溶解し、pH約1のオキシ硫酸チタン水溶液を調製した。このオキシ硫酸チタン水溶液に硝酸ガリウム水和物(和光純薬工業製)0.17gを添加し、溶解させ、ついで31%過酸化水素水46.76gを添加して、赤紫色の混合水溶液を得た。この混合水溶液中のガリウムの量は、チタンに対して0.001mol倍であった。
【0046】
実施例1の〔酸化チタンの調製〕で使用したと同じ1Lフラスコに水300gを入れた後、フラスコを冷却した。pHコントローラーのpH設定値を7とし、水のpHを設定値に調節した。このフラスコ内に、内容物を400rpmで攪拌しながら、上で得られた混合水溶液386.93gを5ml/minで添加し、pHコントローラーによりフラスコ内に供給されるアンモニア水と反応させた。
【0047】
フラスコ内の液のpHは、混合水溶液の添加を開始してから10分間はpH6.0〜7.9であり、添加開始10分後から添加終了まではpH6.9〜7.1であった。添加開始時のフラスコ内の液温は25℃であり、添加終了時の液温は30℃であった。
【0048】
得られたスラリーを、攪拌しながら1時間保持し、ついで25重量%アンモニア水(試薬特級、和光純薬工業製)を供給した後、さらに1時間攪拌して、生成物を熟成した。この間、スラリーの温度は29℃で一定であった。フラスコ内に供給されたアンモニア水の合計量は115gであり、オキシ硫酸チタンを水酸化チタンに変えるのに必要な塩基の化学量論量の2倍であった。
【0049】
熟成後の生成物を含むスラリーを濾過、洗浄、乾燥し、この乾燥物を400℃の空気中で1時間焼成した後、この焼成物を洗浄、乾燥して、粒子状アナターゼ型酸化チタンを得た。
【0050】
この酸化チタンについて、実施例1の〔酸化チタンの活性評価〕と同条件で評価した。この例における二酸化炭素の生成速度は酸化チタン1gあたり14.9μmol/hであった。
【0051】
比較例1
実施例1の〔酸化チタンの調製〕で使用した同じ1Lフラスコに、オキシ硫酸チタン水和物(添川理化学製)102gを水408gに溶解して調製したオキシ硫酸チタン水溶液を入れた後、このフラスコに、400rpmで攪拌しながら、25重量%アンモニア水(試薬特級、和光純薬工業製)を5ml/minで供給してオキシ硫酸チタン水溶液と反応させた。フラスコ内の液のpHは、アンモニア水の添加を開始してから1分間はpH0.7であり、添加終了後はpH4であった。アンモニア水の添加開始時のフラスコ内の液温は62℃であり、添加終了時の液温は65℃であった。フラスコ内に供給したアンモニア水の量は58gであり、オキシ硫酸チタンを水酸化チタンに変えるのに必要な塩基の化学量論量の1倍であった。
【0052】
このスラリーを濾過、洗浄、乾燥し、得られた乾燥物を400℃の空気中で1時間焼成して、粒子状アナターゼ型酸化チタンを得た。
【0053】
この酸化チタンについて、実施例1の〔酸化チタンの活性評価〕と同条件で評価した。この例における二酸化炭素の生成速度は酸化チタン1gあたり0μmol/hであった。
【0054】
【発明の効果】
本発明の製造方法によれば、可視光線の照射に対し優れた光触媒活性を示す酸化チタンを得ることができる。
【図面の簡単な説明】
【図1】pH−亜鉛水酸化物溶解度の相関図。
【図2】pH−ガリウム水酸化物溶解度の相関図。
【図3】pH−インジウム水酸化物溶解度の相関図。
【図4】pH−ジルコニウム水酸化物溶解度の相関図。
【図5】pH−鉄水酸化物溶解度の相関図。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for producing titanium oxide, and more particularly, to a method for producing titanium oxide suitable for photocatalytic applications.
[0002]
[Prior art]
2. Description of the Related Art Conventionally, it has been studied to remove malodorous substances in the atmosphere by using a photocatalytic action and to impart a self-cleaning action to window glass and road walls (see Patent Document 1).
[0003]
[Patent Document 1]
JP-A-9-57912
[0004]
In recent years, photocatalysts made of titanium oxide exhibiting photocatalytic activity against visible light irradiation have been developed, and since a light source capable of irradiating ultraviolet light is not required, it has become widely applicable. For example, application development for indoor use such as in a tunnel, which was previously difficult to apply, is being promoted.
[0005]
On the other hand, in such indoor use, a light beam from an illuminating device such as a fluorescent lamp or a sodium lamp is directly irradiated on the photocatalyst, and thus a sufficient amount of light for obtaining the photocatalytic action may not always be obtained. Therefore, further improvement in activity of titanium oxide as a raw material is demanded so that high photocatalytic activity can be obtained even with a small amount of light.
[0006]
[Problems to be solved by the invention]
An object of the present invention is to provide a method capable of producing titanium oxide having higher photocatalytic activity than conventional ones.
[0007]
[Means for Solving the Problems]
The present inventors have conducted various studies on a method for producing titanium oxide in order to improve the photocatalytic activity of titanium oxide, and as a result, have completed the present invention.
[0008]
That is, the present invention relates to a titanium compound, a group IIa element, a group IIIa element, a group Va element, a group VIa element, a group VIIa element, a group VIII element, a group Ib element, a group IIb element, a group IIIb element, a lanthanoid, silicon, and germanium. , Tin, lead, antimony, bismuth, zirconium and hafnium, a second component comprising the compound or a compound thereof, and a solvent, and mixing the mixture with a base and a hydroxide of the element constituting the second component. Has a solubility of 10 -4 It is intended to provide a method for producing titanium oxide, wherein the reaction is carried out under a condition of g / L or less, and the obtained solid is calcined.
[0009]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described in detail. In the production method of the present invention, first, a titanium compound, a component other than the titanium compound, and a solvent are mixed. The titanium compound used here may be any compound that generates titanium hydroxide by reacting with a base in the presence of water. For example, titanium trichloride [TiCl 3 ], Titanium tetrachloride [TiCl 4 ], Titanium sulfate [Ti (SO 4 ) 2 ・ MH 2 O, 0 ≦ m ≦ 20], titanium oxychloride [TiOCl 2 ], Titanium oxysulfate [TiOSO 4 ・ NH 2 O, 0 ≦ n ≦ 20], among which titanium oxysulfate is preferably used.
[0010]
As components other than the titanium compound, for example, beryllium, magnesium, calcium, strontium, group IIa element such as barium, scandium, group IIIa element such as yttrium, zirconium, group IVa element such as hafnium, vanadium, niobium, Group Va element such as tantalum, chromium, molybdenum, group VIa element such as tungsten, manganese, technetium, group VIIa element such as rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum Group VIII elements such as copper, silver, gold, Group Ib elements such as zinc, cadmium, boron, aluminum, gallium, indium, group IIIb elements such as thallium, silicon, germanium, tin, Like lead Group IVb elements such as IVb elements, antimony and bismuth, lanthanides such as lanthanum, cerium, praseodymium, neodymium, samarium, europium and gadolinium, preferably zinc, zirconium, gallium, indium, iron and niobium And more preferably zinc and niobium. The components other than the titanium compound may be used alone or in combination of two or more. Components other than the titanium compound are usually mixed with the titanium compound in the form of a compound, but may be mixed with the titanium compound alone as long as it can be uniformly dispersed in the solvent. Examples of the compound of the element other than titanium include various inorganic compounds and organic compounds of the element. Examples of the inorganic compound include sulfates, nitrates, and chlorides of these elements. Elemental oxalate, hydrogen oxalate, acetate and the like. It is preferable that the components other than the titanium compound are soluble in the solvent used or can be present as colloidal particles in the solvent. The amount of the component other than the titanium compound is 0.00001 mol times or more, preferably 0.0001 mol times or more, further 0.001 mol times or more, and 0% or less, based on the element constituting the titanium compound. It is preferably at most 0.1 mol times, more preferably at most 0.05 mol times.
[0011]
The solvent only needs to dissolve the titanium compound, and usually, water and aqueous hydrogen peroxide are used.
[0012]
In the present invention, the base is then reacted with a mixture of the titanium compound, a component other than the titanium compound, and the solvent. Examples of the base used herein include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, ammonia, hydrazine, hydroxylamine, monoethanolamine, acyclic amine compounds, and cyclic aliphatic amine compounds. . Among them, application of ammonia is preferred. When the base is used after mixing with a solvent in which the base is soluble in the reaction with the mixture, the concentration of the base is usually 0.05% by weight or more and 50% by weight or less.
[0013]
The reaction between the above mixture and the base is such that the solubility of the hydroxide of the constituent element of the component other than the titanium compound is 10%. -4 g / L or less, preferably 10 -6 g / L or less. When two or more components are mixed with the titanium compound, the solubility of the hydroxides of the elements constituting these components is 10% or less. -4 It is preferable to carry out the reaction under the condition of g / L or less. By performing the reaction under the conditions lower than the solubility, it is not clear why titanium oxide having high photocatalytic activity is obtained, but when a base is reacted with a mixture of a titanium compound and a component other than the titanium compound and a solvent, It is conceivable that the hydroxide of the element constituting this component rarely dissolves in the solvent and remains, and that it is influenced by the uniform incorporation into the generated titanium hydroxide.
[0014]
The reaction is performed when the solubility of the hydroxide is 10 -4 As long as the condition is not more than g / L, the reaction can be carried out by appropriately selecting a solvent and adjusting pH, temperature and the like. In the case where water is used as a solvent and the solubility is adjusted by pH, the solubility of the hydroxide is 10% for each element. -4 The pH below g / L is shown below. As shown in FIGS. 1 to 5, the pH at this time can be obtained from a correlation diagram of pH-metal hydroxide solubility, and zinc hydroxide [Zn (OH) 2 ], The pH is 7.4 to 12.5 as shown in FIG. As an element other than zinc, for example, gallium hydroxide [Ga (OH) 3 ], The pH is 3.5 to 10.5 as shown in FIG. 2 and indium hydroxide [In (OH) 3 ], The pH is 4.2 to 11.8 as shown in FIG. 3, and the zirconium hydroxide [Zr (OH) 2 ・ 2H 2 O], as shown in FIG. 4, the pH is 2.5 or more, and iron hydroxide [Fe (OH) 3 ], The pH is 3.2 or more as shown in FIG. In addition, the solubility of the hydroxide is 10 for each element. -6 The same applies to a pH value of not more than g / L. Zinc hydroxide [Zn (OH) 2 ], PH 8.4 to 10.6 (FIG. 1), gallium hydroxide [Ga (OH) 3 ], The pH is 5.7 to 9.2 (FIG. 2) and the indium hydroxide [In (OH) 3 ], The pH is 5.2 to 9.8 (FIG. 3) and the zirconium hydroxide [Zr (OH) 2 ・ 2H 2 O], the pH is 3.5 to 12.5 (FIG. 4) and the iron hydroxide [Fe (OH) 3 ], The pH is 4.2 or more (FIG. 5).
[0015]
In addition, niobium hydroxide [Nb (OH) 5 ] At a wide range of pH (approximately 1 to 13). -4 For those having a g / L or less, the reaction can be carried out at any pH within this range. In this case, the pH of the reaction is preferably determined in consideration of the mixture of the titanium compound and the components other than the titanium compound and the solvent, and the ease of handling of the reaction product of the base with the mixture. The preferred pH when the element constituting the component is niobium is 3-5.
[0016]
The reaction is preferably performed at 90 ° C. or lower. When the reaction temperature is higher than 90 ° C., the photocatalytic activity of the obtained titanium oxide may decrease. The lower the reaction temperature is, the more preferable it is to obtain titanium oxide exhibiting higher photocatalytic activity. For example, the reaction temperature is preferably 60 ° C or lower, more preferably 40 ° C or lower. On the other hand, in order to maintain a low reaction temperature, the cooling cost becomes high, for example, a large amount of refrigerant is required. The reaction rate at this time is usually 90% or more. The reaction rate can be adjusted by selecting the type of solvent or changing the temperature, time, stirring conditions, and the like. This reaction rate indicates the rate at which the titanium compound was hydrolyzed by the reaction with the base and changed to titanium hydroxide.
[0017]
In the reaction, specifically, after water is put in a container with a cooling jacket, a mixture of the titanium compound and a component other than the titanium compound and water is added to this container while stirring, while maintaining the liquid temperature within a predetermined range. And a method of supplying a base so as to have a predetermined pH, or a mixture of a titanium compound and a component other than the titanium compound and water and a base in a tube with a cooling jacket capable of controlling the reaction temperature, at a predetermined pH. It can be carried out by a continuous supply method or the like while adjusting the respective amounts so as to be as follows.
[0018]
The product obtained by the reaction may be aged. Aging can be performed by a method of keeping the slurry containing the product at a constant temperature in the presence of a base. Aging may be performed, for example, by subjecting a solution containing a salt (eg, ammonium sulfate) produced by the reaction to solid-liquid separation from the mixture after the reaction, adding a base to the obtained solid, and maintaining the solid at a constant temperature. it can. By performing this aging, the titanium oxide obtained by sintering the product exhibits excellent activity against irradiation with visible light. Examples of the base used for aging include ammonia water and the like, and the concentration is usually 0.05% by weight or more and 50% by weight or less. The aging temperature is preferably 0 ° C. or higher, more preferably 10 ° C. or higher, and 110 ° C. or lower, further preferably 80 ° C. or lower. The aging time varies depending on the base concentration and the aging temperature and is not unique, but is usually 0.01 hours or more, preferably 0.5 hours or more, and is 60 hours or less, preferably 24 hours or less. The base used for ripening and the base used for the above-mentioned reaction may be of the same kind and the same concentration, different concentrations of the same kind, or different types.
[0019]
The total amount of base used in the above-mentioned reaction and optional aging may exceed the stoichiometric amount of base required to convert the titanium compound to titanium hydroxide in the presence of water. Preferably, for example, it is preferably at least 1.1 times the stoichiometric amount. Since the photocatalytic activity of the finally obtained titanium oxide tends to increase as the amount of the base used increases, it is more preferably 1.3 times or more. On the other hand, if the amount of the base is too large, the effect of improving the photocatalytic activity commensurate with the amount cannot be obtained. Therefore, the amount is suitably 20 times or less, more preferably 10 times or less.
[0020]
The slurry after the reaction or the slurry containing the product after aging is usually subjected to an operation of separating a solid. Separation can be performed by pressure filtration, vacuum filtration, centrifugation, decantation, or the like, or can be performed by a method in which the slurry is used to evaporate the liquid using a spray dryer or the like. The separated solid is washed and dried if necessary, and then fired. The firing is performed at a temperature of 300 ° C. or higher, preferably 350 ° C. or higher, 600 ° C. or lower, preferably 500 ° C. or lower, more preferably 450 ° C. or lower. If the firing temperature is too high, it becomes difficult to obtain titanium oxide having sufficient photocatalytic activity. The firing can be performed, for example, in a standing furnace, a tunnel furnace, a rotary furnace, or the like. Here, the method of calcining the solid after separating the solid in the slurry has been described.However, the product or the slurry containing the matured product is dried using a flash dryer such as a flash jet drier to produce the product. The product may be calcined without previously performing a solid-liquid separation operation on the slurry containing.
[0021]
The titanium oxide obtained by the above-described production method of the present invention usually has a crystal structure of an anatase type and exhibits high photocatalytic activity against irradiation with visible light. This titanium oxide also shows photocatalytic activity against ultraviolet light irradiation.
[0022]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the examples.
Example 1
(Preparation of titanium oxide)
102 g of titanium oxysulfate hydrate (manufactured by Soegawa Rikagaku) was dissolved in 408 g of water to prepare an aqueous solution of titanium oxysulfate having a pH of about 1. To this aqueous solution of titanium oxysulfate, 1.21 g of zinc sulfate heptahydrate (special grade reagent, manufactured by Wako Pure Chemical Industries, Ltd.) was added and dissolved to obtain a mixed aqueous solution. The amount of zinc in the mixed aqueous solution was 0.01 mol times with respect to titanium.
[0023]
A pH electrode, a pH controller connected to the pH electrode and having a mechanism for supplying 25% by weight of aqueous ammonia (special grade reagent, manufactured by Wako Pure Chemical Industries, Ltd.) to constantly adjust the pH, and using a refrigerant were used. After 300 g of water was put into a 1 L flask having a cooling mechanism, the flask was cooled. The pH set value of the pH controller was set to 9, and the pH of the water was adjusted to the set value. While stirring at 400 rpm, 511.21 g of the mixed aqueous solution obtained above was added at 5 ml / min into the flask, and reacted with ammonia water supplied into the flask by a pH controller. During this time, the amount of 25% by weight aqueous ammonia supplied into the flask was 82.54 g.
[0024]
The pH of the liquid in the flask was pH 9.0 to 9.8 for 12 minutes after the addition of the mixed aqueous solution was started, and pH 8.9 to 9.2 from 12 minutes after the start of the addition to the end of the addition. . During that time, the liquid temperature in the flask was 1.1 to 6.2 ° C. The total amount of supplied ammonia water was 1.4 times the stoichiometric amount of the base required to convert titanium oxysulfate to titanium hydroxide.
[0025]
The obtained slurry was filtered, washed and dried, and the dried product was fired in air at 400 ° C. for 1 hour to obtain particulate titanium oxide. The titanium oxide was analyzed by an X-ray diffractometer (trade name “RAD-IIA”, manufactured by Rigaku Corporation). As a result, the crystal structure was anatase type.
[0026]
(Activity evaluation of titanium oxide)
A glass petri dish having a diameter of 5 cm was placed in a sealed glass reaction vessel having a diameter of 8 cm, a height of 10 cm, and a capacity of about 0.5 L, and 0.3 g of the particulate anatase-type titanium oxide obtained above was placed on the petri dish. I put it. The inside of the reaction vessel was filled with a mixed gas in which the volume ratio of oxygen and nitrogen was 1: 4, and 13.4 μmol of acetaldehyde was sealed. Then, visible light was irradiated from outside the reaction vessel. For irradiation with visible light, a light source device (trade name “Offical Molex® SX-UI500XQ”, manufactured by Ushio Inc.) equipped with a 500 W xenon lamp (trade name “Lanf UXL-500SX”, manufactured by Ushio Inc.) was applied to a wavelength of about 430 nm. A filter equipped with the following UV-cut filter (trade name "Y-45", made by Asahi Techno Glass) and a filter that cuts infrared light with a wavelength of about 830 nm or more (trade name "Super Coulter Filter", manufactured by Ushio Inc.) Was used as a light source. When acetaldehyde is decomposed by irradiation with visible light, carbon dioxide is generated. Therefore, the concentration of carbon dioxide is measured over time with a photoacoustic multi-gas monitor (model number “1312”, manufactured by INNOVA), and carbon dioxide calculated from the change in concentration is measured. The photocatalytic action of titanium oxide on acetaldehyde was evaluated based on the rate of formation of. The generation rate of carbon dioxide in this example was 31.2 μmol / h per 1 g of titanium oxide.
[0027]
Example 2
In a 1 L flask, 102 g of the same titanium oxysulfate hydrate used in Example 1 was dissolved in 408 g of water to prepare a titanium oxysulfate aqueous solution having a pH of about 1. Niobium hydrogen oxalate (manufactured by Mitsuwa Chemicals, Nb 2 O 5 0.39 g) was added and dissolved to prepare a mixed aqueous solution. The amount of niobium in this mixed aqueous solution was 0.001 mol times with respect to titanium.
[0028]
After 300 g of water was placed in the same 1-L flask used in [Preparation of Titanium Oxide] of Example 1, the flask was cooled. The pH set value of the pH controller was set to 4, and the pH of the water was adjusted to the set value. While stirring at 400 rpm, 510.39 g of the mixed aqueous solution obtained above was added at 5 ml / min, and reacted with ammonia water supplied to the flask by a pH controller.
[0029]
The pH of the liquid in the flask was pH 3.2 to 4.9 for 5 minutes after the start of the addition of the mixed aqueous solution, and was pH 3.8 to 4.3 from 5 minutes after the start of the addition to the end of the addition. . The liquid temperature in the flask at the start of the addition was 24 ° C, and the liquid temperature at the end of the addition was 26 ° C.
[0030]
The obtained slurry was held for 1 hour with stirring, then 25% by weight aqueous ammonia (special grade reagent, manufactured by Wako Pure Chemical Industries) was supplied, and the mixture was further stirred for 1 hour to mature the product. During this time, the temperature of the slurry was constant at 24 ° C. The total amount of aqueous ammonia supplied into the flask was 116 g, twice the stoichiometric amount of the base required to convert titanium oxysulfate to titanium hydroxide.
[0031]
The slurry containing the aged product is filtered, washed, and dried. The dried product is fired in air at 400 ° C. for 1 hour, and the fired product is washed and dried to obtain particulate anatase-type titanium oxide. Was.
[0032]
This titanium oxide was evaluated under the same conditions as in [Evaluation of activity of titanium oxide] in Example 1. The generation rate of carbon dioxide in this example was 27.6 μmol / h per 1 g of titanium oxide.
[0033]
Example 3
In a 1 L flask, 102 g of the same titanium oxysulfate hydrate used in Example 1 was dissolved in 238 g of water to prepare an aqueous solution of titanium oxysulfate having a pH of about 1. 0.15 g of indium nitrate trihydrate (manufactured by Kishida Chemical) was added to and dissolved in this aqueous solution of titanium oxysulfate, and then 46.43 g of a 31% hydrogen peroxide solution was added to obtain a red-purple mixed aqueous solution. . The amount of indium in this mixed aqueous solution was 0.001 mol times with respect to titanium.
[0034]
After 300 g of water was placed in the same 1-L flask used in [Preparation of Titanium Oxide] of Example 1, the flask was cooled. The pH set value of the pH controller was set to 6, and the pH of the water was adjusted to the set value. While stirring the content at 400 rpm, 386.58 g of the mixed aqueous solution obtained above was added to the flask at 5 ml / min, and reacted with ammonia water supplied into the flask by a pH controller.
[0035]
The pH of the liquid in the flask was 5.4 to 6.9 for 20 minutes after the addition of the mixed aqueous solution was started, and was 5.9 to 6.1 from 20 minutes after the start of the addition to the end of the addition. . The liquid temperature in the flask at the start of the addition was 24 ° C, and the liquid temperature at the end of the addition was 30 ° C.
[0036]
The obtained slurry was held for 1 hour and 10 minutes with stirring, and then 25% by weight aqueous ammonia (special grade reagent, manufactured by Wako Pure Chemical Industries, Ltd.) was supplied, followed by further stirring for 1 hour to mature the product. During this time, the temperature of the slurry was constant at 27 ° C. The total amount of aqueous ammonia supplied into the flask was 115 g, twice the stoichiometric amount of the base required to convert titanium oxysulfate to titanium hydroxide.
[0037]
The slurry containing the aged product is filtered, washed, and dried. The dried product is fired in air at 400 ° C. for 1 hour, and the fired product is washed and dried to obtain particulate anatase-type titanium oxide. Was.
[0038]
This titanium oxide was evaluated under the same conditions as in [Evaluation of activity of titanium oxide] in Example 1. The generation rate of carbon dioxide in this example was 20.1 μmol / h per 1 g of titanium oxide.
[0039]
Example 4
In a 1 L flask, 102 g of the same titanium oxysulfate hydrate used in Example 1 was dissolved in 158 g of water to prepare an aqueous solution of titanium oxysulfate having a pH of about 1. 0.15 g of zirconium sulfate hydrate (manufactured by Wako Pure Chemical Industries) is added to and dissolved in this aqueous solution of titanium oxysulfate, and then 81.36 g of 31% hydrogen peroxide is added to obtain a red-purple mixed aqueous solution. Was. The amount of zirconium in this mixed aqueous solution was 0.001 mol times with respect to titanium.
[0040]
After 300 g of water was placed in the same 1-L flask used in [Preparation of Titanium Oxide] of Example 1, the flask was cooled. The pH set value of the pH controller was set to 7, and the pH of the water was adjusted to the set value. While stirring the content at 400 rpm, 341.51 g of the mixed aqueous solution obtained above was added at 5 ml / min into the flask, and reacted with ammonia water supplied into the flask by a pH controller.
[0041]
The pH of the liquid in the flask was pH 6.1 to 8.2 for 17 minutes from the start of the addition of the mixed aqueous solution, and was pH 6.9 to 7.0 from 17 minutes after the start of the addition to the end of the addition. . The liquid temperature in the flask at the start of the addition was 23 ° C, and the liquid temperature at the end of the addition was 32 ° C.
[0042]
The obtained slurry was held for 1 hour with stirring, then 25% by weight aqueous ammonia (special grade reagent, manufactured by Wako Pure Chemical Industries) was supplied, and the mixture was further stirred for 1 hour to mature the product. During this time, the temperature of the slurry was constant at 28 ° C. The total amount of aqueous ammonia supplied into the flask was 115 g, twice the stoichiometric amount of the base required to convert titanium oxysulfate to titanium hydroxide.
[0043]
The slurry containing the aged product is filtered, washed, and dried. The dried product is fired in air at 400 ° C. for 1 hour, and the fired product is washed and dried to obtain particulate anatase-type titanium oxide. Was.
[0044]
This titanium oxide was evaluated under the same conditions as in [Evaluation of activity of titanium oxide] in Example 1. The generation rate of carbon dioxide in this example was 22.6 μmol / h per 1 g of titanium oxide.
[0045]
Example 5
In a 1 L flask, 102 g of the same titanium oxysulfate hydrate used in Example 1 was dissolved in 238 g of water to prepare an aqueous solution of titanium oxysulfate having a pH of about 1. 0.17 g of gallium nitrate hydrate (manufactured by Wako Pure Chemical Industries) is added and dissolved in this aqueous solution of titanium oxysulfate, and then 46.76 g of 31% hydrogen peroxide is added to obtain a red-purple mixed aqueous solution. Was. The amount of gallium in the mixed aqueous solution was 0.001 mol times with respect to titanium.
[0046]
After 300 g of water was placed in the same 1-L flask used in [Preparation of Titanium Oxide] of Example 1, the flask was cooled. The pH set value of the pH controller was set to 7, and the pH of the water was adjusted to the set value. While stirring the contents at 400 rpm, 386.93 g of the mixed aqueous solution obtained above was added at 5 ml / min, and reacted with ammonia water supplied to the flask by a pH controller.
[0047]
The pH of the liquid in the flask was 6.0 to 7.9 for 10 minutes after the addition of the mixed aqueous solution was started, and was 6.9 to 7.1 from 10 minutes after the start of the addition to the end of the addition. . The liquid temperature in the flask at the start of the addition was 25 ° C, and the liquid temperature at the end of the addition was 30 ° C.
[0048]
The obtained slurry was held for 1 hour with stirring, then 25% by weight aqueous ammonia (special grade reagent, manufactured by Wako Pure Chemical Industries) was supplied, and the mixture was further stirred for 1 hour to mature the product. During this time, the temperature of the slurry was constant at 29 ° C. The total amount of aqueous ammonia supplied into the flask was 115 g, twice the stoichiometric amount of the base required to convert titanium oxysulfate to titanium hydroxide.
[0049]
The slurry containing the aged product is filtered, washed, and dried. The dried product is fired in air at 400 ° C. for 1 hour, and the fired product is washed and dried to obtain particulate anatase-type titanium oxide. Was.
[0050]
This titanium oxide was evaluated under the same conditions as in [Evaluation of activity of titanium oxide] in Example 1. The generation rate of carbon dioxide in this example was 14.9 μmol / h per 1 g of titanium oxide.
[0051]
Comparative Example 1
The same 1 L flask used in [Preparation of Titanium Oxide] of Example 1 was charged with an aqueous solution of titanium oxysulfate prepared by dissolving 102 g of titanium oxysulfate hydrate (manufactured by Soegawa Rikagaku) in 408 g of water. While stirring at 400 rpm, 25% by weight aqueous ammonia (special grade reagent, manufactured by Wako Pure Chemical Industries, Ltd.) was supplied at 5 ml / min to react with an aqueous solution of titanium oxysulfate. The pH of the liquid in the flask was 0.7 for 1 minute after the start of the addition of the aqueous ammonia, and was 4 after the addition was completed. The liquid temperature in the flask at the start of the addition of the ammonia water was 62 ° C, and the liquid temperature at the end of the addition was 65 ° C. The amount of aqueous ammonia supplied into the flask was 58 g, which was one time the stoichiometric amount of the base required to convert titanium oxysulfate to titanium hydroxide.
[0052]
The slurry was filtered, washed and dried, and the obtained dried product was calcined in air at 400 ° C. for 1 hour to obtain particulate anatase-type titanium oxide.
[0053]
This titanium oxide was evaluated under the same conditions as in [Evaluation of activity of titanium oxide] in Example 1. The generation rate of carbon dioxide in this example was 0 μmol / h per 1 g of titanium oxide.
[0054]
【The invention's effect】
ADVANTAGE OF THE INVENTION According to the manufacturing method of this invention, the titanium oxide which shows the outstanding photocatalytic activity with irradiation of visible light can be obtained.
[Brief description of the drawings]
FIG. 1 is a correlation diagram of pH and solubility of zinc hydroxide.
FIG. 2 is a correlation diagram of pH and gallium hydroxide solubility.
FIG. 3 is a correlation diagram of pH and indium hydroxide solubility.
FIG. 4 is a correlation diagram of pH-zirconium hydroxide solubility.
FIG. 5 is a correlation diagram of pH-iron hydroxide solubility.
Claims (5)
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WO2005051541A1 (en) * | 2003-11-25 | 2005-06-09 | National Institute Of Advanced Industrial Science And Technology | Zirconia-doped titania photocatalyst powder and process for producing the same |
WO2007037321A1 (en) | 2005-09-29 | 2007-04-05 | Sumitomo Metal Industries, Ltd. | Titanium oxide photocatalyst, method for producing same and use thereof |
JP2009291717A (en) * | 2008-06-05 | 2009-12-17 | Sumitomo Chemical Co Ltd | Manufacturing method of tungsten oxide photocatalyst |
CN114349719A (en) * | 2022-01-06 | 2022-04-15 | 润泰化学(泰兴)有限公司 | Preparation method of tetrahydrofurfuryl alcohol isooctanoate |
JPWO2022138187A1 (en) * | 2020-12-22 | 2022-06-30 |
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