CN104640631B - It is loaded with the titanium oxide of transistion metal compound - Google Patents
It is loaded with the titanium oxide of transistion metal compound Download PDFInfo
- Publication number
- CN104640631B CN104640631B CN201380048744.4A CN201380048744A CN104640631B CN 104640631 B CN104640631 B CN 104640631B CN 201380048744 A CN201380048744 A CN 201380048744A CN 104640631 B CN104640631 B CN 104640631B
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- CN
- China
- Prior art keywords
- titanium oxide
- loaded
- metal compound
- transistion metal
- crystal plane
- Prior art date
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 275
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 214
- 150000002736 metal compounds Chemical class 0.000 title claims abstract description 90
- 239000013078 crystal Substances 0.000 claims abstract description 76
- 238000000034 method Methods 0.000 claims description 49
- 238000005374 membrane filtration Methods 0.000 claims description 36
- 238000004519 manufacturing process Methods 0.000 claims description 25
- 230000008569 process Effects 0.000 claims description 25
- 238000012545 processing Methods 0.000 claims description 16
- 150000003623 transition metal compounds Chemical class 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 7
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical group [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 35
- 230000004044 response Effects 0.000 abstract description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Substances OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 73
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 73
- 239000000725 suspension Substances 0.000 description 71
- 150000002506 iron compounds Chemical class 0.000 description 69
- 239000010936 titanium Substances 0.000 description 62
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 52
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 39
- 238000007254 oxidation reaction Methods 0.000 description 39
- 229910052719 titanium Inorganic materials 0.000 description 38
- 238000001914 filtration Methods 0.000 description 36
- 238000004140 cleaning Methods 0.000 description 35
- 239000012528 membrane Substances 0.000 description 32
- 239000000463 material Substances 0.000 description 31
- 230000003647 oxidation Effects 0.000 description 31
- 239000007788 liquid Substances 0.000 description 22
- 239000007789 gas Substances 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 20
- 238000007792 addition Methods 0.000 description 17
- -1 halide ion Chemical class 0.000 description 17
- 239000007864 aqueous solution Substances 0.000 description 16
- 238000011156 evaluation Methods 0.000 description 15
- 239000012535 impurity Substances 0.000 description 15
- 239000003795 chemical substances by application Substances 0.000 description 14
- 239000002609 medium Substances 0.000 description 14
- 230000001590 oxidative effect Effects 0.000 description 13
- 239000012466 permeate Substances 0.000 description 13
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 13
- 239000012141 concentrate Substances 0.000 description 12
- 239000011521 glass Substances 0.000 description 12
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 11
- 239000012510 hollow fiber Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- 150000003609 titanium compounds Chemical class 0.000 description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 239000000460 chlorine Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000004695 Polyether sulfone Substances 0.000 description 8
- 230000007423 decrease Effects 0.000 description 8
- 229920006393 polyether sulfone Polymers 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- 238000000108 ultra-filtration Methods 0.000 description 8
- 230000008859 change Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 229910052723 transition metal Inorganic materials 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000010790 dilution Methods 0.000 description 6
- 239000012895 dilution Substances 0.000 description 6
- 229910000765 intermetallic Inorganic materials 0.000 description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 150000003624 transition metals Chemical class 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- 230000003373 anti-fouling effect Effects 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000004332 deodorization Methods 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 238000001027 hydrothermal synthesis Methods 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 229910052715 tantalum Inorganic materials 0.000 description 5
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 5
- 230000007704 transition Effects 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 238000009825 accumulation Methods 0.000 description 4
- 230000000844 anti-bacterial effect Effects 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 238000003556 assay Methods 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
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- 229920003023 plastic Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- 241000370738 Chlorion Species 0.000 description 2
- 241000195493 Cryptophyta Species 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 229920003235 aromatic polyamide Polymers 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229920002301 cellulose acetate Polymers 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 210000000887 face Anatomy 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 230000002045 lasting effect Effects 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 230000002186 photoactivation Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 2
- NPNPZTNLOVBDOC-UHFFFAOYSA-N 1,1-difluoroethane Chemical compound CC(F)F NPNPZTNLOVBDOC-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 241000186046 Actinomyces Species 0.000 description 1
- 235000001674 Agaricus brunnescens Nutrition 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 241001465805 Nymphalidae Species 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 1
- 229920006266 Vinyl film Polymers 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000002924 anti-infective effect Effects 0.000 description 1
- 230000001046 anti-mould Effects 0.000 description 1
- 239000002546 antimould Substances 0.000 description 1
- 229940045985 antineoplastic platinum compound Drugs 0.000 description 1
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- 239000011230 binding agent Substances 0.000 description 1
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- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
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- 230000003292 diminished effect Effects 0.000 description 1
- PCHPORCSPXIHLZ-UHFFFAOYSA-N diphenhydramine hydrochloride Chemical compound [Cl-].C=1C=CC=CC=1C(OCC[NH+](C)C)C1=CC=CC=C1 PCHPORCSPXIHLZ-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
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- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
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- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 239000007777 multifunctional material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 description 1
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- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 238000012360 testing method Methods 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 description 1
- MTAYDNKNMILFOK-UHFFFAOYSA-K titanium(3+);tribromide Chemical compound Br[Ti](Br)Br MTAYDNKNMILFOK-UHFFFAOYSA-K 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
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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
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/88—Handling or mounting catalysts
-
- 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
- B01J35/30—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
- 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
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- 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
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Abstract
A kind of response to visible ray of present invention offer is excellent, and plays the titanium oxide for being loaded with transistion metal compound of excellent photochemical catalyst ability.The titanium oxide for being loaded with transistion metal compound of the present invention is loaded with transistion metal compound in crystalline titanium oxide, it is characterized in that, average minor axis is below 50nm, and mean aspect ratio (major diameter/minor axis) is more than 1.5.As above-mentioned crystalline titanium oxide, the Titanium Dioxide Rutile Top grade preferably with crystal plane (110) and crystal plane (111) and/or the Titanium Dioxide Rutile Top grade with crystal plane (110), crystal plane (111) and crystal plane (001).
Description
Technical field
The present invention relates to be loaded with transistion metal compound obtained from carrying transition metal compound on titanium oxide
Titanium oxide.The above-mentioned titanium oxide for being loaded with transistion metal compound is excellent to the response of visible ray, can play excellent light
Catalyst ability.
Background technology
Being loaded with the titanium oxide of transistion metal compound has photochemical catalyst ability, by irradiating visible ray or ultraviolet etc.
Light, can play strong oxdiative power and harmful chemical is decomposed into water or carbon dioxide, by being loaded with transition metal
The titanium oxide suspension of compound is coated or mixed, the object being applied or mixed material can be assigned antibacterial, it is mould proof,
Deodorization, air cleaning, purification of water quality and anti-fouling effect etc..Moreover it is known that containing in the titanium oxide for being loaded with transistion metal compound
In the case of having halide ion isoiony impurity, the response to ultraviolet and visible ray can decline.
It is known to there is the titanium oxide for being loaded with transistion metal compound to be manufactured via following processes (with reference to patent document
1st, 2 etc.).
1. titanium oxide manufacturing process：Hydro-thermal process is carried out to titanium compound and titanium oxide suspension is obtained；
2. the process of carrying transition metal compound：By by transistion metal compound addition in titanium oxide suspension and
Obtain being loaded with the titanium oxide suspension of transistion metal compound；
3. refining step：By applying the titanium oxide suspension for being loaded with transistion metal compound using full dose filtering side
The pressurization of formula the processing such as is filtered under diminished pressure or centrifuged and makes separation of solid and liquid to reduce the content of ionic impurity；
But, for the above method, make due to separation of solid and liquid to be loaded with transistion metal compound in refining step
Titanium oxide occur compressionizations so that high activity face the amount of exposing decline, accordingly, there exist can not obtain with enough photocatalysis
The problem of titanium oxide for being loaded with transistion metal compound of agent ability.And then, once there occurs compressionization is loaded with transition
Even if the titanium oxide of metallic compound implements pulverization process etc. and redisperse afterwards, still or sufficient photocatalysis can not be obtained
Agent ability.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 10-158015 publications
Patent document 2：Japanese Unexamined Patent Application 62-235215 publications
The content of the invention
Problems to be solved by the invention
Therefore, it is an object of the present invention to provide a kind of response to visible ray is excellent, and excellent photocatalysis is played
The titanium oxide for being loaded with transistion metal compound of agent ability.
Technical teaching for solving the problem was
The present inventor has carried out research with great concentration to solve the above problems, and as a result finds：Bar-shaped is loaded with transition gold
Belong to the titanium oxide of compound when occurring compressionization by applying the processing of the separation of solid and liquid such as centrifugation, even if passing through afterwards
Crush and redisperse, bar-shaped crystal structure can be also cut off, and because following 1,2 etc. reasons, it is seen that the photocatalysis in light region
Agent ability is remarkably decreased.
1. the mean aspect ratio for being loaded with the titanium oxide of transistion metal compound diminishes, as closer spherical shape,
So the separation property of oxidation reaction and reduction reaction declines, it is impossible to avoid the progress of back reaction or side reaction；
2. because rhabdolith structure is cut off, the oxidation titanium sheet of unsupported transistion metal compound, the oxidation can be produced
Titanium sheet can not play visible light-responded property.
Moreover, in purification procedures, replacing centrifuging when using the membrane filtration processing carried out using cross flow filter mode
When being handled etc. separation of solid and liquid, compressionization would not be occurred by being loaded with the titanium oxide of transistion metal compound, can remain bar-shaped
Ionic impurity is efficiently removed in the state of crystal structure, the content that can obtain ionic impurity is extremely low, and bar-shaped load
There is the titanium oxide of transistion metal compound.It has also been found that：When carrying out hydro-thermal process to being stirred in reaction system, it will obtain
It is minimum to average minor axis, and the titanium oxide for being loaded with transistion metal compound of mean aspect ratio greatly.And it was found that：As described above
The obtained titanium oxide for being loaded with transistion metal compound is excellent to the response of visible ray, can play excellent photochemical catalyst
Ability.The present invention is completed based on these opinions.
That is, the present invention provides a kind of titanium oxide for being loaded with transistion metal compound, and it is loaded on crystalline titanium oxide
There is transistion metal compound, the average minor axis of the titanium oxide for being loaded with transistion metal compound is below 50nm, average length and width
It is more than 1.5 than (major diameter/minor axis).
As above-mentioned crystalline titanium oxide, the Titanium Dioxide Rutile Top grade preferably with crystal plane (110) and crystal plane (111)
And/or the Titanium Dioxide Rutile Top grade with crystal plane (110), crystal plane (111) and crystal plane (001).
Specific surface area is preferably 10m2/ more than g.
The present invention also provides a kind of titanium oxide, and its average minor axis is below 50nm, and mean aspect ratio (major diameter/minor axis) is
More than 1.5.
Invention effect
The average minor axis of the titanium oxide for being loaded with transistion metal compound of the present invention is below 50nm, and mean aspect ratio
(major diameter/minor axis) is more than 1.5.Therefore, the response to visible ray is excellent, can absorb sunshine or incandescent lamp, fluorescent lamp,
The light in the generally living space such as LED, and harmful chemical is decomposed into water or carbon dioxide.That is, of the invention was loaded with
The titanium oxide suspension for crossing metallic compound is preferably used as photoactivation agent under LED illumination.Moreover, can be anti-applied to antibacterial
The various uses such as mould, deodorization, air cleaning, Water warfare, and can be applied in the family based on indoor wallpaper or furniture
Or a wide range of scope such as the depollution of environment, the multifunction of family's electrical article in the communal facility such as hospital, school.
Brief description of the drawings
Fig. 1 is the synoptic diagram of an example of membrane filtration for showing to carry out using crossing current mode；
Fig. 2 is the synoptic diagram of an example of the inverse cleaning of membrane filtration for showing to carry out using crossing current mode；
Fig. 3 is bar-shaped Titanium Dioxide Rutile Top grade with crystal plane (110) (111) and with crystal plane (110)
(111) stereogram of the bar-shaped Titanium Dioxide Rutile Top grade of (001)；
Fig. 4 be obtain in the embodiment 2 photographed using electric field emission type SEM be loaded with iron chemical combination
Photo (× 200000, engineer's scale of the titanium oxide of thing：100nm).
Embodiment
[titanium oxide for being loaded with transistion metal compound]
The titanium oxide for being loaded with transistion metal compound of the present invention is characterised by, transition metal compound loaded in knot
On crystalline substance titanium oxide, the average minor axis for being loaded with the titanium oxide of transistion metal compound is below 50nm, and mean aspect ratio is (long
Footpath/minor axis) it is more than 1.5.
Be loaded with transistion metal compound titanium oxide average minor axis be below 50nm, preferably 5~40nm, it is especially excellent
Elect 5~30nm, most preferably 10~25nm as.When average minor axis is more than above range, oxidation reaction and reduction reaction
Separation property can decline, it is impossible to avoid the progress of back reaction or side reaction, and photochemical catalyst ability declines, therefore not preferred.
In addition, the mean aspect ratio (major diameter/minor axis) for being loaded with the titanium oxide of transistion metal compound is more than 1.5, it is excellent
Elect 1.5~100, more preferably 1.5~50, particularly preferably 1.5~20, most preferably 2~15 as.When mean aspect ratio is less than
During above range, the separation property of oxidation reaction and reduction reaction can decline, it is impossible to avoid the progress of back reaction or side reaction,
And photochemical catalyst ability declines, thus it is not preferred.
In addition, in the present invention, average minor axis and mean aspect ratio are under using the sample obtained with following adjusting methods
State the value that assay method is tried to achieve.
＜ sample preparation methods ＞
1. the titanium oxide for being loaded with transistion metal compound of a small amount of (half of medicine spoon of earpick size or so) is filled
Enter 9mL glass system sample bottle, and add 7mL ethanol, using ultrasonic cleaner, the ultrasonic wave of application 5 minutes disperses it
Into ethanol so as to obtain alcohol dispersion liquid.
2. obtained alcohol dispersion liquid is drawn into 1 with glass system dropper to drip, drip on SEM sample bench, make it certainly
After so drying, the platinum evaporation of 30 seconds is carried out.
＜ assay methods ＞
Using field emission type SEM (trade name " and FE-SEM JSM-6700F ", JEOL's (strain) manufacture,
Accelerating potential：15kV, WD：About 3mm, multiplying power：200000 times), random observation crystalline particle is extracted at representational three, is being extracted
SEM photograph entirety in, extract be located at 30 middle and clear-cut following particles：It was observed that size it is not extreme big also not
The average particle of extremely small size, is photographed on OHP thin slices, to these particles, utilizes image analysis software (trade name
" WinROOFVersion5.6 ", three paddy business (strain) manufacture) each minor axis (width orthogonal with maximum major diameter) is obtained, to these
Value carries out average as average minor axis.In addition, average major diameter (maximum major diameter) is obtained with same method, ratio between two is (flat
Equal major diameter/average minor axis) it is used as mean aspect ratio.
As above-mentioned crystalline titanium oxide, for example, it can enumerate：Titanium Dioxide Rutile Top grade, anatase-type titanium oxide, plate titanium-type
Titanium oxide etc..In the present invention, from from the viewpoint of stable crystal plane is exposed, preferably Titanium Dioxide Rutile Top grade or rutile titania
Ore deposit type titanium oxide, from the viewpoint of it can play more excellent photochemical catalyst ability, more preferably Titanium Dioxide Rutile Top grade is special
You Xuanwei have the Titanium Dioxide Rutile Top grade of crystal plane (110) and crystal plane (111) and/or with crystal plane (110), crystallization
Face (111) and the Titanium Dioxide Rutile Top grade of crystal plane (001).
Transistion metal compound is for example with transition metal ions, transition metal simple substance, transition metal salt, transiting metal oxidation
The state of thing, transition metal hydroxide or transition metal complex is supported.As the load capacity of transistion metal compound,
For example, for more than 50ppm, particularly preferably preferably more than 100ppm, more preferably more than 200ppm, more than 300ppm, most
Preferably more than 500ppm.The upper limit of the load capacity of transistion metal compound is, for example, 5000ppm or so, preferably 3000ppm,
Particularly preferably 2000ppm.When the load capacity of transistion metal compound is less than above range, it is seen that optical Response, which exists, to be declined
Tendency.On the other hand, when transistion metal compound load capacity be more than above range when, excite electronics will because injection electronics
Inversion electron transfer etc. and can not effectively play a role so that photochemical catalyst ability exist decline tendency.
From the separation property for the reacting field that can further improve oxidation reaction and reduction reaction, thus, from can suppress sharp
Generate electricity son and hole in conjunction with and the progress of back reaction can be suppressed and can improve by leaps and bounds photocatalyst activity this
Point sets out, and preferably above-mentioned transistion metal compound surface is optionally carried on the surface of crystalline titanium oxide, particularly preferred mistake
Cross metallic compound and be optionally supported on oxidation reaction face.
In addition, in the present invention, transistion metal compound " surface is optionally " load refers to：Transistion metal compound
Amount more than 50%, preferably more than 70%, particularly preferably more than 80%, it is supported on more than 2 of crystalline titanium oxide
On specific face (for example, specific 1 face or 2 faces etc.) in crystal plane, rather than it is supported on all faces.In addition, surface
The upper limit of selection rate is 100%.Surface can selectively be carried out as follows judgement：By using transmission electron microscope (TEM) or
Energy dispersion type fluorescent x-ray analysis equipment (EDX), confirms the signal of transistion metal compound being derived from each crystal plane.
As transistion metal compound, as long as there is absorption spectrum in visible region, and can excited state to
Conduction band injects the transistion metal compound of electronics, but in the present invention, it is preferred to is periodic table of elements IIIB races~IIIA
Group element compound, wherein preferably periodic table of elements VIII~Group IIIA element compound, particularly preferably iron compound
Or platinum compounds, most preferably ferric iron compound (Fe3+).Because ferric iron compound (Fe3+) titanium oxide is easily adsorbed in, and
Ferro-compound (Fe2+) there is the characteristic for being difficult to adsorb, so by using its characteristic, easily can selectively carry out on ground
Load.
The specific surface area for example, 10m of the above-mentioned titanium oxide for being loaded with transistion metal compound2/ more than g.Specific surface area
Lower limit is preferably 30m2/ g, more preferably 50m2/ g, particularly preferably 60m2/ g, most preferably 70m2/g.The upper limit of specific surface area
For example, 200m2/ g, preferably 150m2/ g, particularly preferably 100m2/g。
The specific surface area of the above-mentioned titanium oxide for being loaded with transistion metal compound is, for example, 10~200m2/ g, preferably 10
~150m2/ g, more preferably 30~150m2/ g, more preferably 50~100m2/ g, particularly preferably 60~100m2/ g, most
Preferably 70~100m2/g.Specific surface area is the titanium oxide high activity face for being loaded with transistion metal compound of above range
Expose that quantitative change is more, therefore, it is possible to play excellent photochemical catalyst ability.
Above-mentioned specific surface area be using high speed specific surface area/fine pore distribution measurement device (trade name " NOVA-1200 ",
Quantachtome.Co is manufactured), under the following conditions, the average value that sample be worth obtained from determining twice is changed, it is described
Sample is to will be loaded with the titanium oxide of transistion metal compound obtained from 100 DEG C of (under vacuum) degassings 60 minutes.
＜ specific area measuring conditions ＞
Measuring principle：Constant volume method (blank correction type)
Detection method：(the adsorption equilibrium pressure (P) in sample room realized using pressure converter is steamed relative pressure with saturation
Air pressure (P0) the ratio between) and the adsorbed gas scale of construction (using pressure converter carry out pressure detecting and using thermistor progress manifold temperature
Degree detection, calculates the injection gas flow under perfect gas)
Adsorbed gas：Nitrogen
Chamber size：Cylindrical cells (chamber vol：1.8cm3, trunk external diameter：9mm)
Measure project：P/P03 points of=0.1,0.2,0.3 absorption side
Analysis project：The specific surface area determined using BET multipoint methods
The titanium oxide for being loaded with transistion metal compound of the present invention is excellent by visible light-responded property, and passes through light irradiation
And excellent photochemical catalyst ability is played, and harmful chemical is decomposed into water or carbon dioxide, antibacterial can be played, prevented
The various effects such as mould, deodorization, air cleaning, purification of water quality, antifouling.
For example, being generated when being aoxidized using the above-mentioned titanium oxide (200mg) for being loaded with transistion metal compound to toluene
CO2Amount for example, more than 300ppm.In addition, the CO generated when being aoxidized to methanol2Amount is, for example, more than 500ppm, excellent
Elect more than 600ppm, particularly preferably more preferably more than 700ppm, more than 750ppm as.
In addition, the CO that generates during to aoxidizing above-mentioned toluene2Measure the method being measured as described below.
The titanium oxide 200mg for being loaded with transistion metal compound is spread in glass dish, loads reaction vessel
(Tedorabaggu (テ ド ラ ー バ ッ グ), material：Polyfurolresin) in, and 100ppm toluene gas 125mL is blown
It is sent in reaction vessel.After the titanium oxide absorption toluene gas for being loaded with transistion metal compound reaches balance, in room temperature
Light irradiation (LED, luminous intensity are carried out under (25 DEG C)：2.5W/cm2, the wavelength of light：455nm), determine 24 hours since light irradiation
CO afterwards2Growing amount.
In addition, the CO generated when being aoxidized to above-mentioned methanol2The assay method of amount is as described below.
The titanium oxide 200mg for being loaded with transistion metal compound is spread in glass dish, loads reaction vessel
(Tedorabaggu, material：Polyfurolresin) in, and 800ppm methanol gas 125mL is blown into reaction vessel.
After the titanium oxide absorption methanol gas for being loaded with transistion metal compound reaches balance, illumination is carried out under room temperature (25 DEG C)
Penetrate (LED, luminous intensity：2.5W/m2, the wavelength of light：455nm), the CO since light irradiation after 24 hours is determined2Growing amount.
As described above, the titanium oxide for being loaded with transistion metal compound of the present invention can play extremely excellent photoresponse
Property, i.e. the response with the light to the wide wave-length coverage from ultraviolet range to visible region, therefore, it is possible to by inhaling
Receive the generally light in living space such as sunshine or incandescent lamp, fluorescent lamp, LED and play higher catalytic activity, and by harmful
It is water or carbon dioxide to learn substance decomposition, thus, plays antibacterial (sterilization such as bacterium, actinomyces, mushroom, algae, kill algae), anti-
Mould, deodorization is (for example, the foul gas such as the sulphur-containing substance such as ammonia, amine, methyl mercaptan, hydrogen sulfide, acetic acid, aldehydes, ethene is removed
It is smelly), air cleaning, purification of water quality, the various effects such as antifouling.In addition, the oxidation for being loaded with transistion metal compound of the present invention
Titanium can be as needed, by the state mixed to binding agent, solvent, dispersant, tackifier, interfacial agent etc.
Under, it is coated or mixed, to assign the effect above to being applied object or mixed material.
Object and mixed material are applied as the titanium oxide for being loaded with transistion metal compound of the invention, for example
It can enumerate：Decoration, interior of building decoration, building coating, wall, wallpaper, floor, window frame, window glass outside building materials, building
Glass, crystallized glass, glass, screen window, rain-water drainage groove, solar heat reflection piece, mailbox, structure member, pavement material, display board,
Traffic sign, road traffic mark reflecting plate, display panel, display filter, road surface display material, road decorative panel,
Fences, door, tunnel use/road lighting device, soundproof wall, grille, tunnel internal decoration, road mirror, vinyl plastic material temperature
Ceiling canopy inner face, bridge, the safety guard of bridge, the interior exterior of automobile/train/ship and application, wheel for vehicle, rolling stock
Body construction, vehicle part, exterior/dust cover/application of mechanical device or article, various display devices, advertising tower, insulation
Body, solar panels, solar-electricity pool cover, solar water heater heat-collecting cover, fuel cell, optical fiber, vehicle lighting lampshade, fishing
Net, rope, flexible pipe, hull bottom part, anti-algae material, shoes, handbag, shutter, curtain, wall cloth, screen, sliding window, plastics are pushed away
Draw window, sliding door, synthetic leather, tablecloth, clothing, raincoat, stationery, book, notebook, paper, carton, the vehicles or household electrical appliances etc. each
Plant plastic body, toy, sports requsites, musical instrument, fishing tackle, upholstery product, plastic containers, card-like, tent, timber/post/day
The structure materials such as card/board wall, furniture, printed plywood, built-in use plate, artificial flower, foliage plant, artificial plant, swimming pool/
Water process filler, the mirrors such as bathing pool/rivers and creeks/sea/plant drainage/living drainage/underground water/pond/artificial rivers and creeks, wash one's face
Basin, ceramic tile, the seam of ceramic tile, bathtub, bathroom components, lavatory are with anti-infection hospital internal in floor finishing material, Hospital
Part, ceramic industry system multifunctional material, glaze liquid, refrigerator inside and outside wall, pedestal, kitchen panel, vegetable sink, micro-wave oven, cooking container, change
Device of air, air-conditioning, heat exchanger, various filters, closet, fiber, non-woven fabrics, mouth mask, clothing, bedding, cap, safety cap,
Doormat, flannelette blanket, medical apparatus, food, fork, knife, soupspoon, tableware, packing timber, food preservative film, food preservation container, meal
Have cleaning device, water purifier, domestic garbage disposer, melamine decorative board, carpet, lighting device, ligthing paraphernalia, illumination
The various films/sheets materials such as lamp, parachute flare, black light lamp, antifouling paint, filter, agricultural vinyl film, Superhydrophilic film, anti-blade
Material, electronic unit, electrical apparatus product, electrical equipment machine, charger, plasma generator, ozone generating-device, exposure dress
Put, humidifier, hand drier, scalp care device, dust catcher, telephone set, mobile terminal, mobile device, touch panel displays
Device, organic EL element/display panel, ink-jet recording apparatus, air purifier, freezing equipment, deduster, ornament, machinery zero
Part, disk, showcase, instrument cover glass, camera, glasses, the camera lens of camera, the eyeglass of glasses, contact lenses, whitening
Agent, dentistry/oral cavity material, tooth-bleaching material, implant, oral cavity utensil, cosmetics, shampoo etc..
(manufacture method for being loaded with the titanium oxide of transistion metal compound)
The titanium oxide for being loaded with transistion metal compound of the present invention can for example be manufactured by following processes.
(crystalline titanium oxide manufacturing process)
Crystalline titanium oxide manufacturing process is the process that crystalline titanium oxide is obtained by titanium compound.Aoxidized as crystallinity
The manufacture method of titanium, can be using known customary way.For example, bar-shaped Titanium Dioxide Rutile Top grade can be by aqueous medium (example
Such as, the mixed liquor of water or water and water-miscible organic solvent) in titanium compound carry out hydro-thermal process [for example, 100~220 DEG C, 2
~48 hours (being preferably 2~15 hours, particularly preferably 5~15 hours)] and synthesize.In addition, carrying out addition during hydro-thermal process
Halide and/or it is stirred (for example, power Pv values needed for stirring：0.1~1500W/m3Left and right) when, can be to be obtained
The size surface area of particle is adjusted, therefore it is preferred that.
As above-mentioned titanium compound, trivalent titanium compound, tetravalent titanium compound can be enumerated.It is used as trivalent titanium compound, example
Titanium trichloride or the halogenated titanium of titanium tribromide three etc. can such as be enumerated.As the trivalent titanium compound of the present invention, from cheap and easy
From the viewpoint of acquisition, preferably titanium trichloride (TiCl3)。
In addition, the tetravalent titanium compound of the present invention is such as can enumerate the compound shown in following formula (1).
Ti(OR)tX4-t (1)
(in formula, R represents alkyl, and X represents halogen atom.T represents 0~3 integer)
As the R alkyl in formula (1), for example, it can enumerate：Methyl, ethyl, propyl group, isopropyl, normal-butyl, sec-butyl, uncle
The C such as butyl1-4Aliphatic alkyl etc..
As the X halogen atoms in formula (1), chlorine, bromine, iodine etc. can be enumerated.
As this tetravalent titanium compound, for example, it can enumerate：TiCl4、TiBr4、Til4Deng titanium tetrahalide；Ti(OCH3)Cl3、
Ti(OC2H5)Cl3、Ti(OC4H9)Cl3、Ti(OC2H5)Br3、Ti(OC4H9)Br3Deng three halogenated alkoxy titaniums；Ti(OCH3)2Cl2、
Ti(OC2H5)2Cl2、Ti(OC4H9)2Cl2、Ti(OC2H5)2Br2Etc. dihalide dialkoxy titanium；Ti(OCH3)3Cl、Ti(OC2H5)3Cl、Ti(OC4H9)3Cl、Ti(OC2H5)3List halogenation tri-alkoxy titanium such as Br etc..As the tetravalent titanium compound of the present invention, honest and clean
Valency and handy viewpoint is set out, preferably titanium tetrahalide, particularly preferred titanium tetrachloride (TiCl4)。
It can be refined by bar-shaped Titanium Dioxide Rutile Top grade obtained from hydro-thermal process using known customary way, example
Such as：Filtering, concentration, distillation, extraction, partial crystallization, recrystallization, column chromatography or the method by these Combination of Methods together.In this hair
In bright, wherein carrying out membrane filtration preferably by following crossing current modes from can obtain following titanium oxide from the viewpoint of this：The oxygen
Change titanium and be able to maintain that the crystal structure of titanium oxide, while the content of ionic impurity can be reduced, and need not implement at crushing
The process that reason etc. just can directly carry out carrying transition metal compound, being capable of high capacity transistion metal compound.
It is below 50nm, preferably 5~40nm by the average minor axis of crystalline titanium oxide obtained from the above method, especially
It is preferred that 5~30nm, most preferably 10~25nm.
In addition, by the mean aspect ratio (major diameter/minor axis) of crystalline titanium oxide obtained from the above method for 1.5 with
On, preferably 1.5~100, more preferably 1.5~50, particularly preferably 1.5~20, most preferably 2~15.
Also, the specific surface area by crystalline titanium oxide obtained from the above method is, for example, 10m2/ more than g.Compare table
The lower limit of area is preferably 30m2/ g, more preferably 50m2/ g, particularly preferably 60m2/ g, most preferably 70m2/g.Specific surface area
The upper limit be, for example, 200m2/ g, preferably 150m2/ g, particularly preferably 100m2/g。
(process of carrying transition metal compound)
The process of carrying transition metal compound is to pass through transition metal compound loaded obtained from above-mentioned operation
So as to obtain being loaded with the process of the titanium oxide of transistion metal compound on crystalline titanium oxide.The load of transistion metal compound
For example can be by by the solution addition containing transistion metal compound is in crystalline titanium oxide and it is impregnated and is carried out.Example
Such as, it is loaded with ferric iron compound (Fe3+) can as the titanium oxide for being loaded with transistion metal compound of transistion metal compound
By the way that the solution containing ferric nitrate (III), ferric sulfate (III), iron chloride (III) etc. is added into crystalline titanium oxide suspension
In and make its impregnate and obtain.
The concentration of solution containing transistion metal compound is, for example, 0.1~40 weight % or so, preferably 1~40 weight
Measure %.In addition, being used as dip time, for example, 1 minute to 24 hours or so, preferably 5 minutes~10 hours.
In the present invention, irradiated during impregnated transition metallic compound exciting light do not need large scale equipment etc. just can easily and
Efficiently in the certain surface optionally carrying transition metal compound of crystalline titanium oxide, therefore it is preferred that.When irradiating the excitation light,
The electronics of the valence band of crystalline titanium oxide will be energized into conduction band, and hole is generated on valence band, in conduction band
Generation excites electronics, and these electronics and hole are spread to particle surface, excites electronics and hole to send out according to the characteristic of each crystal plane
It is estranged from forming oxidation reaction face and reduction reaction face.In this condition, for example, when ferric iron compound is used as transition metal
When compound is impregnated, ferric iron compound (Fe3+) oxidation reaction face is adsorbed in, but in reduction reaction face, ferric iron
Compound (Fe3+) it is reduced into ferro-compound (Fe2+), ferro-compound (Fe2+) there is the characteristic for being difficult to adsorb, it is therefore, molten
Go out into solution, as a result, can obtain optionally being loaded with iron compound (Fe in oxidation reaction face3+) be loaded with iron
The titanium oxide of compound.
Exciting light refers to the light (for example, ultraviolet) with band-gap energy energy above., can as light irradiation device is excited
Using with ultraviolet exposure apparatus according of light source for efficiently producing ultraviolet etc., for example, medium/high medium pressure mercury lamp, Ultra-Violet Laser
Device, UV-LED, black light lamp etc..It is used as the exposure of exciting light, for example, 0.1~300mW/cm2Left and right, preferably 0.5~
100mW/cm2。
Also, in the present invention, it is preferred to add sacrifice agent in dipping., can be in crystallinity oxygen by adding sacrifice agent
Change the specific crystal plane of titanium with high selectivity carrying transition metal compound.As sacrifice agent, preferably use its own and easily release
The organic compound of electronics, for example, can enumerate：The alcohol such as methanol, ethanol；The carboxylic acids such as acetic acid；Ethylenediamine tetra-acetic acid (EDTA), three second
Amine such as hydramine (TEA) etc..
The addition of sacrifice agent can be adjusted suitably, and for example, 0.5~20.0 weight % of crystalline titanium oxide suspension is left
The right side, preferably 1.0~5.0 weight % or so.Sacrifice agent can also be excessively used.
After the process of above-mentioned carrying transition metal compound, refinement treatment is preferable to carry out.In the present invention, never make
The titanium oxide compressionization of transistion metal compound is loaded with, in the state of rhabdolith structure is maintained, can efficiently be removed
Ionic impurity, the content that can obtain ionic impurity is extremely low and for the bar-shaped titanium oxide for being loaded with transistion metal compound
Set out, be preferable to carry out carrying out the processing of membrane filtration using crossing current mode.
(membrane filtration carried out using the mode of crossing current)
The membrane filtration carried out using above-mentioned crossing current mode refers to following methods：Processed water is set to be flowed parallel to filtering face
It is dynamic, while the caused filtering fouling membrane of deposition of filter residue is prevented, while making a part for processed water in the flowing of processed water
Side filtered.By to above-mentioned titanium oxide or being loaded with the titanium oxide suspension of transistion metal compound and applying using horizontal
The membrane filtration that stream mode is carried out, can efficiently remove ionic impurity without the filter in filter membrane surface formation compressionization
Slag, is able to maintain that titanium oxide or is loaded with the crystal structure of the titanium oxide of transistion metal compound, and can reduce extremely lowly from
The content of sub- property impurity.
The titanium oxide for applying the membrane filtration carried out using crossing current mode or the titanium oxide for being loaded with transistion metal compound are hanged
The concentration of supernatant liquid is, for example, 0.1~40 weight % or so (being preferably 0.1~30 weight %).When titanium oxide or be loaded with transition gold
When the concentration for belonging to the titanium oxide suspension of compound departs from above range, the removal efficiency of ionic impurity just has inclining for decline
To.In addition, in situation of the concentration more than above range of titanium oxide or the titanium oxide suspension for being loaded with transistion metal compound
Under, viscosity can become too high, become easy incrustation (blocking).
When to titanium oxide or being loaded with the titanium oxide suspension of transistion metal compound and apply and carried out using crossing current mode
During membrane filtration, ionic impurity will together be separated with permeate and remove, and titanium oxide after being concentrated or be loaded with
Cross the titanium oxide suspension of metallic compound.
Concentration rate is preferably adjusted to 1~400 times or so and (is wherein more preferably 1~20 times, particularly preferably 1~10
Times).When concentration rate is more than above range, it will be difficult to suppress accumulation of the attachment material to face, exist and be difficult to anti-block
Change titanium or be loaded with the tendency of the titanium oxide generation compressionization of transistion metal compound.Further, since attachment material is to face
Accumulation causes that incrustation (blockings) occurs on filter membrane, and membrane lifetime easily declines, there is also must continually carry out it is inverse clean or
Produce the tendency that the rates of filtration such as the situation that filtration treatment can not be operated easily decline.On the other hand, when concentration rate is less than above-mentioned
During scope, the separative efficiency of ionic impurity will decline, the increased tendency of usage amount that there is rinse water.
Above-mentioned concentration rate for example can be by controlling filter pressure, titanium oxide or being loaded with the oxidation of transistion metal compound
Face linear speed (crossflow velocity) of titanium suspension etc. is adjusted.Filter pressure is, for example, 0.001~5.0MPa or so, preferably
0.005~3MPa, particularly preferred 0.01~2.0MPa.
In addition, the face linear speed of the supply liquid containing titanium oxide or the titanium oxide suspension for being loaded with transistion metal compound
It is bigger, more it can suppress accumulation of the attachment material to face, and can obtain high filtration flow (flux).Face linear speed (crossflow velocity)
For example, more than 0.02m/s and less than 3m/s, preferably more than 0.05m/s is less than 1.5m/s.
Preferred pair is via the titanium oxide concentrated using the membrane filtration that crossing current mode is carried out or is loaded with transition metal compound
The titanium oxide suspension of thing repeats to be diluted with water so that titanium oxide or the titanium oxide suspension for being loaded with transistion metal compound
The concentration of liquid turns into above range, then reuses the operation that crossing current mode carries out membrane filtration.Thereby, it is possible to mitigate incrustation
The load of filter membrane caused by (blocking) etc., improves the life-span of filter membrane, while can reduce containing for ionic impurity extremely lowly
Amount.
Fig. 1 is to show titanium oxide or be loaded with the titanium oxide suspension of transistion metal compound to carry out film using crossing current mode
The synoptic diagram of an example (circular form membrane filtration pattern) for filtering.Accumulator tank store containing titanium oxide or be loaded with transition
The supply liquid of the titanium oxide suspension of metallic compound carries out membrane filtration in cross flow filter mode, the titanium oxide that can be concentrated or
It is loaded with the titanium oxide suspension (concentrate) of transistion metal compound.The titanium oxide of concentration is loaded with transistion metal compound
Titanium oxide suspension circulated again to accumulator tank, be diluted with the water (thinned water) of dilution, and with cross flow filter side
Formula carries out membrane filtration.
As filter membrane used in the membrane filtration carried out using the mode of crossing current, for example, it can enumerate：Ultrafiltration membrane, microfiltration
Film, nanofilter, reverse osmosis membrane etc..In the present invention, from the viewpoint of separating property is excellent, exceed wherein preferably using
Filter membrane.
As ultrafiltration membrane, it is 1~20nm or so (being preferably 1~10nm) to preferably use average fine pore, and can be divided
It is that 1000~300000 or so (preferably 1000~50000), material that average grain diameter is 1~10nm or so exceed from molecular weight
Filter membrane.
As the film shape of ultrafiltration membrane, for example, it may be hollow fiber type filter membrane, tubular film, spiral membrane, flat film etc.
Any of, but from being easier to carry out against from the viewpoint of cleaning, preferably use hollow fiber type filter membrane or tubular film.
Caused by polluter is prevented occlusion, improve to from the viewpoint of the doughnut filling rate of membrane module, it is hollow
The internal diameter of the hollow-fibre membrane of fibrous type filter membrane is 0.1~2.0mm or so (being preferably 0.5~1.5mm).
As the material of filter membrane, for example, it can enumerate：Cellulose acetate, polyacrylonitrile, polysulfones, polyether sulfone (PES), poly- third
The common material such as alkene nitrile, aromatic polyamide, Kynoar, polyvinyl chloride, polyethylene, polypropylene, polyimides, ceramics
Matter.In the present invention, wherein it is preferred that cellulose acetate, polysulfones, polyether sulfone (PES), polyacrylonitrile, aromatic polyamide.
In the case of hollow fiber type filter membrane in use, as making titanium oxide or be loaded with the oxygen of transistion metal compound
Change the method (filter type) of titanium Fibre Suspensions, can enumerate：Make in inner side (inner side of hollow-fibre membrane) containing titanium oxide or
The feed streams for being loaded with the titanium oxide suspension of transistion metal compound are moved, and make through water laterally (hollow-fibre membrane
Outside) flowing mode (internal pressure filter type)；Make in outside containing titanium oxide with opposite to that or be loaded with transition metal
The feed streams of the titanium oxide suspension of compound are moved, and make the mode (external pressure filter type) through the inside side flowing of water.
In the present invention, from being able to maintain that from the viewpoint of high crossflow velocity, wherein it is preferred that internal pressure filter type.
In the membrane filtration carried out using the mode of crossing current, in order to prevent attachment material to the accumulation of filtering face, mitigation pair
The burden of filter membrane formation, and carry out carrying out membrane filtration running for a long time, interruption is implemented to filter membrane preferably by rinse water
Inverse cleaning.It is inverse to clean preferred one side control pressure and flow velocity, while being carried out with the predetermined cycle.
As the pressure of inverse cleaning, for example, 0.01~3.0MPa or so, preferably 0.01~2.0MPa are particularly preferably
0.01~1.0MPa, most preferably 0.01~0.5MPa, more preferably 0.05~0.5MPa.In addition, being used as inverse cleaning
Flow velocity, for example, 0.01~10kg/ minute or so, preferably 0.05~5kg/ minutes, particularly preferably 0.1~5kg/ minutes
[or, for example, 1 × 10-7~2 × 10-4M/ seconds or so, preferably 8 × 10-7~9 × 10-5M/ seconds, particularly preferably 1
×10-6~9 × 10-5M/ seconds].As the frequency of inverse cleaning, once left and right was preferably carried out in such as 0.5~3 hour.It is inverse
The time of cleaning is preferably 0.5~10 minute or so.
In addition, as rinse water used in inverse cleaning, preferably using water (for example, Purified Water, distilled water, pure water, ion
Exchanged water etc.).In addition, by inverse cleaning through film rinse water preferably as concentration the transistion metal compound that is loaded with
The thinned water of titanium oxide suspension and recycle (reference picture 2).
In the case where filtering titanium oxide suspension, preferably repeat the membrane filtration carried out using crossing current mode until saturating
Cross liquid pH value turn into more than 1 (be preferably 1~7, particularly preferably 2~6, most preferably 2~5.5).When make utilize crossing current side
Formula carry out membrane filtration permeate pH value turn into above range before at the end of, sometimes ionic impurity (particularly hydrogen from
Son, chlorion, titanium ion) removing can be insufficient, it is difficult to carry out the load of transistion metal compound.
In addition, in the case where the titanium oxide suspension to being loaded with transistion metal compound is filtered, preferably repeating
The membrane filtration carried out using the mode of crossing current is carried out until the electrical conductivity of permeate turns into below 300 μ S/cm (for example, 0.5~300
μ S/cm, preferably 0.5~250 μ S/cm, particularly preferably 1~200 μ S/cm).When the membrane filtration for making to carry out using crossing current mode
At the end of the electrical conductivity of permeate turns into before above range, ionic impurity (particularly iron ion, chlorion) sometimes
Remove insufficient.
Then, the titanium oxide for using crossing current mode be loaded with obtained from membrane filtration transistion metal compound is suspended
(for example, under F.V. (1.3kPa [A]) below) is dried in liquid, is carried out 15 hours or so at 60 DEG C, or in normal pressure (air
Pressure) under with 105 DEG C carry out 1 hour or so, can obtain being loaded with the titanium oxide of transistion metal compound.
Embodiment
Below, the present invention is further illustrated by embodiment, but the present invention is not limited to these embodiments.
Embodiment 1
(preparation of crystalline titanium oxide)
Under room temperature (25 DEG C), titanium tetrachloride aqueous solution (Ti concentration is diluted with pure water：The weight % of 16.5 weight % ± 0.5,
Chlorine ion concentration：The weight % of 31 weight % ± 2, eastern nation's titanium (strain) manufacture), Ti concentration is become 5.6 weight %.After dilution
Titanium tetrachloride aqueous solution 5650g loads the autoclave of capacity 10L tantalum liner and sealed.Using thermal medium, 2 hours are lasted
Above-mentioned high pressure temperature in the kettle is warming up to 140 DEG C.Then, while with power (Pv values) 1360W/m needed for stirring3Stirred
Mix, while in temperature：140 DEG C, pressure：Kept for 5 hours under conditions of the vapour pressure of the temperature, then by being carried out to thermal medium
Cooling, and autoclave is cooled to less than 40 DEG C.Then, further in temperature：140 DEG C, pressure：The bar of the vapour pressure of the temperature
Kept under part 5 hours, then cool down autoclave by carrying out cooling to thermal medium.Confirm that high pressure temperature in the kettle has reached 40 DEG C
Hereinafter, crude oxidation titanium suspension (1) 5650g is further taken out.
(membrane filtration carried out using the mode of crossing current handles (1))
Resulting crude oxidation titanium suspension (1) is diluted to 3 times with pure water, hollow fiber type ultrafiltration membrane is used
(trade name " FS03-FC-FUS03C1 ", material：PES, is nominally classified molecular weight：30000, up to fine membranous system (strain) manufacture), in room
Under warm (25 DEG C), filter pressure 0.02MPa, while the pure water with amount of filtrate same amount is added, while implementing to enter using crossing current mode
Capable filtration treatment.Accumulator tank is circulated again into by concentrate obtained from filtration treatment, and it is straight to repeat filtration treatment
PH value to permeate reaches 4.0.In addition, pH value is determined using pH value test paper.During this period, with the ratio of 1 hour 1 time
Example, with 0.1MPa pressure, the inverse cleaning of the implementation 1 minute of the flow velocity of 2kg/ minutes.By the inverse cleaning through the cleaning of film
Water is recycled to accumulator tank.Then, stop the addition of pure water, concentrate titanium oxide concentration, obtain titanium oxide suspension (1-1).
After titanium oxide suspension (1-1) is dried 1 hour with 105 DEG C at ambient pressure, it can obtain with crystal plane (110) and crystal plane
(111) bar-shaped Titanium Dioxide Rutile Top grade and the bar-shaped golden red with crystal plane (110), crystal plane (111) and crystal plane (001)
The mixture of stone-type titanium oxide is titanium oxide (1) (specific surface area：77m2/ g, mean aspect ratio：6, average minor axis：18nm)525g
(reference picture 3).The toluene oxidation method that resulting titanium oxide (1) is carried out by using following ultraviolets is evaluated and drawn
Photochemical catalyst ability is 625ppm (resolution ratios：94%).
(the load processing of iron compound)
By ferric chloride in aqueous solution (35 weight %) 7.5g additions in titanium oxide suspension obtained above (1-1), in room
Stirred 30 minutes under warm (25 DEG C).Then, addition methanol 95g (1.7 weight % of titanium oxide suspension), uses 100W high pressure
Mercury vapor lamp, ultraviolet (UV) (UV exposures of irradiation 3 hours：5mW/cm2), obtain the rough titanium oxide for being loaded with iron compound
Suspension (1).
(membrane filtration carried out using the mode of crossing current handles (2))
The rough titanium oxide suspension (1) for being loaded with iron compound is diluted to 3 times with pure water, is exceeded using hollow fiber type
Filter membrane (trade name " FS03-FC-FUS03C1 ", material：PES, is nominally classified molecular weight：30000, up to fine membranous system (strain) manufacture),
Under room temperature (25 DEG C), filter pressure 0.02MPa, while adding the pure water with passing through liquid measure same amount, crossing current is utilized while implementing
The filtration treatment that mode is carried out.Accumulator tank is circulated again into by concentrate obtained from filtration treatment, and repeats filtering
Processing reaches 200 μ S/cm until the electrical conductivity of permeate.During this period, with the ratio of 1 hour 1 time, with 0.1MPa pressure,
The flow velocity of 2kg/ minutes implements the inverse cleaning of 1 minute.Accumulator tank is recycled to through the rinse water of film by the inverse cleaning.So
Afterwards, stop the addition of pure water, make the titanium oxide concentration concentration for being loaded with iron compound, obtain being loaded with the titanium oxide of iron compound
Suspension (1-1).During this period, with the ratio of 1 hour 1 time, implemented 1 minute with 0.1MPa pressure, the flow velocity of 2kg/ minutes
Inverse cleaning.Accumulator tank is recycled to through the rinse water of film by the inverse cleaning.
Then, at ambient pressure, dried 1 hour with 105 DEG C, the titanium oxide (1) for obtaining being loaded with iron compound (compares surface
Product：77m2/ g, mean aspect ratio：6, average minor axis：18nm).The iron chemical combination of the obtained titanium oxide (1) for being loaded with iron compound
The content of thing is 800ppm.In addition, the photochemical catalyst drawn by using the methanol oxidizing process evaluation that following visible rays are carried out
Ability is 734ppm.Also, the obtained titanium oxide (1) for being loaded with iron compound is with crystal plane (110) and crystal plane
(111) the bar-shaped Titanium Dioxide Rutile Top grade of iron compound and is only loaded with above-mentioned crystal plane (111) with having crystal plane
(110), crystal plane (111) and crystal plane (001) and it is loaded with iron chemical combination on above-mentioned crystal plane (001) and crystal plane (111)
The mixture of the bar-shaped Titanium Dioxide Rutile Top grade of thing.
Embodiment 2
(preparation of crystalline titanium oxide)
Under room temperature (25 DEG C), titanium tetrachloride aqueous solution (Ti concentration is diluted with pure water：The weight % of 16.5 weight % ± 0.5,
Chlorine ion concentration：The weight % of 31 weight % ± 2, eastern nation's titanium (strain) manufacture), Ti concentration is turned into 5.6 weight %.After dilution
Titanium tetrachloride aqueous solution 5650g loads to be sealed in the autoclave of capacity 10L tantalum liner.Using thermal medium, 2 hours are lasted
Above-mentioned high pressure temperature in the kettle is warming up to 140 DEG C.Then, while with power (Pv values) 220W/m needed for stirring3It is stirred, one
While in temperature：140 DEG C, pressure：Kept for 10 hours under conditions of the vapour pressure of the temperature, then by being cooled down to thermal medium
And cool down autoclave.Confirm that high pressure temperature in the kettle has reached less than 40 DEG C, further take out crude oxidation titanium suspension (2) 5650g.
(membrane filtration carried out using the mode of crossing current handles (1))
Resulting crude oxidation titanium suspension (2) is diluted to 3 times with pure water, hollow fiber type ultrafiltration membrane is used
(trade name " FS03-FC-FUS03C1 ", material：PES, is nominally classified molecular weight：30000, up to fine membranous system (strain) manufacture), in room
Under warm (25 DEG C), filter pressure 0.02MPa, while adding the pure water with passing through liquid measure same amount, mode of flowing over is utilized while implementing
The filtration treatment of progress.Accumulator tank is circulated again into by concentrate obtained from filtration treatment, and repeats filtration treatment
Until the pH value of permeate reaches 4.0.During this period, with the ratio of 1 hour 1 time, with 0.1MPa pressure, the stream of 2kg/ minutes
Speed implements the inverse cleaning of 1 minute.Accumulator tank is recycled to through the rinse water of film by the inverse cleaning.Then, pure water is stopped
Add, concentrate titanium oxide concentration, obtain titanium oxide suspension (2-1).By titanium oxide suspension (2-1) at ambient pressure with
After 105 DEG C of dryings 1 hour, the bar-shaped Titanium Dioxide Rutile Top grade with crystal plane (110) and crystal plane (111) is obtained with having
The mixture of the bar-shaped Titanium Dioxide Rutile Top grade of crystal plane (110), crystal plane (111) and crystal plane (001) is titanium oxide (2)
533g.The light that the toluene oxidation method that resulting titanium oxide (2) is carried out by using following ultraviolets is evaluated and drawn
Catalyst ability is 647ppm (resolution ratios：95%).
(the load processing of iron compound)
Addition ferric chloride in aqueous solution (35 weight %) 7.5g in titanium oxide suspension obtained above (2-1), in room temperature
Stirred 30 minutes under (25 DEG C).Thereafter, addition methanol 95g (1.7 weight % of titanium oxide suspension), uses 100W water under high pressure
Silver-colored lamp, ultraviolet (UV) (UV exposures of irradiation 3 hours：5mW/cm2), obtain the rough titanium oxide for being loaded with iron compound and hang
Supernatant liquid (2).
(membrane filtration carried out using the mode of crossing current handles (2))
The rough titanium oxide suspension (2) for being loaded with iron compound is diluted to 2 times with pure water, it is super using hollow fiber type
Filter membrane (trade name " FS03-FC-FUS03C1 ", material：PES, indicates molecular weight：30000, up to fine membranous system (strain) manufacture),
Under room temperature (25 DEG C), filter pressure 0.02MPa, while adding the pure water with passing through liquid measure same amount, crossing current side is utilized while implementing
The filtration treatment that formula is carried out.Accumulator tank is circulated again into by concentrate obtained from filtration treatment, repeats to apply filtration treatment
Until the electrical conductivity of filtrate reaches 200 μ S/cm.During this period, with the ratio of 1 hour 1 time, divided with 0.1MPa pressure, 2kg/
The flow velocity of clock implements the inverse cleaning of 1 minute.Accumulator tank is recycled to through the rinse water of film by the inverse cleaning.Then, stop
The addition of pure water, makes the titanium oxide concentration concentration for being loaded with iron compound, obtains being loaded with the titanium oxide suspension of iron compound
(2-1).During this period, with the ratio of 1 hour 1 time, 1 minute inverse clear is implemented with 0.1MPa pressure, the flow velocity of 2kg/ minutes
Wash.Accumulator tank is recycled to through the rinse water of film by the inverse cleaning.
Then, at ambient pressure, dried 1 hour with 105 DEG C, obtain the crystalline titanium oxide (2) for being loaded with iron compound
(specific surface area：78m2/ g, mean aspect ratio：3, average minor axis：17nm)530g.What is obtained is loaded with the titanium oxide of iron compound
(2) content of iron compound is 830ppm.In addition, by using following visible rays carry out methanol oxidizing process evaluated and
The photochemical catalyst ability drawn is 775ppm.Also, the resulting titanium oxide (2) for being loaded with iron compound is with crystal plane
(110) and crystal plane (111) and be only loaded with above-mentioned crystal plane (111) the bar-shaped Titanium Dioxide Rutile Top grade of iron compound with
Born with crystal plane (110), crystal plane (111) and crystal plane (001) and on above-mentioned crystal plane (001) and crystal plane (111)
It is loaded with the mixture (Fig. 4) of the bar-shaped Titanium Dioxide Rutile Top grade of iron compound.
Embodiment 3
In above-mentioned (filtration treatment (2) carried out using the mode of crossing current), except the electrical conductivity for being repeated up to permeate
Reach beyond 150 μ S/cm, it is other all same as Example 2, obtain crystalline titanium oxide (the 3) (ratio for being loaded with iron compound
Surface area：78.5m2/ g, mean aspect ratio：3, average minor axis：16nm)530g.What is obtained is loaded with the titanium oxide of iron compound
(3) content of iron compound is 890ppm.In addition, being drawn by using the methanol oxidizing process evaluation that following visible rays are carried out
Photochemical catalyst ability be 795ppm.
Embodiment 4
In above-mentioned (filtration treatment (2) carried out using the mode of crossing current), except the electrical conductivity for being repeated up to permeate
It is other all same as Example 2 beyond reaching untill 100 μ S/cm, obtain the crystalline titanium oxide for being loaded with iron compound
(4) (specific surface area：79m2/ g, mean aspect ratio：3, average minor axis：15nm)530g.What is obtained is loaded with the oxygen of iron compound
The content for changing the iron compound of titanium (4) is 950ppm.In addition, by using the methanol oxidizing process evaluation that following visible rays are carried out
The photochemical catalyst ability drawn is 800ppm.
Embodiment 5
In above-mentioned (filtration treatment (2) carried out using the mode of crossing current), except the electrical conductivity for being repeated up to permeate
Reach beyond 50 μ S/cm, it is other all same as Example 2, obtain crystalline titanium oxide (the 5) (ratio for being loaded with iron compound
Surface area：80m2/ g, mean aspect ratio：3, average minor axis：14nm)530g.The obtained titanium oxide (5) for being loaded with iron compound
Iron compound content be 1200ppm.In addition, being drawn by using the methanol oxidizing process evaluation that following visible rays are carried out
Photochemical catalyst ability is 800ppm.
Embodiment 6
In above-mentioned the processing of iron compound (load), except by the usage amount of ferric chloride in aqueous solution (35 weight %) from 7.5g
It is changed to beyond 6.5g, it is other all same as Example 2, obtain the crystalline titanium oxide (6) for being loaded with iron compound and (compare table
Area：76m2/ g, mean aspect ratio：3, average minor axis：17nm)530g.What is obtained is loaded with the titanium oxide of iron compound (6)
The content of iron compound is 700ppm.In addition, the light drawn by using the methanol oxidizing process evaluation that following visible rays are carried out
Catalyst ability is 780ppm.
Embodiment 7
In above-mentioned the processing of iron compound (load), except by the usage amount of ferric chloride in aqueous solution (35 weight %) from 7.5g
It is changed to beyond 15.0g, it is other all same as Example 2, obtain crystalline titanium oxide (the 7) (ratio for being loaded with iron compound
Surface area：80m2/ g, mean aspect ratio：3, average minor axis：16nm)530g.The obtained titanium oxide (7) for being loaded with iron compound
The content of middle iron compound is 2000ppm.In addition, being drawn by using the methanol oxidizing process evaluation that following visible rays are carried out
Photochemical catalyst ability is 753ppm.
Embodiment 8
In the preparation of above-mentioned crystalline titanium oxide, except reaction temperature (high pressure temperature in the kettle) is changed into 120 from 140 DEG C
It is other all same as Example 2 beyond DEG C, crude oxidation titanium suspension (8) is obtained, to obtained crude oxidation titanium suspension
(8) it is, same as Example 2, after above-mentioned (membrane filtration carried out using the mode of crossing current handles (1)) has been carried out, aoxidized
Titanium suspension (8-1), and the bar-shaped Titanium Dioxide Rutile Top grade with crystal plane (110) and crystal plane (111) is obtained with having knot
The mixture of the bar-shaped Titanium Dioxide Rutile Top grade of crystal face (110), crystal plane (111) and crystal plane (001) is titanium oxide (8)
530g.The photochemical catalyst that resulting titanium oxide (8) is drawn by using the toluene oxidation method evaluation that following ultraviolets are carried out
Ability is 600ppm (CO2Generation rate：90%).
Then, (processing of load iron compound), the membrane filtration carried out using the mode of crossing current are implemented similarly to Example 2
Handle (2), obtain crystalline titanium oxide (8) (specific surface area for being loaded with iron compound：85m2/ g, mean aspect ratio：2, put down
Equal minor axis：10nm).The content of the iron compound of the obtained titanium oxide (8) for being loaded with iron compound is 780ppm.In addition, sharp
The methanol oxidizing process evaluation carried out with following visible rays and the photochemical catalyst ability drawn is 691ppm.
Embodiment 9
In above-mentioned (preparation of crystalline titanium oxide), except reaction temperature (high pressure temperature in the kettle) is changed to from 140 DEG C
It is other all same as Example 2 beyond 160 DEG C, crude oxidation titanium suspension (9) is obtained, obtained crude oxidation titanium is suspended
Liquid (9), it is same as Example 2, after the above-mentioned membrane filtration processing (1) carried out using crossing current mode is implemented, aoxidized
Titanium suspension (9-1), and the bar-shaped Titanium Dioxide Rutile Top grade with crystal plane (110) and crystal plane (111) is obtained with having knot
The mixture of the bar-shaped Titanium Dioxide Rutile Top grade of crystal face (110), crystal plane (111) and crystal plane (001) is titanium oxide (9)
530g.The photochemical catalyst energy that obtained titanium oxide (9) is drawn by using the toluene oxidation method evaluation that following ultraviolets are carried out
Power is 645ppm (resolution ratios：95%).
Then, (processing of load iron compound), the membrane filtration carried out using the mode of crossing current are implemented similarly to Example 2
Handle (2), obtain crystalline titanium oxide (9) (specific surface area for being loaded with iron compound：55m2/ g, mean aspect ratio：12,
Average minor axis：25nm).The content of the iron compound of the obtained titanium oxide (9) for being loaded with iron compound is 820ppm.In addition,
The photochemical catalyst ability drawn using the methanol oxidizing process evaluation that following visible rays are carried out is 727ppm.
Embodiment 10
(preparation of crystalline titanium oxide)
Under room temperature (25 DEG C), titanium tetrachloride aqueous solution (Ti concentration is diluted with pure water：The weight % of 16.5 weight % ± 0.5,
Chlorine ion concentration：The weight % of 31 weight % ± 2, eastern nation's titanium (strain) manufacture), Ti concentration is reached 5.6 weight %.After dilution
Titanium tetrachloride aqueous solution 5650g loads to be sealed in the autoclave of capacity 10L tantalum liner.Using thermal medium, 2 hours are lasted
Above-mentioned high pressure temperature in the kettle is warming up to 140 DEG C.Thereafter, while with power (Pv values) 13W/m needed for stirring3It is stirred,
While in temperature：140 DEG C, pressure：Kept for 10 hours under conditions of the vapour pressure of the temperature, then by cooling down thermal medium to height
Pressure kettle is cooled down.Confirm that high pressure temperature in the kettle has reached less than 40 DEG C, further take out crude oxidation titanium suspension (10) 5650g.
(membrane filtration carried out using the mode of crossing current handles (1))
Obtained crude oxidation titanium suspension (10) is diluted without pure water, hollow fiber type ultrafiltration membrane (trade name is used
" FS03-FC-FUS03C1 ", material：PES, is nominally classified molecular weight：30000, up to fine membranous system (strain) manufacture), in room temperature (25
DEG C), under filter pressure 0.02MPa, while add the pure water with amount of filtrate same amount, the mistake that execution is carried out using the mode of crossing current on one side
Filter is handled.Accumulator tank is circulated again into by concentrate obtained from filtration treatment, and repeats filtration treatment until transmission
The pH value of liquid reaches 4.0.During this period, with the ratio of 1 hour 1 time, 1 is implemented with 0.1MPa pressure, the flow velocity of 2kg/ minutes
The inverse cleaning of minute.Accumulator tank is recycled to through the rinse water of film by the inverse cleaning.Thus, titanium oxide suspension is obtained
(10-1)5650g.After titanium oxide suspension (10-1) is dried 1 hour with 105 DEG C at ambient pressure, obtain with crystal plane
(110) and crystal plane (111) bar-shaped Titanium Dioxide Rutile Top grade with crystal plane (110), crystal plane (111) and crystal plane
(001) mixture of bar-shaped Titanium Dioxide Rutile Top grade is titanium oxide (10).The following purples of utilization of resulting titanium oxide (10)
Toluene oxidation method evaluation that outside line is carried out and the photochemical catalyst ability that draws is 647ppm (resolution ratios：95%).
(processing of load iron compound)
By ferric chloride in aqueous solution (35 weight %) 7.5g additions in titanium oxide suspension obtained above (10-1), in room
Stirred 30 minutes under warm (25 DEG C).Then, addition methanol 95g (1.7 weight % of titanium oxide suspension), uses 100W high pressure
Mercury vapor lamp, ultraviolet (UV) (UV exposures of irradiation 3 hours：5mW/cm2), obtain the rough titanium oxide for being loaded with iron compound
Suspension (10).
(membrane filtration carried out using the mode of crossing current handles (2))
The rough titanium oxide suspension (10) for being loaded with iron compound is diluted without pure water, hollow fiber type hyperfiltration is used
Film (trade name " FS03-FC-FUS03C1 ", material：PES, is nominally classified molecular weight：30000, up to fine membranous system (strain) manufacture),
Under room temperature (25 DEG C), filter pressure 0.02MPa, while adding the pure water with passing through liquid measure same amount, crossing current side is utilized while implementing
The filtration treatment that formula is carried out.Accumulator tank is circulated again into by concentrate obtained from filtration treatment, and is repeated at filtering
Reason reaches 200 μ S/cm until the electrical conductivity of permeate.During this period, with the ratio of 1 hour 1 time, with 0.1MPa pressure,
The flow velocity of 2kg/ minutes implements the inverse cleaning of 1 minute.Accumulator tank is recycled to through the rinse water of film by the inverse cleaning.By
This, obtains being loaded with the titanium oxide suspension (10-1) of iron compound.
Then, at ambient pressure, dried 1 hour with 105 DEG C, obtain the crystalline titanium oxide (10) for being loaded with iron compound
(specific surface area：76m2/ g, mean aspect ratio：5, average minor axis：16nm)530g.What is obtained is loaded with the titanium oxide of iron compound
(10) content of iron compound is 820ppm.In addition, being drawn using the methanol oxidizing process evaluation that following visible rays are carried out
Photochemical catalyst ability is 778ppm.
Embodiment 11
(preparation of crystalline titanium oxide)
Under room temperature (25 DEG C), titanium tetrachloride aqueous solution (Ti concentration is diluted with pure water：The weight % of 16.5 weight % ± 0.5,
Chlorine ion concentration：The weight % of 31 weight % ± 2, eastern nation's titanium (strain) manufacture), Ti concentration is reached 5.6 weight %.After dilution
Titanium tetrachloride aqueous solution 560g loads to be sealed in the autoclave of capacity 1L tantalum liner.Using thermal medium, lasting 2 hours will
Above-mentioned high pressure temperature in the kettle is warming up to 140 DEG C.Then, while with power (Pv values) 13W/m needed for stirring3It is stirred, one
While in temperature：140 DEG C, pressure：Kept for 10 hours under conditions of the vapour pressure of the temperature, then by cooling down thermal medium to high pressure
Kettle is cooled down.Confirm that high pressure temperature in the kettle has reached less than 40 DEG C, further take out crude oxidation titanium suspension (11) 560g.
(membrane filtration carried out using the mode of crossing current handles (1))
Obtained crude oxidation titanium suspension (11) is diluted to 10 times with pure water, hollow fiber type ultrafiltration membrane is used
(trade name " FS03-FC-FUS03C1 ", material：PES, is nominally classified molecular weight：30000, up to fine membranous system (strain) manufacture), in room
Under warm (25 DEG C), filter pressure 0.05MPa, while adding the pure water with passing through liquid measure same amount, mode of flowing over is utilized while implementing
The filtration treatment of progress.Accumulator tank is circulated again into by concentrate obtained from filtration treatment, and repeats filtration treatment
Until the pH value of permeate reaches 2.9.Then, stop the addition of pure water, concentrate titanium oxide concentration, obtain titanium oxide suspension
(11-1).During this period, with the ratio of 1 hour 1 time, implemented 1 minute with 0.15MPa pressure, the flow velocity of 0.1kg/ minutes
Inverse cleaning.Accumulator tank is recycled to through the rinse water of film by the inverse cleaning.By titanium oxide suspension (11-1) under reduced pressure
After being dried 15 hours with 60 DEG C, bar-shaped Titanium Dioxide Rutile Top grade and tool with crystal plane (110) and crystal plane (111) are obtained
There is the mixture i.e. titanium oxide of the bar-shaped Titanium Dioxide Rutile Top grade of crystal plane (110), crystal plane (111) and crystal plane (001)
(11).The photochemical catalyst energy that obtained titanium oxide (11) is drawn by using the toluene oxidation method evaluation that following ultraviolets are carried out
Power is 617ppm (CO2Generation rate：93%).
(processing of load iron compound)
By ferric chloride in aqueous solution (35 weight %) 0.3g additions in titanium oxide suspension obtained above (11-1), in room
Stirred 30 minutes under warm (25 DEG C).Then, addition methanol 9.6g (1.7 weight % of titanium oxide suspension), uses 100W height
Medium pressure mercury lamp, ultraviolet (UV) (UV exposures of irradiation 3 hours：0.9mW/cm2), obtain the rough oxygen for being loaded with iron compound
Change titanium suspension (11).
(membrane filtration carried out using the mode of crossing current handles (2))
The rough titanium oxide suspension (11) for being loaded with iron compound is diluted to 10 times with pure water, hollow fiber type is used
Ultrafiltration membrane (trade name " FS03-FC-FUS03C1 ", material：PES, indicates molecular weight：30000, up to fine membranous system (strain) manufacture),
Under room temperature (25 DEG C), filter pressure 0.05MPa, while adding the pure water with passing through liquid measure same amount, crossing current is utilized while implementing
The filtration treatment that mode is carried out.Accumulator tank is circulated again into by concentrate obtained from filtration treatment, and repeats filtering
Processing is untill the electrical conductivity of permeate reaches 21 μ S/cm.Then, stop the addition of pure water, make to be loaded with iron compound
Titanium oxide concentration is concentrated, and obtains being loaded with the titanium oxide suspension (11-1) of iron compound.During this period, with the ratio of 1 hour 1 time
Example, with 0.15MPa pressure, the inverse cleaning of the implementation 1 minute of the flow velocity of 0.1kg/ minutes.By the inverse cleaning through the clear of film
Wash water is recycled to accumulator tank.
Then, under reduced pressure, dried 15 hours with 60 DEG C, obtain the crystalline titanium oxide (11) for being loaded with iron compound
(specific surface area：71m2/ g, mean aspect ratio：9, average minor axis：20nm)40g.The resulting oxidation for being loaded with iron compound
The content of the iron compound of titanium (11) is 420ppm.In addition, the toluene oxidation method realized using following visible rays evaluate
The photochemical catalyst ability gone out is 416ppm, and the light drawn by using the methanol oxidizing process evaluation of following visible rays progress is urged
Agent ability is 716ppm.
Comparative example 1
(preparation of crystalline titanium oxide)
Under room temperature (25 DEG C), titanium tetrachloride aqueous solution (Ti concentration is diluted with pure water：The weight % of 16.5 weight % ± 0.5,
Chlorine ion concentration：The weight % of 31 weight % ± 2, eastern nation's titanium (strain) manufacture), Ti concentration is reached 5.6 weight %.After dilution
Give in the autoclave of titanium tetrachloride aqueous solution 560g loading capacity 1L tantalum liner closed.Using thermal medium, lasting 2 hours will
Above-mentioned high pressure temperature in the kettle is warming up to 140 DEG C.Then, without stirring, in temperature：140 DEG C, pressure：The vapour pressure of the temperature
Under conditions of keep 10 hours, then autoclave is cooled down by cooling down thermal medium.Confirm that high pressure temperature in the kettle reaches
Less than 40 DEG C, further take out crude oxidation titanium suspension (12) 560g.
In addition to crude oxidation titanium suspension (11) are replaced using crude oxidation titanium suspension (12), it is other all with embodiment
11 is identical, obtains crystalline titanium oxide (12) (specific surface area for being loaded with iron compound：9m2/ g, mean aspect ratio：1.2,
Average minor axis：100nm).The content of the iron compound of the obtained titanium oxide (12) for being loaded with iron compound is 30ppm.In addition,
The photochemical catalyst ability that the methanol oxidizing process carried out by using following visible rays is evaluated and drawn is 250ppm.
The evaluation method ＞ of ＜ photochemical catalyst abilities
(the toluene oxidation method carried out using visible ray)
By using the titanium oxide for being loaded with iron compound obtained by embodiment as photochemical catalyst, first is made in the gas phase
Benzene oxidatoin, and determine the CO of generation2Amount, to evaluate photochemical catalyst ability.
The titanium oxide 200mg for being loaded with iron compound is spread in glass dish, and loads reaction vessel
(Tedorabaggu, material：Polyfurolresin) in, 100ppm toluene gas 125mL is blown into reaction vessel.
Be loaded with after the titanium oxide of iron compound absorption toluene gas reaches balance, carried out under room temperature (25 DEG C) light irradiation (LED,
Luminous intensity：2.5mW/cm2, the wavelength of light：455nm).Using being accompanied with methanation converter (Methanizer) (trade name
" MT221 ", GL Sciences (strain) manufacture) the gas chromatograph (trade name " GC- with flame ionization ditector
14B ", Shimadzu Seisakusho Ltd.'s manufacture), determine the CO since light irradiation after 24 hours2The growing amount (CO in reaction vessel2It is dense
Degree).
(the methanol oxidizing process carried out using visible ray)
By using the titanium oxide for being loaded with iron compound obtained by embodiment and comparative example as photochemical catalyst, in gas
Aoxidize methanol in phase, and determine the CO of generation2Amount, to evaluate photochemical catalyst ability.
The titanium oxide 200mg for being loaded with iron compound is spread in glass dish, and load reaction vessel (Tedorabaggu,
Material：Polyfurolresin) in, 800ppm methanol gas 125mL is blown into reaction vessel.It is being loaded with iron compound
Titanium oxide absorption methanol gas reach balance after, light irradiation (LED, luminous intensity are carried out under room temperature (25 DEG C)：2.5W/m2,
The wavelength of light：455nm).Using being accompanied with methanation converter (Methanizer) (trade name " MT221 ", GL Sciences
(strain) is manufactured) the gas chromatograph (trade name " GC-14B ", Shimadzu Seisakusho Ltd. manufacture) with flame ionization ditector,
Determine the CO since light irradiation after 24 hours2The growing amount (CO in reaction vessel2Concentration).
(the toluene oxidation method carried out using ultraviolet)
By using the titanium oxide obtained by embodiment as photochemical catalyst, toluene oxidation is made in the gas phase, and determine life
Into CO2Amount, to evaluate photochemical catalyst ability.
Titanium oxide 200mg is spread in glass dish, and loads reaction vessel (Tedorabaggu, material：Ethylene fluoride tree
Fat) in, 100ppm toluene gas 125mL is blown into reaction vessel.Balance is reached in the absorption toluene gas of titanium oxide
After, light irradiation (LED, luminous intensity are carried out under room temperature (25 DEG C)：0.1mW/cm2, the wavelength of light：365nm).Using being accompanied with
Methanation converter (Methanizer) methanation converter (Methanizer) (trade name " MT221 ", GL Sciences
(strain) is manufactured) the gas chromatograph (trade name " GC-14B ", Shimadzu Seisakusho Ltd. manufacture) with flame ionization ditector,
Determine the CO since light irradiation after 24 hours2The growing amount (CO in reaction vessel2Concentration).
Industrial applicability
The average minor axis of the titanium oxide for being loaded with transistion metal compound of the present invention is below 50nm, and mean aspect ratio
(major diameter/minor axis) is more than 1.5.Therefore, the response to visible ray is excellent, can absorb sunshine or incandescent lamp, fluorescent lamp,
The light in the generally living space such as LED, and harmful chemical can be decomposed into water or carbon dioxide.That is, load of the invention
The titanium oxide suspension for having transistion metal compound is preferably used as photoactivation agent under LED illumination.Furthermore, it is possible to be used in anti-
The various uses such as bacterium, mould proof, deodorization, air cleaning, Water warfare, antifouling, and can be widely applied to indoor wallpaper or family
The depollution of environment, high performance of family's electrical article in family based on tool or in the communal facility such as hospital, school etc..
Claims (2)
1. a kind of titanium oxide for being loaded with transistion metal compound, it is loaded with transistion metal compound on crystalline titanium oxide
Form, the average minor axis of the titanium oxide for being loaded with transistion metal compound is 10~25nm, mean aspect ratio is major diameter/short
Footpath is more than 1.5,
Crystalline titanium oxide is for the Titanium Dioxide Rutile Top grade with crystal plane (110) and crystal plane (111) and/or with crystal plane
(110), the Titanium Dioxide Rutile Top grade of crystal plane (111) and crystal plane (001),
In the manufacture of crystalline titanium oxide, with 0.1~1500W/m3Stirring needed for power Pv values be stirred to carry out hydro-thermal
Processing, also, after transition metal compound loaded process, carry out membrane filtration by using crossing current mode to implement refined place
Reason.
2. the titanium oxide according to claim 1 for being loaded with transistion metal compound, its specific surface area is 10m2/ more than g.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
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| JP2012206259 | 2012-09-19 | ||
| JP2012-206259 | 2012-09-19 | ||
| PCT/JP2013/074777 WO2014046020A1 (en) | 2012-09-19 | 2013-09-06 | Transition metal compound-loaded titanium oxide |
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| CN104640631A CN104640631A (en) | 2015-05-20 |
| CN104640631B true CN104640631B (en) | 2017-07-14 |
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| JP (1) | JP6263123B2 (en) |
| KR (1) | KR102207479B1 (en) |
| CN (1) | CN104640631B (en) |
| TW (1) | TWI627999B (en) |
| WO (1) | WO2014046020A1 (en) |
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| JP2017095307A (en) * | 2015-11-25 | 2017-06-01 | 株式会社ダイセル | Method for producing aqueous nanodiamond dispersion |
| JP6807629B2 (en) * | 2016-11-17 | 2021-01-06 | 株式会社ダイセル | Iron compound-supported titanium oxide photocatalyst |
| CN109603919B (en) * | 2018-12-13 | 2021-10-15 | 西南林业大学 | Recyclable efficient photocatalytic degradation material and preparation method thereof |
| CN112439268B (en) * | 2020-10-16 | 2022-05-17 | 北京理韩汽车配件有限公司 | Filtering element for filtering gas and purification method |
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| JPS62235215A (en) | 1986-04-07 | 1987-10-15 | Nippon Shokubai Kagaku Kogyo Co Ltd | Production of rutile titanium oxide sol |
| JP3898792B2 (en) | 1996-10-02 | 2007-03-28 | 石原産業株式会社 | Method for producing surface-treated titanium oxide sol |
| JP2004255332A (en) * | 2003-02-27 | 2004-09-16 | Ichikoh Ind Ltd | Visible light response type photocatalyst |
| JP4298425B2 (en) * | 2003-08-01 | 2009-07-22 | 日揮触媒化成株式会社 | Carbon monoxide oxidation catalyst and method for producing the catalyst |
| JP2006224084A (en) * | 2004-03-30 | 2006-08-31 | Toto Ltd | Photocatalytic material and photocatalytic member |
| CN100346874C (en) * | 2005-03-17 | 2007-11-07 | 华中科技大学 | Compound photocatalyst using titanium dioxide as its base, and its prepn. method |
| JP5097408B2 (en) * | 2007-02-02 | 2012-12-12 | 富士フイルム株式会社 | Rutile-type titanium oxide particles and method for producing the same |
| JP5030735B2 (en) * | 2007-02-21 | 2012-09-19 | 国立大学法人九州工業大学 | N- and / or S-doped tubular titanium oxide particles and method for producing the same |
| JP5317486B2 (en) * | 2008-01-31 | 2013-10-16 | 日揮触媒化成株式会社 | Method for producing rutile type titanium oxide fine particles |
| JP2010046621A (en) * | 2008-08-22 | 2010-03-04 | Asahi Kasei Corp | Separation refining method of inorganic nanoparticle |
| JP5591683B2 (en) * | 2010-01-09 | 2014-09-17 | 株式会社ダイセル | Metal ion-supported titanium oxide particles having an exposed crystal face and method for producing the same |
| JP5603272B2 (en) * | 2010-03-25 | 2014-10-08 | 株式会社ダイセル | Method for producing rutile-type titanium oxide having crystal plane (001) |
| JP2012096133A (en) * | 2010-10-29 | 2012-05-24 | Jgc Catalysts & Chemicals Ltd | Deodorizing rutile type titanium oxide fine particle, coating liquid for forming deodorizing coating film containing the fine particle, and substrate with deodorizing coating film |
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| WO2014046020A1 (en) | 2014-03-27 |
| KR20150054782A (en) | 2015-05-20 |
| TW201420182A (en) | 2014-06-01 |
| JPWO2014046020A1 (en) | 2016-08-18 |
| CN104640631A (en) | 2015-05-20 |
| KR102207479B1 (en) | 2021-01-26 |
| TWI627999B (en) | 2018-07-01 |
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