JP2003144937A - Silica gel molded body carried with titanium oxide photocatalyst and manufacturing method therefor - Google Patents
Silica gel molded body carried with titanium oxide photocatalyst and manufacturing method thereforInfo
- Publication number
- JP2003144937A JP2003144937A JP2001345770A JP2001345770A JP2003144937A JP 2003144937 A JP2003144937 A JP 2003144937A JP 2001345770 A JP2001345770 A JP 2001345770A JP 2001345770 A JP2001345770 A JP 2001345770A JP 2003144937 A JP2003144937 A JP 2003144937A
- Authority
- JP
- Japan
- Prior art keywords
- silica gel
- titanium oxide
- group element
- molded body
- element compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 130
- 229910002027 silica gel Inorganic materials 0.000 title claims abstract description 125
- 239000000741 silica gel Substances 0.000 title claims abstract description 125
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 90
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 72
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 62
- 239000011148 porous material Substances 0.000 claims abstract description 28
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000001339 alkali metal compounds Chemical class 0.000 claims abstract description 11
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical group [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical group [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000001341 alkaline earth metal compounds Chemical class 0.000 claims abstract description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 22
- 239000010936 titanium Substances 0.000 claims description 16
- 229910052719 titanium Inorganic materials 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 8
- 229940126062 Compound A Drugs 0.000 claims 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 30
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 abstract description 22
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 abstract description 20
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 18
- 239000000126 substance Substances 0.000 abstract description 15
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 abstract description 11
- 229910000037 hydrogen sulfide Inorganic materials 0.000 abstract description 11
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 abstract description 8
- 238000000465 moulding Methods 0.000 abstract description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 abstract description 5
- 239000008096 xylene Substances 0.000 abstract description 5
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 abstract description 4
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 abstract description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 abstract description 4
- 239000000356 contaminant Substances 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 2
- 230000003287 optical effect Effects 0.000 abstract 1
- 150000002909 rare earth metal compounds Chemical class 0.000 abstract 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 48
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 239000011521 glass Substances 0.000 description 21
- 230000001678 irradiating effect Effects 0.000 description 17
- 239000007864 aqueous solution Substances 0.000 description 15
- 238000000354 decomposition reaction Methods 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 14
- 238000004817 gas chromatography Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 239000007789 gas Substances 0.000 description 11
- 238000001035 drying Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 239000003256 environmental substance Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 230000001699 photocatalysis Effects 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- -1 titanium alkoxide Chemical class 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 239000002274 desiccant Substances 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 238000004806 packaging method and process Methods 0.000 description 5
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 4
- 239000005750 Copper hydroxide Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000001506 calcium phosphate Substances 0.000 description 4
- 229910000389 calcium phosphate Inorganic materials 0.000 description 4
- 235000011010 calcium phosphates Nutrition 0.000 description 4
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 description 4
- 229910001956 copper hydroxide Inorganic materials 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 235000014413 iron hydroxide Nutrition 0.000 description 4
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 4
- YXEUGTSPQFTXTR-UHFFFAOYSA-K lanthanum(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[La+3] YXEUGTSPQFTXTR-UHFFFAOYSA-K 0.000 description 4
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 4
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 4
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 4
- 229940007718 zinc hydroxide Drugs 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000003618 dip coating Methods 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- OVSGBKZKXUMMHS-VGKOASNMSA-L (z)-4-oxopent-2-en-2-olate;propan-2-olate;titanium(4+) Chemical compound [Ti+4].CC(C)[O-].CC(C)[O-].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O OVSGBKZKXUMMHS-VGKOASNMSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- UMHKOAYRTRADAT-UHFFFAOYSA-N [hydroxy(octoxy)phosphoryl] octyl hydrogen phosphate Chemical compound CCCCCCCCOP(O)(=O)OP(O)(=O)OCCCCCCCC UMHKOAYRTRADAT-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- KNKRKFALVUDBJE-UHFFFAOYSA-N 1,2-dichloropropane Chemical compound CC(Cl)CCl KNKRKFALVUDBJE-UHFFFAOYSA-N 0.000 description 1
- 229940044613 1-propanol Drugs 0.000 description 1
- IEKHISJGRIEHRE-UHFFFAOYSA-N 16-methylheptadecanoic acid;propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)CCCCCCCCCCCCCCC(O)=O.CC(C)CCCCCCCCCCCCCCC(O)=O.CC(C)CCCCCCCCCCCCCCC(O)=O IEKHISJGRIEHRE-UHFFFAOYSA-N 0.000 description 1
- IHEDBVUTTQXGSJ-UHFFFAOYSA-M 2-[bis(2-oxidoethyl)amino]ethanolate;titanium(4+);hydroxide Chemical compound [OH-].[Ti+4].[O-]CCN(CC[O-])CC[O-] IHEDBVUTTQXGSJ-UHFFFAOYSA-M 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- KKOHCQAVIJDYAF-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid;propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O.CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O.CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O KKOHCQAVIJDYAF-UHFFFAOYSA-N 0.000 description 1
- KTXWGMUMDPYXNN-UHFFFAOYSA-N 2-ethylhexan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCCC(CC)C[O-].CCCCC(CC)C[O-].CCCCC(CC)C[O-].CCCCC(CC)C[O-] KTXWGMUMDPYXNN-UHFFFAOYSA-N 0.000 description 1
- WZLRYEIJALOESF-UHFFFAOYSA-R 2-ethylhexane-1,3-diolate;hydron;titanium(4+) Chemical compound [H+].[H+].[H+].[H+].[Ti+4].CCCC([O-])C(CC)C[O-].CCCC([O-])C(CC)C[O-].CCCC([O-])C(CC)C[O-].CCCC([O-])C(CC)C[O-] WZLRYEIJALOESF-UHFFFAOYSA-R 0.000 description 1
- AIFLGMNWQFPTAJ-UHFFFAOYSA-J 2-hydroxypropanoate;titanium(4+) Chemical compound [Ti+4].CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O AIFLGMNWQFPTAJ-UHFFFAOYSA-J 0.000 description 1
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- SRORDPCXIPXEAX-UHFFFAOYSA-N CCCCCCCCCCCCCP(CCCCCCCCCCCCC)(O)(OCCCCCCCC)OCCCCCCCC.CCCCCCCCCCCCCP(CCCCCCCCCCCCC)(O)(OCCCCCCCC)OCCCCCCCC Chemical compound CCCCCCCCCCCCCP(CCCCCCCCCCCCC)(O)(OCCCCCCCC)OCCCCCCCC.CCCCCCCCCCCCCP(CCCCCCCCCCCCC)(O)(OCCCCCCCC)OCCCCCCCC SRORDPCXIPXEAX-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 101100321669 Fagopyrum esculentum FA02 gene Proteins 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- DRNPGEPMHMPIQU-UHFFFAOYSA-N O.[Ti].[Ti].CCCCO.CCCCO.CCCCO.CCCCO.CCCCO.CCCCO Chemical compound O.[Ti].[Ti].CCCCO.CCCCO.CCCCO.CCCCO.CCCCO.CCCCO DRNPGEPMHMPIQU-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 102100031083 Uteroglobin Human genes 0.000 description 1
- 108090000203 Uteroglobin Proteins 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 description 1
- 229910052586 apatite Inorganic materials 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 229940095643 calcium hydroxide Drugs 0.000 description 1
- RYAGRZNBULDMBW-UHFFFAOYSA-L calcium;3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Ca+2].COC1=CC=CC(CC(CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O RYAGRZNBULDMBW-UHFFFAOYSA-L 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- HTDKEJXHILZNPP-UHFFFAOYSA-N dioctyl hydrogen phosphate Chemical compound CCCCCCCCOP(O)(=O)OCCCCCCCC HTDKEJXHILZNPP-UHFFFAOYSA-N 0.000 description 1
- XMQYIPNJVLNWOE-UHFFFAOYSA-N dioctyl hydrogen phosphite Chemical compound CCCCCCCCOP(O)OCCCCCCCC XMQYIPNJVLNWOE-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 description 1
- VTIXMGZYGRZMAW-UHFFFAOYSA-N ditridecyl hydrogen phosphite Chemical compound CCCCCCCCCCCCCOP(O)OCCCCCCCCCCCCC VTIXMGZYGRZMAW-UHFFFAOYSA-N 0.000 description 1
- WIEGKKSLPGLWRN-UHFFFAOYSA-N ethyl 3-oxobutanoate;titanium Chemical compound [Ti].CCOC(=O)CC(C)=O WIEGKKSLPGLWRN-UHFFFAOYSA-N 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 229910052587 fluorapatite Inorganic materials 0.000 description 1
- 229940077441 fluorapatite Drugs 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229960001708 magnesium carbonate Drugs 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- KQJBQMSCFSJABN-UHFFFAOYSA-N octadecan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCCCCCCCCCCCCCCCC[O-].CCCCCCCCCCCCCCCCCC[O-].CCCCCCCCCCCCCCCCCC[O-].CCCCCCCCCCCCCCCCCC[O-] KQJBQMSCFSJABN-UHFFFAOYSA-N 0.000 description 1
- 235000019645 odor Nutrition 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 230000001443 photoexcitation Effects 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- LQPWUWOODZHKKW-UHFFFAOYSA-K scandium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Sc+3] LQPWUWOODZHKKW-UHFFFAOYSA-K 0.000 description 1
- UKHWJBVVWVYFEY-UHFFFAOYSA-M silver;hydroxide Chemical compound [OH-].[Ag+] UKHWJBVVWVYFEY-UHFFFAOYSA-M 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- DEXZEPDUSNRVTN-UHFFFAOYSA-K yttrium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Y+3] DEXZEPDUSNRVTN-UHFFFAOYSA-K 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
Landscapes
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Silicon Compounds (AREA)
- Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、酸化チタン光触媒
を担持したシリカゲル成形体の細孔内に、アルカリ金属
化合物、銅族元素化合物、アルカリ土金属化合物、亜鉛
族元素化合物、土類元素化合物、クロム族元素化合物、
マンガン族元素化合物、鉄族元素化合物の少なくとも一
種を含ませることにより、ＮＯx、ホルムアルデヒド、
アセトアルデヒド、トルエン、キシレンなどの環境汚染
物質や硫化メチル、二硫化メチル、スチレン、硫化水
素、メチルメルカプタンなどの悪臭物質を、選択的に吸
着せしめることにより、細孔内に含まれる酸化チタン光
触媒との接触頻度を高め、これらを効率よく分解するこ
とができる酸化チタン光触媒を担持したシリカゲル成形
体およびその製造方法に関するものである。TECHNICAL FIELD The present invention relates to an alkali metal compound, a copper group element compound, an alkaline earth metal compound, a zinc group element compound, an earth element compound, in the pores of a silica gel molded body carrying a titanium oxide photocatalyst. Chromium group element compound,
By including at least one of a manganese group element compound and an iron group element compound, NOx, formaldehyde,
By selectively adsorbing environmental pollutants such as acetaldehyde, toluene, xylene, and malodorous substances such as methyl sulfide, methyl disulfide, styrene, hydrogen sulfide, and methyl mercaptan, the titanium oxide photocatalyst contained in the pores The present invention relates to a silica gel molded article carrying a titanium oxide photocatalyst capable of increasing the contact frequency and efficiently decomposing these, and a method for producing the same.
【０００２】[0002]
【従来の技術】水溶液に半導体の粉末を分散し、その物
質のバンドギャップ以上のエネルギーを持つ光を照射す
ると、光励起により生成した電子と正孔が半導体粒子表
面に移動し、水溶液中のイオン種や分子種に作用して、
水の分解など様々な反応を引き起こすことは、半導体光
触媒反応としてよく知られている。酸化チタンが代表的
な光触媒として挙げられる。2. Description of the Related Art When a semiconductor powder is dispersed in an aqueous solution and irradiated with light having an energy higher than the band gap of the substance, electrons and holes generated by photoexcitation move to the surface of semiconductor particles, and the ionic species in the aqueous solution And acts on molecular species,
It is well known as a semiconductor photocatalytic reaction to cause various reactions such as water decomposition. Titanium oxide is mentioned as a typical photocatalyst.
【０００３】これらに太陽光、蛍光灯、白熱灯、ブラッ
クライト、紫外線ランプ、水銀灯、キセノンランプ、ハ
ロゲンランプ、メタルハライドランプ、冷陰極蛍光ラン
プなどの光を照射することにより、空気中の悪臭や有害
物質の分解除去、廃水処理、浄水処理あるいは水中の微
生物殺菌など環境汚染物質の分解除去を行うことができ
る。By irradiating them with light from sunlight, fluorescent lamps, incandescent lamps, black lights, ultraviolet lamps, mercury lamps, xenon lamps, halogen lamps, metal halide lamps, cold cathode fluorescent lamps, etc. Decomposition and removal of substances, wastewater treatment, clean water treatment, and sterilization of microorganisms in water can be performed to decompose and remove environmental pollutants.
【０００４】これら用途において、微粉末では取り扱い
が困難であるため、特開平６−６５０１２号公報には、
チタンのアルコキシドから酸化チタンのゾルを作り、デ
ィップコーティング法によってガラス基板上にコーティ
ングした後、乾燥、焼成するといった工程を、通常１０
回程度繰り返すことにより、光触媒活性に優れ、かつ透
明で耐水性、耐熱性、耐久性に優れた酸化チタン薄膜光
触媒が提案されている。しかし、これはガラス、セラミ
ックスなど耐熱性の無機物質にしか利用できない上に、
製造に手間が掛かかり過ぎるため高価で、かつ分解反応
は光触媒の表面でしか生じないため、環境汚染物質の分
解除去を連続的に行うには非常に大きな面積を必要とす
るなど実用上大きな問題点があった。Since fine powders are difficult to handle in these applications, JP-A-6-65012 discloses that
The process of preparing a titanium oxide sol from titanium alkoxide, coating it on a glass substrate by a dip coating method, followed by drying and baking is usually performed.
A titanium oxide thin film photocatalyst that is excellent in photocatalytic activity, is transparent, and is excellent in water resistance, heat resistance, and durability by repeating about times is proposed. However, this can only be used for heat-resistant inorganic substances such as glass and ceramics,
Since it takes too much time to manufacture, it is expensive, and since the decomposition reaction only occurs on the surface of the photocatalyst, a very large area is required for continuous decomposition and removal of environmental pollutants, which is a major practical problem. There was a point.
【０００５】特許第２７７５３９９号公報には、シリカ
ゲル等の表面に酸化チタンの多孔質薄膜を形成した多孔
質光触媒が開示されている。これは、チタンのアルコキ
シドから酸化チタンのゾルを作り、ディップコーティン
グ法によって球状のシリカゲルの表面にコーティングし
た後、乾燥、焼成するといった工程を、通常３回以上繰
り返すことにより得られるが、このようにして形成され
た酸化チタンの薄膜は、剥離し易く、水に入れると割れ
ることから、用途が著しく制限されるものであった。加
えてディップコートの際にもシリカゲルが少なからず割
れ、これを３回以上繰り返す必要があるため歩留まりが
著しく悪かった。Japanese Patent No. 2775399 discloses a porous photocatalyst having a porous thin film of titanium oxide formed on the surface of silica gel or the like. This can be obtained by repeating the process of making a sol of titanium oxide from titanium alkoxide, coating the surface of spherical silica gel by the dip coating method, followed by drying and firing, usually three times or more. The titanium oxide thin film formed as described above is easily peeled off and cracks when placed in water, so that its use is extremely limited. In addition, the silica gel was not a little cracked during dip coating, and it was necessary to repeat this three or more times, resulting in a significantly poor yield.
【０００６】また、特開平１１−１３８０１７号公報に
は、上述の欠点を解決するためにシリカゲルの細孔内に
酸化チタンを含ませた光触媒シリカゲルが提案されてい
る。しかし、このようにして得られた光触媒シリカゲル
は球状あるいは粉末状であり、そのままでは処理対象ガ
スを通じたとき通気抵抗が大きいなどの欠点があり、用
途が著しく限定されるものであった。Further, Japanese Patent Application Laid-Open No. 11-138017 proposes a photocatalytic silica gel in which titanium oxide is contained in the pores of silica gel in order to solve the above-mentioned drawbacks. However, the photocatalyst silica gel thus obtained is spherical or powdery and has a drawback that it has a large ventilation resistance when passing through the gas to be treated as it is, and its use is remarkably limited.
【０００７】一方、シリカゲルの成形体としては、特許
第２８８８７４３号公報に粉末状のシリカゲルと粉末状
のバインダーとを用いた吸脱着性能に優れたシリカゲル
集合体およびその製法が開示されており、特開平７−１
０６４７号公報には粉末シリカゲルと水およびバインダ
ーとの混練物のハニカム状成形体が開示されている。し
かし、これらシリカゲルの成形体は吸湿を目的としてな
されたもので、シリカゲルの平均細孔径が小さく低湿度
でも吸湿率が高い一般的なシリカゲル（ＪＩＳＺ０７０
１ 包装用乾燥剤Ａ型あるいはＢ型規格品、または同等
品）が使用されている。これらに有機チタンを含浸して
焼成しても、焼成中に有機チタンがシリカゲルの細孔内
から排出され、酸化チタンとして細孔内にほとんど残ら
ないため、光触媒活性に優れた成形体を得ることができ
なかった。On the other hand, as a molded article of silica gel, Japanese Patent No. 2888743 discloses a silica gel aggregate which uses powdery silica gel and a powdery binder and is excellent in adsorption / desorption performance, and a method for producing the same. Kaihei 7-1
Japanese Patent No. 0647 discloses a honeycomb formed body of a kneaded product of powdered silica gel, water and a binder. However, these molded articles of silica gel are made for the purpose of absorbing moisture, and general silica gel having a small average pore size of silica gel and a high moisture absorption rate even at low humidity (JISZ070).
1 Packaging desiccant A type or B type standard product or equivalent) is used. Even if these are impregnated with organotitanium and fired, the organotitanium is discharged from the pores of the silica gel during firing and hardly remains as titanium oxide in the pores, so that a molded article with excellent photocatalytic activity can be obtained. I couldn't.
【０００８】また、特開２００１−４６８８３公報に
は、光触媒機能を有するシリカゲル成形体が開示されて
いる。しかし、シリカゲルは酸性ガスや中性ガスを吸着
し難い性質があった。Further, Japanese Patent Application Laid-Open No. 2001-46883 discloses a silica gel molded body having a photocatalytic function. However, silica gel has a property that it is difficult to adsorb acidic gas and neutral gas.
【０００９】[0009]
【発明が解決しようとする課題】上述のシリカゲル成形
体に酸化チタン光触媒を担持したものは、酸性ガスや中
性ガスを吸着し難い性質を有するため、これらガスが酸
化チタン光触媒と接触する確率が小さくなって分解効率
が悪くなったり、場合によっては分解生成物が酸化チタ
ン光触媒の表面を覆ってしまって反応を阻害することも
あったことから、分解対象ガスをよく吸着し、効率よく
分解できる酸化チタン光触媒を担持したシリカゲル成形
体が望まれていた。The above-mentioned silica gel molded article carrying a titanium oxide photocatalyst has a property that it is difficult to adsorb an acidic gas or a neutral gas, so that the probability of contact of these gases with the titanium oxide photocatalyst is high. Since it became smaller and the decomposition efficiency worsened, in some cases the decomposition products covered the surface of the titanium oxide photocatalyst and hindered the reaction, so the gas to be decomposed was adsorbed well and it could be decomposed efficiently. A silica gel molded body carrying a titanium oxide photocatalyst has been desired.
【００１０】[0010]
【課題を解決するための手段】上記の目的を達成するた
めに、平均細孔径が６〜１００ｎｍの範囲にあるシリカ
ゲルから主として成る成形体の細孔内にアルカリ金属化
合物、銅族元素化合物、アルカリ土金属化合物、亜鉛族
元素化合物、土類元素化合物、クロム族元素化合物、マ
ンガン族元素化合物、鉄族元素化合物の少なくとも一種
と酸化チタンを１〜７０重量％含ませたことを特徴とす
る酸化チタン光触媒を担持したシリカゲル成形体、およ
び平均細孔径が６〜１００ｎｍの範囲にあるシリカゲル
から主として成る成形体の細孔内に、チタン含有溶液を
含ませてから加熱焼成し、当該シリカゲル成形体の細孔
内に酸化チタンを１〜７０重量％含ませた後、溶媒に可
溶なアルカリ金属化合物、銅族元素化合物、アルカリ土
金属化合物、亜鉛族元素化合物、土類元素化合物、クロ
ム族元素化合物、マンガン族元素化合物、鉄族元素化合
物のうちから選ばれた少なくとも一種を含む溶液を当該
シリカゲル成形体に含ませてから溶媒を除去することを
特徴とする酸化チタン光触媒を担持したシリカゲル成形
体の製造方法を提供するものである。In order to achieve the above-mentioned object, an alkali metal compound, a copper group element compound, and an alkali are contained in the pores of a molded article mainly composed of silica gel having an average pore diameter in the range of 6 to 100 nm. Titanium oxide containing at least one of an earth metal compound, a zinc group element compound, an earth element compound, a chromium group element compound, a manganese group element compound, and an iron group element compound, and 1 to 70% by weight of titanium oxide. A silica-containing molded product carrying a photocatalyst and a molded product mainly composed of silica gel having an average pore diameter in the range of 6 to 100 nm are impregnated with a titanium-containing solution, which is then heated and calcined. After containing 1 to 70% by weight of titanium oxide in the pores, a solvent-soluble alkali metal compound, copper group element compound, alkaline earth metal compound, zinc Characterized by including a solution containing at least one selected from an element compound, an earth element compound, a chromium group element compound, a manganese group element compound, and an iron group element compound in the silica gel molded body, and then removing the solvent. The present invention provides a method for producing a silica gel molded article carrying a titanium oxide photocatalyst.
【００１１】本発明に用いられるシリカゲルは非晶質の
二酸化ケイ素であり、特公平７−６４５４３号公報など
公知の方法により、シリカゲルを構成するコロイド粒子
の大きさを制御することにより、平均細孔径が６〜１０
０ｎｍの範囲にあり、かつ水や有機溶媒に浸漬しても割
れない本発明に用いられるシリカゲルを得ることができ
る。The silica gel used in the present invention is amorphous silicon dioxide, and the average pore diameter is controlled by controlling the size of the colloidal particles constituting the silica gel by a known method such as Japanese Patent Publication No. 7-64543. Is 6-10
It is possible to obtain the silica gel used in the present invention, which is in the range of 0 nm and does not crack when immersed in water or an organic solvent.
【００１２】これらシリカゲルは、包装用乾燥剤（ＪＩ
Ｓ Ｚ ０７０１ 包装用乾燥剤Ａ型規格品またはＢ型規
格品）として一般的に使用されているものとは全く異な
るもので、機械的強度もあり、吸着性能に優れ、水ある
いは有機溶剤に浸漬しても割れない性質もあることから
クロマトグラフィー用や触媒担持用などに用いられてい
るもので、微粉末から粒状品まで各種のものが可能であ
る。また、上述の包装用乾燥剤は水あるいは有機溶剤に
浸漬すると粉々に割れるという致命的な欠点があり、本
発明に用いることはできない。These silica gels are used as a desiccant for packaging (JI
S Z 0701 Packaging desiccant A type standard product or B type standard product) It is completely different from what is generally used, has mechanical strength, has excellent adsorption performance, and is immersed in water or an organic solvent. Since it has the property of not breaking even when used, it is used for chromatography and catalyst loading, and various types from fine powder to granular products are possible. Further, the above desiccant for packaging has a fatal defect that it is broken into pieces when immersed in water or an organic solvent, and cannot be used in the present invention.
【００１３】平均細孔径が６ｎｍ未満のシリカゲルでは
十分な酸化チタンの担持量が得られず、光触媒活性が劣
ることから望ましくなく、平均細孔径が１００ｎｍを越
えるシリカゲルは製造が困難であり、非常に高価なため
望ましくない。Silica gel having an average pore size of less than 6 nm is not desirable because a sufficient amount of titanium oxide cannot be obtained and the photocatalytic activity is inferior. Silica gel having an average pore size of more than 100 nm is difficult to produce and very Not desirable because it is expensive.
【００１４】本発明に関わるシリカゲルの細孔内に含ま
せる酸化チタンの結晶構造は、光触媒活性の高いアナタ
ーゼであることが望ましいが、ルチル、アナターゼなど
の混合物でも利用できる。The crystal structure of titanium oxide contained in the pores of the silica gel according to the present invention is preferably anatase having a high photocatalytic activity, but a mixture of rutile, anatase and the like can also be used.
【００１５】また、シリカゲル成形体の細孔内に含ませ
る酸化チタンの量は１〜７０重量％とすることが望まし
く、７〜１５重量％とすることがより望ましい。１重量
％未満では十分な光触媒活性が得られず、７０重量％を
超えるとシリカゲル成形体の細孔を著しく目詰まりさせ
るため望ましくない。The amount of titanium oxide contained in the pores of the silica gel molded body is preferably 1 to 70% by weight, more preferably 7 to 15% by weight. If it is less than 1% by weight, sufficient photocatalytic activity cannot be obtained, and if it exceeds 70% by weight, the pores of the silica gel molded article are significantly clogged, which is not desirable.
【００１６】本発明に用いられるアルカリ金属化合物、
銅族元素化合物、アルカリ土金属化合物、亜鉛族元素化
合物、土類元素化合物、クロム族元素化合物、マンガン
族元素化合物、および鉄族元素化合物は、溶媒に可溶で
シリカゲルに含ませることができるものであれば、単独
でも混合物でも制限なく利用でき、溶媒としては水、酸
を含む水、アルカリを含む水、有機溶剤などを、単独で
も混合物でも制限なく用いることができる。An alkali metal compound used in the present invention,
Copper group element compounds, alkaline earth metal compounds, zinc group element compounds, earth element compounds, chromium group element compounds, manganese group element compounds, and iron group element compounds are soluble in solvents and can be contained in silica gel. If so, either alone or as a mixture, it can be used without limitation, and as the solvent, water, water containing an acid, water containing an alkali, an organic solvent or the like can be used alone or in a mixture without limitation.
【００１７】本発明に用いられるアルカリ金属化合物と
しては、水酸化ナトリウム、炭酸ナトリウム、炭酸水素
ナトリウム、重クロム酸ナトリウム、チオ硫酸ナトリウ
ム、水酸化カリウム、炭酸カリウム、炭酸水素カリウ
ム、重クロム酸カリウムなどを利用することができ、こ
れらは単独でも混合物でも制限なく利用できる。Examples of the alkali metal compound used in the present invention include sodium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium dichromate, sodium thiosulfate, potassium hydroxide, potassium carbonate, potassium hydrogen carbonate, potassium dichromate and the like. Can be used, and these can be used alone or as a mixture without limitation.
【００１８】本発明に用いられる銅族元素化合物として
は、水酸化銅、塩化銅、酸化銅、水酸化銀等が利用で
き、これらは単独でも混合物でも制限なく利用できる。As the copper group element compound used in the present invention, copper hydroxide, copper chloride, copper oxide, silver hydroxide and the like can be used, and these can be used alone or in a mixture without limitation.
【００１９】本発明に用いられるアルカリ土金属化合物
としては、リン酸カルシウム、水酸アパタイト、炭酸ア
パタイト、フッ化アパタイト、水酸化カルシウム、リン
酸マグネシウム、炭酸マグネシウム等が利用でき、これ
らは単独でも混合物でも制限なく利用できる。As the alkaline earth metal compound used in the present invention, calcium phosphate, hydroxyapatite, carbonate apatite, fluorapatite, calcium hydroxide, magnesium phosphate, magnesium carbonate and the like can be used, and these may be used alone or in a mixture. Available without.
【００２０】本発明に用いられる亜鉛族化合物として
は、水酸化亜鉛、塩化亜鉛、リン酸亜鉛、炭酸亜鉛等が
利用でき、これらは単独でも混合物でも制限なく利用で
きる。As the zinc group compound used in the present invention, zinc hydroxide, zinc chloride, zinc phosphate, zinc carbonate and the like can be used, and these can be used alone or as a mixture without any limitation.
【００２１】本発明に用いられる土類金属化合物として
は、水酸化スカンジウム、水酸化イットリウム、水酸化
ランタン等が利用でき、これらは単独でも混合物でも制
限なく利用できる。As the earth metal compound used in the present invention, scandium hydroxide, yttrium hydroxide, lanthanum hydroxide and the like can be used, and these can be used alone or in a mixture without limitation.
【００２２】本発明に用いられるクロム族元素化合物と
しては、水酸化クロム等が利用でき、これらは単独でも
混合物でも制限なく利用できる。As the chromium group element compound used in the present invention, chromium hydroxide and the like can be used, and these can be used alone or as a mixture without limitation.
【００２３】本発明に用いられるマンガン族元素化合物
としては、水酸化マンガン、塩化マンガン等が利用で
き、これらは単独でも混合物でも制限なく利用できる。As the manganese group element compound used in the present invention, manganese hydroxide, manganese chloride and the like can be used, and these can be used alone or as a mixture without any limitation.
【００２４】本発明に用いられる鉄族元素化合物として
は、水酸化鉄、塩化鉄、硫酸鉄、水酸化コバルト、塩化
コバルト、水酸化ニッケル等が利用でき、これらは単独
でも混合物でも制限なく利用できる。As the iron group element compound used in the present invention, iron hydroxide, iron chloride, iron sulfate, cobalt hydroxide, cobalt chloride, nickel hydroxide and the like can be used, and these can be used alone or in a mixture without limitation. .
【００２５】本発明に関わるシリカゲル成形体は、粉末
状または／および粒状のシリカゲルにバインダー、水な
どを加えて混練し、公知の方法でハニカム形状、柱状、
棒状、円筒状、平板状、波板状、ループ状などに成形し
た後、乾燥または焼成することにより得られる。The silica gel molded body according to the present invention is prepared by adding a binder, water and the like to powdery and / or granular silica gel and kneading the mixture to obtain a honeycomb shape, columnar shape,
It is obtained by molding into a rod shape, a cylindrical shape, a flat plate shape, a corrugated plate shape, a loop shape or the like, and then drying or firing.
【００２６】バインダーとしては、ＭＣ、ＣＭＣ、でん
粉、カルボキシメチルスターチ、ヒドロキシエチルセル
ロース、ヒドロキシプロピルセルロース、リグニンスル
ホン酸ナトリウム、リグニンスルホン酸カルシウム、ポ
リビニルアルコール、アクリル酸エステル、メタクリル
酸エステル、フェノール樹脂、メラミン樹脂等の有機系
バインダー、低融点ガラス、水ガラス、コロイダルシリ
カ、コロイダルアルミナ、コロイダルチタン、ベントナ
イト、モンモリロナイト、リン酸アルミニウムなどの無
機系バインダーを、単独または2種類以上併用して用い
てもよい。As the binder, MC, CMC, starch, carboxymethyl starch, hydroxyethyl cellulose, hydroxypropyl cellulose, sodium lignin sulfonate, calcium lignin sulfonate, polyvinyl alcohol, acrylic acid ester, methacrylic acid ester, phenol resin, melamine resin Organic binders such as, low melting point glass, water glass, colloidal silica, colloidal alumina, colloidal titanium, bentonite, montmorillonite, aluminum phosphate and the like may be used alone or in combination of two or more.
【００２７】なお、成形体の光触媒活性、強度、多孔質
化、吸着能などの向上を目的として蓄光材料、酸化チタ
ン、界面活性剤、ガラス繊維、活性炭、木粉、包装用乾
燥剤に使われるシリカゲル、ゼオライトなどを制限なく
用いてもよい。It is used as a phosphorescent material, titanium oxide, surfactant, glass fiber, activated carbon, wood powder, and desiccant for packaging for the purpose of improving the photocatalytic activity, strength, porosity and adsorption capacity of the molded product. Silica gel, zeolite, etc. may be used without limitation.
【００２８】本発明に関わる酸化チタン光触媒を含ませ
たシリカゲル成形体は、上述のようにして得られたシリ
カゲル成形体をチタン含有溶液に、例えば浸漬すること
により、シリカゲル成形体の細孔内に該溶液を含ませ、
これを必要に応じて乾燥したのち、例えば室温から徐々
に加熱昇温して４００〜１０００℃の最終温度で一定時
間保持した後、室温まで冷却して行うことにより得るこ
とができる。The silica gel molded body containing the titanium oxide photocatalyst according to the present invention is placed in the pores of the silica gel molded body by, for example, immersing the silica gel molded body obtained as described above in a titanium-containing solution. Including the solution,
This can be obtained, for example, by drying it if necessary, gradually heating up from room temperature, holding the final temperature of 400 to 1000 ° C. for a certain period of time, and then cooling to room temperature.
【００２９】焼成温度が４００℃未満では光触媒として
活性の低い非晶質の混じった酸化チタンとなるので好ま
しくなく、１０００℃を越えるとシリカゲルそのものが
変質するので好ましくない。また、担持および焼成を２
回以上行うことにより、酸化チタンの担持量をより多く
することができる。If the baking temperature is lower than 400 ° C., amorphous titanium oxide having a low activity as a photocatalyst is formed, which is not preferable, and if it exceeds 1000 ° C., the silica gel itself is deteriorated, which is not preferable. In addition, carrying and firing 2
By carrying out more than once, the amount of titanium oxide supported can be increased.
【００３０】本発明に用いられるチタン含有溶液として
は、四塩化チタンや金属チタンとアルコールとの反応な
どによって得られるテトライソプロピルチタネート、テ
トラブチルチタネート、ブチルチタネートダイマー、テ
トラキス（２−エチルへキシルオキシ)チタン、テトラ
ステアリルチタネート、トリエタノールアミンチタネー
ト、ジイソプロポキシ・ビス（アセチルアセトナト）チ
タン、ジブトキシ・ビス（トリエタノールアミナト）チ
タン、チタニウムエチルアセトアセテート、チタニウム
イソプロポキシオクチレングリコレート、チタニウムラ
クテートなどのチタンのアルコキシド、およびイソプロ
ピルトリイソステアロイルチタネート、イソプロピルト
リドデシルベンゼンスルホニルチタネート、イソプロピ
ルトリス（ジオクチルパイロホスフェート）チタネー
ト、テトライソプロピルビス（ジオクチルホスファイ
ト）チタネート、テトラオクチルビス（ジトリデシルホ
スファイト）チタネート、テトラ（２、２−ジアリルオ
キシメチル−１−ブチル）ビス（ジトリデシル）ホスフ
ァイトチタネート、ビス（ジオクチルパイロホスフェー
ト）オキシアセテートチタネート、ビス（ジオクチルパ
イロホスフェート）エチレンチタネート、イソプロピル
トリ（ジオクチルホスフェート）チタネート、イソプロ
ピルトリクミルフェニルチタネート、イソプロピルトリ
（Ｎ−アミドエチル・アミノエチル）チタネートなどの
チタネート系カップリング剤などの有機チタン含有溶
液、並びに硫酸チタン、塩化チタン、臭化チタンなどの
無機チタン含有溶液などが挙げられるが、これらに限ら
れるものではない。The titanium-containing solution used in the present invention includes tetraisopropyl titanate, tetrabutyl titanate, butyl titanate dimer, tetrakis (2-ethylhexyloxy) titanium obtained by the reaction of titanium tetrachloride or titanium metal with alcohol. , Tetrastearyl titanate, triethanolamine titanate, diisopropoxy bis (acetylacetonato) titanium, dibutoxy bis (triethanolaminato) titanium, titanium ethyl acetoacetate, titanium isopropoxyoctylene glycolate, titanium lactate, etc. Titanium alkoxides and isopropyl triisostearoyl titanate, isopropyl tridodecylbenzene sulfonyl titanate, isopropyl tris (diocty Lupyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis Titanate coupling agents such as (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumylphenyl titanate, isopropyl tri (N-amidoethyl aminoethyl) titanate. Examples include organic titanium-containing solutions such as, and inorganic titanium-containing solutions such as titanium sulfate, titanium chloride, and titanium bromide. The present invention is not limited to, et al.
【００３１】また、上述のチタン含有溶液は単独でも混
合物でも制限なく利用できるが、これらに限定されるも
のではなく、相溶性のある溶剤で稀釈して用いてもよ
い。相溶性のある溶剤としては、アセト酢酸エチル、ア
セチルアセトン、ジエタノールアミン、エタノール、１
−プロパノール、２−プロパノール、Ｎ−ヘキサン、ベ
ンゼン、トルエン、キシレン、トリクレン、プロピレン
ジクロライド、水などチタン含有溶液と相溶性のあるも
のであれば何でも、単独でも混合物でも制限なく利用で
きる。The above titanium-containing solution may be used alone or as a mixture without limitation, but it is not limited to these and may be used by diluting with a compatible solvent. Compatible solvents include ethyl acetoacetate, acetylacetone, diethanolamine, ethanol, 1
-Propanol, 2-propanol, N-hexane, benzene, toluene, xylene, trichlene, propylene dichloride, water, etc. can be used without limitation as long as they are compatible with the titanium-containing solution.
【００３２】本発明に関わる酸化チタン光触媒を含ませ
たシリカゲル成形体は、上述のようにして得られたシリ
カゲル成形体を、溶媒に可溶なアルカリ金属化合物、銅
族元素化合物、アルカリ土金属化合物、亜鉛族元素化合
物、土類元素化合物、クロム族元素化合物、マンガン族
元素化合物、鉄族元素化合物のうちから選ばれた少なく
とも一種を含む溶液に、例えば浸漬することにより、シ
リカゲル成形体の細孔内に該溶液を含ませ、これを乾燥
もしくは焼成することにより得ることができる。The silica gel molded body containing the titanium oxide photocatalyst according to the present invention is obtained by converting the silica gel molded body obtained as described above into a solvent-soluble alkali metal compound, copper group element compound, alkaline earth metal compound. , A zinc group element compound, an earth element compound, a chromium group element compound, a manganese group element compound, an iron group element compound, for example, by dipping in a solution containing at least one selected, the pores of the silica gel molded body It can be obtained by including the solution in the inside and drying or baking it.
【００３３】なお、アルカリ金属化合物、銅族元素化合
物、アルカリ土金属化合物、亜鉛族元素化合物、土類元
素化合物、クロム族元素化合物、マンガン族元素化合
物、鉄族元素化合物のうちから選ばれた少なくとも一種
を、酸あるいはアルカリに溶かしてから当該シリカゲル
に含ませた場合は、酸の場合はアルカリで、アルカリの
場合は酸で中和してから溶媒を除去してもよい。At least one selected from alkali metal compounds, copper group element compounds, alkaline earth metal compounds, zinc group element compounds, earth element compounds, chromium group element compounds, manganese group element compounds, iron group element compounds. When one is dissolved in an acid or an alkali and then contained in the silica gel, the solvent may be removed after neutralizing with an alkali in the case of an acid or an acid in the case of an alkali.
【００３４】[0034]
【作用】 本発明による酸化チタン光触媒を担持したシ
リカゲル成形体は、任意の形状が得られ利用しやすいだ
けでなく、アルカリ金属化合物、銅族元素化合物、アル
カリ土金属化合物、亜鉛族元素化合物、土類元素化合
物、クロム族元素化合物、マンガン族元素化合物、鉄族
元素化合物の少なくとも一種を含ませることにより、Ｎ
Ｏx、ホルムアルデヒド、アセトアルデヒド、トルエ
ン、キシレンなどの環境汚染物質や硫化メチル、二硫化
メチル、スチレン、トリメチルアミン、硫化水素、メチ
ルメルカプタンなどの悪臭物質に応じて、これら汚染物
質等を効果的に吸着せしめることにより、細孔内に含ま
れる酸化チタン光触媒との接触頻度を高め、これらを効
率よく分解することができる。The silica gel molded article carrying the titanium oxide photocatalyst according to the present invention is not only easy to obtain and can be used in an arbitrary shape, but also has an alkali metal compound, a copper group element compound, an alkaline earth metal compound, a zinc group element compound, an earth By including at least one of a group-element compound, a chromium-group element compound, a manganese-group element compound, and an iron-group element compound, N
According to environmental pollutants such as Ox, formaldehyde, acetaldehyde, toluene, xylene, and malodorous substances such as methyl sulfide, methyl disulfide, styrene, trimethylamine, hydrogen sulfide, and methyl mercaptan, these contaminants can be effectively absorbed. As a result, the contact frequency with the titanium oxide photocatalyst contained in the pores can be increased and these can be decomposed efficiently.
【００３５】[0035]
【発明の実施の形態】本発明を次の例で詳しく説明す
る。
［参考実施例１］本発明に関わるシリカゲル成形体の作
製
１８０℃で乾燥した平均粒径１０μｍのシリカゲル（富
士シリシア化学株式会社製 ＣＡＲｉＡＣＴ Ｇ−１
０、平均細孔径１０ｎｍ、細孔容積１．３ｍｌ、比表面
積３００ｍ2／ｇ）１００重量部、粉末状のメチルセル
ロース（１００メッシュ下）１０重量部、および非結晶
性低融点ガラス（セントラル硝子製、接着温度：４３０
〜６５０℃、転移点：３２０〜４８０℃）１０重量部と
をミキサーで混合した後、イオン交換水７０重量部を添
加し、三本ロールで混練（ロール温度は１０〜１５℃に
制御）した後、押出し成形機に投入し、平板形状の口金
から押出しタイル形状にカットした。The invention will be explained in more detail in the following examples. Reference Example 1 Preparation of Silica Gel Molded Body According to the Present Invention Silica gel dried at 180 ° C. and having an average particle size of 10 μm (CARiACT G-1 manufactured by Fuji Silysia Chemical Ltd.)
0, average pore diameter 10 nm, pore volume 1.3 ml, specific surface area 300 m 2 / g) 100 parts by weight, powdery methyl cellulose (under 100 mesh) 10 parts by weight, and amorphous low melting point glass (made by Central Glass, Adhesion temperature: 430
˜650 ° C., transition point: 320 to 480 ° C.) 10 parts by weight were mixed with a mixer, and then 70 parts by weight of ion-exchanged water was added and kneaded with a three-roll mill (roll temperature controlled to 10 to 15 ° C.). Then, the mixture was put into an extrusion molding machine and cut into a tile shape by extrusion from a flat die.
【００３６】このタイル形状品を６０℃で２４時間の予
備乾燥した後、電気炉を用い室温から徐々に６５０℃ま
で加熱昇温し、６５０℃で３時間保持した後、室温まで
自然放冷した。This tile-shaped product was pre-dried at 60 ° C. for 24 hours, then gradually heated and raised from room temperature to 650 ° C. in an electric furnace, kept at 650 ° C. for 3 hours, and then naturally cooled to room temperature. .
【００３７】得られた成形体を、ジイソプロポキシ・ビ
ス（アセチルアセトナト）チタン（三菱ガス化学製 Ｔ
ＡＡ）に３０分間浸漬した後、過剰のＴＡＡを除去する
ために、イソプロピルアルコールの中で簡単に濯ぎ洗い
してから、室温で２日間乾燥した後、電気炉を用いて室
温から徐々に６００℃まで加熱昇温し、６００℃で２時
間保持した後、室温まで自然放冷して本発明に係るシリ
カゲル成形体を得た。The obtained molded body was treated with diisopropoxy bis (acetylacetonato) titanium (manufactured by Mitsubishi Gas Chemical Co., Ltd.
After being soaked in AA) for 30 minutes, in order to remove the excess TAA, it was briefly rinsed in isopropyl alcohol, dried at room temperature for 2 days, and then gradually heated from room temperature to 600 ° C using an electric furnace. The temperature was raised to 100 ° C., the temperature was maintained at 600 ° C. for 2 hours, and then naturally cooled to room temperature to obtain a silica gel molded body according to the present invention.
【００３８】得られたシリカゲル成形体を粉末にしてＸ
線回折により調べた結果、酸化チタンのピークとしては
アナターゼ型のものだけが観察された。また、真比重測
定値から求めた酸化チタンの含有量は１３．３重量％
（１８０℃乾燥重量基準）であった。The obtained silica gel molded body was powdered and X
As a result of examination by line diffraction, only the anatase type was observed as the peak of titanium oxide. Further, the content of titanium oxide obtained from the measured value of true specific gravity is 13.3% by weight.
(180 ° C. dry weight basis).
【００３９】［実施例１］参考実施例１で得られた酸化
チタン光触媒を含ませたシリカゲル成形体を１重量％炭
酸ナトリウム水溶液に３時間浸漬した後、該シリカゲル
成形体を１２０℃で３時間乾燥して、酸化チタン光触媒
と炭酸ナトリウムを含んだ本発明による酸化チタン光触
媒を担持したシリカゲル成形体を得た。Example 1 The silica gel molded body containing the titanium oxide photocatalyst obtained in Reference Example 1 was immersed in a 1 wt% sodium carbonate aqueous solution for 3 hours, and then the silica gel molded body was heated at 120 ° C. for 3 hours. After drying, a silica gel molded body carrying a titanium oxide photocatalyst and a titanium oxide photocatalyst according to the present invention containing sodium carbonate was obtained.
【００４０】得られた本発明による酸化チタン光触媒を
担持したシリカゲル成形体を用いて悪臭物質の分解除去
試験を行った。まず、テドラーバッグ（容積５Ｌ）の中
に得られた該シリカゲル成形体を５ｃｍ×５ｃｍ×０．
５ｃｍ厚に切断したものをガラス製シャーレに入れて置
いた。テドラーバッグの上方から２０Ｗブラックライト
で紫外線を照射しながら、テドラーバッグ内のトリメチ
ルアミン濃度が１００ｐｐｍとなるようにマイクロシリ
ンジで打ち込み、３時間後にバッグ内の空気に含まれる
トリメチルアミン濃度をガスクロマトグラフにより測定
したところ、トリメチルアミン濃度は０ｐｐｍであっ
た。A test for decomposing and removing malodorous substances was carried out by using the obtained silica gel molded article carrying the titanium oxide photocatalyst according to the present invention. First, the silica gel molded body obtained in a Tedlar bag (volume 5 L) was treated with 5 cm × 5 cm × 0.
The cut piece having a thickness of 5 cm was put in a petri dish made of glass and placed. While irradiating ultraviolet rays with a 20 W black light from above the Tedlar bag, a trimethylamine concentration in the Tedlar bag was set to 100 ppm by a microsyringe, and after 3 hours, the concentration of trimethylamine contained in the air in the bag was measured by gas chromatography. The trimethylamine concentration was 0 ppm.
【００４１】［比較実施例１］参考実施例１で得られた
酸化チタン光触媒だけを含ませたシリカゲル成形体を用
いて悪臭物質の分解除去試験を行った。まず、テドラー
バッグ（容積５Ｌ）の中に得られた該シリカゲル成形体
を５ｃｍ×５ｃｍ×０．５ｃｍ厚に切断したものをガラ
ス製シャーレに入れて置いた。テドラーバッグの上方か
ら２０Ｗブラックライトで紫外線を照射しながら、テド
ラーバッグ内のトリメチルアミン濃度が１００ｐｐｍと
なるようにマイクロシリンジで打ち込み、３時間後にバ
ッグ内の空気に含まれるトリメチルアミン濃度をガスク
ロマトグラフにより測定したところ、トリメチルアミン
濃度は３０ｐｐｍであった。このことから、本発明によ
る酸化チタン光触媒を担持したシリカゲル成形体にはト
リメチルアミンの分解除去効果が顕著に認められた。Comparative Example 1 A test for decomposing and removing malodorous substances was conducted using the silica gel molding containing only the titanium oxide photocatalyst obtained in Reference Example 1. First, the obtained silica gel molded body was cut into a 5 cm × 5 cm × 0.5 cm thick piece in a Tedlar bag (volume: 5 L) and placed in a glass petri dish. While irradiating ultraviolet rays with 20 W black light from above the Tedlar bag, the trimethylamine concentration in the Tedlar bag was set to 100 ppm by a microsyringe, and after 3 hours, the trimethylamine concentration contained in the air in the bag was measured by gas chromatography. The trimethylamine concentration was 30 ppm. From this, the effect of decomposing and removing trimethylamine was remarkably recognized in the silica gel molded article carrying the titanium oxide photocatalyst according to the present invention.
【００４２】［実施例２］参考実施例１で得られた酸化
チタン光触媒を含ませたシリカゲル成形体を１重量％水
酸化銅水溶液（アンモニア水に水酸化銅を溶解）に３時
間浸漬した後、該シリカゲル成形体を１２０℃で３時間
乾燥して、酸化チタン光触媒と水酸化銅を含んだ本発明
による酸化チタン光触媒を担持したシリカゲル成形体を
得た。Example 2 After the silica gel molding containing the titanium oxide photocatalyst obtained in Reference Example 1 was immersed in a 1% by weight copper hydroxide aqueous solution (copper hydroxide was dissolved in ammonia water) for 3 hours. Then, the silica gel molded body was dried at 120 ° C. for 3 hours to obtain a silica gel molded body carrying a titanium oxide photocatalyst and a titanium oxide photocatalyst according to the present invention containing a copper hydroxide.
【００４３】得られた本発明による酸化チタン光触媒を
担持したシリカゲル成形体を用いて悪臭物質の分解除去
試験を行った。まず、テドラーバッグ（容積５Ｌ）の中
に得られた該シリカゲル成形体を５ｃｍ×５ｃｍ×０．
５ｃｍ厚に切断したものをガラス製シャーレに入れて置
いた。テドラーバッグの上方から２０Ｗブラックライト
で紫外線を照射しながら、テドラーバッグ内の硫化水素
濃度が１００ｐｐｍとなるようにマイクロシリンジで打
ち込み、３時間後にバッグ内の空気に含まれる硫化水素
濃度をガスクロマトグラフにより測定したところ、硫化
水素濃度は０ｐｐｍであった。A test for decomposing and removing malodorous substances was carried out by using the obtained silica gel molded article carrying the titanium oxide photocatalyst according to the present invention. First, the silica gel molded body obtained in a Tedlar bag (volume 5 L) was treated with 5 cm × 5 cm × 0.
The cut piece having a thickness of 5 cm was put in a petri dish made of glass and placed. While irradiating ultraviolet rays with a 20 W black light from above the Tedlar bag, it was driven with a microsyringe so that the hydrogen sulfide concentration in the Tedlar bag would be 100 ppm, and after 3 hours, the hydrogen sulfide concentration contained in the air in the bag was measured by a gas chromatograph. However, the hydrogen sulfide concentration was 0 ppm.
【００４４】［比較実施例２］参考実施例１で得られた
酸化チタン光触媒だけを含ませたシリカゲル成形体を用
いて悪臭物質の分解除去試験を行った。まず、テドラー
バッグ（容積５Ｌ）の中に得られた該シリカゲル成形体
を５ｃｍ×５ｃｍ×０．５ｃｍ厚に切断したものをガラ
ス製シャーレに入れて置いた。テドラーバッグの上方か
ら２０Ｗブラックライトで紫外線を照射しながら、テド
ラーバッグ内の硫化水素濃度が１００ｐｐｍとなるよう
にマイクロシリンジで打ち込み、３時間後にバッグ内の
空気に含まれる硫化水素濃度をガスクロマトグラフによ
り測定したところ、硫化水素濃度は５４ｐｐｍであっ
た。このことから、本発明による酸化チタン光触媒を担
持したシリカゲル成形体には硫化水素の分解除去効果が
顕著に認められた。Comparative Example 2 A test for decomposing and removing malodorous substances was carried out using the silica gel molding containing only the titanium oxide photocatalyst obtained in Reference Example 1. First, the obtained silica gel molded body was cut into a 5 cm × 5 cm × 0.5 cm thick piece in a Tedlar bag (volume: 5 L) and placed in a glass petri dish. While irradiating ultraviolet rays with a 20 W black light from above the Tedlar bag, it was driven with a microsyringe so that the hydrogen sulfide concentration in the Tedlar bag would be 100 ppm, and after 3 hours, the hydrogen sulfide concentration contained in the air in the bag was measured by a gas chromatograph. However, the hydrogen sulfide concentration was 54 ppm. From this fact, the effect of decomposing and removing hydrogen sulfide was remarkably recognized in the silica gel molded article carrying the titanium oxide photocatalyst according to the present invention.
【００４５】［実施例３］参考実施例１で得られた酸化
チタン光触媒を含ませたシリカゲル成形体を１重量％リ
ン酸カルシウム水溶液（リン酸にリン酸カルシウムを溶
解）に３時間浸漬した後、該シリカゲル成形体を１２０
℃で３時間乾燥した後、当該シリカゲル成形体を３重量
％水酸化ナトリウム水溶液に１時間浸漬してから、再度
１２０℃で３時間乾燥して、酸化チタン光触媒とリン酸
カルシウムを含んだ本発明による酸化チタン光触媒を担
持したシリカゲル成形体を得た。Example 3 The silica gel molded body containing the titanium oxide photocatalyst obtained in Reference Example 1 was immersed in a 1% by weight aqueous solution of calcium phosphate (dissolving calcium phosphate in phosphoric acid) for 3 hours, and then the silica gel molding was carried out. Body 120
After drying at 3 ° C for 3 hours, the silica gel molding is dipped in a 3 wt% sodium hydroxide aqueous solution for 1 hour, and then dried again at 120 ° C for 3 hours to oxidize the titanium oxide photocatalyst and calcium phosphate according to the present invention. A silica gel molded body carrying a titanium photocatalyst was obtained.
【００４６】得られた本発明による酸化チタン光触媒を
担持したシリカゲル成形体を用いて悪臭物質の分解除去
試験を行った。まず、テドラーバッグ（容積５Ｌ）の中
に得られた該シリカゲル成形体を５ｃｍ×５ｃｍ×０．
５ｃｍ厚に切断したものをガラス製シャーレに入れて置
いた。テドラーバッグの上方から２０Ｗブラックライト
で紫外線を照射しながら、テドラーバッグ内のアセトア
ルデヒド濃度が１００ｐｐｍとなるようにマイクロシリ
ンジで打ち込み、３時間後にバッグ内の空気に含まれる
アセトアルデヒド濃度をガスクロマトグラフにより測定
したところ、アセトアルデヒド濃度は０ｐｐｍであっ
た。A test for decomposing and removing malodorous substances was carried out by using the obtained silica gel molded article carrying the titanium oxide photocatalyst according to the present invention. First, the silica gel molded body obtained in a Tedlar bag (volume 5 L) was treated with 5 cm × 5 cm × 0.
The cut piece having a thickness of 5 cm was put in a petri dish made of glass and placed. While irradiating ultraviolet rays with a 20 W black light from above the Tedlar bag, the acetaldehyde concentration in the Tedlar bag was hammered in with a microsyringe so that the acetaldehyde concentration in the air in the bag was measured 3 hours later by gas chromatography. The acetaldehyde concentration was 0 ppm.
【００４７】［比較実施例３］参考実施例１で得られた
酸化チタン光触媒だけを含ませたシリカゲル成形体を用
いて悪臭物質の分解除去試験を行った。[Comparative Example 3] A decomposition and removal test of a malodorous substance was carried out using the silica gel molded body containing only the titanium oxide photocatalyst obtained in Reference Example 1.
【００４８】まず、テドラーバッグ（容積５Ｌ）の中に
得られた該シリカゲル成形体を５ｃｍ×５ｃｍ×０．５
ｃｍ厚に切断したものをガラス製シャーレに入れて置い
た。テドラーバッグの上方から２０Ｗブラックライトで
紫外線を照射しながら、テドラーバッグ内のアセトアル
デヒド水素濃度が１００ｐｐｍとなるようにマイクロシ
リンジで打ち込み、３時間後にバッグ内の空気に含まれ
るアセトアルデヒド濃度をガスクロマトグラフにより測
定したところ、アセトアルデヒド濃度は３４ｐｐｍであ
った。このことから、本発明による酸化チタン光触媒を
担持したシリカゲル成形体にはアセトアルデヒドの分解
除去効果が顕著に認められた。First, the silica gel molded body obtained in a Tedlar bag (volume: 5 L) was 5 cm × 5 cm × 0.5.
The piece cut into cm thickness was put in a petri dish made of glass and placed. While irradiating ultraviolet rays with 20 W black light from above the Tedlar bag, the acetaldehyde hydrogen concentration in the Tedlar bag was set with a microsyringe so that the hydrogen concentration was 100 ppm, and after 3 hours, the acetaldehyde concentration in the air in the bag was measured by gas chromatography. The acetaldehyde concentration was 34 ppm. From this, the effect of decomposing and removing acetaldehyde was remarkably recognized in the silica gel molded body carrying the titanium oxide photocatalyst according to the present invention.
【００４９】［実施例４］参考実施例１で得られた酸化
チタン光触媒を含ませたシリカゲル成形体を１重量％水
酸化亜鉛水溶液（希硝酸に水酸化亜鉛を溶解）に３時間
浸漬した後、当該シリカゲル成形体を３重量％水酸化ナ
トリウム水溶液に１時間浸漬してから、再度１２０℃で
３時間乾燥して、酸化チタン光触媒と水酸化亜鉛を含ん
だ本発明による酸化チタン光触媒を担持したシリカゲル
成形体を得た。Example 4 The silica gel molded body containing the titanium oxide photocatalyst obtained in Reference Example 1 was immersed in a 1% by weight aqueous zinc hydroxide solution (zinc hydroxide dissolved in dilute nitric acid) for 3 hours. The silica gel molded body was immersed in a 3 wt% sodium hydroxide aqueous solution for 1 hour and then dried again at 120 ° C. for 3 hours to support the titanium oxide photocatalyst and the titanium oxide photocatalyst according to the present invention containing zinc hydroxide. A silica gel molded body was obtained.
【００５０】得られた本発明による酸化チタン光触媒を
担持したシリカゲル成形体を用いて環境物質の分解除去
試験を行った。まず、テドラーバッグ（容積５Ｌ）の中
に得られた該シリカゲル成形体を５ｃｍ×５ｃｍ×０．
５ｃｍ厚に切断したものをガラス製シャーレに入れて置
いた。テドラーバッグの上方から２０Ｗブラックライト
で紫外線を照射しながら、テドラーバッグ内のＮＯ濃度
が１００ｐｐｍとなるように調製した後、３時間後にバ
ッグ内の空気に含まれるＮＯ濃度をＮＯＸ計により測定
したところ、ＮＯ濃度は０ｐｐｍであった。Using the obtained silica gel molded article carrying the titanium oxide photocatalyst according to the present invention, a test for decomposing and removing environmental substances was conducted. First, the silica gel molded body obtained in a Tedlar bag (volume 5 L) was treated with 5 cm × 5 cm × 0.
The cut piece having a thickness of 5 cm was put in a petri dish made of glass and placed. While irradiating ultraviolet rays with a 20 W black light from above the Tedlar bag, the NO concentration in the Tedlar bag was adjusted to 100 ppm, and after 3 hours, the NO concentration contained in the air in the bag was measured by a NO X meter. The NO concentration was 0 ppm.
【００５１】［比較実施例４］参考実施例１で得られた
酸化チタン光触媒だけを含ませたシリカゲル成形体を用
いて環境物質の分解除去試験を行った。まず、テドラー
バッグ（容積５Ｌ）の中に得られた該シリカゲル成形体
を５ｃｍ×５ｃｍ×０．５ｃｍ厚に切断したものをガラ
ス製シャーレに入れて置いた。テドラーバッグの上方か
ら２０Ｗブラックライトで紫外線を照射しながら、テド
ラーバッグ内のＮＯ濃度が１００ｐｐｍとなるように調
製して、３時間後にバッグ内の空気に含まれるＮＯ濃度
をガスクロマトグラフにより測定したところ、ＮＯ濃度
は３４ｐｐｍであった。このことから、本発明による酸
化チタン光触媒を担持したシリカゲル成形体にはＮＯの
除去効果が顕著に認められた。[Comparative Example 4] A decomposition removal test of environmental substances was carried out using the silica gel molded body containing only the titanium oxide photocatalyst obtained in Reference Example 1. First, the obtained silica gel molded body was cut into a 5 cm × 5 cm × 0.5 cm thick piece in a Tedlar bag (volume: 5 L) and placed in a glass petri dish. While irradiating 20 W black light from above the Tedlar bag with ultraviolet rays, the NO concentration in the Tedlar bag was adjusted to 100 ppm, and after 3 hours, the NO concentration in the air in the bag was measured by gas chromatography. The concentration was 34 ppm. From this, the effect of removing NO was remarkably observed in the silica gel molded body carrying the titanium oxide photocatalyst according to the present invention.
【００５２】［実施例５］参考実施例１で得られた酸化
チタン光触媒を含ませたシリカゲル成形体を１重量％水
酸化ランタン水溶液（希硝酸に水酸化ランタンを溶解）
に３時間浸漬した後、当該シリカゲル成形体を３重量％
水酸化ナトリウム水溶液に１時間浸漬してから、再度１
２０℃で３時間乾燥して、酸化チタン光触媒と水酸化ラ
ンタンを含んだ本発明による酸化チタン光触媒を担持し
たシリカゲル成形体を得た。Example 5 A 1 wt% lanthanum hydroxide aqueous solution (lanthanum hydroxide dissolved in dilute nitric acid) was prepared from the silica gel molded body containing the titanium oxide photocatalyst obtained in Reference Example 1.
3 hours by immersing the silica gel molded body in 3% by weight
Immerse in sodium hydroxide aqueous solution for 1 hour, then repeat 1
After drying at 20 ° C. for 3 hours, a silica gel molded article carrying a titanium oxide photocatalyst and a titanium oxide photocatalyst according to the present invention containing a lanthanum hydroxide was obtained.
【００５３】得られた本発明による酸化チタン光触媒を
担持したシリカゲル成形体を用いて環境物質の分解除去
試験を行った。Using the obtained silica gel molded article carrying the titanium oxide photocatalyst according to the present invention, a test for decomposing and removing environmental substances was conducted.
【００５４】まず、テドラーバッグ（容積５Ｌ）の中に
得られた該シリカゲル成形体を５ｃｍ×５ｃｍ×０．５
ｃｍ厚に切断したものをガラス製シャーレに入れて置い
た。テドラーバッグの上方から２０Ｗブラックライトで
紫外線を照射しながら、テドラーバッグ内のＮＯ濃度が
１００ｐｐｍとなるように調製した後、３時間後にバッ
グ内の空気に含まれるＮＯ濃度をＮＯＸ計により測定し
たところ、ＮＯ濃度およびＮＯ２濃度は０ｐｐｍであっ
た。First, the silica gel molded body obtained in a Tedlar bag (volume: 5 L) was 5 cm × 5 cm × 0.5.
The piece cut into cm thickness was put in a petri dish made of glass and placed. While irradiating ultraviolet rays with a 20 W black light from above the Tedlar bag, the NO concentration in the Tedlar bag was adjusted to 100 ppm, and after 3 hours, the NO concentration contained in the air in the bag was measured by a NO X meter. The NO concentration and NO 2 concentration were 0 ppm.
【００５５】［比較実施例５］参考実施例１で得られた
酸化チタン光触媒だけを含ませたシリカゲル成形体を用
いて環境物質の分解除去試験を行った。Comparative Example 5 Using the silica gel molded body containing only the titanium oxide photocatalyst obtained in Reference Example 1, a decomposition and removal test of environmental substances was conducted.
【００５６】まず、テドラーバッグ（容積５Ｌ）の中に
得られた該シリカゲル成形体を５ｃｍ×５ｃｍ×０．５
ｃｍ厚に切断したものをガラス製シャーレに入れて置い
た。テドラーバッグの上方から２０Ｗブラックライトで
紫外線を照射しながら、テドラーバッグ内のＮＯ濃度が
１００ｐｐｍとなるように調製して、３時間後にバッグ
内の空気に含まれるＮＯ濃度をガスクロマトグラフによ
り測定したところ、ＮＯ濃度は２３ｐｐｍでＮＯ２濃度
は３０ｐｐｍであった。このことから、本発明による酸
化チタン光触媒を担持したシリカゲル成形体にはＮＯの
除去効果が顕著に認められた。First, the silica gel molded body obtained in a Tedlar bag (volume: 5 L) was 5 cm × 5 cm × 0.5.
The piece cut into cm thickness was put in a petri dish made of glass and placed. While irradiating 20 W black light from above the Tedlar bag with ultraviolet rays, the NO concentration in the Tedlar bag was adjusted to 100 ppm, and after 3 hours, the NO concentration in the air in the bag was measured by gas chromatography. The concentration was 23 ppm and the NO 2 concentration was 30 ppm. From this, the effect of removing NO was remarkably observed in the silica gel molded body carrying the titanium oxide photocatalyst according to the present invention.
【００５７】［実施例６］参考実施例１で得られた酸化
チタン光触媒を含ませたシリカゲル成形体を１重量％水
酸化クロム水溶液（希硝酸に水酸化クロムを溶解）に３
時間浸漬した後、当該シリカゲル成形体を３重量％水酸
化ナトリウム水溶液に１時間浸漬してから、再度１２０
℃で３時間乾燥して、酸化チタン光触媒と水酸化クロム
を含んだ本発明による酸化チタン光触媒を担持したシリ
カゲル成形体を得た。Example 6 A silica gel molded body containing the titanium oxide photocatalyst obtained in Reference Example 1 was mixed with 1% by weight of a chromium hydroxide aqueous solution (chromium hydroxide dissolved in dilute nitric acid).
After soaking for 1 hour, the silica gel molded body is soaked in a 3% by weight sodium hydroxide aqueous solution for 1 hour, and then 120 times again.
After drying at 3 ° C. for 3 hours, a silica gel molded article carrying the titanium oxide photocatalyst and the titanium oxide photocatalyst according to the present invention containing chromium hydroxide was obtained.
【００５８】得られた本発明による酸化チタン光触媒を
担持したシリカゲル成形体を用いて環境物質の分解除去
試験を行った。まず、テドラーバッグ（容積５Ｌ）の中
に得られた該シリカゲル成形体を５ｃｍ×５ｃｍ×０．
５ｃｍ厚に切断したものをガラス製シャーレに入れて置
いた。テドラーバッグの上方から２０Ｗブラックライト
で紫外線を照射しながら、テドラーバッグ内のトルエン
濃度が１００ｐｐｍとなるように調製した後、３時間後
にバッグ内の空気に含まれるトルエン濃度をガスクロマ
トグラフにより測定したところ、トルエン濃度は０ｐｐ
ｍであった。Using the obtained silica gel molded article carrying the titanium oxide photocatalyst of the present invention, a decomposition and removal test of environmental substances was conducted. First, the silica gel molded body obtained in a Tedlar bag (volume 5 L) was treated with 5 cm × 5 cm × 0.
The cut piece having a thickness of 5 cm was put in a petri dish made of glass and placed. While irradiating ultraviolet rays from above the Tedlar bag with 20 W black light, the toluene concentration in the Tedlar bag was adjusted to 100 ppm, and after 3 hours, the toluene concentration in the air in the bag was measured by gas chromatography. The concentration is 0pp
It was m.
【００５９】［比較実施例６］参考実施例１で得られた
酸化チタン光触媒だけを含ませたシリカゲル成形体を用
いて環境物質の分解除去試験を行った。[Comparative Example 6] A decomposition removal test of environmental substances was carried out using the silica gel molded body containing only the titanium oxide photocatalyst obtained in Reference Example 1.
【００６０】まず、テドラーバッグ（容積５Ｌ）の中に
得られた該シリカゲル成形体を５ｃｍ×５ｃｍ×０．５
ｃｍ厚に切断したものをガラス製シャーレに入れて置い
た。テドラーバッグの上方から２０Ｗブラックライトで
紫外線を照射しながら、テドラーバッグ内のトルエン濃
度が１００ｐｐｍとなるように調製して、３時間後にバ
ッグ内の空気に含まれるトルエン濃度をガスクロマトグ
ラフにより測定したところ、トルエン濃度は１８ｐｐｍ
であった。このことから、本発明による酸化チタン光触
媒を担持したシリカゲル成形体にはトルエンの分解除去
効果が顕著に認められた。First, the silica gel molded body obtained in a Tedlar bag (volume: 5 L) was 5 cm × 5 cm × 0.5.
The piece cut into cm thickness was put in a petri dish made of glass and placed. While irradiating ultraviolet rays with 20 W black light from above the Tedlar bag, the toluene concentration in the Tedlar bag was adjusted to 100 ppm, and after 3 hours, the toluene concentration in the air in the bag was measured by gas chromatography. The concentration is 18ppm
Met. From this, the effect of decomposing and removing toluene was remarkably recognized in the silica gel molded body carrying the titanium oxide photocatalyst according to the present invention.
【００６１】［実施例７］参考実施例１で得られた酸化
チタン光触媒を含ませたシリカゲル成形体を１重量％水
酸化マンガン水溶液（希硝酸に水酸化マンガンを溶解）
に３時間浸漬した後、当該シリカゲル成形体を３重量％
水酸化ナトリウム水溶液に１時間浸漬してから、再度１
２０℃で３時間乾燥して、酸化チタン光触媒と水酸化マ
ンガンを含んだ本発明による酸化チタン光触媒を担持し
たシリカゲル成形体を得た。Example 7 A silica gel molded body containing the titanium oxide photocatalyst obtained in Reference Example 1 was treated with a 1 wt% manganese hydroxide aqueous solution (manganese hydroxide was dissolved in dilute nitric acid).
3 hours by immersing the silica gel molded body in 3% by weight
Immerse in sodium hydroxide aqueous solution for 1 hour, then repeat 1
After drying at 20 ° C. for 3 hours, a silica gel molded article carrying a titanium oxide photocatalyst and a titanium oxide photocatalyst according to the present invention containing a manganese hydroxide was obtained.
【００６２】得られた本発明による酸化チタン光触媒を
担持したシリカゲル成形体を用いて環境物質の分解除去
試験を行った。Using the obtained silica gel molded product carrying the titanium oxide photocatalyst according to the present invention, a decomposition and removal test of environmental substances was conducted.
【００６３】まず、テドラーバッグ（容積５Ｌ）の中に
得られた該シリカゲル成形体を５ｃｍ×５ｃｍ×０．５
ｃｍ厚に切断したものをガラス製シャーレに入れて置い
た。テドラーバッグの上方から２０Ｗブラックライトで
紫外線を照射しながら、テドラーバッグ内の二硫化メチ
ル濃度が１００ｐｐｍとなるように調製した後、３時間
後にバッグ内の空気に含まれる二硫化メチル濃度をガス
クロマトグラフにより測定したところ、二硫化メチル濃
度は０ｐｐｍであった。First, the silica gel molded body obtained in a Tedlar bag (volume: 5 L) was 5 cm × 5 cm × 0.5.
The piece cut into cm thickness was put in a petri dish made of glass and placed. While irradiating ultraviolet rays with 20 W black light from above the Tedlar bag, the concentration of methyl disulfide in the Tedlar bag was adjusted to 100 ppm, and after 3 hours, the concentration of methyl disulfide contained in the air in the bag was measured by gas chromatography. As a result, the methyl disulfide concentration was 0 ppm.
【００６４】［比較実施例７］参考実施例１で得られた
酸化チタン光触媒だけを含ませたシリカゲル成形体を用
いて環境物質の分解除去試験を行った。[Comparative Example 7] A decomposition and removal test of environmental substances was carried out using the silica gel molded body containing only the titanium oxide photocatalyst obtained in Reference Example 1.
【００６５】まず、テドラーバッグ（容積５Ｌ）の中に
得られた該シリカゲル成形体を５ｃｍ×５ｃｍ×０．５
ｃｍ厚に切断したものをガラス製シャーレに入れて置い
た。テドラーバッグの上方から２０Ｗブラックライトで
紫外線を照射しながら、テドラーバッグ内の二硫化メチ
ル濃度が１００ｐｐｍとなるように調製して、３時間後
にバッグ内の空気に含まれる二硫化メチル濃度をガスク
ロマトグラフにより測定したところ、二硫化メチル濃度
は３０ｐｐｍであった。このことから、本発明による酸
化チタン光触媒を担持したシリカゲル成形体には二硫化
メチルの分解除去効果が顕著に認められた。First, the silica gel molded body obtained in a Tedlar bag (volume: 5 L) was 5 cm × 5 cm × 0.5.
The piece cut into cm thickness was put in a petri dish made of glass and placed. While irradiating ultraviolet rays from above the Tedlar bag with 20 W black light, the concentration of methyl disulfide in the Tedlar bag was adjusted to 100 ppm, and after 3 hours, the concentration of methyl disulfide contained in the air in the bag was measured by gas chromatography. As a result, the methyl disulfide concentration was 30 ppm. From this fact, the effect of decomposing and removing methyl disulfide was remarkably recognized in the silica gel molded body carrying the titanium oxide photocatalyst according to the present invention.
【００６６】［実施例８］参考実施例１で得られた酸化
チタン光触媒を含ませたシリカゲル成形体を１重量％水
酸化鉄水溶液（希硝酸に水酸化鉄を溶解）に３時間浸漬
した後、当該シリカゲル成形体を３重量％水酸化ナトリ
ウム水溶液に１時間浸漬してから、再度１２０℃で３時
間乾燥して、酸化チタン光触媒と水酸化鉄を含んだ本発
明による酸化チタン光触媒を担持したシリカゲル成形体
を得た。Example 8 The silica gel molded body containing the titanium oxide photocatalyst obtained in Reference Example 1 was immersed in a 1 wt% iron hydroxide aqueous solution (iron hydroxide was dissolved in dilute nitric acid) for 3 hours. The silica gel molded body was immersed in a 3 wt% sodium hydroxide aqueous solution for 1 hour and then dried again at 120 ° C. for 3 hours to support the titanium oxide photocatalyst and the titanium oxide photocatalyst according to the present invention containing iron hydroxide. A silica gel molded body was obtained.
【００６７】得られた本発明による酸化チタン光触媒を
担持したシリカゲル成形体を用いて環境物質の分解除去
試験を行った。Using the obtained silica gel molded article carrying the titanium oxide photocatalyst of the present invention, a decomposition and removal test of environmental substances was conducted.
【００６８】まず、テドラーバッグ（容積５Ｌ）の中に
得られた該シリカゲル成形体を５ｃｍ×５ｃｍ×０．５
ｃｍ厚に切断したものをガラス製シャーレに入れて置い
た。テドラーバッグの上方から２０Ｗブラックライトで
紫外線を照射しながら、テドラーバッグ内のスチレン濃
度が１００ｐｐｍとなるように調製した後、３時間後に
バッグ内の空気に含まれるスチレン濃度をガスクロマト
グラフにより測定したところ、スチレン濃度は０ｐｐｍ
であった。First, the silica gel molded body obtained in a Tedlar bag (volume: 5 L) was 5 cm × 5 cm × 0.5.
The piece cut into cm thickness was put in a petri dish made of glass and placed. While irradiating ultraviolet rays from above the Tedlar bag with 20 W black light, the styrene concentration in the Tedlar bag was adjusted to 100 ppm, and after 3 hours, the styrene concentration in the air in the bag was measured by gas chromatography. The concentration is 0ppm
Met.
【００６９】［比較実施例８］参考実施例１で得られた
酸化チタン光触媒だけを含ませたシリカゲル成形体を用
いて環境物質の分解除去試験を行った。[Comparative Example 8] Using the silica gel molded body containing only the titanium oxide photocatalyst obtained in Reference Example 1, a decomposition and removal test of environmental substances was conducted.
【００７０】まず、テドラーバッグ（容積５Ｌ）の中に
得られた該シリカゲル成形体を５ｃｍ×５ｃｍ×０．５
ｃｍ厚に切断したものをガラス製シャーレに入れて置い
た。テドラーバッグの上方から２０Ｗブラックライトで
紫外線を照射しながら、テドラーバッグ内のスチレン濃
度が１００ｐｐｍとなるように調製して、３時間後にバ
ッグ内の空気に含まれるスチレン濃度をガスクロマトグ
ラフにより測定したところ、スチレン濃度は３２ｐｐｍ
であった。このことから、本発明による酸化チタン光触
媒を担持したシリカゲル成形体にはスチレンの分解除去
効果が顕著に認められた。First, the silica gel molded body obtained in a Tedlar bag (volume: 5 L) was 5 cm × 5 cm × 0.5.
The piece cut into cm thickness was put in a petri dish made of glass and placed. While irradiating ultraviolet rays from above the Tedlar bag with 20 W black light, the styrene concentration in the Tedlar bag was adjusted to 100 ppm, and after 3 hours, the styrene concentration contained in the air in the bag was measured by gas chromatography. The concentration is 32 ppm
Met. From this fact, the effect of decomposing and removing styrene was remarkably recognized in the silica gel molded article carrying the titanium oxide photocatalyst according to the present invention.
【００７１】[0071]
【発明の効果】本発明による酸化チタン光触媒を担持し
たシリカゲル成形体は、取扱いも容易で、分解対象とす
るガスの種類に応じて吸着特性が変えられることから、
空気中の悪臭や有害物質を多量に吸着でき、従来のもの
よりも、迅速にかつ効率よく分解除去できる。EFFECTS OF THE INVENTION The silica gel molded article carrying the titanium oxide photocatalyst according to the present invention is easy to handle, and its adsorption property can be changed according to the kind of gas to be decomposed.
It can adsorb a large amount of bad odors and harmful substances in the air, and can decompose and remove it faster and more efficiently than conventional ones.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｂ０１Ｊ 23/26 Ｂ０１Ｊ 23/72 Ａ 23/34 27/182 Ａ 23/72 27/232 23/745 Ｃ０１Ｂ 33/14 27/182 Ｂ０１Ｄ 53/36 Ｇ 27/232 Ｈ Ｃ０１Ｂ 33/14 １０２Ｄ Ｂ０１Ｊ 23/74 ３０１Ａ (72)発明者 山田 善市 愛知県豊川市穂ノ原３丁目１番地 新東ブ イセラックス株式会社内 Ｆターム(参考） 4D048 AA06 AA17 AA22 AB03 BA02X BA06X BA07X BA14X BA16X BA18X BA25X BA28X BA35X BA36X BA41X BA44X EA01 EA04 4G069 AA03 AA08 BA02A BA02B BA04A BA04B BA48A BB05B BB14B BB16B BC02B BC09B BC31B BC35B BC42B BC58B BC62B BC66B CA10 CA11 CA13 CA17 DA06 EA11 EC12X EC13X EC14X FA02 FB14 4G072 AA28 AA37 BB05 BB15 CC10 DD03 KK09 QQ02 TT08 UU15─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 7 Identification code FI theme code (reference) B01J 23/26 B01J 23/72 A 23/34 27/182 A 23/72 27/232 23/745 C01B 33 / 14 27/182 B01D 53/36 G 27/232 H C01B 33/14 102D B01J 23/74 301A (72) Inventor Yoshida Yamada 3-1-1 Honohara, Toyokawa City, Aichi Prefecture Shinto Busselax Co., Ltd. F-term (Reference) 4D048 AA06 AA17 AA22 AB03 BA02X BA06X BA07X BA14X BA16X BA18X BA25X BA28X BA35X BA36X BA41X BA44X EA01 EA04 EA01 CA02 BC02 BC14 BC58B13B13B6B6B6B6B6B6B11B6B11B6B11B6B11B6B6B6B6B6B6B6B11B6B11B6B6B6B6B6B6B6B6B11B6B11B6B11B6B11B6B11B6B11B6B11B6B11B6B11B6B11B6B11B6B11B6B11B6B11B6B11B6B11B6B11B11B6B11B6B11B11B11B4B11B11B11B11B11B11B11B02B11B11B02B11B11B02B11B11B11 but also FA02 FB14 4G072 AA28 AA37 BB05 BB15 CC10 DD03 KK09 QQ02 TT08 UU15
Claims (2)
るシリカゲルから主として成る成形体の細孔内にアルカ
リ金属化合物、銅族元素化合物、アルカリ土金属化合
物、亜鉛族元素化合物、土類元素化合物、クロム族元素
化合物、マンガン族元素化合物、鉄族元素化合物の少な
くとも一種と酸化チタンを１〜７０重量％含ませたこと
を特徴とする酸化チタン光触媒を担持したシリカゲル成
形体。1. An alkali metal compound, a copper group element compound, an alkaline earth metal compound, a zinc group element compound, an earth element compound in the pores of a molded body mainly composed of silica gel having an average pore size of 6 to 100 nm. A silica gel molded article carrying a titanium oxide photocatalyst, comprising at least one of a chromium group element compound, a manganese group element compound and an iron group element compound and 1 to 70% by weight of titanium oxide.
るシリカゲルから主として成る成形体の細孔内に、チタ
ン含有溶液を含ませてから加熱焼成し、当該シリカゲル
成形体の細孔内に酸化チタンを１〜７０重量％含ませた
後、溶媒に可溶なアルカリ金属化合物、銅族元素化合
物、アルカリ土金属化合物、亜鉛族元素化合物、土類元
素化合物、クロム族元素化合物、マンガン族元素化合
物、鉄族元素化合物のうちから選ばれた少なくとも一種
を含む溶液を当該シリカゲル成形体に含ませてから溶媒
を除去することを特徴とする酸化チタン光触媒を担持し
たシリカゲル成形体の製造方法。2. A titanium-containing solution is contained in the pores of a molded article mainly composed of silica gel having an average pore size of 6 to 100 nm, and the mixture is heated and baked to oxidize the pores of the silica gel molded article. After containing 1 to 70% by weight of titanium, a solvent-soluble alkali metal compound, copper group element compound, alkaline earth metal compound, zinc group element compound, earth element compound, chromium group element compound, manganese group element compound A method for producing a silica gel molded body carrying a titanium oxide photocatalyst, characterized in that a solvent containing at least one selected from iron group element compounds is included in the silica gel molded body, and then the solvent is removed.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001345770A JP2003144937A (en) | 2001-11-12 | 2001-11-12 | Silica gel molded body carried with titanium oxide photocatalyst and manufacturing method therefor |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001345770A JP2003144937A (en) | 2001-11-12 | 2001-11-12 | Silica gel molded body carried with titanium oxide photocatalyst and manufacturing method therefor |
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| Publication Number | Publication Date |
|---|---|
| JP2003144937A true JP2003144937A (en) | 2003-05-20 |
Family
ID=19159055
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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| JP (1) | JP2003144937A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100387336C (en) * | 2005-10-09 | 2008-05-14 | 天津大学 | Method for preparing nano-catalyst of Cu2+/TiO2-SiO2 |
| CN100532486C (en) * | 2006-03-31 | 2009-08-26 | 中国科学院过程工程研究所 | Adhesive for absorbing formol |
| JP2010063979A (en) * | 2008-09-09 | 2010-03-25 | Totoku Electric Co Ltd | Method for manufacturing photocatalyst fiber |
| JP2010213655A (en) * | 2009-03-18 | 2010-09-30 | Daicel Chem Ind Ltd | Cigarette filter material, and cigarette filter using the same |
| CN103694815A (en) * | 2013-12-06 | 2014-04-02 | 华阳新兴科技（天津）集团有限公司 | Scrapable formaldehyde closed film and preparation method thereof |
| JP2015145854A (en) * | 2014-02-04 | 2015-08-13 | 日本電子株式会社 | Manufacturing method of staining agent for electron microscope observation, staining method of sample for electron microscope observation, and stock solution of the staining agent for electron microscope observation |
| CN106435237A (en) * | 2016-09-20 | 2017-02-22 | 天津大学 | Preparation method of nano titania reinforced copper-based composite material |
| KR102501315B1 (en) | 2022-09-20 | 2023-02-22 | 한국건설기술연구원 | Method for manufacturing highly porous silica photo catalyst including iron oxide and manganese oxide, and method for removing synthetic organic chemicals in aqua using the same |
-
2001
- 2001-11-12 JP JP2001345770A patent/JP2003144937A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100387336C (en) * | 2005-10-09 | 2008-05-14 | 天津大学 | Method for preparing nano-catalyst of Cu2+/TiO2-SiO2 |
| CN100532486C (en) * | 2006-03-31 | 2009-08-26 | 中国科学院过程工程研究所 | Adhesive for absorbing formol |
| JP2010063979A (en) * | 2008-09-09 | 2010-03-25 | Totoku Electric Co Ltd | Method for manufacturing photocatalyst fiber |
| JP2010213655A (en) * | 2009-03-18 | 2010-09-30 | Daicel Chem Ind Ltd | Cigarette filter material, and cigarette filter using the same |
| CN103694815A (en) * | 2013-12-06 | 2014-04-02 | 华阳新兴科技（天津）集团有限公司 | Scrapable formaldehyde closed film and preparation method thereof |
| JP2015145854A (en) * | 2014-02-04 | 2015-08-13 | 日本電子株式会社 | Manufacturing method of staining agent for electron microscope observation, staining method of sample for electron microscope observation, and stock solution of the staining agent for electron microscope observation |
| CN106435237A (en) * | 2016-09-20 | 2017-02-22 | 天津大学 | Preparation method of nano titania reinforced copper-based composite material |
| KR102501315B1 (en) | 2022-09-20 | 2023-02-22 | 한국건설기술연구원 | Method for manufacturing highly porous silica photo catalyst including iron oxide and manganese oxide, and method for removing synthetic organic chemicals in aqua using the same |
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