JPH05261284A - Catalyst for water treatment and its production - Google Patents
Catalyst for water treatment and its productionInfo
- Publication number
- JPH05261284A JPH05261284A JP4092265A JP9226592A JPH05261284A JP H05261284 A JPH05261284 A JP H05261284A JP 4092265 A JP4092265 A JP 4092265A JP 9226592 A JP9226592 A JP 9226592A JP H05261284 A JPH05261284 A JP H05261284A
- Authority
- JP
- Japan
- Prior art keywords
- metal
- oxide
- platinum group
- catalyst
- water treatment
- 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
- 239000003054 catalyst Substances 0.000 title claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 60
- 239000002184 metal Substances 0.000 claims abstract description 58
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 33
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000004703 alkoxides Chemical class 0.000 claims abstract description 13
- 229920005989 resin Polymers 0.000 claims abstract description 10
- 239000011347 resin Substances 0.000 claims abstract description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 9
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011521 glass Substances 0.000 claims abstract description 6
- 230000001590 oxidative effect Effects 0.000 claims abstract description 6
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 229920000592 inorganic polymer Polymers 0.000 claims abstract description 4
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 4
- 239000000919 ceramic Substances 0.000 claims abstract 3
- 239000000463 material Substances 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- 239000010955 niobium Substances 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910001510 metal chloride Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 2
- 239000010953 base metal Substances 0.000 claims 1
- 239000007800 oxidant agent Substances 0.000 claims 1
- 229910052703 rhodium Inorganic materials 0.000 claims 1
- 239000010948 rhodium Substances 0.000 claims 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims 1
- -1 platinum group metals Chemical class 0.000 abstract description 8
- 239000000460 chlorine Substances 0.000 abstract description 2
- 238000007598 dipping method Methods 0.000 abstract description 2
- 238000005470 impregnation Methods 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 abstract 2
- 238000000576 coating method Methods 0.000 abstract 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 229910052801 chlorine Inorganic materials 0.000 abstract 1
- 150000001805 chlorine compounds Chemical class 0.000 abstract 1
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 150000004045 organic chlorine compounds Chemical class 0.000 description 7
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 239000000499 gel Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000005357 flat glass Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical group [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-M Glycolate Chemical compound OCC([O-])=O AEMRFAOFKBGASW-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 150000004683 dihydrates Chemical class 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011224 oxide ceramic Substances 0.000 description 2
- 229910052574 oxide ceramic Inorganic materials 0.000 description 2
- 238000002256 photodeposition Methods 0.000 description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 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
- 239000002351 wastewater Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229940005989 chlorate ion Drugs 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- VTIFZEWTSPUKPP-UHFFFAOYSA-L dichloroplatinum pentahydrate Chemical compound O.O.O.O.O.[Pt](Cl)Cl VTIFZEWTSPUKPP-UHFFFAOYSA-L 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
- 238000001035 drying Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000011494 foam glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、水処理用触媒に関する
ものであり、特に飲料水や排水に含まれる次亜塩素酸塩
や有機塩素化合物等の化合物の分解において優れている
水処理用触媒及びその製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water treatment catalyst, and particularly to a water treatment catalyst which is excellent in decomposing compounds such as hypochlorite and organic chlorine compounds contained in drinking water and waste water. And a manufacturing method thereof.
【０００２】[0002]
【従来技術及び発明が解決しようとする課題】今日、水
中に含まれる次亜塩素酸塩や有機塩素化合物等の化合物
を低減化処理する技術がいくつか知られているが、従来
の技術としては、粒状、粉末状あるいは繊維状の活性炭
を用いて吸着処理するものが主流であつた。しかしなが
ら、活性炭は、吸着量に限界があつて、長期に亘る連続
使用ができず、交換等のメンテナンスが頻繁に必要にな
るという問題がある。2. Description of the Related Art Today, some techniques for reducing compounds such as hypochlorite and organic chlorine compounds contained in water are known. The mainstream method is adsorption treatment using granular, powdery or fibrous activated carbon. However, activated carbon has a problem in that it has a limited adsorption amount, cannot be used continuously for a long period of time, and requires frequent maintenance such as replacement.
【０００３】これに対し、化学的に安定で長期に亘る連
続使用に耐えられるものとして、金属酸化物や貴金属担
持した金属酸化物からなる触媒を単独またはこれらの混
合、さらには活性炭等の他触媒と併用して次亜塩素酸塩
や有機塩素化合物等の化合物を光や熱等で分解処理する
ことが提唱されている。この様な触媒として、例えば、
ものとして、特開昭６３−１３０１４１号公報、特開平
３−１９３１９１号公報が知られている。On the other hand, as a catalyst that is chemically stable and can withstand continuous use over a long period of time, a catalyst composed of a metal oxide or a metal oxide carrying a noble metal is used alone or in a mixture thereof, and other catalysts such as activated carbon are used. It has been proposed that a compound such as a hypochlorite or an organic chlorine compound be decomposed by light or heat in combination with. As such a catalyst, for example,
Japanese Patent Laid-Open No. 63-130141 and Japanese Patent Laid-Open No. 3-193191 are known.
【０００４】前者のものは、白金族金属酸化物を含む金
属酸化物からなる分解触媒に関するものであるが、この
種の触媒では、白金族金属酸化物の粒子の微細さや分散
状態によつて触媒性能が大きく左右されるものである。
しかしながらこのものは、触媒製造をする際の乾燥過程
において、高分散状態である金属塩が酸化性雰囲気中で
加熱する焼成過程で凝集し、この結果、粒径が比較的大
きく、しかも不均一な金属酸化物になつてしまう欠点が
あり、前述した触媒性能に対する影響が大きいものにな
る。The former relates to a decomposition catalyst composed of a metal oxide containing a platinum group metal oxide. In this type of catalyst, the catalyst is determined by the fineness and dispersion state of the particles of the platinum group metal oxide. Performance is greatly affected.
However, this is because the metal salt in a highly dispersed state agglomerates in the baking process of heating in an oxidizing atmosphere in the drying process in the catalyst production, resulting in a relatively large particle size and non-uniformity. There is a drawback that it becomes a metal oxide, which greatly affects the above-mentioned catalyst performance.
【０００５】また、後者のものは、白金等の貴金属を担
持した酸化チタンなどの金属酸化物を成分とする光触媒
に関するものであるが、このものでは、光電析法により
白金等の貴金属を酸化チタン等の金属酸化物上に担持さ
せる必要がある。しかしながら、光電析法では、金属酸
化物の光照射された細孔部位にのみ貴金属が担持される
ものであるため、光照射されない金属酸化物の細孔部位
には貴金属が担持されないことになつて、金属酸化物上
の貴金属の分散性が悪く触媒性能が低下するという問題
があり、信頼性の高い安定したものを提供することが難
しい。The latter relates to a photocatalyst containing a metal oxide such as titanium oxide carrying a noble metal such as platinum as a component. In this case, the noble metal such as platinum is converted into titanium oxide by a photo-deposition method. It is necessary to support it on a metal oxide such as. However, in the photodeposition method, the noble metal is supported only on the light-irradiated pores of the metal oxide, so that the noble metal is not supported on the light-irradiated pores of the metal oxide. However, there is a problem that the dispersibility of the noble metal on the metal oxide is poor and the catalytic performance is deteriorated, and it is difficult to provide a reliable and stable product.
【０００６】[0006]
【課題を解決するための手段】本発明は、上記の如き実
情に鑑みこれらの欠点を一掃することができる水処理用
触媒及びその製造方法を提供することを目的として創案
されたものであつて、一つの発明は、白金族金属または
その酸化物を超高分散担持させた多孔質組織の担体金属
酸化物を母材にコートしてなることを特徴とする水処理
用触媒である。また、別の発明は、白金族金属の塩化物
と金属アルコキシドを溶解させたゾルに母材をデイツプ
して含浸させた後、白金族金属−酸素−担体金属なる構
造の無機高分子を含有するゲルとし、これを、酸化性雰
囲気で加熱して白金族金属の酸化物を担持させた金属酸
化物とするか、または酸化性雰囲気で加熱後、還元処理
して白金族金属の酸化物のみを還元し、白金族金属を担
持させた金属酸化物とすることを特徴とする水処理用触
媒の製造方法である。SUMMARY OF THE INVENTION The present invention was devised with the object of providing a catalyst for water treatment and a method for producing the same, which can eliminate these drawbacks in view of the above-mentioned circumstances. According to one aspect of the present invention, there is provided a water treatment catalyst characterized in that a base material is coated with a carrier metal oxide having a porous structure in which a platinum group metal or an oxide thereof is carried in an ultrahigh dispersion. Another aspect of the present invention is to include an inorganic polymer having a structure of platinum group metal-oxygen-support metal after dipping and impregnating a base material in a sol in which a chloride of a platinum group metal and a metal alkoxide are dissolved. A gel, which is heated in an oxidizing atmosphere to form a metal oxide supporting a platinum group metal oxide, or heated in an oxidizing atmosphere and then subjected to a reduction treatment to remove only the platinum group metal oxide. A method for producing a water treatment catalyst, which comprises reducing the metal oxide to carry a platinum group metal.
【０００７】さらに詳しくは、本発明は金属アルコキシ
ド法を用いることにより、優れた比活性を示す多孔質で
超高分散の担持金属触媒を製造できるということに着目
し、金属アルコキシド法により、次亜塩素酸塩及び有機
塩素化合物の分解に優れている触媒が得られるという知
見に基づいてなされたものである。More specifically, the present invention focuses on the fact that a porous and ultrahighly dispersed supported metal catalyst exhibiting an excellent specific activity can be produced by using the metal alkoxide method. It was made based on the finding that a catalyst excellent in decomposition of chlorate and organic chlorine compounds can be obtained.
【０００８】次に、本発明を構成要素ごとに説明する。 ［白金族金属またはその酸化物］本発明で使用される白
金族金属またはその酸化物の金属元素としては、Ｒｕ
（ルテニウム）、Ｉｒ（イリジウム）、Ｐｄ（パラジウ
ム）及びＰｔ（白金）の白金族金属から選ばれる一種類
または複数種類のものである。これらの白金族金属また
はその酸化物は、本発明における活性成分であり、次亜
塩素酸塩及び有機塩素化合物の分解に優れた活性を示す
ものである。特に、Ｐｔについては、これを酸化チタン
に超高分散担持させることにより、有機塩素化合物の優
れた光分解触媒となる。ここで、白金族金属としては、
金属自体でも金属酸化物と同様、充分な活性を示すが、
水中での安定性を考慮したときには、酸化物にすること
が好ましい。Next, the present invention will be described for each component. [Platinum group metal or oxide thereof] The metal element of the platinum group metal or oxide thereof used in the present invention is Ru.
(Ruthenium), Ir (iridium), Pd (palladium), and Pt (platinum). These platinum group metals or oxides thereof are the active ingredients in the present invention and exhibit excellent activity for decomposing hypochlorite and organic chlorine compounds. Particularly, when Pt is carried on titanium oxide in an extremely high dispersion, it becomes an excellent photolysis catalyst for organic chlorine compounds. Here, as the platinum group metal,
The metal itself shows sufficient activity as well as the metal oxide,
Considering the stability in water, it is preferable to use an oxide.
【０００９】［担体金属酸化物］本発明で使用される白
金族金属またはその酸化物を担持させるための担体金属
酸化物の金属元素としては、Ａｌ（アルミニウム）、Ｓ
ｉ（珪素）、Ｔｉ（チタン）、Ｆｅ（鉄）、Ｃｏ（コバ
ルト）、Ｎｉ（ニツケル）、Ｚｎ（亜鉛）、Ｚｒ（ジル
コニウム）、Ｎｂ（ニオブ）、Ｓｎ（スズ）、Ｔａ（タ
ンタル）及びＷ（タングステン）から選ばれる一種類ま
たは複数種類のものである。そして、これらの金属元素
は、安定な金属酸化物を形成し、水中でも安定的に存在
することになる。また、これらの金属酸化物は、金属ア
ルコキシド法によつて製造されるため、多孔質組織であ
る。[Carrier Metal Oxide] The metal elements of the carrier metal oxide for supporting the platinum group metal or its oxide used in the present invention include Al (aluminum) and S.
i (silicon), Ti (titanium), Fe (iron), Co (cobalt), Ni (nickel), Zn (zinc), Zr (zirconium), Nb (niobium), Sn (tin), Ta (tantalum) and One or more kinds selected from W (tungsten). Then, these metal elements form a stable metal oxide and stably exist in water. Further, since these metal oxides are produced by the metal alkoxide method, they have a porous structure.
【００１０】［母材］本発明で使用される母材として
は、酸化物系セラミツクス、ガラス、活性炭、樹脂及び
金属から選ばれる一種類または複数種類のものである。
酸化物系セラミツクスとしては、シリカゲル、ゼオライ
ト、シリカ、アルミナ、チタニアなどを例示することが
できる。ガラスとしては、板ガラス、泡ガラス、ガラス
繊維などを例示することができる。活性炭としては、粒
状、粉末状、あるいは繊維状の活性炭などを例示するこ
とができる。金属としては、耐食性のステンレス、チタ
ン、ニツケル、アルミニウムなどを例示することができ
る。さらに、樹脂としては、金属酸化物との接着性が優
れた極性の高い樹脂が好ましく、アクリル樹脂、塩化ビ
ニル樹脂、ＡＢＳ樹脂、ポリアミド樹脂、ポリカーボネ
ート樹脂、ポリアセタール樹脂、ポリスチレン樹脂、不
飽和ポリエステル樹脂、フエノール樹脂、ポリエステル
樹脂などの熱可塑性あるいは熱硬化性樹脂を例示するこ
とができる。なお、母材としては、小粒径であつたり多
孔質であつたりして表面積の大きいものほど適してい
る。[Base Material] The base material used in the present invention is one or more kinds selected from oxide ceramics, glass, activated carbon, resin and metal.
Examples of oxide ceramics include silica gel, zeolite, silica, alumina, titania, and the like. Examples of glass include plate glass, foam glass, and glass fiber. Examples of the activated carbon include granular, powdery or fibrous activated carbon. Examples of the metal include corrosion resistant stainless steel, titanium, nickel and aluminum. Further, as the resin, a highly polar resin having excellent adhesiveness with a metal oxide is preferable, and an acrylic resin, a vinyl chloride resin, an ABS resin, a polyamide resin, a polycarbonate resin, a polyacetal resin, a polystyrene resin, an unsaturated polyester resin, Examples thereof include thermoplastic or thermosetting resins such as phenol resin and polyester resin. In addition, as the base material, a material having a large surface area such as a small particle diameter or a porous material is more suitable.
【００１１】本発明の触媒を製造するには、金属アルコ
キシド法を用いる。本方法では白金族金属の塩化物を、
２価アルコールに溶解させ、白金族金属の金属グリコレ
ートを調整した後、担体成分である金属元素を含有する
金属アルコキシドを混合し、水及び酸を添加してできた
ゾルに母材をデイツプして、含浸した後、８０〜１２０
℃で乾燥させ、母材表面でゲル化させる。得られたゲル
中には、白金族金属−酸素−担体金属という構造を持つ
た無機高分子が存在している。このように化学結合され
た白金族金属は固定化されており、酸化性雰囲気下、３
００〜４００℃で加熱する焼成過程においても移動でき
ないものとなる。その結果、焼成後は微細な白金族金属
の酸化物クラスターとして担体である金属酸化物中に高
分散状態で存在することになる。従つて、これを水素雰
囲気下中、約７００℃での加熱還元処理により、高分散
状態の白金族金属を含む金属酸化物を得ることができ
る。The metal alkoxide method is used to produce the catalyst of the present invention. In this method, the platinum group metal chloride is
After dissolving in a dihydric alcohol to adjust the metal glycolate of the platinum group metal, a metal alkoxide containing a metal element as a carrier component is mixed, and a base material is dipped into a sol formed by adding water and an acid. After impregnation, 80-120
Dry at ℃ and gel on the surface of the base material. In the obtained gel, an inorganic polymer having a structure of platinum group metal-oxygen-support metal is present. The platinum group metal chemically bonded in this way is fixed and is kept in an oxidizing atmosphere for 3 days.
It cannot move even in the firing process of heating at 00 to 400 ° C. As a result, after firing, they will be present in a highly dispersed state in the metal oxide as a carrier as fine platinum group metal oxide clusters. Therefore, a metal oxide containing a platinum group metal in a highly dispersed state can be obtained by subjecting this to a heat reduction treatment at about 700 ° C. in a hydrogen atmosphere.
【００１２】この様にして生成する担体の金属酸化物は
多孔質となる。ここで、母材に樹脂を用いた場合は、前
記ゾルにデイツプ・含浸後、８０〜１２０℃で乾燥させ
ゲル化させるだけでよい。白金族金属の塩化物として
は、ＲｕＣｌ3・ｎＨ2Ｏ（塩化ルテニウムの水和物）、
ＲｈＣｌ4・３Ｈ2Ｏ（塩化ロジウムの水和物）ＰｔＣｌ
4・５Ｈ2Ｏ（塩化白金の水和物）、Ｈ2ＰｔＣｌ6（水素
化塩化白金）、ＩｒＣｌ4（塩化イリジウム）を挙げる
ことができる。２価アルコールとしてはエチレングリコ
ール、１，３−ブタンジオールなどを挙げることができ
る。さらに、２価アルコールは白金族金属の塩化物と反
応して、白金族金属の金属グリコレートを調整するため
のものであると共に、金属アルコキシドが水によつて加
水分解される際に急激にゲル化することを防止するため
のもの、そのほか加水分解物の縮合反応を調節しながら
水分を除去するためのものでもある。また、水は金属ア
ルコキシドを加水分解させるためのもので、水和してい
る白金族金属の塩化物を用いた場合には、この水和して
いる水を用いることができ、さらに別途、必要に応じて
添加することもできる。The metal oxide of the carrier thus produced becomes porous. Here, when a resin is used as the base material, it is sufficient that the sol is dipped and impregnated and then dried at 80 to 120 ° C. for gelation. As the chloride of the platinum group metal, RuCl 3 · nH 2 O (hydrate of ruthenium chloride),
RhCl 4 · 3H 2 O (dihydrate of rhodium chloride) PtCl
4 · 5H 2 O (dihydrate of chloroplatinic), H 2 PtCl 6 (hydrogenated chloroplatinic), mention may be made of IrCl 4 (iridium chloride). Examples of the dihydric alcohol include ethylene glycol and 1,3-butanediol. Further, the dihydric alcohol reacts with the chloride of the platinum group metal to adjust the metal glycolate of the platinum group metal, and rapidly gels when the metal alkoxide is hydrolyzed by water. It also prevents the formation of water, and also removes water while controlling the condensation reaction of the hydrolyzate. Further, water is used to hydrolyze the metal alkoxide, and when hydrated platinum group metal chloride is used, this hydrated water can be used, and it is necessary separately. It can also be added according to.
【００１３】また、酸は金属アルコキシドの加水分解触
媒として使用されるもので、硝酸、塩酸、酢酸、硫酸、
フツ酸、マレイン酸などの無機酸及び有機酸を挙げるこ
とができる。さらに、金属アルコキシドとしては、Ａｌ
（ｉ−ＯＣ3Ｈ7）3、Ｓｉ（ＯＣ2Ｈ5）4、Ｔｉ（ｉ−Ｏ
Ｃ3Ｈ7）4、Ｆｅ（ｉ−ＯＣ3Ｈ7）3、Ｃｏ（ＯＣ
Ｈ3）2、Ｎｉ（ＯＣＨ3）2、Ｚｎ（ＯＣ2Ｈ5）2、Ｚｒ
（ＯＣＨ3）4、Ｎｂ（ｉ−ＯＣ3Ｈ7）5、Ｓｎ（ＯＣ2Ｈ
5）2、Ｔｄ（ＯＣ3Ｈ7）5、Ｗ（ＯＣ2Ｈ5）6などを挙げ
ることができる。Acids are used as a hydrolysis catalyst for metal alkoxides, and include nitric acid, hydrochloric acid, acetic acid, sulfuric acid,
Inorganic and organic acids such as hydrofluoric acid and maleic acid can be mentioned. Further, as the metal alkoxide, Al
(I-OC 3 H 7) 3, Si (OC 2 H 5) 4, Ti (i-O
C 3 H 7) 4, Fe (i-OC 3 H 7) 3, Co (OC
H 3) 2, Ni (OCH 3) 2, Zn (OC 2 H 5) 2, Zr
(OCH 3) 4, Nb ( i-OC 3 H 7) 5, Sn (OC 2 H
5 ) 2 , Td (OC 3 H 7 ) 5 , W (OC 2 H 5 ) 6 and the like.
【００１４】[0014]
【発明の効果】本発明の触媒は、多孔質で超高分散の担
持白金族金属系触媒であり、水中での安定性に優れ、比
活性に優れているため、飲料水や排水に含まれる次亜塩
素酸塩及び有機塩素化合物を短時間で効率的に分解でき
る。INDUSTRIAL APPLICABILITY The catalyst of the present invention is a porous and ultra-highly dispersed supported platinum group metal-based catalyst, which has excellent stability in water and excellent specific activity, and therefore is contained in drinking water and waste water. It can decompose hypochlorite and organic chlorine compounds efficiently in a short time.
【００１５】実施例１ ルテニウム元素として０．０３モル（ｍｏｌ）を含む塩
化ルテニウムの水和物を１５０ミリリツトル（ｍｌ）の
１，３−ブタンジオールに溶解させ、シリコンテトラエ
トキシド３０ｍｌと硝酸３ｍｌを添加して調整する。こ
のゾルを室温で３時間撹拌した後、直径３ミリメータ
（ｍｍ）のアルミナ球（比表面積２９８平方メートル／
グラム（ｍ2／ｇ）平均細孔径４５オングストローム
（Å））を１分間、デイツプし、その後、水蒸気中に放
置し、アルミナ球の表面でゲル化させる。これを１１０
℃で１２時間乾燥し、次いで、４００℃で４時間焼成さ
せて、ルテニウム元素として、０．４重量パーセント
（ｗｔ％）の担持率であるＲｕＯ2／ＳｉＯ2／Ａｌ2Ｏ3
触媒を得た。この様にして得られた触媒２．５ｇを、濃
度１０ｍｇ／ｌの次亜塩素酸塩ナトリウム水溶液の１リ
ツトル（ｌ）に入れ、室温で３０分間撹拌した後、液体
を濾過して触媒と分離した。そして、分離した液体につ
いて次亜塩素酸塩イオン濃度を測定したところ５ｍｇ／
ｌまで減少しているのが観測された。Example 1 A hydrate of ruthenium chloride containing 0.03 mol (mol) as ruthenium element was dissolved in 150 milliliter (ml) of 1,3-butanediol, and 30 ml of silicon tetraethoxide and 3 ml of nitric acid were dissolved. Add and adjust. After stirring this sol at room temperature for 3 hours, alumina spheres having a diameter of 3 millimeters (mm) (specific surface area 298 square meters /
Gram (m 2 / g) average pore size 45 Å (Å)) is dipped for 1 minute and then left in water vapor to gel on the surface of alumina spheres. 110 this
After being dried at 400 ° C. for 12 hours and then baked at 400 ° C. for 4 hours, RuO 2 / SiO 2 / Al 2 O 3 having a ruthenium element support rate of 0.4 weight percent (wt%).
A catalyst was obtained. 2.5 g of the catalyst thus obtained was placed in 1 liter (l) of a sodium hypochlorite aqueous solution having a concentration of 10 mg / l, stirred at room temperature for 30 minutes, and then the liquid was filtered to separate from the catalyst. did. Then, when the hypochlorite ion concentration of the separated liquid was measured, it was 5 mg /
It was observed to decrease to l.
【００１６】実施例２ 塩化白金の５水和物１２ｇを１５０ｍｌの１，３−ブタ
ンジオールに溶解させ、チタンイソプロポキシド３０ｍ
ｌと硝酸３ｍｌを添加して調整する。このゾルを室温で
３時間撹拌した後、厚さ１ｍｍの板ガラスをデイツプし
た後、水蒸気中に放置し、板ガラス表面でゲル化させ
る。これを１１０℃で３時間乾燥し、４００℃で４時間
焼成後、水素雰囲気中で７００℃、４時間還元して、Ｐ
ｔ／ＴｉＯ2／板ガラス触媒を得た。この様にして得ら
れた触媒付き板ガラス１００ｍｍ×１００ｍｍを濃度１
０ｍｇ／ｌの次亜塩素酸塩ナトリウム水溶液にトリハロ
メタンを約１００ピーピービー（ｐｐｂ）に調整した水
溶液の１ｌに入れ、１３ワツト（ｗ）の紫外線灯を用い
て紫外線照射しながら室温で３０分間撹拌した。この様
にして処理した水溶液について、トリハロメタンの検出
を常法に基づき試みたが検出されなかつた。また、塩素
酸塩イオン濃度は２ｍｇ／ｌまで減少していることが観
測された。Example 2 Platinum chloride pentahydrate (12 g) was dissolved in 150 ml of 1,3-butanediol, and titanium isopropoxide (30 m) was added.
1 and 3 ml of nitric acid are added to adjust. After stirring this sol at room temperature for 3 hours, a plate glass having a thickness of 1 mm is dipped and then left in water vapor to cause gelation on the surface of the plate glass. This is dried at 110 ° C. for 3 hours, calcined at 400 ° C. for 4 hours, then reduced in a hydrogen atmosphere at 700 ° C. for 4 hours, and then P
It was obtained t / TiO 2 / glass sheet catalyst. The catalyst-containing plate glass 100 mm × 100 mm thus obtained was concentrated to 1
Into 1 liter of 0 mg / l sodium hypochlorite aqueous solution containing trihalomethane adjusted to about 100 ppb, stir at room temperature for 30 minutes while irradiating with ultraviolet light using a 13 watt (w) ultraviolet lamp. did. In the aqueous solution treated in this manner, an attempt was made to detect trihalomethane based on a conventional method, but none was detected. It was also observed that the chlorate ion concentration had decreased to 2 mg / l.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０２Ｆ 1/58 Ａ 1/72 Ｚ 9045−4Ｄ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Office reference number FI technical display location C02F 1/58 A 1/72 Z 9045-4D
Claims (8)
担持させた多孔質組織の担体金属酸化物を母材にコート
してなることを特徴とする水処理用触媒。1. A catalyst for water treatment, characterized in that a base metal is coated with a carrier metal oxide having a porous structure in which a platinum group metal or an oxide thereof is carried in ultra-high dispersion.
リジウム、パラジウム及び白金から選ばれた少なくとも
１種の白金族金属またはその酸化物であることを特徴と
する請求項１記載の水処理用触媒。2. The catalyst for water treatment according to claim 1, wherein the metal or its oxide is at least one platinum group metal selected from ruthenium, iridium, palladium and platinum, or its oxide.
素、チタン、鉄、コバルト、ニツケル、亜鉛、ジルコニ
ウム、ニオブ、スズ、タンタル及びタングステンから選
ばれた少なくとも１種の金属の酸化物であることを特徴
とする請求項１または２記載の水処理用触媒。3. The carrier metal oxide is an oxide of at least one metal selected from aluminum, silicon, titanium, iron, cobalt, nickel, zinc, zirconium, niobium, tin, tantalum and tungsten. The water treatment catalyst according to claim 1 or 2.
活性炭、樹脂、金属から選ばれた少なくとも１種である
ことを特徴とする請求項１〜３いずれか１項記載の水処
理用触媒。4. The base material is an oxide-based ceramic, glass,
The water treatment catalyst according to any one of claims 1 to 3, which is at least one selected from activated carbon, resin, and metal.
を溶解させたゾルに母材をデイツプして含浸させた後、
白金族金属−酸素−担体金属なる構造の無機高分子を含
有するゲルとし、これを、酸化性雰囲気で加熱して白金
族金属の酸化物を担持させた金属酸化物とするか、また
は酸化性雰囲気で加熱後、還元処理して白金族金属の酸
化物のみを還元し、白金族金属を担持させた金属酸化物
とすることを特徴とする水処理用触媒の製造方法。5. A sol in which a chloride of a platinum group metal and a metal alkoxide are dissolved is dipped and impregnated with a base material,
A gel containing an inorganic polymer having a structure of platinum group metal-oxygen-supporting metal, which is heated in an oxidizing atmosphere to be a metal oxide carrying an oxide of a platinum group metal, or an oxidizing agent A method for producing a catalyst for water treatment, which comprises heating after heating in an atmosphere and then reducing it to reduce only an oxide of a platinum group metal to obtain a metal oxide carrying a platinum group metal.
イリジウム、ロジウム及び白金から選ばれた少なくとも
１種の白金族金属の塩化物であることを特徴とする請求
項５記載の水処理用触媒の製造方法。6. The metal chloride is ruthenium, palladium,
The method for producing a water treatment catalyst according to claim 5, which is a chloride of at least one platinum group metal selected from iridium, rhodium and platinum.
素、チタン、鉄、コバルト、ニツケル、亜鉛、ジルコニ
ウム、ニオブ、スズ、タンタル及びタングステンから選
ばれた少なくとも１種の金属の金属アルコキシドである
ことを特徴とする請求項５または６記載の水処理用触媒
の製造方法。7. The metal alkoxide is a metal alkoxide of at least one metal selected from aluminum, silicon, titanium, iron, cobalt, nickel, zinc, zirconium, niobium, tin, tantalum and tungsten. The method for producing the water treatment catalyst according to claim 5 or 6.
活性炭、樹脂、金属から選ばれた少なくとも１種である
ことを特徴とする請求項５〜７いずれか１項記載の水処
理用触媒の製造方法。8. The base material is an oxide-based ceramic, glass,
It is at least 1 sort (s) chosen from activated carbon, resin, and metal, The manufacturing method of the catalyst for water treatment of any one of Claims 5-7 characterized by the above-mentioned.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4092265A JPH05261284A (en) | 1992-03-18 | 1992-03-18 | Catalyst for water treatment and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4092265A JPH05261284A (en) | 1992-03-18 | 1992-03-18 | Catalyst for water treatment and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05261284A true JPH05261284A (en) | 1993-10-12 |
Family
ID=14049573
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4092265A Pending JPH05261284A (en) | 1992-03-18 | 1992-03-18 | Catalyst for water treatment and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05261284A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0866635A (en) * | 1993-12-14 | 1996-03-12 | Toto Ltd | Photocatalytic thin film and its formation |
| WO2001080993A1 (en) * | 2000-04-20 | 2001-11-01 | Ngk Insulators, Ltd. | Method for preparing decomposition catalyst for organic halide and method for manufacturing filter for use in decomposing organic halide |
| WO2001087478A1 (en) | 2000-05-15 | 2001-11-22 | Ngk Insulators, Ltd. | Adsorbent having capability of decomposing organic halogen compound and method for producing the same |
| WO2002102511A1 (en) * | 2001-06-18 | 2002-12-27 | Battelle Memorial Institute | Textured catalysts comprising catalyst metal and metal oxide on carbon support, methods of making textured catalysts, and use in hydrogenation reactions conducted in hydrothermal conditions |
| JP2006224000A (en) * | 2005-02-17 | 2006-08-31 | Institute Of National Colleges Of Technology Japan | Method of synthesizing photocatalyst and photocatalyst precursor |
| JP2007071866A (en) * | 2005-08-10 | 2007-03-22 | Tokyo Univ Of Science | Film for gas sensor, element for gas sensor and method for manufacturing the element for gas sensor |
| US7811959B2 (en) * | 2003-11-13 | 2010-10-12 | Samsung Sdi Co., Ltd. | Metal oxide-carbon composite catalyst support and fuel cell comprising the same |
| WO2011108683A1 (en) * | 2010-03-04 | 2011-09-09 | 住友化学株式会社 | Method for manufacturing supported ruthenium oxide and method for manufacturing chlorine |
| JP2011183238A (en) * | 2010-03-04 | 2011-09-22 | Sumitomo Chemical Co Ltd | Method of producing carried ruthenium oxide and method of producing chlorine |
| JP2013504683A (en) * | 2009-09-15 | 2013-02-07 | エイビーエス マテリアルズ インコーポレイテッド | Swellable material and method of use |
| US9144784B2 (en) | 2005-09-30 | 2015-09-29 | Abs Materials | Sorbent material and method for using the same |
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1992
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Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0866635A (en) * | 1993-12-14 | 1996-03-12 | Toto Ltd | Photocatalytic thin film and its formation |
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