JPH06320011A - Photocatalyst for removal of heavy metal ion in solution and device for removing heavy metal ion in solution - Google Patents
Photocatalyst for removal of heavy metal ion in solution and device for removing heavy metal ion in solutionInfo
- Publication number
- JPH06320011A JPH06320011A JP5136766A JP13676693A JPH06320011A JP H06320011 A JPH06320011 A JP H06320011A JP 5136766 A JP5136766 A JP 5136766A JP 13676693 A JP13676693 A JP 13676693A JP H06320011 A JPH06320011 A JP H06320011A
- Authority
- JP
- Japan
- Prior art keywords
- titanium oxide
- heavy metal
- metal ions
- photocatalyst
- liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 49
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 25
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 50
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 50
- 150000002500 ions Chemical class 0.000 claims abstract description 45
- 239000003365 glass fiber Substances 0.000 claims abstract description 22
- 239000010936 titanium Substances 0.000 claims abstract description 22
- 239000002243 precursor Substances 0.000 claims abstract description 15
- 239000011347 resin Substances 0.000 claims abstract description 15
- 229920005989 resin Polymers 0.000 claims abstract description 15
- 239000002759 woven fabric Substances 0.000 claims abstract description 15
- 239000004744 fabric Substances 0.000 claims abstract description 14
- 238000010304 firing Methods 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims description 31
- 230000001678 irradiating effect Effects 0.000 claims description 5
- 238000006482 condensation reaction Methods 0.000 abstract description 5
- 239000011248 coating agent Substances 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 abstract description 4
- 230000018044 dehydration Effects 0.000 abstract description 4
- 238000006297 dehydration reaction Methods 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 238000002485 combustion reaction Methods 0.000 abstract description 2
- 238000006731 degradation reaction Methods 0.000 abstract 1
- 238000007598 dipping method Methods 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 20
- 239000011521 glass Substances 0.000 description 20
- 239000000243 solution Substances 0.000 description 13
- 238000001179 sorption measurement Methods 0.000 description 9
- 229910010413 TiO 2 Inorganic materials 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000010409 thin film Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 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 6
- 238000000034 method Methods 0.000 description 5
- 238000003980 solgel method Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910052793 cadmium Inorganic materials 0.000 description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229910008051 Si-OH Inorganic materials 0.000 description 2
- 229910006358 Si—OH Inorganic materials 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000004453 electron probe microanalysis Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000005283 ground state Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002256 photodeposition Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- -1 titanium alkoxide Chemical class 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- 101000856234 Clostridium acetobutylicum (strain ATCC 824 / DSM 792 / JCM 1419 / LMG 5710 / VKM B-1787) Butyrate-acetoacetate CoA-transferase subunit A Proteins 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910003089 Ti–OH Inorganic materials 0.000 description 1
- INNSZZHSFSFSGS-UHFFFAOYSA-N acetic acid;titanium Chemical compound [Ti].CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O INNSZZHSFSFSGS-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical group [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- RCYJPSGNXVLIBO-UHFFFAOYSA-N sulfanylidenetitanium Chemical compound [S].[Ti] RCYJPSGNXVLIBO-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Landscapes
- Water Treatment By Sorption (AREA)
- Catalysts (AREA)
- Physical Water Treatments (AREA)
- Removal Of Specific Substances (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、光を照射することによ
り液中に存在する水銀、鉛、カドミウム、砒素、銅、マ
ンガン、６価クロム等の重金属イオンを吸着して除去す
る、即ち、重金属イオンを還元して重金属として光触媒
の表面に析出させて除去する液中重金属イオン除去用光
触媒とそれを利用した液中重金属イオン除去装置に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention adsorbs and removes heavy metal ions such as mercury, lead, cadmium, arsenic, copper, manganese, and hexavalent chromium existing in a liquid by irradiating light, that is, The present invention relates to a photocatalyst for removing heavy metal ions in a liquid, which removes heavy metal ions as heavy metals by depositing them on the surface of the photocatalyst, and a device for removing heavy metal ions in a liquid using the photocatalyst.
【０００２】[0002]
【従来の技術】従来、光触媒を利用して液中の重金属イ
オンを除去する方法としては、酸化チタン粉体を液中に
分散させてこれに重金属イオンを含む溶液を流し込み、
光を照射して吸着除去する方法や、ガラス棒やガラス球
にＣＶＤ法やゾルゲル法で酸化チタン膜を被覆したもの
を液中に配置し、これに重金属イオンを含む溶液を流
し、光を照射して吸着除去する方法が知られている。ま
た、重金属イオンの吸着効率を高めるために、白金、パ
ラジウム、ロジウム、金、銀、ルテニウム等の貴金属を
酸化チタンに担持させて光触媒機能を向上させようとす
る方法がとられている。2. Description of the Related Art Conventionally, as a method of removing heavy metal ions in a liquid using a photocatalyst, titanium oxide powder is dispersed in the liquid and a solution containing heavy metal ions is poured into the liquid.
A method of irradiating light to adsorb and remove it, or a glass rod or glass sphere coated with a titanium oxide film by the CVD method or sol-gel method is placed in the liquid, and a solution containing heavy metal ions is flown into this to irradiate the light. Then, a method of adsorbing and removing is known. Further, in order to improve the adsorption efficiency of heavy metal ions, a method has been adopted in which a precious metal such as platinum, palladium, rhodium, gold, silver and ruthenium is supported on titanium oxide to improve the photocatalytic function.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、前記従
来の酸化チタン粉体を液中に分散させる方法は、粉体と
液体を分離するために、下流側に濾過膜を設ける必要が
あり、そのために圧力損失が高くなる。また、粉体を液
中に分散させると光が最外層のみで吸収され、照射光が
内部まで透過しにくくなり、吸着効率が小さくなるとい
う欠点を有する。また、前記従来の酸化チタン膜を被覆
したガラス棒やガラス球を用いる方法は、粉体を回収す
る濾過膜の設置は必要なく、光も透過するが、水や気相
との接触界面が少なくなり吸着効率が悪いという欠点を
有する。更に、従来法であるＣＶＤ法やゾルゲル法で酸
化チタン膜を被覆した場合には、基材であるガラス繊維
上に酸化チタンがガラス繊維との間にＳｉ−Ｏ−Ｔｉ結
合層を介在することなく単独で存在するため、長時間の
使用の結果、膜の脱落等の問題があった。本発明は、こ
れら従来技術の欠点を解消し、高効率で使いやすい液中
重金属イオン除去用光触媒とこれを利用した液中重金属
イオン除去装置を提供することを目的としている。However, in the conventional method of dispersing the titanium oxide powder in the liquid, it is necessary to provide a filtration membrane on the downstream side in order to separate the powder and the liquid. High pressure loss. In addition, when the powder is dispersed in the liquid, light is absorbed only in the outermost layer, and it becomes difficult for the irradiation light to penetrate to the inside, so that the adsorption efficiency is reduced. Further, the conventional method using a glass rod or a glass sphere coated with a titanium oxide film does not require the installation of a filtration film for collecting powder and allows light to pass through, but has a small contact interface with water or a gas phase. However, it has the disadvantage of poor adsorption efficiency. Furthermore, when the titanium oxide film is coated by the conventional CVD method or sol-gel method, the titanium oxide should intervene the Si—O—Ti bonding layer between the glass fiber and the glass fiber as the base material. Since it is not present and is present alone, there is a problem that the film may come off as a result of long-term use. An object of the present invention is to provide a photocatalyst for removing heavy metal ions in liquid, which is highly efficient and easy to use, and a device for removing heavy metal ions in liquid, which uses the photocatalyst for eliminating these drawbacks of the prior art.
【０００４】[0004]
【課題を解決するための手段】本発明者等は、前記欠点
を解決するため鋭意検討の結果、加熱により酸化チタン
になる前駆体と有機物樹脂とを相溶性のある溶媒に溶解
してなる溶液にガラス繊維からなる織布を浸漬した後、
乾燥、焼成することにより、従来品の不具合を解消し得
ることを知見し、本発明を完成させた。Means for Solving the Problems As a result of intensive studies for solving the above-mentioned drawbacks, the present inventors have found that a solution obtained by dissolving a precursor that becomes titanium oxide by heating and an organic resin in a compatible solvent. After immersing the woven fabric made of glass fiber in
The present invention has been completed by finding that the defects of conventional products can be eliminated by drying and firing.
【０００５】即ち、本発明の液中重金属イオン除去用光
触媒はガラス繊維からなる織布に酸化チタンを被覆した
液中重金属イオン除去用光触媒であって、前記ガラス繊
維からなる織布を、加熱により酸化チタンになる前駆体
と有機物樹脂とを相溶性のある溶媒に溶解してなる溶液
に浸漬した後、乾燥、焼成することにより前記ガラス繊
維と前記酸化チタンの間にＳｉ−Ｏ−Ｔｉ結合層を形成
したことを特徴とする。That is, the photocatalyst for removing heavy metal ions in liquid of the present invention is a photocatalyst for removing heavy metal ions in liquid, which is obtained by coating a woven cloth made of glass fiber with titanium oxide, and the woven cloth made of glass fiber is heated by heating. A Si-O-Ti bonding layer is formed between the glass fiber and the titanium oxide by immersing in a solution prepared by dissolving a precursor of titanium oxide and an organic resin in a compatible solvent, followed by drying and firing. Is formed.
【０００６】前記ガラス繊維からなる織布の目付け（ｇ
／ｍ2 ）は、いくらのものでも構わないが、取扱い性や
吸着効率の関係から、通常１００〜９００ｇ／ｍ2 のも
のを用いる。また、織布を構成するガラス繊維の種類と
しては、石英ガラス、高石英ガラス、Ｅガラス、Ｃガラ
ス、Ｓガラス、Ａガラス等、光を透すならばどのような
組成でも構わないが、経済性からＥガラス繊維が好まし
い。また、ガラス繊維の平均繊維径は、特に限定される
ものではないが、製造可能でしかも液体との接触面積を
確保して効率を得るため５〜２０ミクロンが好ましい。
また、織布の織り方は平織、綾織、朱子織など、どのよ
うな織り方でも構わないが、光透過性の観点から平織が
好ましい。また、打込み密度、厚さ、引張強度は特に限
定されるものではないが、液体に対する強度の観点か
ら、各々タテ、ヨコ共に１０〜８０本／２５ｍｍ、０．
０１〜２．０ｍｍ、５ｋｇｆ／２５ｍｍ巾以上が好まし
い。Fabric weight of the above-mentioned glass fiber (g
/ M 2 ) may be anything, but in view of handleability and adsorption efficiency, usually 100 to 900 g / m 2 is used. Further, as the kind of glass fiber constituting the woven cloth, any composition may be used, such as quartz glass, high quartz glass, E glass, C glass, S glass, A glass, etc., as long as it allows light to pass through. E glass fiber is preferable from the viewpoint of the property. The average fiber diameter of the glass fibers is not particularly limited, but is preferably 5 to 20 μm in order to be manufacturable and to secure the contact area with the liquid to obtain efficiency.
The weave may be any weave, such as plain weave, twill weave and satin weave, but plain weave is preferred from the viewpoint of light transmission. Further, the implantation density, the thickness, and the tensile strength are not particularly limited, but from the viewpoint of strength against liquid, both vertical and horizontal are 10 to 80 pieces / 25 mm, 0.
The width is preferably 01 to 2.0 mm and 5 kgf / 25 mm or more.
【０００７】また、前記加熱により酸化チタンとなる前
駆体としては、チタンアルコキシド、チタン塩化物、チ
タン硫化物、チタン酢酸塩等が使用できるが、有機物樹
脂との相溶性の関係から、アルコール類を相溶性溶媒と
する場合はチタンアルコキシド、水を相溶性溶媒とする
場合はチタン塩化物を選択することが好ましい。しか
し、前記前駆体と有機物樹脂が相溶する場合はどのよう
な組み合わせを選択しても構わない。As the precursor which becomes titanium oxide by the heating, titanium alkoxide, titanium chloride, titanium sulfide, titanium acetate, etc. can be used, but alcohols are used because of their compatibility with organic resin. When a compatible solvent is used, titanium alkoxide is preferably selected, and when water is used as a compatible solvent, titanium chloride is preferably selected. However, if the precursor and the organic resin are compatible with each other, any combination may be selected.
【０００８】また、前記有機物樹脂はアクリル系、オレ
フィン系等が一般的であるが、製造工程中の焼成工程で
酸化分解することが必要であるため、分解温度が２００
℃以上且つ焼成温度以下の樹脂で、更に該酸化チタン前
駆体との相溶性があれば良く、モノマーの種類や分子量
によって特に限定されるものではない。The organic resin is generally an acrylic resin, an olefin resin or the like, but the decomposition temperature is 200 because it needs to be oxidized and decomposed in the firing step in the manufacturing process.
It is only necessary that the resin has a temperature of not less than ° C and not more than the firing temperature and has compatibility with the titanium oxide precursor, and is not particularly limited depending on the type and molecular weight of the monomer.
【０００９】このようにして選定された有機物樹脂と酸
化チタン前駆体の溶液に、前記織布を浸漬した後乾燥す
る。乾燥温度は相溶性溶媒の沸点により異なるが、４０
〜１５０℃の範囲で行うのが好ましい。次に、乾燥膜を
焼成することにより、有機物樹脂や酸化チタンの前駆体
を構成している有機残基を取り除く。この焼成で酸化チ
タン前駆体は酸化チタンに変化し、有機物樹脂は酸化分
解されたＳｉ−Ｏ−Ｔｉ結合を有する薄膜が得られる。The woven fabric is dipped in a solution of the organic resin and the titanium oxide precursor thus selected, and then dried. The drying temperature depends on the boiling point of the compatible solvent.
It is preferably carried out in the range of up to 150 ° C. Next, the dried film is baked to remove the organic residues constituting the organic resin and the titanium oxide precursor. By this firing, the titanium oxide precursor is changed to titanium oxide, and the organic resin is a thin film having oxidatively decomposed Si-O-Ti bonds.
【００１０】被覆する酸化チタン膜の厚さは、膜の接着
性や光透過性から１μｍ以下が好ましい。１μｍを越え
ると膜の剥離が生じ、水の濁りや吸着効率の低下が生じ
る。また、光の透過性も悪くなり、織布内部まで光が到
達しにくくなり吸着効率的にも好ましくない。また、酸
化チタンの厚さは、溶液の酸化チタン前駆体の濃度を調
整するか、前記作製工程を繰り返すことにより変化させ
ることが可能である。The thickness of the titanium oxide film to be coated is preferably 1 μm or less in view of the adhesiveness and light transmittance of the film. If it exceeds 1 μm, peeling of the film occurs, resulting in turbidity of water and deterioration of adsorption efficiency. In addition, the light transmittance also deteriorates, and it becomes difficult for light to reach the inside of the woven fabric, which is also undesirable in terms of adsorption efficiency. In addition, the thickness of titanium oxide can be changed by adjusting the concentration of the titanium oxide precursor in the solution or by repeating the above production process.
【００１１】また、織布全体から考えると、被覆した酸
化チタン膜の織布全体に対する量の比率は４０ｗｔ％以
下が好ましい。この場合も４０ｗｔ％を越えると光の透
過性が悪くなり、酸化チタンの剥離も生ずるため好まし
くない。Considering the entire woven fabric, the ratio of the amount of the coated titanium oxide film to the entire woven fabric is preferably 40 wt% or less. Also in this case, if it exceeds 40 wt%, the light transmittance is deteriorated and the titanium oxide is also peeled off, which is not preferable.
【００１２】尚、予め貴金属が担持されている光触媒を
重金属イオンの除去に利用した場合、貴金属イオンは還
元されて原子となって酸化チタンの表面に析出され、重
金属イオンも同じ還元作用を利用して重金属として吸着
除去するため、酸化チタンの吸着量に限界があり、貴金
属イオンの付着量だけ重金属イオンの吸着量が減少して
触媒機能が低下するので、貴金属の担持は好ましくな
い。When a photocatalyst on which a noble metal is supported in advance is used to remove heavy metal ions, the noble metal ions are reduced to form atoms and are deposited on the surface of titanium oxide, and the heavy metal ions also use the same reducing action. Since it is adsorbed and removed as heavy metal, the amount of adsorbed titanium oxide is limited, and the adsorbed amount of heavy metal ions is reduced by the adhering amount of noble metal ions to lower the catalytic function.
【００１３】また、本発明の液中重金属イオン除去装置
は重金属イオンを含む溶液を通過させる容器内に前記液
中重金属イオン除去用光触媒を配置すると共に該光触媒
に光を照射するための光源を備えたことを特徴とする。
前記装置は例えば、容器をプラスチック類、ホウ珪酸塩
ガラス或いは、石英ガラス等による透明容器に構成し
て、該容器の外部から光を照射するようにしてもよく、
或いは、該容器を特に透明容器にすることなく該容器内
に光源を配置するようにしてもよい。また、前記光源と
しては、低圧水銀灯やブラックライト蛍光灯等を用い
る。Further, the apparatus for removing heavy metal ions in liquid of the present invention comprises a photocatalyst for removing heavy metal ions in liquid and a light source for irradiating the photocatalyst with light in a container through which a solution containing heavy metal ions passes. It is characterized by that.
In the above apparatus, for example, the container may be configured as a transparent container made of plastics, borosilicate glass, quartz glass or the like, and light may be irradiated from the outside of the container,
Alternatively, the light source may be arranged in the container without forming the container as a transparent container. As the light source, a low pressure mercury lamp, a black light fluorescent lamp, or the like is used.
【００１４】[0014]
【作用】従来、知られているＣＶＤ法やゾルゲル法によ
り基材と薄膜の間にＳｉ−Ｏ−Ｔｉなる結合を形成せし
めようとした場合、６００℃以上の高温が必要となる。
これは、本反応が基材表面のＳｉ−ＯＨ基と薄膜のＴｉ
−ＯＨ基の間の脱水縮合反応によるものであるためで、
一般にこの縮合反応は−ＯＨ基の自由度が大きくなる６
００℃以上で起こるとされている。このため、汎用性が
高く耐熱性の小さいＡガラス、Ｃガラス、Ｅガラス等に
被覆することは不可能であり、被覆する基材が限定され
ていた。本発明において、Ｓｉ−Ｏ−Ｔｉ結合の生成が
基材表面のＳｉ−ＯＨ基と薄膜のＴｉ−ＯＨ基の間の脱
水縮合反応によるものである点は前記ＣＶＤ法やゾルゲ
ル法と同様である。しかしながら本発明では、有機物樹
脂および酸化チタン前駆体を構成している有機残基の酸
化分解反応により生成する燃焼熱により表面のみ局部的
に加熱できるので前記脱水縮合反応が進行し、比較的低
温でＳｉ−Ｏ−Ｔｉ結合が形成される。このため、耐熱
性の小さいガラス等の基材を用いた場合でも、Ｓｉ−Ｏ
−Ｔｉ結合を持つ層を有した薄膜を形成することが可能
となり、強固な酸化チタン膜を得ることができる。更
に、このＳｉ−Ｏ−Ｔｉ結合の存在によって重金属イオ
ンの吸着が促進される。酸化チタン光触媒を用いた場
合、重金属イオンの吸着は、光析出反応によって起こ
る。即ち、光の照射により酸化チタンの基底状態にある
電子が伝導帯に励起され、重金属イオンが酸化チタンか
ら励起電子を受け取り重金属となって酸化チタン表面に
析出する。このとき、Ｓｉ−Ｏ−Ｔｉ結合が存在すると
酸化チタン構造の乱れが生じ、酸化チタンの基底状態と
励起状態のエネルギーの差（バンドギャップ）は、小さ
くなる。即ち、酸化チタンの電子が励起される確率が高
くなるため、重金属イオンが重金属となって酸化チタン
表面に析出され易くなる。このため前記重金属イオンの
吸着を促進することができる。更に、該光触媒はフレキ
シブルであり、どのような形状の容器にも設置すること
ができる。When a known CVD method or sol-gel method is used to form a bond of Si-O-Ti between the substrate and the thin film, a high temperature of 600 ° C or higher is required.
This is because the reaction is based on the Si-OH group on the substrate surface and the Ti
Because it is due to a dehydration condensation reaction between —OH groups,
Generally, this condensation reaction increases the degree of freedom of the —OH group 6
It is said to occur above 00 ° C. For this reason, it is impossible to coat A glass, C glass, E glass and the like, which have high versatility and low heat resistance, and the substrates to be coated have been limited. In the present invention, the formation of the Si—O—Ti bond is due to the dehydration condensation reaction between the Si—OH group on the surface of the base material and the Ti—OH group of the thin film, as in the CVD method and the sol-gel method. . However, in the present invention, since only the surface can be locally heated by the combustion heat generated by the oxidative decomposition reaction of the organic residues constituting the organic resin and the titanium oxide precursor, the dehydration condensation reaction proceeds, and at a relatively low temperature. Si-O-Ti bonds are formed. Therefore, even when a substrate such as glass having low heat resistance is used, Si--O
A thin film having a layer having a —Ti bond can be formed, and a strong titanium oxide film can be obtained. Furthermore, the presence of this Si-O-Ti bond promotes the adsorption of heavy metal ions. When a titanium oxide photocatalyst is used, the adsorption of heavy metal ions occurs by a photodeposition reaction. That is, electrons in the ground state of titanium oxide are excited to the conduction band by the irradiation of light, and heavy metal ions receive excited electrons from titanium oxide and become heavy metals to be deposited on the titanium oxide surface. At this time, if the Si—O—Ti bond is present, the titanium oxide structure is disturbed, and the energy difference (band gap) between the ground state and the excited state of titanium oxide becomes small. That is, since the probability that the electrons of titanium oxide are excited increases, heavy metal ions become heavy metals and are easily deposited on the titanium oxide surface. Therefore, the adsorption of the heavy metal ions can be promoted. Further, the photocatalyst is flexible and can be installed in a container of any shape.
【００１５】[0015]
【実施例】以下、本発明の実施例を図面に基づき説明す
る。図１は本発明液中重金属イオン除去装置の一実施例
を示すもので、図中１は透明石英管からなる容器を示
し、該容器１内には液中重金属イオン除去用光触媒２が
配置され、該容器１内にポンプ３を介して重金属イオン
を含む溶液を循環通過させるようにし、容器１の近傍に
設けた光源４から光を照射して重金属イオンを除去する
ように構成してある。尚、図中５は集光用ミラー、６は
重金属イオンを除去された溶液を取り出すための取出
口、７は新たな重金属イオンを含む溶液を供給するため
の取入口を示す。Embodiments of the present invention will be described below with reference to the drawings. FIG. 1 shows an embodiment of the apparatus for removing heavy metal ions in liquid according to the present invention. In FIG. 1, reference numeral 1 denotes a container made of a transparent quartz tube, in which a photocatalyst 2 for removing heavy metal ions in liquid is arranged. A solution containing heavy metal ions is circulated in the container 1 via a pump 3, and light is emitted from a light source 4 provided in the vicinity of the container 1 to remove the heavy metal ions. In the figure, 5 is a converging mirror, 6 is an outlet for taking out the solution from which heavy metal ions have been removed, and 7 is an inlet for supplying a solution containing new heavy metal ions.
【００１６】次に、前記装置の使用例に即し、具体的な
実施例を比較例と共に説明する。 （実施例）平均繊維径７μｍのＥガラスモノフィラメン
ト（単一繊維）からなるヤーンを織ってなる目付け５０
０ｇ／ｍ2 のガラス織布（ガラスクロス）を、酸化チタ
ン前駆体であるチタンイソプロポキシド１０ｇとアクリ
ル系樹脂１０ｇをエチルアルコール１８０ｇに溶解した
溶液に浸漬した。このガラス織布を溶液から取り出し、
６０℃で１時間乾燥した後毎分１℃の速度で４５０℃ま
で昇温し、４５０℃で５時間保持することにより、有機
物樹脂を完全に酸化分解し、同時にチタンイソプロポキ
シドもＴｉＯ2 に変化させ、ガラス繊維表面にＴｉＯ2
膜を形成した。このときのＴｉＯ2 膜の厚さは約０．３
μｍであり、強固に付着していた。この場合、被覆した
酸化チタンのガラス織布全体に対する量の比率は１８％
であった。この膜についてＥＰＭＡ（測定にはＸ線マイ
クロアナライザー，日本電子製，ＪＥＭ−２０００ＦＸ
IIを使用）およびＥＳＣＡ（測定にはＸ線光電子分光装
置，島津・クレイトス社製，ＸＳＡＭ８００を使用）に
より分析を行ったところ、Ｓｉ−Ｏ−Ｔｉ結合の存在が
確認された。ここで図２は本実施例による膜の断面図で
あり、Ａはガラス繊維、ＢはＴｉＯ2 薄膜、ＣはＳｉ−
Ｏ−Ｔｉ結合層を示している。この織布（触媒）を直径
１２ｍｍ、長さ５００ｍｍの透明石英管に詰め、水銀７
０ｐｐｍ、カドミウム９０ｐｐｍを含有する反応液１０
０リットルをポンプにより循環させた。約２時間光照射
を行いながら循環させたところ、水銀０．０２ｐｐｍ以
下、カドミウム０．０５ｐｐｍ以下の処理水を得た。こ
の場合、水の濁りはなかった。Next, a concrete embodiment will be described together with a comparative example in accordance with a usage example of the apparatus. (Example) A basis weight 50 formed by weaving a yarn made of E glass monofilament (single fiber) having an average fiber diameter of 7 μm
A glass woven fabric (glass cloth) of 0 g / m 2 was immersed in a solution of 10 g of titanium isopropoxide as a titanium oxide precursor and 10 g of an acrylic resin in 180 g of ethyl alcohol. Remove this woven glass cloth from the solution,
After being dried at 60 ° C for 1 hour, the temperature was raised to 450 ° C at a rate of 1 ° C / min and kept at 450 ° C for 5 hours to completely oxidize and decompose the organic resin and at the same time convert titanium isopropoxide to TiO 2 . Change the TiO 2 on the glass fiber surface.
A film was formed. At this time, the thickness of the TiO 2 film is about 0.3.
It was μm and was firmly attached. In this case, the ratio of the coated titanium oxide to the entire glass woven fabric is 18%.
Met. About this film, EPMA (X-ray micro analyzer for measurement, JEM-2000FX manufactured by JEOL Ltd.)
II) and ESCA (using an X-ray photoelectron spectrometer, XSAM800 manufactured by Shimadzu-Kraitos Co., Ltd. for measurement), the presence of Si—O—Ti bonds was confirmed. Here, FIG. 2 is a cross-sectional view of the film according to the present embodiment, where A is glass fiber, B is a TiO 2 thin film, and C is Si-.
The O-Ti bond layer is shown. This woven fabric (catalyst) was packed in a transparent quartz tube with a diameter of 12 mm and a length of 500 mm,
Reaction liquid 10 containing 0 ppm and 90 ppm of cadmium
0 liter was circulated by the pump. When circulating while irradiating with light for about 2 hours, treated water containing 0.02 ppm or less of mercury and 0.05 ppm or less of cadmium was obtained. In this case, there was no turbidity in the water.
【００１７】（比較例）実施例で用いたガラス織布を用
い、従来のゾルゲル法によりＴｉＯ2 薄膜の形成を試み
た。ガラス織布を浸漬させる液をチタンイソプロポキシ
ド１０ｇと濃硫酸０．１ｇおよびエチルアルコール１９
０ｇを混合した溶液に変えた以外は実施例と同様の方法
とした。結果形成されたＴｉＯ2 膜の厚さは約０．３μ
ｍであったが、弱い付着で簡単に剥離した。この場合、
被覆した酸化チタンのガラス織布全体に対する量の比率
は１８％であった。この膜について前記実施例と同様に
ＥＰＭＡおよびＥＳＣＡにより分析を行ったところ、Ｓ
ｉ−Ｏ−Ｔｉ結合の存在は確認されなかった。ここで、
図３は本比較例による膜の断面図であり、Ａはガラス繊
維、ＢはＴｉＯ2 膜を示している。この織布（触媒）を
直径１２ｍｍ、厚さ５００ｍｍの透明石英管に詰め、実
施例１と同じ反応液をポンプにより循環させた。約２時
間光照射後、水銀１ｐｐｍ以下、カドミウム２ｐｐｍ以
下になったが、酸化チタンの脱落により水がかなり濁っ
た。Comparative Example Using the glass woven cloth used in the examples, an attempt was made to form a TiO 2 thin film by the conventional sol-gel method. The liquid in which the glass woven cloth is dipped is 10 g of titanium isopropoxide, 0.1 g of concentrated sulfuric acid and 19 of ethyl alcohol.
The same method as in Example was used except that 0 g was changed to a mixed solution. The resulting TiO 2 film has a thickness of about 0.3 μm.
It was m, but peeled off easily due to weak adhesion. in this case,
The ratio of the amount of coated titanium oxide to the entire glass woven fabric was 18%. When this film was analyzed by EPMA and ESCA in the same manner as in the above example, S
The presence of i-O-Ti bond was not confirmed. here,
FIG. 3 is a cross-sectional view of a film according to this comparative example, where A is glass fiber and B is a TiO 2 film. This woven fabric (catalyst) was packed in a transparent quartz tube having a diameter of 12 mm and a thickness of 500 mm, and the same reaction solution as in Example 1 was circulated by a pump. After irradiation with light for about 2 hours, the mercury content was 1 ppm or less and the cadmium content was 2 ppm or less, but the water became considerably cloudy due to the dropping of titanium oxide.
【００１８】[0018]
【発明の効果】このように、本発明による織布は、光透
過性が良く、かつ水や気体との接触面積が大きいため、
液中の重金属イオンを高効率で除去できるという効果を
有する。また、織布を構成する繊維にＳｉ−Ｏ−Ｔｉ結
合により強固に酸化チタン膜が被覆されているため、酸
化チタンの剥離や脱落がなく、長期に渡り高効率を維持
し、また水の濁りもないので粉体等を回収する必要がな
い、という効果を有する。更にＳｉ−Ｏ−Ｔｉ結合が存
在するため、酸化チタンの電子が励起され易く、重金属
イオンの光析出反応を促進させるといった効果を有す
る。また、フレキシブル性を有するので、複雑な形状の
容器にも適用することが可能となり、カラム化も可能で
ある、という効果を有する。As described above, the woven fabric according to the present invention has good light transmittance and a large contact area with water or gas.
It has an effect that heavy metal ions in the liquid can be removed with high efficiency. In addition, since the fibers constituting the woven fabric are strongly covered with the titanium oxide film by Si-O-Ti bonds, the titanium oxide is not peeled off or dropped off, high efficiency is maintained for a long time, and turbidity of water is caused. Since it is not necessary, it has an effect that it is not necessary to collect powder and the like. Furthermore, since the Si—O—Ti bond is present, the electrons of titanium oxide are easily excited, and the effect of promoting the photodeposition reaction of heavy metal ions is obtained. Further, since it has flexibility, it can be applied to a container having a complicated shape and can be columnized.
【図１】本発明の液中重金属イオン除去装置の一実施例
の説明図FIG. 1 is an explanatory diagram of an embodiment of a device for removing heavy metal ions in liquid according to the present invention.
【図２】本発明の液中重金属イオン除去用光触媒の被覆
の形成状態を示す拡大断面図FIG. 2 is an enlarged cross-sectional view showing a formation state of a coating of the photocatalyst for removing heavy metal ions in liquid of the present invention.
【図３】比較例による液中重金属イオン除去用光触媒の
被覆の形成状態を示す拡大断面図FIG. 3 is an enlarged cross-sectional view showing a state of forming a coating of a photocatalyst for removing heavy metal ions in liquid according to a comparative example.
１ 容器 ２ 液中重金属イオン除去用光触媒 ３ ポンプ ４ 光源 ５ 集光用ミラー ６ 取出口 ７ 取入口 Ａ ガラス繊維 Ｂ ＴｉＯ2 薄膜 Ｃ Ｓｉ−Ｏ−Ｔｉ結合層1 Container 2 Photocatalyst for Removal of Heavy Metal Ions in Liquid 3 Pump 4 Light Source 5 Focusing Mirror 6 Inlet 7 Inlet A Glass Fiber B TiO 2 Thin Film C Si-O-Ti Bonding Layer
───────────────────────────────────────────────────── 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 1/62 Ｚ (72)発明者 村林 眞行 神奈川県横浜市旭区笹野台４−25−14 (72)発明者 伊藤 公紀 東京都目黒区目黒本町１−16−13−906─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification number Internal reference number FI Technical indication C02F 1/62 Z (72) Inventor Masayuki Murabayashi 4-25-14 Sasanodai, Asahi-ku, Yokohama-shi, Kanagawa (72) Inventor Koki Ito 1-16-13-906 Megurohonmachi, Meguro-ku, Tokyo
Claims (4)
被覆した液中重金属イオン除去用光触媒であって、前記
ガラス繊維からなる織布を、加熱により酸化チタンにな
る前駆体と有機物樹脂とを相溶性のある溶媒に溶解して
なる溶液に浸漬した後、乾燥、焼成することにより前記
ガラス繊維と前記酸化チタンの間にＳｉ−Ｏ−Ｔｉ結合
層を形成したことを特徴とする液中重金属イオン除去用
光触媒。1. A photocatalyst for removing heavy metal ions in a liquid, comprising a woven cloth made of glass fibers coated with titanium oxide, wherein a woven cloth made of glass fibers is heated with a precursor to become titanium oxide and an organic resin. A heavy metal in liquid characterized by forming a Si-O-Ti bond layer between the glass fiber and the titanium oxide by immersing in a solution prepared by dissolving in a compatible solvent, followed by drying and firing. Photocatalyst for removing ions.
ることを特徴とする請求項１記載の液中重金属イオン除
去用光触媒。2. The photocatalyst for removing heavy metal ions in a liquid according to claim 1, wherein the titanium oxide has a thickness of 1 μm or less.
対して４０ｗｔ％以下であることを特徴とする請求項１
または２記載の液中重金属イオン除去用光触媒。3. The amount of titanium oxide is 40 wt% or less with respect to the glass fiber woven fabric.
Alternatively, the photocatalyst for removing heavy metal ions in liquid according to the item 2.
透過性の容器内に前記請求項１乃至３の何れかに記載の
光触媒を配置すると共に前記容器内に光を照射するため
の光源を備えたことを特徴とする液中重金属イオン除去
装置。4. The photocatalyst according to any one of claims 1 to 3 is arranged in a light-transmissive container that allows a solution containing heavy metal ions to pass therethrough, and a light source for irradiating light into the container is provided. An apparatus for removing heavy metal ions in liquid, characterized in that
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13676693A JP3502414B2 (en) | 1993-05-15 | 1993-05-15 | Method for producing photocatalyst for removing heavy metal ions in liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13676693A JP3502414B2 (en) | 1993-05-15 | 1993-05-15 | Method for producing photocatalyst for removing heavy metal ions in liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06320011A true JPH06320011A (en) | 1994-11-22 |
| JP3502414B2 JP3502414B2 (en) | 2004-03-02 |
Family
ID=15183016
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13676693A Expired - Fee Related JP3502414B2 (en) | 1993-05-15 | 1993-05-15 | Method for producing photocatalyst for removing heavy metal ions in liquid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3502414B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997032664A1 (en) * | 1996-03-04 | 1997-09-12 | Tao Inc. | Molded product having photocatalytic function |
| WO1999064364A1 (en) * | 1998-06-10 | 1999-12-16 | Saint-Gobain Recherche | Substrate with a photocatalytic coating |
| JP2000063118A (en) * | 1998-08-14 | 2000-02-29 | Jsr Corp | Titanium dioxide precursor composition and titanium dioxide |
-
1993
- 1993-05-15 JP JP13676693A patent/JP3502414B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997032664A1 (en) * | 1996-03-04 | 1997-09-12 | Tao Inc. | Molded product having photocatalytic function |
| US6074748A (en) * | 1996-03-04 | 2000-06-13 | Tao Inc. | Molded product having photocatalytic function |
| WO1999064364A1 (en) * | 1998-06-10 | 1999-12-16 | Saint-Gobain Recherche | Substrate with a photocatalytic coating |
| FR2779751A1 (en) * | 1998-06-10 | 1999-12-17 | Saint Gobain Isover | SUBSTRATE WITH PHOTOCATALYTIC COATING |
| JP2000063118A (en) * | 1998-08-14 | 2000-02-29 | Jsr Corp | Titanium dioxide precursor composition and titanium dioxide |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3502414B2 (en) | 2004-03-02 |
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