JP2001259435A - Photocatalyst-supporting body - Google Patents
Photocatalyst-supporting bodyInfo
- Publication number
- JP2001259435A JP2001259435A JP2000083505A JP2000083505A JP2001259435A JP 2001259435 A JP2001259435 A JP 2001259435A JP 2000083505 A JP2000083505 A JP 2000083505A JP 2000083505 A JP2000083505 A JP 2000083505A JP 2001259435 A JP2001259435 A JP 2001259435A
- Authority
- JP
- Japan
- Prior art keywords
- photocatalyst carrier
- carrier according
- alkoxide
- photocatalyst
- drying
- 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
- 239000004065 semiconductor Substances 0.000 claims abstract description 27
- 239000000919 ceramic Substances 0.000 claims abstract description 26
- 150000004703 alkoxides Chemical class 0.000 claims abstract description 24
- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
- 239000002184 metal Substances 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 10
- 239000000758 substrate Substances 0.000 claims abstract description 10
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 37
- 239000011941 photocatalyst Substances 0.000 claims description 25
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 14
- -1 silicon alkoxide Chemical class 0.000 claims description 13
- 238000010304 firing Methods 0.000 claims description 11
- 239000004408 titanium dioxide Substances 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 10
- 238000005507 spraying Methods 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 230000001699 photocatalysis Effects 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052878 cordierite Inorganic materials 0.000 claims description 3
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 230000001112 coagulating effect Effects 0.000 claims 2
- 239000011148 porous material Substances 0.000 abstract description 5
- 238000005245 sintering Methods 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 238000000354 decomposition reaction Methods 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 241000264877 Hippospongia communis Species 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 150000001491 aromatic compounds Chemical class 0.000 description 3
- 238000003618 dip coating Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000007420 reactivation Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 102100032566 Carbonic anhydrase-related protein 10 Human genes 0.000 description 1
- 101000867836 Homo sapiens Carbonic anhydrase-related protein 10 Proteins 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012526 feed medium Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 229910021426 porous silicon Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Abstract
Description
【０００１】[0001]
【発明の属する分野】この発明は、空気中の臭気物質や
有害物質を分解除去する光触媒担持体に関する。The present invention relates to a photocatalyst carrier for decomposing and removing odorous substances and harmful substances in the air.
【０００２】[0002]
【従来の技術】従来、異臭物質、有害物質を含んだ空気
を二酸化チタン等の光反応性半導体に接触させて、紫外
光を照射し、半導体表面において悪臭物質、有害物質を
分解、除去する装置は公知であり、空気清浄機やルーム
エアコンに利用されている。これらの装置に使用される
光反応性半導体を担持した光触媒フィルターには、主と
して二酸化チタンが光反応性半導体として採用され、二
酸化チタンの微粒子を漉き込んだ酸化チタン含有紙をコ
ルゲート加工して通気性を有する蜂の巣（ハニカム）状
に形成したものが一般的である。2. Description of the Related Art Conventionally, an apparatus which decomposes and removes malodorous substances and harmful substances on a semiconductor surface by contacting air containing an off-odor substance and harmful substances with a photoreactive semiconductor such as titanium dioxide and irradiating the semiconductor with ultraviolet light. Is known and is used for air purifiers and room air conditioners. Titanium dioxide is mainly used as the photoreactive semiconductor in the photocatalytic filter supporting the photoreactive semiconductor used in these devices, and titanium oxide-containing paper into which titanium dioxide fine particles have been formed is corrugated to provide air permeability. Generally, it is formed in a honeycomb shape having a honeycomb structure.
【０００３】しかしながら、かかる酸化チタン含有紙か
らなる紙質コルゲートハニカムフィルターは、活性炭等
の吸着助剤を酸化チタンと共に含浸させて初期吸着力を
増大させ得る利点はあるが、基質が脆弱で吸着飽和後の
水洗による再賦活処理が出来ない欠点を有している。
又、ベンゼン、トルエン等の芳香族化合物の分解能が低
く、これらのガスは未分解のままフィルターを通過して
しまう。芳香族化合物を含めて、ＶＯＣ対策は環境浄化
の重要問題であり、これらの難分解性物質に対する分解
能の改善、改良は重要な課題となっている。[0003] However, the paper corrugated honeycomb filter made of the titanium oxide-containing paper has an advantage that the initial adsorbing force can be increased by impregnating an adsorbent such as activated carbon with titanium oxide, but the substrate is weak and the adsorbent becomes saturated after adsorption. Has the drawback that reactivation by water washing cannot be performed.
Also, the resolution of aromatic compounds such as benzene and toluene is low, and these gases pass through the filter without decomposition. VOC countermeasures, including aromatic compounds, are an important issue in environmental purification, and improving and improving the resolution of these hardly decomposable substances is an important issue.
【０００４】紙質ハニカムの脆弱な基質の改善として
は、耐久性のあるセラミック質若しくは金属質の剛性基
材の利用が考えられる。これら剛性基材への酸化チタン
の担持は、焼付による触媒成膜を必要とし、漉き込みの
如き安易な手段で酸化チタンを担持可能な紙質ハニカム
に比して酸化チタンの担持は困難となるが、水洗による
再賦活処理を容易に行い得る利点を有している。[0004] To improve the fragile substrate of paper honeycomb, the use of a durable ceramic or metal rigid base material can be considered. The loading of titanium oxide on these rigid substrates requires the formation of a catalyst by baking, and the loading of titanium oxide is more difficult than that of paper honeycombs that can support titanium oxide by simple means such as staking. This has the advantage that the reactivation treatment by washing with water can be easily performed.
【０００５】[0005]
【発明が解決しようとする課題】この発明は、セラミッ
ク質の剛性基材に、細孔性気孔に富み且高い膜強度を有
する高活性の光反応性半導体を定着した光触媒担持体を
得ることを課題とする。An object of the present invention is to provide a photocatalyst carrier in which a highly active photoreactive semiconductor rich in porous pores and having high film strength is fixed on a ceramic base material. Make it an issue.
【０００６】[0006]
【課題を解決するための手段】上記課題を解決するため
にこの発明が採った手段は、金属アルコキシドを含有す
る光反応性半導体を、アルミナ、アルミナシリカ、炭化
珪素等のセラミック質の多孔性基材に塗工し乾燥、凝固
させた膜を、２５０℃から６００℃の高温で焼成して得
られる微細多孔性焼成膜を数次積層することを特徴とす
る。In order to solve the above-mentioned problems, the present invention employs a method in which a photoreactive semiconductor containing a metal alkoxide is converted into a ceramic porous substrate such as alumina, alumina silica or silicon carbide. It is characterized in that a microporous fired film obtained by firing a film coated on a material, dried and solidified at a high temperature of 250 ° C. to 600 ° C. is laminated several times.
【０００７】又、金属アルコキシドを含有する光反応性
半導体をセラミック質の多孔性基材に塗工し、乾燥凝固
させた膜を焼成して、微細孔性の膜を形成したことを特
徴とする。Further, a photoreactive semiconductor containing a metal alkoxide is applied to a ceramic porous substrate, and a dried and solidified film is fired to form a microporous film. .
【０００８】更に、光反応性半導体の微細孔性の膜を複
数次積層したことを特徴とする。[0008] Furthermore, a plurality of microporous films of a photoreactive semiconductor are laminated.
【０００９】更に、光触媒性半導体を吹付手段により塗
工し乾燥凝固させ焼成した成膜に、浸漬手段により塗工
し乾燥凝固させ焼成した成膜を積層したことを特徴とす
る。Further, the present invention is characterized in that a photocatalytic semiconductor is applied by spraying means, dried and solidified and fired, and a film formed by applying, drying and solidifying and firing by immersion means is laminated.
【００１０】更に、吹付手段による塗工、乾燥、焼成の
成膜を複数次繰り返すことを特徴とする。Further, the invention is characterized in that a plurality of coating, drying and firing film formations by spraying means are repeated.
【００１１】更に、金属アルコキシドが、室温において
比較的安定な金属のエーテルであることを特徴とする。Further, the metal alkoxide is an ether of a metal which is relatively stable at room temperature.
【００１２】更に、金属アルコキシドが、シリコンアル
コキシド、アルミニウムアルコキシド、チタンアルコキ
シド及びジルコニウムアルコキシドのいずれかであるこ
とを特徴とする。Further, the metal alkoxide is one of a silicon alkoxide, an aluminum alkoxide, a titanium alkoxide and a zirconium alkoxide.
【００１３】更に、光反応性半導体が、二酸化チタンで
あることを特徴とする。Further, the photoreactive semiconductor is titanium dioxide.
【００１４】更に、金属アルコキシドを含有する光反応
性半導体が、アナターゼ型の酸化チタンを金属アルコキ
シドとアルコールの存在下でゾル液に調整されているこ
とを特徴とする。Further, the photoreactive semiconductor containing a metal alkoxide is characterized in that an anatase type titanium oxide is prepared into a sol solution in the presence of a metal alkoxide and an alcohol.
【００１５】更に、ゾル液は、酸化チタン３〜１０％、
アルコキシド分１〜３％含有されていることを特徴とす
る。Further, the sol solution contains 3 to 10% of titanium oxide,
The alkoxide content is 1 to 3%.
【００１６】更に、塗工された光反応性半導体を、１０
０℃前後の温度で乾燥することを特徴とする。Further, the coated photoreactive semiconductor is
It is characterized by drying at a temperature of about 0 ° C.
【００１７】更に、乾燥した光反応性半導体を、２５０
〜６００℃で焼成することを特徴とする。Furthermore, the dried photoreactive semiconductor is
It is characterized by firing at ~ 600 ° C.
【００１８】更に、セラミック質の基材が、８０〜９０
％の空孔率を有することを特徴とする。Further, the ceramic base material is 80 to 90%.
% Porosity.
【００１９】更に、セラミック質の基材が、アルミナ
質、アルミナシリカ質、コージライト質のいずれかであ
ることを特徴とする。Further, the ceramic base material is one of alumina, alumina-silica and cordierite.
【００２０】更に、セラミック質の基材が、炭化珪素質
であることを特徴とする。Further, the ceramic base material is made of silicon carbide.
【００２１】金属アルコキシドは、シリコンアルコキシ
ド、アルミニウムアルコキシド、チタンアルコキシド及
びジルコニウムアルコキシドのような室温で比較的安定
なものがよい。光反応性半導体は、二酸化チタンであり
アナターゼ型が光活性が高くこれを金属アルコキシドと
アルコール及び水の共存下でゾル液として調整する。二
酸化チタンは３〜１０％、アルコキシド分は１〜３％の
含量が塗工性が良好である。このような光反応性半導体
と金属アルコキシドからなる光反応性有害物質除去剤
は、例えば特許第２６１８２８７号公報に開示されてい
る。金属アルコキシド・二酸化チタン液は、乾燥、高温
焼成により細孔性気孔に富み且つ高い膜強度を有する高
活性光触媒をもたらすものであり、この発明による適切
な基材の選択と有効な塗工焼成方法により高性能の光触
媒担持体を得ることが可能となった。The metal alkoxide is preferably one which is relatively stable at room temperature, such as silicon alkoxide, aluminum alkoxide, titanium alkoxide and zirconium alkoxide. The photoreactive semiconductor is titanium dioxide, the anatase type of which has high photoactivity, and is prepared as a sol in the presence of metal alkoxide, alcohol and water. Titanium dioxide content of 3 to 10% and alkoxide content of 1 to 3% give good coatability. Such a photoreactive harmful substance remover comprising a photoreactive semiconductor and a metal alkoxide is disclosed in, for example, Japanese Patent No. 2618287. The metal alkoxide / titanium dioxide solution is dried and baked at high temperature to provide a highly active photocatalyst rich in porous pores and high film strength. As a result, a high-performance photocatalyst carrier can be obtained.
【００２２】酸化チタンの目付量は、好ましくは１００
〜３００ｇ／ｍ2を目安とし、１回で３０〜１００ｇ／
ｍ2／回に分けて複数回塗工するのが好ましい。塗工方
法として、先ずスプレーコーティング吹付け塗工で下地
を形成し、その後ディップコーティング含浸塗工する。
スプレーコーティングのみでは、成膜厚が十分でなく触
媒性能が劣るため、ディップコーティングによる塗工が
必要とされる。焼成温度は、高温度が必要であり、２５
０℃〜６００℃、好ましくは４００〜６００℃である。
焼成炉内では、温度の偏りがないように留意しつつ３０
分以上一定の温度を保持する。The basis weight of titanium oxide is preferably 100
３００300 g / m 2 as a guide, 30 to 100 g / m
It is preferred to apply a plurality of times at m 2 / time. As a coating method, first, a base is formed by spray coating spray coating, followed by dip coating impregnation coating.
With spray coating alone, the film thickness is not sufficient and the catalytic performance is inferior, so that dip coating is required. The sintering temperature requires a high temperature, 25
It is 0 to 600 ° C, preferably 400 to 600 ° C.
In the firing furnace, 30
Maintain a constant temperature for at least a minute.
【００２３】セラミック質の基材は、８０〜９０％の空
孔率を有し、ガス接触面積及び光反応性半導体の担持量
が大きく、洗浄が容易で圧力損失が低いことが望まし
い。基材は、アルミナ質、アルミナシリカ質、コージラ
イト質或は炭化珪素質の多孔体若しくはハニカム構造体
があげられる。これらの表面性状は、粗で塗工性が良く
表面積が大であり、ガスとの接触面が大きいほど光触媒
反応性が向上する。軟質ポリウレタン発泡体を裁断し、
これに粉体セラミックススラリーを含浸させ、乾燥焼成
したセラミック骨格多孔体は連続気孔で通気性が高く、
耐熱性、耐薬品性に優れている。又、粉体セラミックス
スラリーを押し出し成形焼成したハニカム構造体は、機
械的強度は高いが骨格表面積は発泡多孔体よりも少な
い。It is desirable that the ceramic base material has a porosity of 80 to 90%, a large gas contact area and a large amount of a photoreactive semiconductor, easy cleaning, and low pressure loss. Examples of the substrate include a porous body or a honeycomb structure made of alumina, alumina-silica, cordierite, or silicon carbide. These surface properties are rough, have good coatability and a large surface area, and the larger the contact surface with the gas, the higher the photocatalytic reactivity. Cutting flexible polyurethane foam,
This is impregnated with a powdered ceramic slurry, and the dried and fired ceramic skeleton porous body has continuous pores and high air permeability,
Excellent heat and chemical resistance. Further, the honeycomb structure obtained by extruding and firing the powder ceramic slurry has a high mechanical strength, but has a smaller skeleton surface area than that of the foamed porous body.
【００２４】[0024]
【発明の実施の形態】この発明の好ましい実施の形態
を、以下に詳細に説明する。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention will be described in detail below.
【実施例１】金属アルコキシド・二酸化チタンコート液
〔多木化学株式会社製、タイノック（商標）、ＴｉＯ2
＝５％、金属アルコキシド＝１.２５％〕を、アルミナ
シリカセラミック多孔体（Ａｌ2Ｏ3＝７６％、ＳｉＯ2
＝１９％、空孔率８５％）の両面にスプレーガンにより
ＴｉＯ2を目付量６０ｇ／ｍ2吹付けて塗工し、１００℃
前後の温度で１時間乾燥後、焼成炉において４５０℃で
１時間焼成して成膜を得た。その後再度、同様にスプレ
ーガンによる吹付け、乾燥、焼成を行って成膜を得、光
触媒フィルターＡを作成した。このフィルターＡを前記
金属アルコキシド・二酸化チタンコート液に更に２０分
間浸漬した後液切りを行って、ＴｉＯ2を目付量９０ｇ
／ｍ2含浸塗工させた後、前記と同様に１００℃前後で
１時間乾燥後、４５０℃で１時間焼成して成膜を行い、
光触媒フィルターＢを得た。ＴｉＯ 2の目付量は、合計
で２１０ｇ／ｍ2であった。Example 1 Metal alkoxide / titanium dioxide coating liquid
[Taiki Chemical Co., Ltd., Taynock (trademark), TiOTwo
= 5%, metal alkoxide = 1.25%]
Porous silica ceramic (AlTwoOThree= 76%, SiOTwo
= 19%, porosity 85%)
TiOTwo60 g / mTwoSpray and apply, 100 ℃
After drying for 1 hour at the temperature before and after, at 450 ° C in a firing furnace
The film was fired for 1 hour to obtain a film. Then again, spray
-A film is formed by spraying, drying and firing with a gun,
A catalyst filter A was prepared. Filter A
20 minutes in metal alkoxide / titanium dioxide coating solution
After immersion for a while, drain the solutionTwo90g
/ MTwoAfter the impregnation coating, at about 100 ℃ as above
After drying for 1 hour, baking at 450 ° C. for 1 hour to form a film,
Photocatalyst filter B was obtained. TiO TwoIs the total
210g / mTwoMet.
【００２５】[0025]
【試験例１】前記光触媒フィルターＡ及びＢを、図１の
構造を有する小型空気清浄機（フィルター０.０２４ｍ2
３段、紫外線ランプ１０Ｗ ２本搭載）にセットし、
４立方メートルの試験室に設置し、予め充填したホルム
アルデヒドガスの分解残留濃度経過を測定した。表１は
その結果を示し、フィルターＡは９０分で３３％の分解
除去率であったが、フィルターＢは９０分で９４％の高
い分解除去率であり、スプレー塗工後ディップ塗工を行
い多層化処理することが非常に効果的であることが分か
った。[Test Example 1] The photocatalytic filter A and B, a small air cleaner having the structure of FIG. 1 (Filter 0.024 2
3 steps, two UV lamps 10W mounted)
It was set in a test room of 4 cubic meters, and the progress of the decomposition residual concentration of the formaldehyde gas filled in advance was measured. Table 1 shows the results. The filter A had a decomposition removal rate of 33% in 90 minutes, while the filter B had a high decomposition removal rate of 94% in 90 minutes. Dip coating was performed after spray coating. It has been found that multi-layer processing is very effective.
【００２６】[0026]
【表１】 [Table 1]
【００２７】[0027]
【実施例２】金属アルコキシド・酸化チタンコート液
（前記製品）を、炭化珪素セラミック多孔体（ＳｉＣ＝
６７％、Ａｌ2Ｏ3＝１２％、ＳｉＯ2＝１９％、空孔率
８５％）の両面にスプレーガンによりＴｉＯ2目付量６
０ｇ／ｍ2を吹付け塗工し、１００℃前後の温度で１時
間乾燥後、焼成炉において４５０℃で１時間焼付け成膜
を再度繰り返した後、金属アルコキシド・二酸化チタン
コート液に２０分間浸漬し液切りし、ＴｉＯ2目付量９
０ｇ／ｍ2を含浸塗工後、前記と同様に１００℃で１時
間乾燥後、４５０℃で１時間焼付成膜を行い光触媒フィ
ルターＣを得た。ＴｉＯ2の目付量合計は、２１０ｇ／
ｍ2であった。Example 2 A metal alkoxide / titanium oxide coating liquid (the above product) was applied to a silicon carbide ceramic porous body (SiC =
67%, Al 2 O 3 = 12%, SiO 2 = 19%, TiO 2 basis weight by a spray gun on both surfaces of the porosity 85%) 6
After spray coating at 0 g / m 2 and drying at a temperature of about 100 ° C. for 1 hour, baking was repeated at 450 ° C. for 1 hour in a firing furnace, and then immersed in a metal alkoxide / titanium dioxide coating liquid for 20 minutes. Drain and drain, TiO 2 basis weight 9
After impregnation coating with 0 g / m 2 , the film was dried at 100 ° C. for 1 hour and baked at 450 ° C. for 1 hour to obtain a photocatalyst filter C. The total basis weight of TiO 2 is 210 g /
m 2 .
【００２８】[0028]
【試験例２】前記光触媒フィルターＡ及びＢ（アルミナ
シリカセラミック多孔体）、フィルターＣ（炭化珪素セ
ラミック多孔体）及びペーパーハニカムフィルターＤ、
アルミ箔ハニカムフィルターＥ、アルミ繊維マットフィ
ルターＦを図１の構造を有する中型空気清浄機（フィル
ター０.１４４ｍ2 ５段、紫外線ランプ２０Ｗ ８本搭
載）を３０立方メートルの試験室に設置し、予めアセト
アルデヒドガスを充填し分解除去残留濃度経過から分解
除去速度（ml／min）を求めた。表２はその結果であ
る。分解除去速度はフィルターＢ、Ａ、Ｃ、Ｄ、Ｅ、Ｆ
の順であった。本発明にかかるセラミック多孔体フィル
ターが高い性能を示しているのに対し、非セラミック対
のフィルターＤ、Ｅ、Ｆの性能は低く、本発明のセラミ
ック多孔体フィルターの優位性が理解される。フィルタ
ーＡ或はＢとＣの差は、アルミナシリカ粉体粒度が炭化
珪素の粉体粒度より細かく骨格表面が良く、塗工性が良
好であることによると考えられる。フィルターＤ、Ｅ、
Ｆのコルゲート化或は堆積マット化したものでは、比表
面積が少なく酸化チタンの担持量を大きくとれないこと
によるものと推測される。Test Example 2 Photocatalyst filters A and B (porous alumina-silica ceramic), filter C (porous silicon carbide ceramic) and paper honeycomb filter D
Aluminum foil honeycomb filter E, established the aluminum fiber mat filter F Medium air cleaner having the structure of FIG. 1 (filter 0.144 m 2 5-stage ultraviolet lamp 20W 8 present mounted) to the test chamber 30 cu.m., Pre-acetaldehyde The gas was charged and the decomposition removal rate (ml / min) was determined from the progress of the residual concentration for decomposition removal. Table 2 shows the results. Decomposition and removal rates are shown for filters B, A, C, D, E, F
It was in order. While the porous ceramic filter according to the present invention shows high performance, the performance of the non-ceramic pair filters D, E, and F is low, which indicates the superiority of the porous ceramic filter of the present invention. It is considered that the difference between filters A or B and C is due to the fact that the alumina silica powder particle size is finer than the silicon carbide powder particle size, the skeleton surface is good, and the coatability is good. Filters D, E,
It is presumed that when F is formed into a corrugated or deposited mat, the specific surface area is small and the amount of titanium oxide carried cannot be increased.
【００２９】[0029]
【表２】 [Table 2]
【００３０】[0030]
【試験例３】前記光触媒フィルターＢ（アルミナシリカ
セラミック多孔体）の有機性ガスの分解性のテストを図
１の構造を有する高照射強度空気清浄機（フィルター
０.１４４ｍ2 ５段、紫外線ランプ２０Ｗ １２本搭
載）を３０立方メートルの試験室に設置し、予め充填し
た目標ガスの分解残留濃度経過から分解除去速度（ml／
min）を求めた。表３はその結果である。酢酸、アセト
アルデヒド、ホルムアルデヒドの分解除去速度は比較的
大であった。従来トルエンの分解反応はホルムアルデヒ
ドに比して非常に遅いと言われていたが、本発明にかか
るフィルターでは、トルエンの分解反応はホルムアルデ
ヒドのそれに近く、又ベンゼンは難分解性とされていた
が分解可能であり、十分実用性のあることが分かった。Test Example 3 A test for decomposing organic gas of the photocatalyst filter B (porous alumina-silica ceramic) was conducted using a high irradiation intensity air cleaner having a structure shown in FIG. 1 (filter 0.144 m 2, 5-stage, ultraviolet lamp 20 W). 12 tubes) were installed in a 30 cubic meter test room, and the decomposition removal rate (ml /
min). Table 3 shows the results. The removal rates of acetic acid, acetaldehyde and formaldehyde were relatively high. Conventionally, it was said that the decomposition reaction of toluene was much slower than that of formaldehyde.However, in the filter according to the present invention, the decomposition reaction of toluene was close to that of formaldehyde, and benzene was considered to be hardly decomposable. It was found to be possible and practical.
【００３１】[0031]
【表３】 [Table 3]
【００３２】[0032]
【試験例４】近年、生活環境における揮発性有機性ガス
（ＶＯＣ）の毒性が指摘されている。そこで、本発明の
アルミナシリカセラミック多孔体の光触媒フィルターに
よる生活環境クラスの低濃度（ｐｐｂ）レベルの有機性
ガスの分解性能テストを図１の構造を有する小型空気清
浄機（フィルター０.０２４ｍ2 ３段、紫外線ランプ１
０Ｗ ２本搭載）において行った。テストは上流及び下
流のガスをサンプリングし、ガスクロマトグラフ法で行
った。表４，５はその結果である。難分解性とされてい
るトルエン、ベンゼン共に充分に分解され、高い除去率
（ワンバスカット率）の高性能フィルターであることが
分かった。Test Example 4 In recent years, the toxicity of volatile organic gas (VOC) in the living environment has been pointed out. Therefore, the decomposition performance test of the low concentration (ppb) levels of organic gases living environment class by the photocatalyst filter of alumina-silica ceramic porous body of the present invention a small air cleaner having the structure of FIG. 1 (Filter 0.024 2 3 Step, UV lamp 1
0W with two wires). In the test, upstream and downstream gases were sampled, and the test was performed by gas chromatography. Tables 4 and 5 show the results. Both toluene and benzene, which are considered to be hardly decomposable, were sufficiently decomposed, indicating that the filter was a high-performance filter with a high removal rate (one bath cut rate).
【００３３】[0033]
【表４】 [Table 4]
【００３４】[0034]
【表５】 [Table 5]
【００３５】[0035]
【試験例５】アンモニア、メチルメルカプタン等のガス
を処理した場合、副生成物によりフィルターが汚染され
性能が劣化することは良く知られており、ペーパーハニ
カムは劣化後廃棄するほかなかった。これに対し、本願
のセラミック多孔体フィルターは耐久性があり再生可能
である。図１の構造を有する小型空気清浄機（フィルタ
ー０.０２４ｍ2 ３段、紫外線ランプ１０Ｗ ２本搭
載）を４立方メートルの試験室に設置し、予め充填した
アンモニアガスの分解除去残留濃度経過を測定した。表
６はその結果である。初回のテスト１では６０分で９３
％を除去し、次回のテスト２では９３％の除去に７０分
を要し、三回目のテスト３では１２０分後７％除去と逐
次能力の低下が認められた。第４回目のテスト４では劣
化したフィルターを８０℃の湯槽に２０分間浸漬後水洗
乾燥して再度アンモニアテストを行った結果であり、性
能が完全に復活し、再使用可能となっている。Test Example 5 It is well known that when a gas such as ammonia or methyl mercaptan is treated, the filter is contaminated with by-products and the performance is deteriorated, and the paper honeycomb has to be discarded after the deterioration. On the other hand, the ceramic porous filter of the present application is durable and reproducible. A small air purifier having the structure shown in FIG. 1 (with a filter of 0.024 m 2, three stages and two ultraviolet lamps of 10 W) was installed in a test room of 4 cubic meters, and the progress of decomposition and removal of ammonia gas previously filled was measured. . Table 6 shows the results. 93 in 60 minutes for the first test 1
% Was removed, the next test 2 required 70 minutes to remove 93%, and the third test 3 showed a 7% removal after 120 minutes, a sequential decrease in performance. In the fourth test 4, the deteriorated filter was immersed in a water bath at 80 ° C. for 20 minutes, washed with water and dried, and then subjected to the ammonia test again. The performance was completely restored and the filter can be reused.
【００３６】[0036]
【表６】 [Table 6]
【００３７】[0037]
【発明の効果】この発明によれば、細孔性気孔に富み且
つ高い膜強度を有する高活性の光半導体を形成すること
が出来るため、空気中の悪臭物質や有害物質を効果的に
分解除去することが出来る。特に、難分解性物質である
ベンゼン、トルエン等の芳香族化合物の分解、除去が可
能であり、ＶＯＣ対策を含めて環境浄化に適した光触媒
担持体を提供することが出来る。According to the present invention, it is possible to form a highly active optical semiconductor which is rich in porous pores and has high film strength, so that malodorous substances and harmful substances in the air are effectively decomposed and removed. You can do it. In particular, it is possible to decompose and remove aromatic compounds such as benzene and toluene, which are hardly decomposable substances, and to provide a photocatalyst carrier suitable for environmental purification including VOC measures.
【図１】試験例に用いられた空気清浄機の構造を示す図FIG. 1 is a diagram showing a structure of an air purifier used in a test example.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 栗屋野 伸樹 神奈川県横浜市都筑区川向町957−７ 盛 和工業株式会社内 (72)発明者 石川 栄 神奈川県横浜市都筑区川向町957−７ 盛 和工業株式会社内 (72)発明者 高瀬 昭三 千葉県鎌ヶ谷市馬込沢13−５ Ｆターム(参考） 4D048 AA22 AB03 BA03X BA03Y BA06X BA06Y BA07X BA07Y BA08Y BA10X BA10Y BA41X BA41Y BA45X BA45Y BA50X BA50Y BB03 CA06 EA01 4G069 AA01 AA03 AA08 BA01A BA01B BA02A BA02B BA03A BA03B BA13A BA13B BA37 BA48A BA48C BB04A BB04B BB15A BB15B BB19A BB19B BC51A BE06A BE06B CA10 CA17 EA08 EB10 EC22X EC22Y EE06 FA03 FB23 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Nobuki Kuriyano 957-7 Kawamukai-cho, Tsuzuki-ku, Yokohama-shi, Kanagawa Prefecture Inside Moriwa Industry Co., Ltd. (72) Inventor Sakae Ishikawa 957-7 Kawamukai-cho, Tsuzuki-ku, Yokohama-shi, Kanagawa Seiwa Industry Co., Ltd. (72) Inventor Shozo Takase 13-5 Magomezawa, Kamagaya-shi, Chiba F-term (reference) AA08 BA01A BA01B BA02A BA02B BA03A BA03B BA13A BA13B BA37 BA48A BA48C BB04A BB04B BB15A BB15B BB19A BB19B BC51A BE06A BE06B CA10 CA17 EA08 EB10 EC22X EC22Y EE06 FA03 FB23
Claims (14)
体をセラミック質の多孔性基材に塗工し、乾燥凝固させ
た膜を焼成して、微細孔性の膜を形成したことを特徴と
する光触媒担持体。1. A microporous film is formed by applying a photoreactive semiconductor containing a metal alkoxide to a ceramic porous substrate, and baking the dried and solidified film. Photocatalyst carrier.
層したことを特徴とする請求項１記載の光触媒担持体。2. The photocatalyst carrier according to claim 1, wherein a plurality of microporous films of a photoreactive semiconductor are laminated.
燥凝固させ焼成した成膜に、浸漬手段により塗工し乾燥
凝固させ焼成した成膜を積層したことを特徴とする請求
項１又は２記載の光触媒担持体。3. A film formed by applying a photocatalytic semiconductor by spraying means, drying and coagulating and firing, and a film formed by applying, drying, coagulating and firing by means of immersion means is laminated. The photocatalyst carrier according to the above.
複数次繰り返すことを特徴とする請求項３記載の光触媒
担持体。4. The photocatalyst carrier according to claim 3, wherein coating, drying and baking by spraying means are repeated a plurality of times.
安定な金属のエーテルであることを特徴とする請求項１
記載の光触媒担持体。5. The method according to claim 1, wherein the metal alkoxide is a metal ether which is relatively stable at room temperature.
The photocatalyst carrier according to the above.
ド、アルミニウムアルコキシド、チタンアルコキシド及
びジルコニウムアルコキシドのいずれかであることを特
徴とする請求項１記載の光触媒担持体。6. The photocatalyst carrier according to claim 1, wherein the metal alkoxide is any one of silicon alkoxide, aluminum alkoxide, titanium alkoxide and zirconium alkoxide.
とを特徴とする請求項１乃至３のいずれかに記載の光触
媒担持体。7. The photocatalyst carrier according to claim 1, wherein the photoreactive semiconductor is titanium dioxide.
体が、アナターゼ型の酸化チタンを金属アルコキシドと
アルコールの存在下でゾル液に調整されていることを特
徴とする請求項１記載の光触媒担持体。8. The photocatalyst carrier according to claim 1, wherein the photoreactive semiconductor containing a metal alkoxide is prepared by converting anatase-type titanium oxide into a sol solution in the presence of a metal alkoxide and an alcohol. .
キシド分１〜３％含有されていることを特徴とする請求
項８記載の光触媒担持体。9. The photocatalyst carrier according to claim 8, wherein the sol solution contains 3 to 10% of titanium oxide and 1 to 3% of alkoxide.
前後の温度で乾燥することを特徴とする請求項１乃至４
記載の光触媒担持体。10. The coated photoreactive semiconductor is heated to 100 ° C.
5. The method according to claim 1, wherein the drying is performed at a temperature before or after the drying.
The photocatalyst carrier according to the above.
００℃で焼成することを特徴とする請求項１乃至４記載
の光触媒担持体。11. The method of claim 1, wherein the dried photoreactive semiconductor is 250 to 6
5. The photocatalyst carrier according to claim 1, wherein the photocatalyst carrier is calcined at 00.degree.
空孔率を有することを特徴とする請求項１記載の光触媒
担持体。12. The photocatalyst carrier according to claim 1, wherein the ceramic base material has a porosity of 80 to 90%.
ルミナシリカ質、コージライト質のいずれかであること
を特徴とする請求項１記載の光触媒担持体。13. The photocatalyst carrier according to claim 1, wherein the ceramic substrate is one of alumina, alumina-silica, and cordierite.
ることを特徴とする請求項１記載の光触媒担持体。14. The photocatalyst carrier according to claim 1, wherein the ceramic base is silicon carbide.
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|---|---|---|---|
| JP2000083505A JP2001259435A (en) | 2000-03-24 | 2000-03-24 | Photocatalyst-supporting body |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000083505A JP2001259435A (en) | 2000-03-24 | 2000-03-24 | Photocatalyst-supporting body |
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|---|---|
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Family
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003053194A (en) * | 2001-08-21 | 2003-02-25 | Seiwa Kogyo Kk | Photocatalyst supporting body and method of manufacturing porous base material for the same |
| JP2005246223A (en) * | 2004-03-03 | 2005-09-15 | Saga Prefecture | Silica gel photocatalyst coated porous material and manufacturing method therefor |
| EP1656985A1 (en) * | 2003-04-23 | 2006-05-17 | National Institute of Advanced Industrial Science and Technology | Three-dimensional fine cell structured photocatalyst filter responding to visible light and method for production thereof, and clarification device |
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| EP1656985A4 (en) * | 2003-04-23 | 2008-10-29 | Nat Inst Of Advanced Ind Scien | Three-dimensional fine cell structured photocatalyst filter responding to visible light and method for production thereof, and clarification device |
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