JPH0788367A - Ethylene degradation photocatalyst - Google Patents
Ethylene degradation photocatalystInfo
- Publication number
- JPH0788367A JPH0788367A JP25775293A JP25775293A JPH0788367A JP H0788367 A JPH0788367 A JP H0788367A JP 25775293 A JP25775293 A JP 25775293A JP 25775293 A JP25775293 A JP 25775293A JP H0788367 A JPH0788367 A JP H0788367A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- ethylene
- outer coating
- carrier
- layer
- 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
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000005977 Ethylene Substances 0.000 title claims abstract description 61
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 26
- 230000015556 catabolic process Effects 0.000 title abstract 5
- 238000006731 degradation reaction Methods 0.000 title abstract 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002245 particle Substances 0.000 claims abstract description 15
- 239000010410 layer Substances 0.000 claims description 53
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 41
- 239000011247 coating layer Substances 0.000 claims description 35
- 238000000926 separation method Methods 0.000 claims description 26
- 238000000354 decomposition reaction Methods 0.000 claims description 24
- 239000000377 silicon dioxide Substances 0.000 claims description 20
- 239000011230 binding agent Substances 0.000 claims description 15
- 230000005540 biological transmission Effects 0.000 claims description 11
- 239000013078 crystal Substances 0.000 claims description 11
- 239000010419 fine particle Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 6
- 238000002834 transmittance Methods 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 abstract description 102
- 239000000463 material Substances 0.000 abstract description 6
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000835 fiber Substances 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 235000012055 fruits and vegetables Nutrition 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012495 reaction gas Substances 0.000 description 3
- 229910002012 Aerosil® Inorganic materials 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000004113 Sepiolite Substances 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 238000007719 peel strength test Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000029058 respiratory gaseous exchange Effects 0.000 description 2
- 229910052624 sepiolite Inorganic materials 0.000 description 2
- 235000019355 sepiolite Nutrition 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 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 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Landscapes
- Storage Of Fruits Or Vegetables (AREA)
- Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、青果物の呼吸作用の進
行に伴って発生するエチレンを光化学的に分解するため
の触媒に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst for photochemically decomposing ethylene produced by the progress of respiration of fruits and vegetables.
【０００２】[0002]
【従来の技術】エチレンガスは青果物の呼吸作用の進行
に伴って発生し、このエチレンガスの作用により青果物
の完熟および老化が促進され、その結果として青果物の
日持ちが悪くなる。したがって、収穫後青果物の移送中
もしくは貯蔵中における鮮度を保持するためには、これ
らから発生するエチレンガスを効率よく除去することが
好ましい。2. Description of the Related Art Ethylene gas is generated along with the progress of respiration of fruits and vegetables, and the action of ethylene gas promotes maturity and aging of fruits and vegetables, resulting in poor shelf life of fruits and vegetables. Therefore, in order to maintain the freshness of the fruits and vegetables after harvesting during transportation or storage, it is preferable to efficiently remove ethylene gas generated from these.
【０００３】本発明者は、先にエチレンガスを効率よく
除去するため、特定粒子径の酸化チタン微粒子を反応ガ
スおよび光が流通可能な白色多孔質担体に担持させ特定
温度で焼成することによって、疎水性を持ちエチレンガ
スを飛躍的に効率よく除去できる白色エチレン分解触媒
を見いだし、特願平４−３５４３１４号として出願した
が、該担体がハニカム構造や三次元網状構造を有してい
るため、担持方法が難しく担体自体の価格が高価である
ことと相まって、結局触媒全体の価格を高いものとして
いた。そこで、さらに改良を重ね製法が簡単で安価であ
るにもかかわらず、光により極めて高いエチレン分解能
を有するシート状エチレン分解触媒を開発し、特願平５
−１１５４０３号として出願した。In order to efficiently remove ethylene gas, the inventor of the present invention supports fine particles of titanium oxide having a specific particle diameter on a white porous carrier through which a reaction gas and light can flow, and calcinates them at a specific temperature. A white ethylene decomposition catalyst having hydrophobicity and capable of dramatically efficiently removing ethylene gas was found, and an application was filed as Japanese Patent Application No. 4-354314. However, since the carrier has a honeycomb structure or a three-dimensional network structure, Combined with the difficulty of the loading method and the expensive price of the carrier itself, the price of the entire catalyst was ultimately high. Therefore, we have developed a sheet-shaped ethylene decomposition catalyst that has an extremely high ethylene resolution by light, even though the manufacturing method is simple and inexpensive, after repeated improvements.
-115403 filed.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、剥離強
度およびエチレン分解能をさらに改善する余地が残って
おり、触媒の剥離強度を改善するとともにエチレン分解
能をさらに改善し光により極めて高いエチレン分解能を
発揮するエチレン分解光触媒を開発することが望まれて
いた。However, there is still room for further improving the peeling strength and the ethylene decomposing ability, and it is possible to improve the peeling strength of the catalyst and further improve the ethylene decomposing ability so that ethylene, which exhibits an extremely high ethylene decomposing ability by light, can be obtained. It was desired to develop a decomposition photocatalyst.
【０００５】[0005]
【課題を解決するための手段】本発明者はこのような問
題点を解決すべく鋭意研究を重ねた結果、高反射率表面
をもつ担体に光の透過性の良いバインダ−を用いて下地
処理し電価分離層を形成することにより、触媒の担持強
度ならびにエチレン分解能をさらに改善できることを見
いだし、さらに触媒活性成分を担持した触媒の上を同様
な光の透過性の良いバインダ−でオ−バ−コ−トするこ
とにより外被膜層を形成すると、剥離強度の向上のみな
らず、不思議なことにエチレン分解能をも一層改善でき
ることを見いだした。本発明はかかる知見に基づいて完
成したものである。As a result of intensive studies to solve the above problems, the present inventor has conducted a surface treatment using a carrier having a high reflectance surface and a binder having a good light transmission property. It was found that the formation of the charge separation layer can further improve the supporting strength of the catalyst and the ethylene decomposing ability, and over the catalyst supporting the catalytically active component with the same binder with good light transmission. -It was found that forming an outer coating layer by coating can not only improve the peel strength but also mysteriously improve the ethylene resolution. The present invention has been completed based on such findings.
【０００６】すなわち、本発明の第一の態様は、高反射
率表面をもつ担体上に光の透過性の良い電価分離層を設
け、その上に１００〜５００オングストローム、好まし
くは１５０〜３００オングストロームの結晶粒子径を有
する酸化チタン微粒子を、担持させたことを特徴とする
エチレン分解光触媒を提供することである。That is, according to the first aspect of the present invention, a charge separation layer having good light transmission is provided on a carrier having a high reflectance surface, and 100 to 500 angstroms, preferably 150 to 300 angstroms is provided thereon. It is intended to provide an ethylene decomposition photocatalyst, characterized in that titanium oxide fine particles having a crystal particle diameter of (3) are carried.
【０００７】本発明の第二の態様は、高反射率表面をも
つ担体上に１００〜５００オングストローム、好ましく
は１５０〜３００オングストロームの結晶粒子径を有す
る酸化チタン微粒子を担持させ、その上に光の透過性の
良い外被膜層を設けることを特徴とするエチレン分解光
触媒を提供することである。In a second aspect of the present invention, titanium oxide fine particles having a crystal grain size of 100 to 500 angstroms, preferably 150 to 300 angstroms are supported on a carrier having a high reflectance surface, and light particles of light are deposited thereon. It is intended to provide an ethylene decomposition photocatalyst characterized by providing an outer coating layer having good permeability.
【０００８】本発明の第三の態様は、高反射率表面をも
つ担体上に光の透過性の良い電化分離層を設け、その上
に１００〜５００オングストローム、好ましくは１５０
〜３００オングストロームの結晶粒子径を有する酸化チ
タン微粒子を担持させ、さらにその上に光の透過性の良
い外被膜層を設けることを特徴とするエチレン分解光触
媒を提供することである。A third aspect of the present invention is to provide a charge separating layer having a good light transmission property on a carrier having a high reflectance surface, and 100 to 500 angstrom, preferably 150, on the charge separating layer.
It is intended to provide an ethylene decomposition photocatalyst, characterized in that titanium oxide fine particles having a crystal particle diameter of ˜300 Å are supported, and an outer coating layer having good light transmission is further provided thereon.
【０００９】[0009]
【構成の詳細】本発明のエチレン分解光触媒の一成分は
高反射率表面をもつ担体である。その１つとしては、白
色の紙状物がある。他の１つは鏡やアルミニウムシート
のように高い反射率表面を構成する鏡面を有するシート
状物である。前記紙状物の構成要素は、例えばコ−ジラ
イト、アルミナ、シリカアルミナ、チタニアシリカ、ジ
ルコニア、ゼオライト、セピオライト等の白色無機物ま
たは天然、半合成あるいは合成高分子よりなる有機物で
ある。また、前記シート状物としては、鏡面をもつ金属
シートを例示することができる。これらの金属シート
は、耐水性に優れており、シ−トの厚さを選択すること
によって任意の機械強度をもたせることができ、さらに
簡便に成形加工できる。なお、金属箔使用の場合は、紙
などの補強材を裏面に積層して使用してもよい。これら
のシート状担体は、触媒の担持前あるいは担持後に耐水
化処理を行うことができる。DETAILED DESCRIPTION OF THE STRUCTURE One component of the ethylene decomposition photocatalyst of the present invention is a carrier having a high reflectance surface. One of them is a white paper-like material. The other one is a sheet-like material having a mirror surface forming a high reflectance surface such as a mirror or an aluminum sheet. The constituents of the paper-like material are, for example, white inorganic materials such as cordierite, alumina, silica-alumina, titania silica, zirconia, zeolite and sepiolite, or organic materials composed of natural, semi-synthetic or synthetic polymers. Further, as the sheet-like material, a metal sheet having a mirror surface can be exemplified. These metal sheets are excellent in water resistance, can be given arbitrary mechanical strength by selecting the thickness of the sheet, and can be easily molded. When a metal foil is used, a reinforcing material such as paper may be laminated on the back surface for use. These sheet-shaped carriers can be subjected to water resistance treatment before or after the catalyst is loaded.
【００１０】シート状エチレン分解光触媒は筒状体とし
て使用することが好ましく、筒状体の形態は、円筒状、
多面柱状などを採ることができる。また、シートを波状
に成形してから筒状体にして使用することにより表面積
の拡大を計ることもできる。なお、光の利用効率は低下
するが、筒状に加工しないシート状エチレン分解光触媒
をそのまま使用することを制限するものではない。The sheet-shaped ethylene decomposition photocatalyst is preferably used as a tubular body, and the tubular body has a cylindrical shape,
For example, a polygonal column can be adopted. Further, the surface area can be increased by forming the sheet into a wavy shape and then using it as a tubular body. It should be noted that although the utilization efficiency of light is reduced, the use of the sheet-shaped ethylene-decomposing photocatalyst that is not processed into a tubular shape as it is is not limited.
【００１１】エチレン含有ガスのガス拡散効率を良く
し、エチレン分解に必要な触媒の量（受光面積）を確保
するために、光源と触媒表面との距離は少なくとも１０
ｍｍ以上、好ましくは２０ｍｍ以上必要である。即ち、
直径１５ｍｍの棒状ランプを用いる場合には、筒状体の
直径は、３５ｍｍ以上、好ましくは５５ｍｍ以上である
ことが好ましい。The distance between the light source and the catalyst surface is at least 10 in order to improve the gas diffusion efficiency of the ethylene-containing gas and to secure the amount of the catalyst (light receiving area) necessary for the decomposition of ethylene.
mm or more, preferably 20 mm or more. That is,
When a rod-shaped lamp having a diameter of 15 mm is used, the diameter of the tubular body is preferably 35 mm or more, more preferably 55 mm or more.
【００１２】多孔質担体としては、反応ガスおよび光が
流通可能で、かつ光を良く反射する白色担体であって、
酸化チタンが担持できるものであれば良い。例えばコ−
ジライト、アルミナ、シリカアルミナ、チタニアシリ
カ、ゼオライト、セピオライト等の白色無機質担体が適
している。担体の色を、光エネルギ−の反射率の高い白
色にすることによって、エチレン分解能を高めることが
でき、清潔感を醸し出すこともできる。多孔質担体は、
反応ガスおよび光の流通が容易なハニカム構造体もしく
は三次元網状構造体が好ましい。該ハニカム構造は、例
えば特公昭５９−１５０２８号公報に提案されているよ
うなセラミック繊維の集合体（ハニクル担体）、すなわ
ち珪酸ゲルにより互いに結合されているシリカ繊維、ア
ルミナ繊維、アルミノシリケ−ト繊維、ジルコニア繊維
などの無機繊維から選択されるセラミック繊維のシ−ト
状集合体をハニカム状に積層して構成されるハニカム構
造であれば圧力損失も少なく幾何学表面積も大きいので
より好ましい。また該三次元網状構造体としては、例え
ば特公昭５７−３５０４８号公報に開示されているよう
なセラミック多孔体が光を良く透過し圧力損失も少なく
幾何学表面積も大きいので特に好ましいものである。The porous carrier is a white carrier through which a reaction gas and light can flow and which reflects light well,
Any material that can support titanium oxide may be used. For example
White inorganic carriers such as gillite, alumina, silica-alumina, titania silica, zeolite, sepiolite are suitable. By changing the color of the carrier to white, which has a high reflectance of light energy, the ethylene resolution can be increased and a clean feeling can be produced. The porous carrier is
A honeycomb structure or a three-dimensional network structure which allows easy passage of the reaction gas and light is preferable. The honeycomb structure is composed of an aggregate of ceramic fibers (hanicle carrier) as proposed in Japanese Patent Publication No. 59-15028, that is, silica fibers, alumina fibers, aluminosilicate fibers which are bonded to each other by silica gel. A honeycomb structure formed by stacking a sheet-shaped aggregate of ceramic fibers selected from inorganic fibers such as zirconia fibers in a honeycomb shape is more preferable because it has a small pressure loss and a large geometric surface area. Further, as the three-dimensional network structure, for example, a ceramic porous body as disclosed in Japanese Patent Publication No. 57-35048 is particularly preferable because it transmits light well, has a small pressure loss, and has a large geometric surface area.
【００１３】本発明においては、光源と前記多孔質触媒
の組合せに加えて、光源と反対方向の該触媒の背後に反
射板を設けたエチレン分解装置とすることにより、光の
照射効率を一層向上させることができる。さらに、該触
媒の厚さを調整することにより、光の透過をより容易に
し、エチレンの分解効率を向上させることができる。す
なわち、該触媒の厚さは、薄すぎるとエチレンの分解性
能が低下するのみならず、機械的強度も低下し、僅かな
衝撃によっても崩壊し、厚すぎても反応に寄与しない部
分が多くなり触媒として不経済となるので、５〜４０ｍ
ｍとするのが好適である。In the present invention, in addition to the combination of the light source and the porous catalyst, an ethylene decomposing device is provided with a reflecting plate behind the catalyst in the direction opposite to the light source, whereby the light irradiation efficiency is further improved. Can be made. Furthermore, by adjusting the thickness of the catalyst, light can be more easily transmitted and the decomposition efficiency of ethylene can be improved. That is, when the thickness of the catalyst is too thin, not only the decomposition performance of ethylene is lowered, but also the mechanical strength is lowered, the catalyst is disintegrated even by a slight impact, and if it is too thick, there are many portions that do not contribute to the reaction. 5-40m as it becomes uneconomical as a catalyst
It is preferable that it is m.
【００１４】本発明のエチレン分解光触媒のもう一つの
構成成分は、担体上に形成された光の透過性の良い電価
分離層である。この電価分離層は、担体と触媒活性成分
との電気絶縁性を良好なものとし、触媒金属の電子が担
体へ放出され、活性が低下すること防止するものである
と推定される。さらにこの電気絶縁性と相まって、この
電価分離層は触媒活性成分を強固に担体上に保持し、光
の透過性が良く光エネルギ−を損なわない特性を合わせ
持つものであることが好ましい。この電価分離層は、光
の透過性のよいシリカ系バインダ−を用いて、エアスプ
レ−法、浸漬法等の従来法によって担体上に形成するこ
とができる。電価分離層の担持量は、０．０５〜０．３
ｍｇ／ｃｍ2（電価分離層の厚さに換算すると０．５〜
３μｍ）、好ましくは０．１〜０．２ｍｇ／ｃｍ2（電
価分離層の厚さに換算すると１〜２μｍ）である。Another component of the ethylene-decomposing photocatalyst of the present invention is a charge separation layer formed on a carrier and having good light transmittance. It is presumed that the charge separation layer has good electric insulation between the carrier and the catalytically active component, and prevents electrons of the catalytic metal from being released to the carrier and thus deteriorating the activity. Further, in combination with this electric insulation property, it is preferable that the charge separation layer has a property of firmly holding the catalytically active component on the carrier, has a good light transmission property and does not impair the light energy. This charge separation layer can be formed on the carrier by a conventional method such as an air spray method or a dipping method using a silica-based binder having good light transmittance. The carrying amount of the charge separation layer is 0.05 to 0.3.
mg / cm 2 (0.5 to when converted to the thickness of the charge separation layer)
3 μm), preferably 0.1 to 0.2 mg / cm 2 (1 to 2 μm when converted to the thickness of the charge separation layer).
【００１５】本発明のエチレン分解光触媒の他のもう一
つの構成成分は光触媒成分であって、金属酸化物半導体
系光触媒としての酸化チタンである。酸化チタンの結晶
粒子経は１００〜５００オングストローム、好ましくは
１５０〜３００オングストロームのものが特に光による
エチレン分解能が優れている。光触媒成分の担持量は光
源の強さに依存するが、バインダーとの合計でシート状
担体の面積（ｃｍ2）当たり０．３〜５．０ｍｇ（触媒
層の厚さに換算すると３〜５０μｍ）、好ましくは０．
５〜３．０ｍｇ（触媒層の厚さに換算すると５〜３０μ
ｍ）である。好ましい触媒層の厚みを得るための光触媒
成分の担持量は、担体がハニカム構造体からなるものに
ついては、バインダーとの合計で触媒構造体全容積に対
して２０〜２００ｇ／ｌ、好ましくは５０〜１５０ｇ／
ｌ、セラミック繊維の集合体からなるものについては１
０〜１００ｇ／ｌ、好ましくは２０〜５０ｇ／ｌ、三次
元網状構造体からなるものについては２〜５０ｇ／ｌ、
さらに好ましくは２〜１５ｇ／ｌであり、これが担体に
バインダ−により保持される。バインダーは、光の透過
率のよいシリカ系バインダーが好ましく、光触媒成分の
重量の１０〜３０％の量で使用する。Another component of the ethylene decomposition photocatalyst of the present invention is a photocatalyst component, which is titanium oxide as a metal oxide semiconductor photocatalyst. Titanium oxide having a crystal particle size of 100 to 500 angstroms, preferably 150 to 300 angstroms, is particularly excellent in the ability to decompose ethylene by light. The amount of the photocatalyst component carried depends on the strength of the light source, but the total amount with the binder is 0.3 to 5.0 mg per area (cm 2 ) of the sheet-like carrier (3 to 50 μm when converted to the thickness of the catalyst layer). , Preferably 0.
5 to 3.0 mg (5 to 30 μ when converted to the thickness of the catalyst layer
m). The supported amount of the photocatalyst component for obtaining a preferable thickness of the catalyst layer is 20 to 200 g / l, preferably 50 to 50 with respect to the total volume of the catalyst structure when the carrier is composed of a honeycomb structure, in total with the binder. 150 g /
l, 1 for a composite of ceramic fibers
0 to 100 g / l, preferably 20 to 50 g / l, 2 to 50 g / l for a three-dimensional network structure,
More preferably, it is 2 to 15 g / l, which is held on the carrier by a binder. The binder is preferably a silica-based binder having good light transmittance, and is used in an amount of 10 to 30% by weight of the photocatalyst component.
【００１６】本発明のエチレン分解光触媒のさらなる構
成成分は、触媒層の上に設けられた機械強度が高く光の
透過性の良い外被膜層である。この外被膜層は、光エネ
ルギ−を無駄に吸収せず光を良く透過するものであっ
て、外被膜層形成時に触媒層にも浸透して触媒層の酸化
チタンの結晶粒子と、バインダーとして用いたシリカ系
成分に起因するＳｉＯ2の結晶粒子をさらに緊密に結合
させる。このようにシリカ系オーバーコート層（外被膜
層）を設けたにもかかわらず、驚くことに触媒層の透明
性が増加し、その結果、光の透過性を改善することがで
きた。この外被膜層はシリカ微粒子によって構成するこ
とが好ましい。すなわち、この外被膜層は、光の透過性
のよいシリカ系バインダ−を用いて、エアスプレ−法、
浸漬法等の従来法によって触媒層の上に形成できる。外
被膜層の担持量は、０．０５〜１．０ｍｇ／ｃｍ2（外
被膜層の厚さに換算すると０．５〜１０μｍ）、好まし
くは０．１〜０．５ｍｇ／ｃｍ2（外被膜層の厚さに換
算すると１〜５μｍ）である。A further constituent component of the ethylene decomposition photocatalyst of the present invention is an outer coating layer provided on the catalyst layer and having high mechanical strength and good light transmission. This outer coating layer does not wastefully absorb light energy and transmits light well, and when the outer coating layer is formed, it penetrates into the catalyst layer and serves as titanium oxide crystal particles in the catalyst layer and as a binder. The SiO 2 crystal particles resulting from the silica-based component are further tightly bonded. Even though the silica-based overcoat layer (outer coating layer) was thus provided, the transparency of the catalyst layer was surprisingly increased, and as a result, the light transmittance could be improved. This outer coating layer is preferably composed of silica fine particles. That is, this outer coating layer is formed by using a silica-based binder having a good light transmission property by an air spray method,
It can be formed on the catalyst layer by a conventional method such as a dipping method. The supported amount of the outer coating layer is 0.05 to 1.0 mg / cm 2 (0.5 to 10 μm when converted to the thickness of the outer coating layer), preferably 0.1 to 0.5 mg / cm 2 (outer coating It is 1 to 5 μm when converted to the layer thickness.
【００１７】光源としては、酸化チタンを光化学的に励
起させるものであればよく、３.２ｅＶ以上のバンドギ
ャップを有し、波長が３８８ｎｍ以下の紫外線を放出
し、触媒成分に光エネルギーを供給するものであればよ
い。The light source may be any one that photochemically excites titanium oxide, has a band gap of 3.2 eV or more, emits ultraviolet rays having a wavelength of 388 nm or less, and supplies light energy to the catalyst component. Anything will do.
【００１８】[0018]
【実施例】以下の実施例により本発明を更に詳しく説明
するが、本発明はこれら実施例によって何ら限定される
ものではない。The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
【００１９】実施例１ 日産化学工業社製のスノーテックス−ＯＵＰ（ＳｉＯ2
を２０重量％含有）をイオン交換水で希釈しＳｉＯ2の
含有量が５重量％のシリカ溶液を調製た。１５０ｍｍ×
２９８ｍｍに切断したアルミニウム板に、前記シリカ溶
液をエア−スプレ−法により均一に塗布した後、１５０
℃の温度で３時間乾燥して、０．１５ｍｇ／ｃｍ2（電
価分離層の厚さに換算すると１．５μｍ）のＳｉＯ2か
らなる電価分離層をアルミニウム板に担持形成し、下地
処理担体を得た。イオン交換水３０００ｇに６０重量％
の濃硝酸６ｇを加えた溶液に、バインダ−として５００
ｇの日産化学工業社製のスノーテックス−ＯＵＰ（Ｓｉ
Ｏ2を２０重量％含有）を加えて混合した。この溶液に
５００ｇの日本アエロジル社製酸化チタン粉末Ｐ−２５
をターボミキサーで混合しながら加え、ＳｉＯ2を２.５
重量％、ＴｉＯ2を１２.５重量％含有する触媒スラリー
溶液４０００ｇを得た。得られた上記の下地処理担体
に、前記触媒スラリー溶液をエア−スプレ−法により均
一に塗布した後、１５０℃の温度で３時間乾燥して、Ｔ
ｉＯ2とＳｉＯ2との合計量で０．７ｍｇ／ｃｍ2（触媒
層の厚さに換算すると７μｍ）を担持したシ−ト状触媒
を得た。得られたシ−ト状触媒を筒状体に丸め、触媒Ａ
を調製した。Example 1 Snowtex-OUP (SiO 2 manufactured by Nissan Chemical Industries, Ltd.
Of 20% by weight) was diluted with ion-exchanged water to prepare a silica solution having a SiO 2 content of 5% by weight. 150 mm x
The silica solution was uniformly applied to an aluminum plate cut into 298 mm by an air spray method, and then 150
After drying for 3 hours at a temperature of ℃, 0.15 mg / cm 2 (1.5 μm in terms of the thickness of the charge separation layer) of a charge separation layer made of SiO 2 is supported and formed on an aluminum plate, and the surface treatment is performed. A carrier was obtained. 60% by weight in 3000 g of ion-exchanged water
To the solution containing 6 g of concentrated nitric acid, 500 as a binder
Snowtex-OUP (Si manufactured by Nissan Chemical Industries, Ltd.
The O 2 was added and mixed 20 wt% content). 500 g of titanium dioxide powder P-25 manufactured by Nippon Aerosil Co., Ltd. was added to this solution.
While mixing with a turbo mixer, add SiO 2 to 2.5
By weight, 4000 g of a catalyst slurry solution containing 12.5% by weight of TiO 2 was obtained. The catalyst slurry solution was uniformly applied to the obtained base treatment carrier by an air spray method, and then dried at a temperature of 150 ° C. for 3 hours to obtain T
A sheet-like catalyst supporting 0.7 mg / cm 2 (7 μm in terms of the thickness of the catalyst layer) in the total amount of iO 2 and SiO 2 was obtained. The obtained sheet-shaped catalyst was rolled into a cylindrical body, and a catalyst A
Was prepared.
【００２０】比較例１ 下地処理をせず（電価分離層を有さない）、１５０ｍｍ
×２９８ｍｍに切断したアルミニウム板をそのまま用い
た以外は、実施例１と同様にして、ＴｉＯ2とＳｉＯ2と
の合計量で１．０ｍｇ／ｃｍ2（触媒層の厚さに換算す
ると１０μｍ）を担持したシ−ト状触媒を調製し、得ら
れたシ−ト状触媒を筒状体に丸め、触媒Ｘを得た。Comparative Example 1 No base treatment (no charge separation layer), 150 mm
The total amount of TiO 2 and SiO 2 was 1.0 mg / cm 2 (10 μm when converted to the thickness of the catalyst layer) in the same manner as in Example 1 except that the aluminum plate cut to × 298 mm was used as it was. A supported sheet-like catalyst was prepared, and the obtained sheet-like catalyst was rolled into a cylindrical body to obtain a catalyst X.
【００２１】実施例２ 比較例１で得られた触媒Ｘの触媒層の上に、実施例１の
下地処理に用いたと同じ５重量％シリカ溶液を、エア−
スプレ−法により均一に塗布した後、１５０℃の温度で
３時間乾燥して、ＳｉＯ2を０．１７ｍｇ／ｃｍ2（外被
膜層の厚さに換算すると１．７μｍ）をさらにオ−バ−
コ−ト担持し、外被膜層をその上に形成したオ−バ−コ
−トシ−ト状触媒を得た。得られたシ−ト状触媒を、筒
状体に丸めた触媒Ｂを調製した。Example 2 On the catalyst layer of the catalyst X obtained in Comparative Example 1, the same 5 wt% silica solution used for the base treatment of Example 1 was air-dried.
Spray - it was uniformly applied by law, and dried 3 hours at a temperature of 0.99 ° C., (when converted into the thickness of the outer coating layer 1.7 [mu] m) the SiO 2 0.17mg / cm 2 for an additional O - Ba -
An overcoat-sheet-like catalyst having a coat supported thereon and an outer coating layer formed thereon was obtained. The obtained sheet-shaped catalyst was rolled into a tubular body to prepare a catalyst B.
【００２２】実施例３ 実施例２において、比較例１で得られた触媒Ｘに代えて
実施例１で得られた触媒Ａを用いたことを除いて同様に
して、０．１５ｍｇ／ｃｍ2（外被膜層の厚さに換算す
ると１．５μｍ）のＳｉＯ2をさらに実施例１で得られ
た触媒Ａにオ−バ−コ−ト担持し、外被膜層を有するシ
−ト状触媒を得た。得られたシ−ト状触媒を筒状体に丸
め、触媒Ｃを調製した。実施例２および実施例３におい
て得られた外被膜層を有する触媒は、外被膜層を担持形
成する際、シリカ溶液が触媒層にも浸透し触媒層自体の
透明度も改善されていることが視認された。前記実施例
１〜３で得られた触媒Ａ〜Ｃおよび比較例１で得られた
触媒Ｘを用いて下記のエチレン分解能評価試験１を行っ
た。Example 3 In the same manner as in Example 2, except that the catalyst A obtained in Example 1 was used in place of the catalyst X obtained in Comparative Example 1, 0.15 mg / cm 2 ( SiO 2 ( 1.5 μm in terms of the thickness of the outer coating layer) was further carried on the catalyst A obtained in Example 1 in an overcoat to obtain a sheet-like catalyst having an outer coating layer. It was The sheet-like catalyst thus obtained was rolled into a cylindrical body to prepare a catalyst C. In the catalysts having the outer coating layer obtained in Examples 2 and 3, when the outer coating layer was supported and formed, it was visually confirmed that the silica solution penetrated into the catalyst layer and the transparency of the catalyst layer itself was improved. Was done. Using the catalysts A to C obtained in Examples 1 to 3 and the catalyst X obtained in Comparative Example 1, the following ethylene decomposition evaluation test 1 was conducted.
【００２３】エチレン分解能評価試験１ 波長が２５４ｎｍの紫外線を放出する１２Ｗのプリンス
社製紫外線殺菌ランプ（ＱＧＵＬＲ−１１−２００Ｎ）
を、載架した筒状試料触媒の中心軸上に挿入載架し、そ
の下方部に大気の循環用のファンを設置した１６リッタ
ーのガラスケースに、９９.６％のエチレン１.６ｍｌを
注入し、ガラスケース内のエチレン濃度を１００ｐｐｍ
に調整した。試料触媒を設置した後、試料触媒のエチレ
ン吸着性能を見るため、最初の十分間はファンにより大
気を循環させるのみで該ランプを点燈しないで、エチレ
ン濃度の変化を測定したが、エチレン濃度は変化せずエ
チレンは試料触媒には吸着されていないことがわかっ
た。１０分経過した後、該ランプを点灯し、点灯後５０
分経過後のエチレン濃度を測定した。その結果を表１、
２に示す。なお、筒状試料触媒の一部を重ね合わすよう
に巻き込むことによって筒体の直径を調整した。Ethylene resolution evaluation test 1 12 W Prince germ UV lamp (QGULR-11-200N) that emits ultraviolet rays having a wavelength of 254 nm
Was inserted and mounted on the central axis of the mounted cylindrical sample catalyst, and 1.6 ml of 99.6% ethylene was injected into a 16-liter glass case in which a fan for circulating the atmosphere was installed in the lower part. The ethylene concentration in the glass case to 100 ppm
Adjusted to. After installing the sample catalyst, in order to see the ethylene adsorption performance of the sample catalyst, the change in ethylene concentration was measured without first turning on the lamp by circulating the atmosphere with a fan for the first ten minutes. It was found that ethylene remained unchanged and was not adsorbed on the sample catalyst. After 10 minutes, turn on the lamp, and then turn on 50
After a lapse of minutes, the ethylene concentration was measured. The results are shown in Table 1,
2 shows. The diameter of the cylindrical body was adjusted by winding the cylindrical sample catalysts so that they overlap each other.
【００２４】[0024]
【表１】 [Table 1]
【００２５】[0025]
【表２】 表１、２から明らかなように、本発明のシ−ト状触媒
Ａ、ＢおよびＣはいずれも、電価分離層も外被膜層も持
たない従来の触媒Ｘに比べて極めて優れたエチレン分解
性能を有することが裏付けられた。[Table 2] As is clear from Tables 1 and 2, all of the sheet-like catalysts A, B and C of the present invention are extremely excellent in the decomposition of ethylene as compared with the conventional catalyst X having neither a charge separation layer nor an outer coating layer. It has been proved that it has performance.
【００２６】実施例４ 日産化学工業社製のスノーテックス−ＯＵＰ（ＳｉＯ2
を２０重量％含有）をイオン交換水で希釈しＳｉＯ2の
含有量が２重量％のシリカ溶液を調製した。この２重量
％シリカ溶液に、アルミノシリケ−ト繊維のシ−ト状集
合体によって構成されるハニカム構造体を有するニチア
ス社製白色ハニクル担体（２００セル、縦６０ｍｍ、横
１５０ｍｍ、厚さ１０ｍｍ）を浸漬し、取り出し、余剰
のスラリーを空気を吹き付けて除去した後、１５０℃の
温度で６時間乾燥し、触媒の容積１リッター当り３ｇの
ＳｉＯ2（０．２ｍｇ／ｃｍ2に相当し、電価分離層の厚
さに換算すると２μｍ）を担持し、電価分離層を形成し
た下地処理ハニクル担体を得た。イオン交換水３０００
ｇに６０重量％の濃硝酸６ｇを加えた溶液に、バインダ
−として１０００ｇの日産化学工業社製のスノーテック
ス−ＯＵＰ（ＳｉＯ2を２０重量％含有）を加えて混合
した。この溶液に５００ｇの日本アエロジル社製酸化チ
タン粉末Ｐ−２５をターボミキサーで混合しながら加
え、ＳｉＯ2を２.５重量％、ＴｉＯ2を１２.５重量％含
有する触媒スラリー溶液４０００ｇを得た。上記下地処
理ハニクル担体を、得られた触媒スラリー溶液に浸漬
し、取り出し、余剰のスラリーを空気を吹き付けて除去
した後、１５０℃の温度で６時間乾燥し、５００℃の温
度で１時間焼成して、触媒の容積１リッター当りＴｉＯ
2とＳｉＯ2との合計量で３７ｇ（２．４７ｍｇ／ｃｍ2
に相当し、触媒層の厚さに換算すると２４．７μｍ）を
担持した触媒Ｄを得た。Example 4 Snowtex-OUP (SiO 2 manufactured by Nissan Chemical Industries, Ltd.
Of 20% by weight) was diluted with ion-exchanged water to prepare a silica solution having a SiO 2 content of 2% by weight. A 2% by weight silica solution was dipped in a white hanicle carrier (200 cells, length 60 mm, width 150 mm, thickness 10 mm) manufactured by Nichias Co., which has a honeycomb structure composed of a sheet-shaped aggregate of aluminosilicate fibers. After removing the excess slurry by blowing air, the slurry was dried at a temperature of 150 ° C. for 6 hours to obtain 3 g of SiO 2 (corresponding to 0.2 mg / cm 2 ) per 1 liter of the volume of the catalyst. (2 μm in terms of the thickness), and an undertreated hanicle carrier having a charge separation layer formed thereon was obtained. Ion-exchanged water 3000
To a solution obtained by adding 6 g of 60% by weight concentrated nitric acid to g, 1000 g of Snowtex-OUP (containing 20% by weight of SiO 2 ) manufactured by Nissan Chemical Industries, Ltd. was added and mixed as a binder. The solution of 500g Nippon Aerosil Co., Ltd. titanium oxide powder P-25 was added with mixing at turbomixer, a SiO 2 2.5 wt%, to obtain a catalyst slurry solution 4000g containing TiO 2 12.5% by weight . The above-mentioned base treatment hanicle carrier is immersed in the obtained catalyst slurry solution, taken out, and excess slurry is blown off with air to be removed, followed by drying at a temperature of 150 ° C. for 6 hours and firing at a temperature of 500 ° C. for 1 hour. TiO2 per 1 liter volume of catalyst
The total amount of 2 and SiO 2 is 37 g (2.47 mg / cm 2
Corresponding to the above, and converted into the thickness of the catalyst layer, a catalyst D carrying 24.7 μm) was obtained.
【００２７】比較例２ 担体に下地処理を行わないことを除いて実施例１と同様
にして、触媒の容積１リッター当りＴｉＯ2とＳｉＯ2と
の合計量で３８ｇ（２．５３ｍｇ／ｃｍ2に相当し、触
媒層の厚さに換算すると２５．３μｍ）を担持した触媒
Ｙ（電価分離層、外皮膜層なし）を得た。Comparative Example 2 In the same manner as in Example 1 except that the carrier was not subjected to a base treatment, the total amount of TiO 2 and SiO 2 per liter of the catalyst was 38 g (equivalent to 2.53 mg / cm 2). Then, when converted to the thickness of the catalyst layer, a catalyst Y (without a charge separation layer and an outer coating layer) carrying 25.3 μm) was obtained.
【００２８】実施例５ 比較例２の触媒Ｙを、実施例４の２重量％のシリカ溶液
に浸漬し、取り出し、余剰のスラリーを空気を吹き付け
て除去した後、１５０℃の温度で６時間乾燥し、触媒の
容積１リッター当り３ｇのＳｉＯ2（０．２ｍｇ／ｃｍ2
に相当し、外被膜層の厚さに換算すると２μｍ）よりな
る外被膜層をもつ触媒Ｅを得た。Example 5 The catalyst Y of Comparative Example 2 was dipped in the 2% by weight silica solution of Example 4, taken out, the excess slurry was blown with air to remove it, and then dried at a temperature of 150 ° C. for 6 hours. 3 g of SiO 2 (0.2 mg / cm 2
And a catalyst E having an outer coating layer of 2 μm in terms of the thickness of the outer coating layer was obtained.
【００２９】実施例６ 比較例２の触媒Ｙに代えて実施例４の触媒Ｄを用いたこ
とを除いて比較例３と同様にして、触媒の容積１リッタ
ー当り３ｇのＳｉＯ2（０．２ｍｇ／ｃｍ2に相当し、外
被膜層の厚さに換算すると２μｍ）を担持し、さらに、
その上に外被膜層を形成し、触媒Ｆを得た。実施例５お
よび実施例６において得られたオ−バ−コ−ト層、すな
わち外被膜層を有する触媒Ｅおよび触媒Ｆは、実施例２
および実施例３の外被膜層を有する触媒Ｂおよび触媒Ｃ
と同様に、外被膜層を担持形成する際に、外被膜を形成
するためのシリカ溶液がすでに担持されている触媒層に
も浸透し全体の透明度も改善されることが視認された。
前記実施例４〜６で得られた触媒Ｄ〜Ｆおよび比較例２
で得られた触媒Ｙを用いて下記のエチレン分解能評価試
験２を行った。Example 6 The procedure of Comparative Example 3 was repeated except that the catalyst Y of Comparative Example 2 was replaced with the catalyst D of Example 4, and 3 g of SiO 2 (0.2 mg) was added per 1 liter of the catalyst volume. / Cm2, which corresponds to 2 μm when converted to the thickness of the outer coating layer, and further,
An outer coating layer was formed thereon to obtain a catalyst F. The catalyst E and the catalyst F having the overcoat layer, that is, the outer coating layer, obtained in Examples 5 and 6 were the same as those in Example 2
And Catalyst B and C with the outer coating layer of Example 3.
Similarly, when supporting and forming the outer coating layer, it was visually confirmed that the silica solution for forming the outer coating penetrates into the already-supported catalyst layer to improve the overall transparency.
Catalysts D to F obtained in Examples 4 to 6 and Comparative Example 2
The following ethylene decomposition evaluation test 2 was conducted using the catalyst Y obtained in 1.
【００３０】エチレン分解能評価試験２ 波長が２５４ｎｍの紫外線を放出する１２Ｗのプリンス
社製紫外線殺菌ランプ（ＱＧＵＬＲ−１１−２００Ｎ）
を使用し、該ランプの照射効率を上げるため、アルミ板
等の反射材をその背後に設置し、該ランプから４ｃｍの
距離を置いた位置に試料触媒を載架し、その下方部に大
気の循環用のファンを設置した１６リッターのガラスケ
ースに、９９.６％のエチレン１.６ｍｌを注入し、ガラ
スケース内のエチレン濃度を１００ｐｐｍに調整した。
試料触媒を設置した後、試料触媒のエチレン吸着性能を
見るため、最初の十分間はファンにより大気を循環させ
るのみで該ランプを点燈しないで、エチレン濃度の変化
を測定したが、エチレン濃度は変化せずエチレンは試料
触媒には吸着されていないことがわかった。１０分経過
した後、該ランプを点灯し、点灯後５０分経過後のエチ
レン濃度を測定した。その結果を表３に示す。Ethylene resolution evaluation test 2 12 W Prince UV ultraviolet sterilization lamp (QGULR-11-200N) which emits ultraviolet rays having a wavelength of 254 nm.
In order to increase the irradiation efficiency of the lamp, a reflector such as an aluminum plate is installed behind it, and the sample catalyst is placed at a position 4 cm away from the lamp, and the atmosphere below the sample catalyst. 1.6 ml of 99.6% ethylene was injected into a 16-liter glass case equipped with a circulation fan, and the ethylene concentration in the glass case was adjusted to 100 ppm.
After installing the sample catalyst, in order to check the ethylene adsorption performance of the sample catalyst, the change in ethylene concentration was measured without first turning on the lamp by circulating the atmosphere with a fan for the first ten minutes. It was found that ethylene remained unchanged and was not adsorbed on the sample catalyst. After 10 minutes, the lamp was turned on, and the ethylene concentration was measured 50 minutes after the lighting. The results are shown in Table 3.
【００３１】[0031]
【表３】 表３から明らかなように、本発明のハニクル担体触媒
Ｄ，ＥおよびＦはいずれも、電価分離層も外被膜層も持
たない従来の触媒Ｙに比べて極めて優れたエチレン分解
性能を有することが裏付けられた。[Table 3] As is clear from Table 3, all of the hanicle carrier catalysts D, E and F of the present invention have extremely excellent ethylene decomposing performance as compared with the conventional catalyst Y having neither a charge separation layer nor an outer coating layer. Was backed up.
【００３２】つぎに、触媒の剥離強度を調べるため、比
較例２の触媒Ｙおよび実施例４の触媒Ｄを用いて下記の
超音波振動剥離強度試験を行った。Next, in order to examine the peel strength of the catalyst, the following ultrasonic vibration peel strength test was conducted using the catalyst Y of Comparative Example 2 and the catalyst D of Example 4.
【００３３】超音波振動剥離強度試験 試料を、１５０℃の温度で２時間加熱し後、試料の重量
を測定した。ついで、超音波洗浄装置（島津製作所製
ＳＵＳ−１０３型）の水槽の水中に試料を入れ、４５ｋ
Ｈｚの周波数で２０分間処理した。超音波処理した試料
を１５０℃の温度で２時間乾燥した後、重量を測定し、
超音波処理前後の重量差から試料の剥離量を求めた。電
価分離層を有する実施例４の触媒Ｄの剥離量が１．８ｍ
ｇ／ｇであるのに対して、電価分離層も外被膜層ももた
ない比較例２の触媒Ｙの剥離量は５．０ｍｇ／ｇと多か
ったが、これにより電価分離層をもつだけでも剥離強度
が改善されたことが裏付けられた。電価分離層に加え
て、さらに外被膜層を形成した触媒の剥離量はさらに少
なく、測定値は誤差範囲で実質的に剥離は認められなか
った。すなわち、シリカバインダ−で、下地処理または
オ−バ−コ−ト処理の一方もしくは両方を施した本発明
の触媒の機械強度の改善が裏付けられた。Ultrasonic Vibration Peel Strength Test After heating the sample at a temperature of 150 ° C. for 2 hours, the weight of the sample was measured. Next, ultrasonic cleaning device (manufactured by Shimadzu Corporation)
Put the sample in the water of the water tank of SUS-103 type), 45k
It was treated at a frequency of Hz for 20 minutes. After the ultrasonically treated sample was dried at a temperature of 150 ° C. for 2 hours, the weight was measured,
The amount of peeling of the sample was determined from the weight difference before and after ultrasonic treatment. The stripping amount of the catalyst D of Example 4 having a charge separation layer was 1.8 m.
In contrast to g / g, the amount of peeling of the catalyst Y of Comparative Example 2 having neither the charge separation layer nor the outer coating layer was as large as 5.0 mg / g, which resulted in the charge separation layer. It was confirmed that the peel strength was improved even by itself. In addition to the charge separation layer, the amount of peeling of the catalyst on which the outer coating layer was further formed was smaller, and the measured value was within the error range, and substantially no peeling was observed. That is, the improvement of the mechanical strength of the catalyst of the present invention which was subjected to one or both of the base treatment and the overcoat treatment with the silica binder was proved.
【００３４】[0034]
【発明の効果】本発明のエチレン分解光触媒は、電価分
離層を担体と触媒層の間に設けることによってエチレン
分解能が改善され、また触媒成分がより強固に担体に保
持されるため触媒層に割れや亀裂が入り難くなり触媒層
の剥離が少ないという顕著な効果を奏する。さらに、外
被膜層をその上に形成した本発明のエチレン分解光触媒
は、外被膜層形成時にシリカバインダ−が触媒層にも浸
透して触媒層の酸化チタンの結晶粒子とＳｉＯ2の結晶
粒子をさらに緊密に結合させるために、触媒層の透明性
が増加し光の透過性が改善されるためエチレン分解能が
向上するのみならず、触媒層の下に設けられた電価分離
層の働きと相まって触媒活性成分の剥離強度をさらに増
加させるという極めて顕著な効果を奏する。INDUSTRIAL APPLICABILITY The ethylene decomposition photocatalyst of the present invention improves the ethylene decomposing ability by providing the charge separation layer between the carrier and the catalyst layer, and since the catalyst component is more firmly retained on the carrier, It has a remarkable effect that cracks and cracks are less likely to occur and the catalyst layer is less likely to be peeled off. Furthermore, in the ethylene decomposition photocatalyst of the present invention having the outer coating layer formed thereon, the silica binder penetrates into the catalyst layer during the formation of the outer coating layer to form titanium oxide crystal particles and SiO 2 crystal particles in the catalyst layer. In order to bond more closely, the transparency of the catalyst layer is increased and the light transmission is improved, so not only the ethylene decomposing ability is improved, but also in combination with the action of the charge separation layer provided under the catalyst layer. It has a very remarkable effect of further increasing the peel strength of the catalytically active component.
Claims (6)
の良い電価分離層を設け、その上に１００〜５００オン
グストロームの結晶粒子径を有する酸化チタン微粒子を
担持させたことを特徴とするエチレン分解光触媒。1. A charge separation layer having good light transmittance is provided on a carrier having a high reflectance surface, and titanium oxide fine particles having a crystal particle size of 100 to 500 angstroms are carried thereon. And ethylene decomposition photocatalyst.
００オングストロームの結晶粒子径を有する酸化チタン
微粒子を担持させ、その上に光の透過性の良い外被膜層
を設けることを特徴とするエチレン分解光触媒。2. 100 to 5 on a carrier having a high reflectance surface.
An ethylene decomposition photocatalyst comprising titanium oxide fine particles having a crystal particle diameter of 00 angstrom supported thereon, and an outer coating layer having good light transmittance provided thereon.
の良い電化分離層を設け、その上に１００〜５００オン
グストロームの結晶粒子径を有する酸化チタン微粒子を
担持させ、さらにその上に光の透過性の良い外被膜層を
設けることを特徴とするエチレン分解光触媒。3. A charge separation layer having good light transmission is provided on a carrier having a high reflectance surface, and titanium oxide fine particles having a crystal particle diameter of 100 to 500 angstroms are carried thereon, and further thereon. An ethylene decomposition photocatalyst, which is provided with an outer coating layer having good light transmission.
がシリカ系バインダ−により構成されている請求項１、
２または３記載のエチレン分解光触媒。4. The method according to claim 1, wherein the charge separation layer and / or the outer coating layer is composed of a silica-based binder.
The ethylene decomposition photocatalyst according to 2 or 3.
の厚みが、それぞれ０．５〜３μｍ、０．５〜１０μｍ
である請求項１、２、３または４記載のエチレン分解光
触媒。5. The thickness of the charge separation layer and / or the outer coating layer is 0.5 to 3 μm and 0.5 to 10 μm, respectively.
The ethylene decomposition photocatalyst according to claim 1, 2, 3, or 4.
〜３００オングストロームである請求項１、２、３、４
または５記載のエチレン分解光触媒。6. The titanium oxide fine particles have a particle size of 150.
~ 300 angstroms.
Or the ethylene decomposition photocatalyst according to 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25775293A JP3499585B2 (en) | 1993-09-21 | 1993-09-21 | Ethylene decomposition photocatalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25775293A JP3499585B2 (en) | 1993-09-21 | 1993-09-21 | Ethylene decomposition photocatalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0788367A true JPH0788367A (en) | 1995-04-04 |
| JP3499585B2 JP3499585B2 (en) | 2004-02-23 |
Family
ID=17310612
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25775293A Expired - Lifetime JP3499585B2 (en) | 1993-09-21 | 1993-09-21 | Ethylene decomposition photocatalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3499585B2 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09230810A (en) * | 1995-12-22 | 1997-09-05 | Toto Ltd | Outdoor display board and its cleaning method |
| EP0812619A1 (en) * | 1996-06-12 | 1997-12-17 | Eastman Kodak Company | Inorganic transparent photocatalytic composition |
| JPH11512336A (en) * | 1995-09-15 | 1999-10-26 | ロディア シミ | Substrate with photocatalytic coating based on titanium dioxide and organic dispersion based on titanium dioxide |
| KR20020048057A (en) * | 2000-12-15 | 2002-06-22 | 서평원 | The preparation method of flower preservatives of highly effective preservation of freshness and prolongation of life using titanium oxide photocatalyst |
| EP1483972A1 (en) * | 2003-06-02 | 2004-12-08 | Université Catholique de Louvain | Method and apparatus for preserving agricultural products |
| JP2008523979A (en) * | 2004-12-17 | 2008-07-10 | アルミン | Amorphous composite structures for photocatalysis |
| EP2486785B1 (en) * | 2009-10-09 | 2018-04-25 | Fujitsu Limited | Protective bag |
-
1993
- 1993-09-21 JP JP25775293A patent/JP3499585B2/en not_active Expired - Lifetime
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11512336A (en) * | 1995-09-15 | 1999-10-26 | ロディア シミ | Substrate with photocatalytic coating based on titanium dioxide and organic dispersion based on titanium dioxide |
| JPH09230810A (en) * | 1995-12-22 | 1997-09-05 | Toto Ltd | Outdoor display board and its cleaning method |
| EP0812619A1 (en) * | 1996-06-12 | 1997-12-17 | Eastman Kodak Company | Inorganic transparent photocatalytic composition |
| FR2749777A1 (en) * | 1996-06-12 | 1997-12-19 | Kodak Pathe | INORGANIC TRANSPARENT PHOTOCATALYTIC COMPOSITION |
| US5972831A (en) * | 1996-06-12 | 1999-10-26 | Eastman Kodak Company | Inorganic transparent photocatalytic composition |
| KR20020048057A (en) * | 2000-12-15 | 2002-06-22 | 서평원 | The preparation method of flower preservatives of highly effective preservation of freshness and prolongation of life using titanium oxide photocatalyst |
| EP1483972A1 (en) * | 2003-06-02 | 2004-12-08 | Université Catholique de Louvain | Method and apparatus for preserving agricultural products |
| WO2004105497A1 (en) * | 2003-06-02 | 2004-12-09 | Certech Asbl | Method and device for preserving agricultural products |
| JP2008523979A (en) * | 2004-12-17 | 2008-07-10 | アルミン | Amorphous composite structures for photocatalysis |
| EP2486785B1 (en) * | 2009-10-09 | 2018-04-25 | Fujitsu Limited | Protective bag |
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| Publication number | Publication date |
|---|---|
| JP3499585B2 (en) | 2004-02-23 |
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