JP4182212B2 - Photocatalyst performance evaluation method - Google Patents
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- JP4182212B2 JP4182212B2 JP2003343233A JP2003343233A JP4182212B2 JP 4182212 B2 JP4182212 B2 JP 4182212B2 JP 2003343233 A JP2003343233 A JP 2003343233A JP 2003343233 A JP2003343233 A JP 2003343233A JP 4182212 B2 JP4182212 B2 JP 4182212B2
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- 238000011156 evaluation Methods 0.000 title claims description 43
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Description
本発明は、光触媒の性能評価方法に関するものであり、更に詳しくは、標準物質として、フタル酸水素カリウム、他のフタル酸水素金属塩（例えば、ナトリウム、リチウム塩等）、フタル酸塩又はフタル酸（以下、ＫＨＰと記載することがある。）を使用し、紫外線（ＵＶ）検出又は導電率検出イオン排除型イオンクロマトグラフィーを、その計測法として使用した、新しい光触媒の性能評価方法に関するものである。光触媒による、水又は大気等の浄化技術が、新しい環境技術として注目されている中で、光触媒の特性又は性能を客観的に評価することは、光触媒を応用する技術分野における今後の発展、並びに新しい技術の開拓に当たって、重要な課題となるものである。本発明は、光触媒技術の分野において、流通式光触媒性能評価装置を利用して、標準物質であるフタル酸水素カリウム等の光酸化分解過程をモニターすることにより、光触媒の性能を客観的に評価することができる新しい光触媒性能評価方法及びその装置を提供するものである。 The present invention relates to a method for evaluating the performance of a photocatalyst. More specifically, as a standard substance, potassium hydrogen phthalate, other hydrogen phthalate metal salts (for example, sodium, lithium salts, etc.), phthalate or phthalic acid (Hereinafter, sometimes referred to as KHP) and relates to a new photocatalyst performance evaluation method using ultraviolet (UV) detection or conductivity detection ion-exclusion ion chromatography as its measurement method. . While the purification technology of water or air by photocatalyst is attracting attention as a new environmental technology, objective evaluation of the characteristics or performance of the photocatalyst is not only the future development in the technical field to which the photocatalyst is applied, but also new This is an important issue when developing technology. The present invention objectively evaluates the performance of a photocatalyst in the field of photocatalyst technology by monitoring the photo-oxidative decomposition process of a standard material such as potassium hydrogen phthalate using a flow-type photocatalyst performance evaluation apparatus. The present invention provides a new photocatalyst performance evaluation method and an apparatus therefor.
近年、光触媒は、ＵＶあるいは可視光を照射するのみで、例えば、ＳＯｘ、ＮＯｘ等の無機酸性ガス、シックハウス症候群の原因物質とされているホルムアルデヒドのような有機ガス、あるいは焼却処理により発生するダイオキシン等の環境ホルモン物質等を、二次汚染なしに安全に分解、無害化する環境材料として、大気、水質、土壌の各分野で注目を集めている[非特許文献1、2]。また、このような光触媒の特性を生かし、ガラス食器や観葉植物等の生活製品から高速道路や建築物の外壁等の工業用品まで幅広い分野で光触媒の実用化及び製品化が盛んに進められつつある。
In recent years, photocatalysts only irradiate UV or visible light. For example, inorganic acid gases such as SOx and NOx, organic gases such as formaldehyde that are considered to cause sick house syndrome, or dioxins generated by incineration As environmental materials that safely decompose and detoxify environmental hormone substances, etc. without secondary pollution, they are attracting attention in the air, water quality, and soil fields [Non-patent
しかしながら、光触媒を用いた様々な製品の光触媒性能の評価は十分に行われているとは言い難く、今後の光触媒産業の発展と光触媒製品の世界市場への普及・発展を実現するためには、光触媒性能の評価試験法の標準化が急務とされている。 However, it is difficult to say that the photocatalytic performance of various products using photocatalysts has been sufficiently evaluated. To realize the future development of the photocatalyst industry and the spread and development of photocatalyst products in the global market, There is an urgent need for standardization of photocatalytic performance evaluation test methods.
最近では、メチレンブルーの脱色により評価する方法が提案されている。光触媒性能評価試験法の、具体例は、例えば、平面形状の光触媒製品上にメチレンブルーを滴下し、光照射によって、その消失具合を観察する液相フィルム密着法[非特許文献3]や、アセトアルデヒドガスを満たしたテドラーバッグに光触媒製品を配置し、アルデヒドガスの濃度減少をガスクロマトグラフィーによって計測するガスバックＡ法[非特許文献4]及びＢ法[非特許文献5]を挙げることができ、各分野での光触媒製品の性能評価に適用されている。しかしながら、特に、水溶液を流通しながら光触媒の水質浄化能を評価する試験法については開発途上の段階である。 Recently, a method of evaluating by decolorization of methylene blue has been proposed. Specific examples of the photocatalyst performance evaluation test method include, for example, a liquid phase film adhesion method in which methylene blue is dropped on a planar photocatalyst product and the disappearance state is observed by light irradiation [Non-patent Document 3], acetaldehyde gas Gas back A method [Non-patent Document 4] and B method [Non-patent Document 5] in which a photocatalyst product is placed in a Tedlar bag that satisfies the above conditions and the concentration reduction of aldehyde gas is measured by gas chromatography. It has been applied to the performance evaluation of photocatalytic products in Japan. However, in particular, a test method for evaluating the water purification ability of a photocatalyst while circulating an aqueous solution is still in the development stage.
こうした問題点を解決するために、本発明者らは、光触媒の評価試験法の開発に関し、例えば、水質浄化のための光触媒とその形状に合わせた性能評価システム(反応液タンク、送液ポンプ、反応容器、光照射装置、分析装置からなるシステム)の開発及び評価を進めてきた。 In order to solve such problems, the present inventors have developed a photocatalyst evaluation test method, for example, a photocatalyst for water purification and a performance evaluation system (reaction liquid tank, liquid feed pump, We have been developing and evaluating a reaction vessel, a light irradiation device, and an analysis system.
これまで、光触媒の評価試験に用いられる主な性能評価標準物質としては、ＵＶ−可視光への耐光性が強く、また目視法やＵＶ吸光法での確認が容易である点から、メチレンブルーが汎用されている。しかしながら、本発明者らの検討したところによれば、メチレンブルーが、光触媒分解された際に発生する分解生成物の帰属が、メチレンブルーの構造式の複雑さゆえに、大変困難であり、メチレンブルーに代わる効率的な光触媒の性能評価、特に、水質浄化処理における評価を可能にする、標準物質の選定とその計測法の確立が強く要請されていた。 Until now, methylene blue has been widely used as the main standard for performance evaluation used in photocatalyst evaluation tests because of its strong light resistance to UV-visible light and easy confirmation by visual and UV absorption methods. Has been. However, according to the study by the present inventors, it is very difficult to assign a decomposition product generated when methylene blue is photocatalytically decomposed due to the complexity of the structural formula of methylene blue. There was a strong demand for the selection of standard materials and the establishment of measurement methods that would enable the evaluation of the performance of typical photocatalysts, particularly in water purification processes.
このような状況の中で、本発明者らは、上記従来技術に鑑みて、光触媒の性能を客観的に評価することが可能な新しい評価試験を開発することを目標として鋭意研究を重ねた結果、フタル酸水素カリウム等を標準物質とする新しい光触媒の性能の評価システムを開発することに成功し、本発明を完成するに至った。
本発明は、光触媒の国際標準試験法として利用し得る性能評価試験法及びその装置を提供することを目的とするものである。
本発明は、光触媒の性能評価試験に好適な標準物質として、フタル酸水素カリウム等を用いた、光触媒性能評価試験法及びそれに用いる装置を提供することを目的とするものである。
また、本発明は、希酸を溶離液とするイオン排除型カラムを用いる、ＵＶ検出イオン排除型イオンクロマトグラフィー、又は導電率検出イオン排除型イオンクロマトグラフィーにより、光触媒によって分解された生成物を分離、分析することを含む、光触媒性能評価試験法及びそれに用いる装置を提供することを目的とするものである。
更に、本発明は、光触媒全般の技術に適用でき、簡便で、迅速で、高感度な、光触媒性能評価試験法及びそれに用いる装置を提供することを目的とするものである。
In such a situation, in view of the above prior art, the present inventors have conducted extensive research with the goal of developing a new evaluation test capable of objectively evaluating the performance of the photocatalyst. The inventors have succeeded in developing a new photocatalyst performance evaluation system using potassium hydrogen phthalate or the like as a standard substance, and have completed the present invention.
The object of the present invention is to provide a performance evaluation test method and apparatus which can be used as an international standard test method for photocatalysts.
An object of the present invention is to provide a photocatalyst performance evaluation test method using potassium hydrogen phthalate or the like as a standard material suitable for a photocatalyst performance evaluation test and an apparatus used therefor.
In addition, the present invention separates the product decomposed by the photocatalyst by UV detection ion exclusion type ion chromatography or conductivity detection ion exclusion type ion chromatography using an ion exclusion column using dilute acid as an eluent. An object of the present invention is to provide a photocatalyst performance evaluation test method including analysis, and an apparatus used therefor.
Furthermore, an object of the present invention is to provide a photocatalyst performance evaluation test method and an apparatus used therefor that can be applied to general photocatalyst techniques, are simple, rapid, and highly sensitive.
上記課題を解決するための本発明は、以下の技術手段から構成される。
（１）光触媒の性能を評価する方法において、フタル酸水素カリウム、他のフタル酸水素金属塩、フタル酸塩又はフタル酸（以下、ＫＨＰという。）を標準物質として、光照射のもとで、光触媒と接触させることにより、ＫＨＰの光酸化分解過程及び／又は酸化分解生成物を分析することにより光触媒の性能を評価する光触媒の性能評価方法であって、上記ＫＨＰの光酸化分解過程及び／又は酸化分解生成物を、希酸あるいは水を溶離液とするイオン排除型カラムを用いるＵＶ検出イオン排除型イオンクロマトグラフィー又は導電率検出イオン排除型イオンクロマトグラフィーにより分析し、フタル酸イオンの溶出ピークの変化、フタル酸イオンの溶出挙動の変化、又はフタル酸イオン濃度あるいは酸化分解過程で生成する酢酸若しくはギ酸濃度の経時変化をモニターすることを特徴とする光触媒の性能評価方法。
（２）ＫＨＰの光酸化分解過程及び／又は酸化分解生成物を、希酸を溶離液とする、イオン排除型カラムを用いる導電率検出イオン排除型イオンクロマトグラフィーにより分析する、前記（１）に記載の光触媒の性能評価方法。
（３）流通式反応装置を使用して、ＫＨＰ溶液を光触媒と接触させる、前記（１）又は（２）に記載の光触媒の性能評価方法。
（４）ＫＨＰの光酸化分解による濃度減少を計測して得られた値を指標として光触媒の性能を評価する、前記（１）に記載の光触媒の性能評価方法。
（５）ＫＨＰの光酸化分解による酸化分解過程及び／又は酸化分解生成物をモニターすることにより、光触媒による有機酸の酸化分解性能を評価する、前記（１）に記載の光触媒の性能評価方法。
（６）内部に光触媒を収容できる流通反応容器、該容器中の光触媒に光を照射する光源、標準物質であるＫＨＰを貯蔵する容器、流通反応容器にＫＨＰ溶液を流通させる搬送装置を構成要素として含み、ＫＨＰ溶液を光照射のもとで、光触媒と接触させることによりＫＨＰの光酸化分解反応を行うようにした流通式光触媒反応装置と、ＫＨＰの光酸化分解過程及び／又は酸化分解生成物を分析し、フタル酸イオンの溶出ピークの変化、フタル酸イオンの溶出挙動の変化、又はフタル酸イオン濃度あるいは酸化分解過程で生成する酢酸若しくはギ酸濃度の経時変化をモニターするための測定手段を組み合わせた光触媒の性能評価装置であって、測定手段として、希酸を溶離液とするイオン排除型カラムを用いる、ＵＶ検出イオン排除型イオンクロマトグラフィー又は導電率検出イオン排除型イオンクロマトグラフィーを用いることを特徴とする光触媒性能評価装置。
The present invention for solving the above problems comprises the following technical means.
(1) In the method for evaluating the performance of the photocatalyst, potassium hydrogen phthalate, other metal phthalates, phthalate or phthalic acid (hereinafter referred to as KHP) is used as a standard substance under light irradiation. A photocatalytic performance evaluation method for evaluating the photocatalytic performance by analyzing a photooxidative decomposition process and / or oxidative decomposition product of KHP by contacting with a photocatalyst, wherein the photooxidative decomposition process of the KHP and / or The oxidative degradation products are analyzed by UV detection ion-exclusion ion chromatography or conductivity detection ion-exclusion ion chromatography using an ion exclusion column with dilute acid or water as the eluent . Changes, changes in elution behavior of phthalate ions, or phthalate ion concentration or acetic acid or formic acid produced during oxidative degradation Performance Evaluation of the photocatalyst characterized by monitoring the time course of degree.
(2) The photo-oxidative decomposition process and / or oxidative decomposition product of KHP is analyzed by conductivity detection ion-exclusion ion chromatography using an ion-exclusion column using dilute acid as an eluent. The photocatalyst performance evaluation method described.
(3) The method for evaluating the performance of a photocatalyst according to (1) or (2) above, wherein the KHP solution is brought into contact with the photocatalyst using a flow reactor.
(4) The method for evaluating the performance of a photocatalyst according to (1), wherein the performance of the photocatalyst is evaluated using a value obtained by measuring a decrease in concentration due to photooxidative decomposition of KHP as an index.
(5) The method for evaluating the performance of a photocatalyst according to (1) , wherein the oxidative decomposition process and / or oxidative decomposition product of KHP by photo-oxidative decomposition is monitored to evaluate the oxidative decomposition performance of the organic acid by the photocatalyst.
(6) A flow reaction container that can accommodate a photocatalyst therein, a light source that irradiates light to the photocatalyst in the container, a container that stores KHP as a standard substance, and a transport device that circulates the KHP solution in the flow reaction container wherein, under light irradiation of KHP solution, a flow-type photocatalytic reaction device to perform photo-oxidation decomposition reaction of KHP by contacting a photocatalyst, a photooxidation degradation processes and / or oxidative degradation products of KHP Analyze and combine measurement means to monitor changes in elution peak of phthalate ions, changes in elution behavior of phthalate ions, or changes in phthalate ion concentration or acetic acid or formic acid concentration generated during oxidative degradation process An apparatus for evaluating the performance of a photocatalyst, which uses an ion exclusion column using dilute acid as an eluent as a measuring means, and a UV detection ion exclusion ion filter. Photocatalytic performance evaluation device, which comprises using the Mato chromatography or conductivity detection ion exclusion chromatography.
次に、本発明について更に詳細に説明する。
これまで、光触媒の性能評価試験においては、研究者等は、異なる試験方法を使ってそれぞれ、開発材料等を評価していたケースが多いため、適正な比較ができない場合があった。このため、光触媒の基礎的な特性を評価する標準試験法の確立は強く望まれていた。そして、標準試験法において、標準物質は、定量的な目盛りの役割を果たすと共に、機器の使用条件、特性、試験担当者等に起因する誤差を補正する役割を担っており、標準物質の正確な使用による試験結果の客観性の確保は、相互比較、商取引、各種の規制、安全対策等の基盤として不可欠なものである。したがって、標準試験法において、試験装置、操作手順等と共に、標準物質の適切な選択は非常に重要な事項である。
Next, the present invention will be described in more detail.
Until now, in photocatalyst performance evaluation tests, researchers often evaluated the developed materials using different test methods, and therefore, there were cases where proper comparison could not be made. For this reason, establishment of a standard test method for evaluating the basic characteristics of the photocatalyst has been strongly desired. In the standard test method, the reference material serves as a quantitative scale, and also serves to correct errors caused by equipment usage conditions, characteristics, test personnel, etc. Ensuring objectivity of test results by use is indispensable as a basis for mutual comparison, commerce, various regulations, safety measures, etc. Therefore, in the standard test method, along with the test equipment, operation procedures, etc., appropriate selection of the standard substance is a very important matter.
本発明は、フタル酸水素カリウム等（ＫＨＰ）を標準物質として、光照射のもとで、光触媒と接触させることによりＫＨＰの光酸化分解過程及び／又は酸化分解生成物を、分析することにより、光触媒の性能を評価することを特徴とするものである。本発明では、フタル酸水素カリウム等が標準物質として用いられるが、ＫＨＰは、光触媒の性能評価を可能にする標準物質として、化学的酸素量（ＣＯＤ）や全酸素消費量(ＴＯＤ) の標準試料として一般的に用いられている（JIS K0101 (1998)、参照）。本発明では、フタル酸水素カリウム等（ＫＨＰ）をモデル物質として使用し、その光触媒分解における濃度減少、及び分解生成物を、イオン排除作用を利用したＵＶ検出又は導電率検出イオンクロマトグラフィーを採用することによって、簡便・迅速で高感度な分離計測を可能とするものであり、また、光触媒の酸化分解過程を明確に捕らえることができるモニタリングシステムを提供することを可能とするものである。本発明において、光触媒の性能試験に用いる、標準物質（モデル水）としてＫＨＰを採用した理由としては、ＫＨＰが単純な化学構造であると共に、ＵＶでの吸収を有し、しかも、容量分析、例えば、中和滴定でアルカリ溶液の濃度を決定する分析操作、の標準物質として用いられていることから、試薬の購入や操作が非常に簡便であることが挙げられる。 The present invention uses potassium hydrogen phthalate or the like (KHP) as a standard substance, and by analyzing the photo-oxidative decomposition process and / or oxidative decomposition product of KHP by contacting with a photocatalyst under light irradiation, It is characterized by evaluating the performance of the photocatalyst. In the present invention, potassium hydrogen phthalate or the like is used as a standard substance, but KHP is a standard substance that allows chemical catalyst performance evaluation, and a standard sample of chemical oxygen (COD) and total oxygen consumption (TOD). (See JIS K0101 (1998)). In the present invention, potassium hydrogen phthalate or the like (KHP) is used as a model substance, and the concentration reduction in the photocatalytic decomposition and the decomposition product are subjected to UV detection or ion conductivity detection using ion exclusion action. Thus, it is possible to provide a simple, rapid and highly sensitive separation measurement and to provide a monitoring system capable of clearly capturing the oxidative decomposition process of the photocatalyst. In the present invention, the reason why KHP is used as a standard substance (model water) used for the performance test of the photocatalyst is that KHP has a simple chemical structure, has absorption in UV, and has a capacity analysis, for example, Since it is used as a standard substance for analytical operations for determining the concentration of an alkaline solution by neutralization titration, it can be mentioned that the purchase and operation of reagents are very simple.
また、本発明では、ＫＨＰの光分解によるＵＶ吸光度の減少をモニタリングするための計測方法として、イオン排除型イオンクロマトグラフィーが導入されるが、それは、通常使用されているイオン交換型イオンクロマトグラフィーでは、ＫＨＰ自身の弱い陰イオン交換能のために、十分な分解能が得られず、検出時において共存している他の有機物や無機物の妨害を避けるのが困難であることによる。
In the present invention, ion-exclusion ion chromatography is introduced as a measurement method for monitoring the decrease in UV absorbance due to photolysis of KHP, which is generally used in ion exchange ion chromatography. This is because, due to the weak anion exchange ability of KHP itself, sufficient resolution cannot be obtained, and it is difficult to avoid interference with other organic substances and inorganic substances present at the time of detection.
一方、イオン排除型イオンクロマトグラフィーは、試料のイオン交換樹脂への浸透、反発及び吸着の大きさによってイオンを分離分析する方法であり、特にアルキル鎖やベンゼン環のような疎水基を有するイオン種の分離に関しては、以下の文献に記載されているように、非常に効果的な分析方法である。
(1) K. Tanaka、T. Ishizuka、H. Sunahara：J.
Chromatogr. A,174,153 (1979)
(2)田中一彦： 環境技術、26,674 (1997)
(3) 田中一彦： 工業用水、463,37 (1997)
(4) K. Tanaka,S. Chikara，W. Hu,K. Hasebe：
J.Chromatogr. A,850、187 (1999)。
(5) K. Tanaka,K. Ohta,J.S. Fritz,Y.-S.
Lee,S.-B. Shim： J. Chromatogr． A,706,385 (1997)、参照）
更に、この分析手法を用いる利点としては、水又は低濃度の酸（希酸）を溶離液とし、１本の分離カラム、１台の検出器のみで、多成分の試料を同時に計測することが可能である点を挙げることができる。
On the other hand, ion-exclusion ion chromatography is a method for separating and analyzing ions according to the degree of penetration, repulsion and adsorption of a sample into an ion exchange resin, and in particular, an ion species having a hydrophobic group such as an alkyl chain or a benzene ring. As described in the following documents, this is a very effective analytical method.
(1) K. Tanaka, T. Ishizuka, H. Sunahara: J.
Chromatogr. A, 174,153 (1979)
(2) Kazuhiko Tanaka: Environmental Technology, 26,674 (1997)
(3) Kazuhiko Tanaka: Industrial water, 463,37 (1997)
(4) K. Tanaka, S. Chikara, W. Hu, K. Hasebe:
J. Chromatogr. A, 850, 187 (1999).
(5) K. Tanaka, K. Ohta, JS Fritz, Y.-S.
Lee, S.-B. Shim: J. Chromatogr. A, 706,385 (1997))
Furthermore, the advantage of using this analysis method is that water or a low-concentration acid (dilute acid) is used as an eluent, and a multi-component sample can be measured simultaneously using only one separation column and one detector. The points that are possible can be mentioned.
この手法を用いることにより、標準物質であるＫＨＰを光触媒によって酸化分解した際に、ＫＨＰの濃度減少が簡便に観察できるだけでなく、その酸化分解生成物(例えば、炭酸水素イオン、酢酸イオン、蟻酸イオン等)を同時に計測できるため、光触媒性能評価に重要な酸化分解メカニズムの解明に非常に効果的な情報を得ることができる。 最近では、環境モニタリングのオンサイト化を目指したポータブル型イオンクロマトグラフの開発が盛んであることから、これを光触媒性能評価装置に接続することにより、オンラインでＫＨＰの酸化分解過程を追跡することも可能となる。したがって、本発明は、高効率、かつ高精度な光触媒材料の性能のモニターを実行し得るポテンシャルの高い光触媒性能評価手段であると位置づけることができる。 By using this technique, when the standard substance KHP is oxidatively decomposed with a photocatalyst, not only the decrease in the concentration of KHP can be easily observed, but also its oxidative decomposition products (for example, bicarbonate ion, acetate ion, formate ion) Etc.) can be measured simultaneously, so that it is possible to obtain information that is very effective for elucidating the oxidative degradation mechanism important for photocatalytic performance evaluation. Recently, the development of a portable ion chromatograph aimed at on-site environmental monitoring has been actively developed. By connecting this to a photocatalyst performance evaluation device, the oxidative decomposition process of KHP can be traced online. It becomes possible. Therefore, the present invention can be positioned as a photocatalyst performance evaluation means with high potential capable of monitoring the performance of the photocatalyst material with high efficiency and high accuracy.
本発明では、好適には、例えば、図１に示すような、反応溶液タンク１、ＵＶランプ２、流通反応容器３、ペリスタポンプ４、チタニア系光触媒５、からなる反応装置が使用されるが、これに制限されるものではなく、同等ないし同様の機能を有する装置であれば同様に使用できる。また、これらの反応装置の具体的な構成は、試験目的に応じて任意に設計することができる。また、ＫＨＰの計測手段としては、イオン排除型イオンクロマトグラフィーが使用され、ＫＨＰの検出手段として分離カラム（イオン交換樹脂），ＵＶ−検出器、分光光度計等が使用されるが、これらの種類及び操作方法に特に制限されるものではない。本発明では、被評価試料の光触媒材料を、上記反応装置の流通式反応容器内に充填し、光源からの光照射下で溶液タンクからＫＨＰ溶液を反応容器内に所定の流量で送液し、循環させ、ＫＨＰの濃度変化等を測定することにより、試料の光触媒性能を評価する。光照射条件として、例えば、紫外線強度が約２mW/cm２前後の光照射が例示されるが、試験方法に応じて、光源の種類、紫外光、可視光等を任意に選択することが可能であり、それらに制限されることはない。ＫＨＰの濃度は好適には、１〜１０ppm、流量は好適には２００〜４００mL/minが例示されるが、これらに制限されるものではない。
In the present invention, for example, a reaction apparatus comprising a
上述のように、本発明は、光触媒の性能評価モデルとして化学構造が単純な化合物であるフタル酸水素カリウム等（ＫＨＰ）が用いられ、計測法としてイオン排除型イオンクロマトグラフィーが用いられる。それによって、光酸化分解反応後のＫＨＰの濃度減少及び分解生成物を高精度に計測することができる。イオン排除型イオンクロマトグラフィーは、多成分同時分離が可能であるという特徴を有することから、本発明では、ＫＨＰから脂肪族カルボン酸、そして、炭酸水素イオンに至るまでの化学種とその濃度変化を、同時に検出することができる。したがって、本発明では、光触媒による有機酸の酸化分解メカニズムを解明するのに大きな役割を果たす。 As described above, in the present invention, potassium hydrogen phthalate (KHP), which is a compound having a simple chemical structure, is used as a performance evaluation model of a photocatalyst, and ion exclusion ion chromatography is used as a measurement method. Thereby, the decrease in the concentration of KHP and the decomposition product after the photo-oxidative decomposition reaction can be measured with high accuracy. Since ion exclusion type ion chromatography has the feature that multi-component simultaneous separation is possible, in the present invention, chemical species ranging from KHP to aliphatic carboxylic acid and bicarbonate ions and their concentration changes are analyzed. Can be detected simultaneously. Therefore, the present invention plays a major role in elucidating the oxidative degradation mechanism of organic acids by photocatalysts.
また、ＫＨＰは、色素(例えば、メチレンブルー)とは異なり、光触媒や反応容器に対して吸着力が小さいので、光触媒の光照射による再生処理や実験後の反応容器の洗浄等の作業をスムーズに行なうことができる。ＫＨＰは、単純な化学構造とＵＶ領域での吸収を有し、しかも、容量分析の標準物質として広く用いられており、試薬の購入や操作が非常に簡便である。また、酢酸やプロピオン酸などの脂肪族カルボン酸よりも揮発性が低く、長期間にわたり保存しても、安定な計測結果を得ることができる。イオンクロマト装置や分離カラムの利用が困難な場合であっても、ＵＶ吸光度検出器を使用し、吸収極大波長付近である240nmのスペクトルピークをモニターすることによって、光触媒作用によるＫＨＰの分解過程が観察できる。 In addition, KHP, unlike a dye (for example, methylene blue), has a low adsorbing power to the photocatalyst and the reaction vessel, and therefore performs smooth operations such as regeneration treatment by photoirradiation of the photocatalyst and washing of the reaction vessel after the experiment. be able to. KHP has a simple chemical structure and absorption in the UV region, and is widely used as a standard substance for volumetric analysis, so that it is very easy to purchase and operate the reagent. Further, it is less volatile than aliphatic carboxylic acids such as acetic acid and propionic acid, and stable measurement results can be obtained even when stored for a long period of time. Even when it is difficult to use an ion chromatograph or a separation column, the UV absorbance detector is used to monitor the spectral peak at 240 nm, which is near the absorption maximum wavelength, to observe the degradation process of KHP due to photocatalysis. it can.
更に、本発明では、ＵＶ吸光度検出器が装備されていない、イオンクロマトグラフ装置しか利用できない状態であっても、電気伝導度検出器があれば良好な計測結果を得ることができる。また、ＫＨＰが酸化分解されて生成する分解生成物には、いくつか毒性の高いものがあるが、本発明では、そういった生成物でも光照射によって完全に分解することが可能であるので、実験後の廃液処理が非常に簡便に行なえる利点がある。 Furthermore, in the present invention, even if only an ion chromatograph apparatus that is not equipped with a UV absorbance detector can be used, a good measurement result can be obtained with an electrical conductivity detector. In addition, some of the decomposition products produced by oxidative decomposition of KHP are highly toxic. In the present invention, even such products can be completely decomposed by light irradiation. There is an advantage that the waste liquid treatment can be performed very easily.
以上のように、本発明により、（１）光触媒の性能評価における、標準物質としてのＫＨＰの使用は、種々な実験室のレベルに対応が可能である、（２）また、イオン排除型イオンクロマトグラフィーを導入することによって、光触媒性能評価に対する情報量が格段に増大することが期待できる、（３）本発明は、例えば、希硫酸を溶離液としたＵＶ検出又は導電率検出イオン排除型イオンクロマトグラフィーシステムを導入し、例えば、標準物質として、1ppm〜10ppmのＫＨＰを含むモデル水を用いて、光触媒の分解効果を評価することを可能とするものである、（４）有機物（ＫＨＰ）の酸化分解過程及び分解生成物のモニターを高精度かつ高効率に実行できる光触媒の性能評価法及びその装置を提供するものとして有用である、という効果が奏される。 As described above, according to the present invention, (1) the use of KHP as a standard substance in the performance evaluation of a photocatalyst can correspond to various laboratory levels. (2) In addition, ion exclusion ion chromatography It is expected that the amount of information for photocatalyst performance evaluation will be greatly increased by introducing the chromatography. (3) The present invention is, for example, UV detection or conductivity detection ion exclusion ion chromatography using dilute sulfuric acid as an eluent. (4) Oxidation of organic matter (KHP), which enables the evaluation of photocatalytic decomposition effects using model water containing, for example, 1 ppm to 10 ppm of KHP as a standard substance The effect that it is useful as a device for evaluating the performance of a photocatalyst capable of monitoring a decomposition process and decomposition products with high accuracy and high efficiency, and an apparatus therefor. It is so.
次に、本発明を実施例に基づいて具体的に説明するが、本発明は、以下の実施例によって何ら限定されるものではない。 EXAMPLES Next, although this invention is demonstrated concretely based on an Example, this invention is not limited at all by the following Examples.
（１）反応装置
本実施例では、光触媒材料を水質浄化処理試験に適用した一例を示す。反応装置としては、図1に示すように、大気浄化性能試験法(JIS-TRZ0018：333×104×48mm)で使用している流通式反応容器と同様のものを用いた。ＵＶ光源（ナショナル製FL20S-BLBランプ（20W））を２本並列に設置し、紫外線強度が、約2mW/cm２になるように、光源の高さを調節した。
(1) Reactor In this example, an example in which a photocatalyst material is applied to a water purification treatment test is shown. As the reaction apparatus, as shown in FIG. 1, the same flow reactor as used in the air purification performance test method (JIS-TRZ0018: 333 × 104 × 48 mm) was used. Two UV light sources (National FL20S-BLB lamp (20W)) were installed in parallel, and the height of the light source was adjusted so that the ultraviolet intensity was about 2 mW / cm 2 .
図1の反応装置において、1は反応溶液タンク、2はＵＶランプ、3は流通式反応容器、4はペリスタポンプ、5はチタニア系光触媒、である。本反応装置に用いたチタニア系光触媒試料は、直径2．5mmφのガラスビーズ表面上に、ゾル-ゲル法により二酸化チタンをコーティングしたものであり、この光触媒材料を反応容器中に設置したアクリル板上に均等に充填した。
反応溶液タンク１から反応容器３へのＫＨＰ（フタル酸水素カリウム）溶液の送液は、ペリスタポンプ４（Cole-Parmer社製：Master Flex 7518-10）により200〜400mL/minの流量で循環させて使用した。
In the reaction apparatus of FIG. 1, 1 is a reaction solution tank, 2 is a UV lamp, 3 is a flow-type reaction vessel, 4 is a peristaltic pump, and 5 is a titania photocatalyst. The titania-based photocatalyst sample used in this reactor was a glass bead surface with a diameter of 2.5 mmφ coated with titanium dioxide by the sol-gel method. This photocatalyst material was placed on an acrylic plate placed in a reaction vessel. Were evenly filled.
The solution of KHP (potassium hydrogen phthalate) solution from the
（２）ＫＨＰ（フタル酸水素カリウム）の計測及び検出
ＫＨＰの計測は、イオンクロマトグラフ（東ソー製）を用いて行った。この装置は、LC-8020-Model IIクロマトグラフデータプロセッサー（東ソー製）によって制御されたDP-8020デュアルポンプ（溶離液流量：1mL/min）、SD-8022型オンラインデガッサー、CO-8020カラムオーブン（40℃）及びAS-8020オートサンプラー（注入量：100μL）から構成されていた。ＫＨＰの検出は、UV-8020UV検出器（東ソー製）を用い、ＫＨＰの極大吸収波長付近である240nmで行い、分離カラムとして、弱酸性陽イオン交換樹脂TSKgel
Super IC-A/C(15cm×7.8mmID) （東ソー製）を用いた。一方、ＵＶ分光法によるＫＨＰの測定は、U-3200型自記分光光度計（日立製）を用いて行った。
(2) Measurement of KHP (potassium hydrogen phthalate) and detection KHP was measured using an ion chromatograph (manufactured by Tosoh Corporation). This instrument is a DP-8020 dual pump (eluent flow rate: 1 mL / min) controlled by an LC-8020-Model II chromatograph data processor (manufactured by Tosoh), SD-8022 type online degasser, CO-8020 column oven (40 ° C.) and AS-8020 autosampler (injection volume: 100 μL). KHP is detected using a UV-8020UV detector (manufactured by Tosoh Corporation) at 240 nm, which is near the maximum absorption wavelength of KHP, and a weakly acidic cation exchange resin TSKgel is used as a separation column.
Super IC-A / C (15 cm × 7.8 mm ID) (manufactured by Tosoh Corporation) was used. On the other hand, the measurement of KHP by UV spectroscopy was performed using a U-3200 type self-recording spectrophotometer (manufactured by Hitachi).
（３）結果
以下に、実施結果について説明する。
図２は、ＫＨＰのイオン排除型イオンクロマトグラフィーにおける最適溶離液条件を検討するための、水及び硫酸溶離液における、ＫＨＰの各々のイオンクロマトグラムを比較したものである。操作条件を以下に示す。(A)は水を溶離液とし、(B)は、0.5mM硫酸(pH＝3.1)の希硫酸を溶離液とした場合を示す。分離カラムには、TSKgel
Super IC-A/Cを使用し、溶離液流速を1 mL/minとし、生成物の検出には、ＵＶ (検出波長＝240 nm)を用いた。標準物質の試料は、1ppmフタル酸水素カリウム水溶液とし、試料注入量は、100μLであった。
(3) Results The implementation results will be described below.
FIG. 2 is a comparison of ion chromatograms of KHP in water and sulfuric acid eluents for examining optimum eluent conditions in ion exclusion ion chromatography of KHP. The operating conditions are shown below. (A) shows the case where water is used as the eluent, and (B) shows the case where 0.5 mM sulfuric acid (pH = 3.1) dilute sulfuric acid is used as the eluent. For the separation column, TSKgel
Super IC-A / C was used, the eluent flow rate was 1 mL / min, and UV (detection wavelength = 240 nm) was used for product detection. The sample of the standard substance was a 1 ppm potassium hydrogen phthalate aqueous solution, and the sample injection amount was 100 μL.
図２−(A)に示すように、水を溶離液とした場合には、ＫＨＰの溶離ピークはブロードであり、低分解能な分離を示すことが分かる。そこで、溶離液のｐＨを、フタル酸の酸解離定数よりも減少させてイオン排除（吸着）分離を行う方法について検討した結果、溶離液として、希酸、例えば、希硫酸、安息香酸、サリチル酸、を用いたときは、いずれもＫＨＰのピーク形状は、図２−(B)に見られるように、改善され、高分解能なイオン排除（吸着）分離が達成されることが分かった。
更に、ＫＨＰのＵＶ検出器応答（ピーク面積）及び保持時間における溶離液中の硫酸濃度の影響における比較検討を実施した結果、最適な硫酸濃度は0.2mMであった。
As shown in FIG. 2- (A), it can be seen that when water is used as the eluent, the elution peak of KHP is broad, indicating low-resolution separation. Therefore, as a result of examining a method for performing ion exclusion (adsorption) separation by reducing the pH of the eluent below the acid dissociation constant of phthalic acid, as an eluent, dilute acids such as dilute sulfuric acid, benzoic acid, salicylic acid, As shown in FIG. 2- (B), the peak shape of KHP was improved and high resolution ion exclusion (adsorption) separation was achieved.
Furthermore, as a result of conducting a comparative study on the influence of the KHP UV detector response (peak area) and the sulfuric acid concentration in the eluent on the retention time, the optimum sulfuric acid concentration was 0.2 mM.
図３は、反応容器中に25ｇのチタニア系光触媒を配置し、10ppmのＫＨＰを400mL/min流量下で３時間ＵＶ照射した時の、ＫＨＰの酸化分解過程において得られたクロマトグラムを示す。ここでは、ＵＶ照射を３時間継続し、反応試料水溶液（標準物質）の濃度を、10ppmフタル酸水素カリウムとし、試料を流量が400mL/minで、流通式反応器に流通させた。検出には、ＵＶ(240
nm)を用い、溶離液は、0.2mMの硫酸(pH＝3.4)を用いた。その他、分離条件は、図２において説明した条件と同じとした。図３における、矢印が検出されたフタル酸のピークを示す。これより、光触媒の存在下においてＫＨＰの濃度は、ＵＶの照射時間の増大に伴い急激に減少し、光触媒作用によって、ＫＨＰが酸化分解されていることが示された。また、イオン排除型イオンクロマトグラフィーを用いることによって、ＫＨＰの分解過程（〜15分）における、光触媒中の不純物（陰イオン）や、ＫＨＰの光酸化分解過程において生成する有機酸（酢酸、ギ酸）のピークも同時に認めることが可能であることが分かった。
FIG. 3 shows a chromatogram obtained in the oxidative decomposition process of KHP when 25 g of titania-based photocatalyst is placed in a reaction vessel and 10 ppm of KHP is irradiated with UV at 400 mL / min for 3 hours. Here, UV irradiation was continued for 3 hours, the concentration of the reaction sample aqueous solution (standard material) was 10 ppm potassium hydrogen phthalate, and the sample was circulated through the flow reactor at a flow rate of 400 mL / min. For detection, UV (240
nm) and 0.2 mM sulfuric acid (pH = 3.4) was used as the eluent. Other separation conditions were the same as those described in FIG. The phthalic acid peak in which the arrow in FIG. 3 was detected is shown. From this, the concentration of KHP in the presence of the photocatalyst decreased rapidly with increasing UV irradiation time, indicating that KHP was oxidatively decomposed by the photocatalytic action. In addition, by using ion-exclusion ion chromatography, impurities (anions) in the photocatalyst in the decomposition process of KHP (up to 15 minutes) and organic acids (acetic acid, formic acid) generated in the photooxidative decomposition process of KHP It was found that the peak of can also be recognized at the same time.
図４は、モデル水の容量を変化させたときのＫＨＰの光触媒作用に基づいた濃度減少を、ピーク面積によって示したものである。表1に光触媒の水質浄化性能評価試験における試験条件を示す。 FIG. 4 shows the decrease in concentration based on the photocatalytic action of KHP when the capacity of the model water is changed, as a peak area. Table 1 shows the test conditions in the water purification performance evaluation test of the photocatalyst.
分解された試料は、イオン排除型イオンクロマトグラフィーにより分離され、ＵＶ分光法により、検出波長240nm、で生成物を測定した。図中、◆は試料１、□は試料２、▲は試料３、○は試料４、×は試料５、を示す。
The decomposed sample was separated by ion exclusion ion chromatography, and the product was measured by UV spectroscopy at a detection wavelength of 240 nm. In the figure, ♦ indicates
図4に示すように、試料No.１における、光触媒が存在しない場合のＫＨＰの濃度は、ＵＶランプの照射熱により、ＫＨＰが蒸発するために、ＵＶ照射時間の増大と共に、僅かな減少が見られた。また、試料No.２における光触媒存在下において光照射を行わない場合は、ＫＨＰは光触媒へ吸着されるので、僅かな濃度減少が認められた。試料No.3〜5における光触媒の存在下での光照射実験では、流通式反応容器へ送液する流量を増大させると共に、すなわち、光触媒と反応液中のＫＨＰとの接触時間を増大させると共に、ＫＨＰの濃度の減少程度が増大することが分かり、最終的には、表１の試料No.5のように、３時間のＵＶ照射によってＫＨＰはほぼ完全に酸化分解された。光触媒によるＫＨＰの計測を、ＵＶ分光法を用いて行った結果は、イオン排除型イオンクロマトグラフィーによるものと一致し、本発明が光触媒の水質浄化評価法として有用な計測手段であることが分かった。 As shown in FIG. 4, the concentration of KHP in the case of no photocatalyst in sample No. 1 decreases slightly as the UV irradiation time increases because KHP evaporates due to the irradiation heat of the UV lamp. It was. In addition, when light irradiation was not performed in the presence of the photocatalyst in sample No. 2, a slight decrease in concentration was observed because KHP was adsorbed to the photocatalyst. In the light irradiation experiment in the presence of the photocatalyst in sample Nos. 3 to 5, while increasing the flow rate to be sent to the flow type reaction vessel, that is, increasing the contact time between the photocatalyst and KHP in the reaction solution, It was found that the degree of decrease in the concentration of KHP increased. Finally, as shown in Sample No. 5 in Table 1, KHP was almost completely oxidatively decomposed by UV irradiation for 3 hours. The result of KHP measurement using a photocatalyst using UV spectroscopy is consistent with that obtained by ion exclusion ion chromatography, and it was found that the present invention is a useful measurement means as a water purification purification evaluation method for photocatalysts. .
以上詳述したように、本発明は、フタル酸水素カリウム等を標準物質とした光触媒性能の評価方法に係るものであり、本発明により、例えば、光触媒の水質浄化性能を観察する上で、フタル酸水素カリウム等(ＫＨＰ)をモデル水とし、イオン排除型イオンクロマトグラフィーにより計測することによって、簡便に酸化分解過程をモニターすることができる。本発明は、光触媒の性能評価方法として有用であると同時に、例えば、光触媒による化合物の分解過程を詳細に追跡できるので、ＫＨＰの中間生成物である有機酸等の挙動解明に有用な化学情報を提供することができる。また、本発明は、ポータブル型イオンクロマトグラフィーと、流通式光触媒反応装置とを組み合わせることにより、ＫＨＰの濃度をモニターすることが可能な流通式光触媒性能評価装置を提供することができる。更に、本発明は、比較的単純なシステムでありながら、様々な種類の光触媒の酸化分解作用を迅速に計測、評価することができるため、光触媒の技術分野で、その性能評価法の国際標準、新しい光触媒評価システムを提供することができる。 As described above in detail, the present invention relates to a photocatalytic performance evaluation method using potassium hydrogen phthalate or the like as a standard substance. According to the present invention, for example, when observing the water purification performance of a photocatalyst, By using potassium oxyhydrogen (KHP) as model water and measuring by ion exclusion ion chromatography, the oxidative decomposition process can be easily monitored. The present invention is useful as a method for evaluating the performance of photocatalysts, and at the same time, for example, since the decomposition process of a compound by a photocatalyst can be traced in detail, chemical information useful for elucidating the behavior of organic acids and the like that are intermediate products of KHP Can be provided. In addition, the present invention can provide a flow-through photocatalyst performance evaluation device capable of monitoring the concentration of KHP by combining a portable ion chromatography and a flow-through photocatalytic reaction device. Furthermore, the present invention can measure and evaluate the oxidative decomposition action of various types of photocatalysts quickly while being a relatively simple system. Therefore, in the technical field of photocatalysts, A new photocatalyst evaluation system can be provided.
（図１の符号）
1：反応溶液タンク(ＫＨＰ)
2：ＵＶランプ
3：流通式反応容器
4：ペリスタポンプ
5：チタニア系光触媒
(Reference in FIG. 1)
1: Reaction solution tank (KHP)
2: UV lamp
3: Flow reaction container
4: Perista pump
5: Titania photocatalyst
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