JP2019013871A - Catalyst for VOC treatment - Google Patents

Catalyst for VOC treatment Download PDF

Info

Publication number
JP2019013871A
JP2019013871A JP2017131884A JP2017131884A JP2019013871A JP 2019013871 A JP2019013871 A JP 2019013871A JP 2017131884 A JP2017131884 A JP 2017131884A JP 2017131884 A JP2017131884 A JP 2017131884A JP 2019013871 A JP2019013871 A JP 2019013871A
Authority
JP
Japan
Prior art keywords
catalyst
cobalt
platinum
voc
cerium
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
Application number
JP2017131884A
Other languages
Japanese (ja)
Other versions
JP2019013871A5 (en
JP7119256B2 (en
Inventor
井上研一郎
Kenichiro Inoue
染川正一
Masakazu Somekawa
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tokyo Metropolitan Industrial Technology Research Instititute (TIRI)
Original Assignee
Tokyo Metropolitan Industrial Technology Research Instititute (TIRI)
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Tokyo Metropolitan Industrial Technology Research Instititute (TIRI) filed Critical Tokyo Metropolitan Industrial Technology Research Instititute (TIRI)
Priority to JP2017131884A priority Critical patent/JP7119256B2/en
Priority to CN201880029094.1A priority patent/CN110621399A/en
Priority to PCT/JP2018/024929 priority patent/WO2019009216A1/en
Publication of JP2019013871A publication Critical patent/JP2019013871A/en
Publication of JP2019013871A5 publication Critical patent/JP2019013871A5/ja
Application granted granted Critical
Publication of JP7119256B2 publication Critical patent/JP7119256B2/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Abstract

To provide a catalyst that enables a simultaneous treatment of a VOC containing an aromatic group and a VOC containing no aromatic group in a temperature range lower than 300°C.SOLUTION: A catalyst for a VOC treatment, in which platinum is directly carried on a cobalt-cerium system complex oxide, is intended to be used in a combustion treatment of a VOC-containing gas. The mass ratio of the cobalt-cerium system complex oxide is 80% or more based on the total mass of the catalyst. When a (unit: mass%) is a content of the platinum based on the mass of the cobalt-cerium complex oxide, a satisfies 0<a≤20. The catalyst may be or may not be carried on an inert carrier.SELECTED DRAWING: Figure 2

Description

本発明は揮発性有機化合物（ＶＯＣ）処理用の白金直接担持コバルト・セリウム系複合酸化物触媒に関する。   The present invention relates to a platinum-supported cobalt-cerium-based composite oxide catalyst for treating volatile organic compounds (VOC).

塗装工場、印刷工場、化学工場等からの排ガスによる悪臭苦情や大気汚染の問題、家庭・オフィスで使用される建材から放散され健康被害の原因となりうる揮発性有機化合物（Volatile Organic Compounds：以下「ＶＯＣ」と表記する）を簡易的に処理する技術が求められている。処理方法としては直接燃焼法、触媒燃焼法、物理化学的吸着法、生物処理法、プラズマ法等、各種の方法が提案されているが、これらの中で、触媒燃焼法は装置及び維持管理が比較的容易であることから特に広く用いられている。   Volatile Organic Compounds (VOC), which can cause foul odor complaints and air pollution problems caused by exhaust gas from painting factories, printing factories, chemical factories, etc. The technology which processes simply) is called for. Various treatment methods such as direct combustion method, catalytic combustion method, physicochemical adsorption method, biological treatment method, plasma method, etc. have been proposed. Among them, catalytic combustion method has equipment and maintenance management. It is particularly widely used because it is relatively easy.

しかしながら、触媒燃焼法による処理には一般に３００〜３５０℃程度の温度が必要なため、加熱のための電気代、燃料費がかかるという問題点があった。またこの方法を家庭・オフィス向け装置に応用する場合においても電気代が高く、安全性確保や小型化実現等の課題が生じ、適用範囲が限定されていた。適応範囲を拡大するためにも、より低温で高活性を示す触媒が求められている。   However, since the treatment by the catalytic combustion method generally requires a temperature of about 300 to 350 ° C., there is a problem that an electricity bill for heating and a fuel cost are required. In addition, when this method is applied to a home / office device, the cost of electricity is high, causing problems such as ensuring safety and realizing miniaturization, and the scope of application is limited. In order to expand the application range, a catalyst exhibiting high activity at a lower temperature is demanded.

発明者らは、次に示す特許文献１〜３で、コバルト・セリウム系複合酸化物触媒がＶＯＣ処理に有効であることや新しい触媒担持方法を提案した。これらにより、低コスト且つ白金触媒と同等以上の性能を確保できるようになった。   The inventors proposed in Patent Documents 1 to 3 below that the cobalt-cerium-based composite oxide catalyst is effective for VOC treatment and a new catalyst loading method. As a result, it has become possible to secure the same performance as the platinum catalyst at a low cost.

ＶＯＣの種類によって処理性能に差が生じることが多く、たとえば、市販の白金担持アルミナ触媒（Ｐｔ／Ａｌ２Ｏ３）を用いた場合、トルエンのような芳香族の化合物は２００〜２５０℃程度の比較的低温で処理できるが、芳香環を含まない酢酸エチル等は３００〜３５０℃程度の高温で処理する必要がある。一方、コバルト・セリウム系複合酸化物触媒（Ｃｏ３Ｏ４−ＣｅＯ２）を用いた場合は、逆に芳香環を含まないＶＯＣは２００〜２５０℃程度の比較的低温で処理できるが芳香族の化合物の処理は３００℃程度の高温で処理する必要が生じる。このため、芳香環を含むＶＯＣとそれを含まないＶＯＣを個別に処理する場合はよいが、両者のＶＯＣを３００℃より低い温度領域で同時に処理するための新しい用途のために新たな触媒を開発する課題が生じた。 The processing performance often varies depending on the type of VOC. For example, when a commercially available platinum-supported alumina catalyst (Pt / Al 2 O 3 ) is used, an aromatic compound such as toluene is about 200 to 250 ° C. Although it can be processed at a relatively low temperature, ethyl acetate or the like containing no aromatic ring needs to be processed at a high temperature of about 300 to 350 ° C. On the other hand, when a cobalt-cerium composite oxide catalyst (Co 3 O 4 —CeO 2 ) is used, VOCs that do not contain an aromatic ring can be processed at a relatively low temperature of about 200 to 250 ° C. The compound needs to be treated at a high temperature of about 300 ° C. For this reason, it is good to treat VOCs containing aromatic rings and VOCs not containing them separately, but a new catalyst has been developed for new applications to treat both VOCs simultaneously in a temperature range lower than 300 ° C. A problem has arisen.

上記課題を解決するために鋭意研究を行った発明者らは、コバルト・セリウム系複合酸化物触媒に直接担持、さらに好ましくはコロイド溶液を原料とするという方法で所定量の白金を担持させるという新規な組み合わせにより、コバルト・セリウム系複合酸化物触媒の低温活性がより高まることを見出した。以下、具体的に説明する。なお、発明のカテゴリーに関わらず、何れかの請求項に係る発明を説明するにあたり行う用語の定義等は、その記載順などに関わらず性質上許される範囲で他の請求項に係る発明にも適用されるものとする。
The inventors who have conducted intensive research in order to solve the above-mentioned problems are novel that a predetermined amount of platinum is supported by a method of directly supporting a cobalt-cerium-based composite oxide catalyst, more preferably using a colloidal solution as a raw material. It has been found that the low temperature activity of the cobalt-cerium composite oxide catalyst is further increased by such a combination. This will be specifically described below. Regardless of the category of the invention, the definitions of terms used to describe the invention according to any claim are applicable to the invention according to other claims as long as it is permitted in nature regardless of the description order. Shall apply.

本件発明は、これらの課題を解決しようとするものであり、芳香環を含む含まないに関わらず低温で高い活性が持続可能なＶＯＣ処理用触媒に関する発明である。   The present invention is intended to solve these problems, and relates to a VOC treatment catalyst that can sustain high activity at low temperatures regardless of whether or not it contains an aromatic ring.

本発明で提案するＶＯＣ処理用触媒を用いれば市販の白金アルミナ触媒やコバルト・セリウム系複合酸化物触媒と比較して低い温度で性能を確保できる。これにより、工場等での処理温度を低下させることによる電気代、燃料費の削減や家庭・オフィス向け小型触媒処理装置の実用化が可能となる。さらに既存の触媒では対応が困難であった低温仕様の触媒の処理技術分野への用途拡大を図ることで、大気環境、室内環境の改善に貢献できる。また、本発明で提案する製造方法によれば、上記ＶＯＣ処理用触媒を製造することができる。   If the VOC treatment catalyst proposed in the present invention is used, performance can be ensured at a lower temperature than commercially available platinum alumina catalysts and cobalt-cerium composite oxide catalysts. This makes it possible to reduce electricity costs and fuel costs by lowering the processing temperature in factories and the like, and to put to practical use a small catalyst processing apparatus for homes and offices. Furthermore, it can contribute to the improvement of the air environment and the indoor environment by expanding the use of low-temperature specification catalysts, which was difficult to handle with existing catalysts, to the field of processing technology. Moreover, according to the production method proposed in the present invention, the VOC treatment catalyst can be produced.

特許第５４２２３２０号公報Japanese Patent No. 5422320 特許第５４１４７１９号公報Japanese Patent No. 5414719 特許第５７１７４９１号公報Japanese Patent No. 5717491

（請求項１記載の発明の特徴）
請求項１記載の発明は、ＶＯＣを含有するガス燃焼処理用の、白金をコバルト・セリウム系複合酸化物上に直接担持させたＶＯＣ処理用触媒に係るものである点に最大の特徴がある。ここで 触媒全体の質量に占めるコバルト・セリウム系複合酸化物の質量割合が８０％以上であり、コバルト・セリウム系複合酸化物の質量に占める白金の含有量をａ（単位：質量％）とすると、０＜ａ≦２０の範囲であることが好ましい。すなわち、従来であれば、酸化アルミニウム等の担体に白金を担持させていたが、本件発明に係るＶＯＣ処理用触媒は、コバルト・セリウム系の酸化物上に直接担持させるという新規な組み合わせによるものである。なお、当該ＶＯＣ処理用触媒は、不活性担体に担持してなるものとならないものの双方を含み、担持してなる場合の当該質量は不活性担体の質量を含まない。 (Characteristics of the invention of claim 1)
The invention according to claim 1 has the greatest feature in that it relates to a VOC treatment catalyst in which platinum is directly supported on a cobalt-cerium-based composite oxide for gas combustion treatment containing VOC. Here, the mass ratio of the cobalt-cerium composite oxide in the total mass of the catalyst is 80% or more, and the content of platinum in the mass of the cobalt-cerium composite oxide is a (unit: mass%). , 0 <a ≦ 20 is preferable. That is, conventionally, platinum was supported on a carrier such as aluminum oxide, but the VOC treatment catalyst according to the present invention is based on a novel combination of directly supporting on a cobalt-cerium-based oxide. is there. Note that the VOC treatment catalyst includes both those that are not supported on an inert carrier, and the mass when supported is not the mass of the inert carrier.

（請求項２記載の発明の特徴）
請求項２記載の発明は、請求項１記載の発明の好ましい態様として、前記白金は、分散剤で保護された白金コロイドの溶液を原料とするＶＯＣ処理用触媒に係るものであることに特徴がある。分散剤としては、たとえばポリビニルピロリドン（Polyvinylpyrrolidone、ＰＶＰ）を好適に用いることができる。 (Characteristics of the invention described in claim 2)
The invention according to claim 2 is characterized in that, as a preferred embodiment of the invention according to claim 1, the platinum is related to a catalyst for VOC treatment using a solution of platinum colloid protected with a dispersant as a raw material. is there. As the dispersant, for example, polyvinylpyrrolidone (PVP) can be suitably used.

（請求項３記載の発明の特徴）
請求項３記載の発明は、請求項１または２記載の発明の好ましい態様として、前記触媒は、バインダー成分とともに成型してなる、或いは所望形状のステンレス鋼、鉄鋼、銅合金、アルミニウム合金、及びセラミックス材の何れか１つの担体に担持されていることを特徴とする。 (Characteristics of Claim 3)
According to a third aspect of the present invention, as a preferred embodiment of the first or second aspect of the present invention, the catalyst is formed by molding with a binder component, or stainless steel, steel, copper alloy, aluminum alloy, and ceramics having a desired shape. It is supported on any one of the materials.

（請求項４記載の発明の特徴）
請求項４記載の発明は、請求項１ないし３いずれか記載のＶＯＣ処理用触媒の製造方法であって、前記コバルト・セリウム系複合酸化物とは、コバルトとセリウムの炭酸塩を前駆体とする化合物を空気中３００〜５００℃で焼成し、その後粉砕処理して作製することを特徴とする。 (Feature of the invention of claim 4)
Invention of Claim 4 is a manufacturing method of the catalyst for VOC processing in any one of Claim 1 thru | or 3, Comprising: The said cobalt cerium type complex oxide makes a carbonate of cobalt and cerium a precursor. The compound is produced by firing in air at 300 to 500 ° C. and then pulverizing.

（請求項５記載の発明の特徴）
請求項５記載の発明は、請求項１ないし３いずれか記載のＶＯＣ処理用触媒を用いたＶＯＣ処理方法であって、運転温度が、１００〜３００℃であることを特徴とするＶＯＣ処理方法。請求項１ないし３いずれか記載のＶＯＣ処理用触媒を用いることにより、上記低温度領域において処理することができる。 (Feature of the invention of claim 5)
A fifth aspect of the present invention is a VOC processing method using the VOC processing catalyst according to any one of the first to third aspects, wherein the operating temperature is 100 to 300 ° C. By using the VOC treatment catalyst according to any one of claims 1 to 3, the treatment can be performed in the low temperature region.

ＶＯＣ触媒処理用の触媒充填管を示す図である。It is a figure which shows the catalyst filling pipe | tube for VOC catalyst processing. トルエン燃焼時におけるＣＯ２生成率（燃焼率）の温度依存性を示す図である。It is a graph showing the temperature dependence of the CO 2 generation rate during toluene combustion (combustion ratio). 酢酸エチル燃焼時におけるＣＯ２生成率（燃焼率）の温度依存性を示す図である。CO 2 production rates at ethyl acetate combustion is a graph showing the temperature dependence of the (combustion ratio). トルエン燃焼により触媒表面に蓄積したコーキングの燃焼に伴う二酸化炭素の発生を示す図である。It is a figure which shows generation | occurrence | production of the carbon dioxide accompanying combustion of the coking accumulated on the catalyst surface by toluene combustion. 酸化セリウムの細孔径分布を示す図である。It is a figure which shows the pore diameter distribution of a cerium oxide.

本発明は上記のとおりの特徴をもつものであるが、以下に、本発明を実施するための形態を説明する。本発明のＶＯＣ処理用触媒は、ＶＯＣを含有するガス燃焼処理用の、白金をコバルト・セリウム系複合酸化物上に直接担持させた触媒である。ここで触媒全体の質量に占めるコバルト・セリウム系複合酸化物の質量割合が８０％以上であり、コバルト・セリウム系複合酸化物の質量に占める白金の含有量をａ（単位：質量％）とすると、０＜ａ≦２０の範囲であることが好ましい。上記範囲外であると白金の凝集が生じやすくなるため望ましくないからである。なお、当該ＶＯＣ処理用触媒は、不活性担体（バインダーを含む。以下同じ）に担持してなるものとならないものの双方を含み、担持してなる場合の当該質量は後述する不活性担体の質量を含まない。   The present invention has the features as described above. Hereinafter, modes for carrying out the present invention will be described. The catalyst for VOC treatment of the present invention is a catalyst in which platinum is directly supported on a cobalt-cerium composite oxide for gas combustion treatment containing VOC. Here, when the mass ratio of the cobalt-cerium composite oxide in the total mass of the catalyst is 80% or more, and the platinum content in the mass of the cobalt-cerium composite oxide is a (unit: mass%). , 0 <a ≦ 20 is preferable. This is because if it is out of the above range, platinum aggregation tends to occur, which is not desirable. The VOC treatment catalyst includes both those that are not supported on an inert carrier (including a binder; the same applies hereinafter), and the mass when supported is the mass of the inert carrier described later. Not included.

コバルト・セリウム系複合酸化物は、コバルトとセリウムの炭酸塩を前駆体とする化合物を空気中３００〜５００℃で焼成し、その後粉砕処理して作製することができる。粉砕処理によりコバルト・セリウム系複合酸化物上の細孔、特にミクロ孔が崩壊され、これによって後述する分散剤で保護された白金コロイドの拡散性が向上し白金が表面に均一に分散するためコーキング量が減少すると考えられる。ミクロ孔とは細孔の直径が２ｎｍ以下の細孔のことをいうが、この細孔を崩壊させることによってコーキング量をより効率的に減少させることができる。コーキング量の減少により低温で高い活性が持続可能となる。   The cobalt-cerium-based composite oxide can be produced by firing a compound having a carbonate of cobalt and cerium as a precursor at 300 to 500 ° C. in air and then pulverizing it. The pores on the cobalt-cerium composite oxide, especially micropores, are destroyed by the pulverization treatment, which improves the diffusibility of the platinum colloid protected by the dispersant described later, and platinum is uniformly dispersed on the surface. The amount is thought to decrease. The micropore means a pore having a diameter of 2 nm or less, and the amount of coking can be reduced more efficiently by collapsing the pore. By reducing the amount of coking, high activity can be sustained at low temperatures.

白金は、分散剤で保護された白金コロイドの溶液を原料とすることが好ましい。白金コロイド溶液を原料としたのは、担持される白金粒子の分散性を高くするという点で有利と考えられるからである。白金コロイドの保護剤としては、ポリビニルポロリドンが好適であるが、それ以外にも、たとえば、ポリビニルポロリドン以外の高分子、配位子、ミセル等を使用することを妨げない。   Platinum is preferably made from a solution of platinum colloid protected with a dispersant. The reason why the colloidal platinum solution is used as a raw material is that it is considered advantageous in terms of increasing the dispersibility of the supported platinum particles. As the protective agent for the platinum colloid, polyvinyl pororidone is suitable, but other than that, for example, it does not prevent the use of polymers, ligands, micelles and the like other than polyvinyl pororidone.

特に限定されるものではないものの、触媒は、バインダー成分とともに成型してなる、或いは所望形状のステンレス鋼、鉄鋼、銅合金、アルミニウム合金、及びセラミックス材の何れか１つの不活性担体に担持されていてよい。前者において粉末あるいは粉末成型触媒を触媒充填層に充填した場合、空隙が小さくなることによる充填層の閉塞を避けることができる。   Although not particularly limited, the catalyst is molded with a binder component, or is supported on an inert carrier of any one of stainless steel, steel, copper alloy, aluminum alloy, and ceramic material having a desired shape. It's okay. In the former case, when the catalyst packed bed is filled with powder or a powder molded catalyst, blockage of the packed bed due to the small gap can be avoided.

上記した構造のＶＯＣ処理用触媒を用いたＶＯＣ処理の運転温度が、１００〜３００℃の範囲が好適である。上記ＶＯＣ処理用触媒を用いれば３００℃を超えなくてもＶＯＣ処理ができるからである。この状態を保持すれば、従来の処理方法に比べ電気代や燃料費を削減することができる。逆に言えば、３００℃を超えて運転することは、上記ＶＯＣ処理触媒の低温度でも処理できるという特徴を稀釈化してしまうので特段の事情がない限り好ましいことではない。１００℃以下の運転温度は、コーキングの蓄積を招きやすいため避けるべきである。   The operating temperature of the VOC treatment using the VOC treatment catalyst having the structure described above is preferably in the range of 100 to 300 ° C. This is because if the above-mentioned catalyst for VOC treatment is used, VOC treatment can be performed without exceeding 300 ° C. If this state is maintained, electricity costs and fuel costs can be reduced as compared with conventional processing methods. In other words, it is not preferable to operate at a temperature exceeding 300 ° C. unless there is a special circumstance because it dilutes the feature that the VOC treatment catalyst can be treated even at a low temperature. Operating temperatures below 100 ° C. should be avoided because they tend to cause coking accumulation.

触媒性能評価は実施例１、比較例１〜３ともに以下のように行った。
図１に示すヒーター付の管状電気炉内に設置した触媒充填管内にＶＯＣ処理触媒を充填し、この充填層にＶＯＣ含有ガスを連続的に流通させた。ＶＯＣ含有ガスの組成は乾燥空気にトルエン若しくは酢酸エチルの蒸気を含有させたものとし、トルエン、酢酸エチル濃度は、それぞれ４００ｐｐｍ、９００ｐｐｍ、乾燥空気流速は１００ｍＬ・ｍｉｎ−１とした。作製した触媒粉末はいったんペレット化し、それを適度な大きさに砕いて充填管内を閉塞しないように充填した。 Catalyst performance evaluation was performed as follows for both Example 1 and Comparative Examples 1-3.
A catalyst-filled tube installed in a tubular electric furnace with a heater shown in FIG. 1 was filled with a VOC-treated catalyst, and a VOC-containing gas was continuously circulated through this packed bed. The composition of the VOC-containing gas was a mixture of dry air containing toluene or ethyl acetate vapor, the toluene and ethyl acetate concentrations were 400 ppm and 900 ppm, respectively, and the dry air flow rate was 100 mL · min −1 . The prepared catalyst powder was once pelletized and then crushed to an appropriate size and filled so as not to block the filling tube.

管状電気炉のヒーター温度を調整することにより触媒充填層の温度を調整した。トルエン燃焼においては３００℃、酢酸エチル燃焼においては４００℃に昇温した後、１時間その温度を保持し、その後３０℃まで１分間に１℃ずつ降温させた。降温時に熱伝導度検出器付きガスクロマトグラフを用いてガス中の二酸化炭素濃度、及びトルエン若しくは酢酸エチル濃度を測定した。トルエン若しくは酢酸エチルが完全燃焼した際のガス中の二酸化炭素濃度をＣ１、触媒充填層を通過したガス中の二酸化炭素濃度をＣ２とした時、ＣＯ２生成率（燃焼率）ｃ（％）はｃ＝Ｃ２／Ｃ１×１００の式から求めた。 The temperature of the catalyst packed bed was adjusted by adjusting the heater temperature of the tubular electric furnace. In toluene combustion, the temperature was raised to 300 ° C., and in ethyl acetate combustion, the temperature was maintained for 1 hour, and the temperature was maintained for 1 hour. Thereafter, the temperature was lowered to 30 ° C. by 1 ° C. per minute. When the temperature was lowered, the carbon dioxide concentration in the gas and the toluene or ethyl acetate concentration were measured using a gas chromatograph with a thermal conductivity detector. When the carbon dioxide concentration in the gas when toluene or ethyl acetate completely burns is C1, and the carbon dioxide concentration in the gas that has passed through the catalyst packed bed is C2, the CO 2 production rate (combustion rate) c (%) is It calculated | required from the formula of c = C2 / C1 * 100.

触媒のコーキング生成評価は実施例１、比較例４ともに以下のように行った。
同じく図１に示す管状電気炉内に設置した触媒充填管内に触媒を充填し、この充填層にトルエンの蒸気を含有させた乾燥空気（ＶＯＣ含有ガス）を連続的に流通させた。トルエン濃度は４００ｐｐｍ、乾燥空気流速は１００ｍＬ・ｍｉｎ−１とした。作製した触媒粉末はいったんペレット化し、それを適度な大きさに砕いて充填管内を閉塞しないように充填した。管状電気炉を用いて触媒層の温度を調整した。１５０℃若しくは１７０℃に昇温した後、２４時間その温度を保持しトルエンの蒸気を含有させた乾燥空気を連続的に流通させ、トルエンの燃焼を継続させた。その後、乾燥空気のみを流して３０℃まで降温し、乾燥空気のみを流したまま３００℃まで１分間に１℃ずつ昇温させ、触媒表面に蓄積したコーキングの燃焼に伴う二酸化炭素の発生を熱伝導度検出器付きガスクロマトグラフで測定した。 Evaluation of coking generation of the catalyst was performed as follows in both Example 1 and Comparative Example 4.
Similarly, a catalyst filling tube installed in the tubular electric furnace shown in FIG. 1 was filled with a catalyst, and dry air (VOC-containing gas) containing toluene vapor was continuously circulated through the packed bed. The toluene concentration was 400 ppm, and the dry air flow rate was 100 mL · min −1 . The prepared catalyst powder was once pelletized and then crushed to an appropriate size and filled so as not to block the filling tube. The temperature of the catalyst layer was adjusted using a tubular electric furnace. After raising the temperature to 150 ° C. or 170 ° C., the temperature was maintained for 24 hours, and dry air containing toluene vapor was continuously circulated to continue the combustion of toluene. After that, only dry air is flowed and the temperature is lowered to 30 ° C., and only dry air is flowed, and the temperature is raised to 300 ° C. by 1 ° C. per minute, and the generation of carbon dioxide accompanying combustion of coking accumulated on the catalyst surface is heated. It was measured with a gas chromatograph equipped with a conductivity detector.

（白金担持コバルト・セリウム複合酸化物）
＜１＞触媒の作製
コバルト炭酸塩とセリウムの炭酸塩の前駆体を空気中、３００℃で１時間焼成してコバルト・セリウム複合酸化物を作製した。これをポリビニルピロリドンで保護された白金コロイド（田中貴金属工業株式会社製）の水溶液に浸漬させ、撹拌及び加温しながら、溶液を蒸発させた。白金の担持率は、コバルト・セリウム複合酸化物に対して重量比で１、２、５％とした。乾燥した試料を空気中で１分間に０．９℃ずつ徐々に昇温して最終的に３００℃で１時間焼成することにより目的触媒を得た。 (Platinum-supported cobalt-cerium composite oxide)
<1> Production of Catalyst A cobalt-cerium composite oxide was produced by firing a precursor of cobalt carbonate and cerium carbonate in air at 300 ° C. for 1 hour. This was immersed in an aqueous solution of platinum colloid protected by polyvinylpyrrolidone (manufactured by Tanaka Kikinzoku Kogyo Co., Ltd.), and the solution was evaporated while stirring and heating. The platinum loading was 1, 2, 5% by weight with respect to the cobalt-cerium composite oxide. The dried sample was gradually heated in air at a rate of 0.9 ° C. per minute and finally calcined at 300 ° C. for 1 hour to obtain the target catalyst.

＜２＞触媒の性能評価
トルエン及び酢酸エチルに対するＣＯ２生成率（燃焼率）の温度依存性 図２のＡ（トルエン、白金（１％、白金コロイド）担持コバルト・セリウム複合酸化物）、Ｂ（トルエン、白金（２％、白金コロイド）担持コバルト・セリウム複合酸化物）、Ｃ（トルエン、白金（５％、白金コロイド）担持コバルト・セリウム複合酸化物）、図３のＡ（酢酸エチル、白金（１％、白金コロイド）担持コバルト・セリウム複合酸化物）、Ｂ（酢酸エチル、白金（２％、白金コロイド）担持コバルト・セリウム複合酸化物）、Ｃ（酢酸エチル、白金（５％、白金コロイド）担持コバルト・セリウム複合酸化物）
１５０℃で２４時間燃焼を継続した後のコーキング生成評価 図４のＡ（１５０℃、粉砕前の酸化セリウムを使用）
１７０℃で２４時間燃焼を継続した後のコーキング生成評価 図４のＢ（１７０℃、粉砕前の酸化セリウムを使用） <2> Performance evaluation of catalyst Temperature dependency of CO 2 production rate (combustion rate) with respect to toluene and ethyl acetate A (toluene, platinum (1%, platinum colloid) -supported cobalt-cerium composite oxide), B ( Toluene, platinum (2%, platinum colloid) -supported cobalt-cerium composite oxide), C (toluene, platinum (5%, platinum colloid) -supported cobalt-cerium composite oxide), A in FIG. 3 (ethyl acetate, platinum ( 1%, platinum colloid) -supported cobalt-cerium composite oxide), B (ethyl acetate, platinum (2%, platinum colloid) -supported cobalt-cerium composite oxide), C (ethyl acetate, platinum (5%, platinum colloid) Supported cobalt-cerium composite oxide)
Evaluation of coking formation after burning for 24 hours at 150 ° C. FIG. 4A (150 ° C., using cerium oxide before grinding)
Evaluation of coking formation after burning for 24 hours at 170 ° C B in Fig. 4 (170 ° C, using cerium oxide before grinding)

前述のとおり、芳香族のＶＯＣと芳香環を含まないＶＯＣで触媒処理温度（燃焼温度）が大きく異なる。芳香族の典型的なＶＯＣとしてトルエン、芳香環を含まない典型的なＶＯＣとして酢酸エチルを選び試験を実施した。ＣＯ２の生成率が９０〜１００％に達する燃焼温度に着目し、触媒処理可能な温度を整理した。ポリビニルピロリドンで保護された白金コロイドの水溶液を用いて白金を担持したコバルト・セリウム複合酸化物を用いた場合、酢酸エチルのＣＯ２生成率が９０〜１００％に達する温度は２００〜２５０℃程度に（図３のＡ、Ｂ、Ｃ）、トルエンの同温度は約２００℃以下に（図２のＡ、Ｂ、Ｃ）減少した。白金担持率の増加に伴い、燃焼温度が減少することも見出された。芳香族のＶＯＣと芳香環を含まないＶＯＣを同時に概ね２５０℃以下で処理することが可能となった。 As described above, the catalyst treatment temperature (combustion temperature) differs greatly between an aromatic VOC and a VOC that does not contain an aromatic ring. The test was conducted with toluene selected as the typical aromatic VOC and ethyl acetate as the typical VOC containing no aromatic ring. Focusing on the combustion temperature at which the CO 2 production rate reaches 90 to 100%, the temperatures at which the catalyst treatment is possible were arranged. When cobalt-cerium composite oxide supporting platinum using an aqueous solution of platinum colloid protected with polyvinylpyrrolidone is used, the temperature at which the CO 2 production rate of ethyl acetate reaches 90 to 100% is about 200 to 250 ° C. (A, B, C in FIG. 3), the same temperature of toluene decreased to about 200 ° C. or less (A, B, C in FIG. 2). It has also been found that the combustion temperature decreases with increasing platinum loading. An aromatic VOC and a VOC that does not contain an aromatic ring can be simultaneously treated at about 250 ° C. or less.

トルエン燃焼により触媒表面に蓄積したコーキングの燃焼に伴うＣＯ２の発生に関して、酸化セリウムを粉砕せず、コバルト・セリウム複合酸化物を合成し、ポリビニルピロリドンで保護された白金コロイドの水溶液を用いて白金を担持した触媒では、１５０℃・２４時間のトルエン燃焼後の触媒（図４のＡ）、１７０℃・２４時間のトルエン燃焼後の触媒（図４のＢ）ともにＣＯ２が生成し、コーキングの存在が認められた。 Regarding the generation of CO 2 due to the combustion of coking accumulated on the catalyst surface by toluene combustion, platinum was prepared using an aqueous solution of platinum colloid protected with polyvinylpyrrolidone by synthesizing cobalt-cerium composite oxide without crushing cerium oxide. In the catalyst supporting toluene, CO 2 is formed in both the catalyst after toluene combustion at 150 ° C. for 24 hours (A in FIG. 4) and the catalyst after toluene combustion at 170 ° C. for 24 hours (B in FIG. 4). Existence was recognized.

［比較例１］
白金担持コバルト・セリウム複合酸化物（塩化白金酸を用いた担持）
＜１＞触媒の作製
コバルト炭酸塩とセリウムの炭酸塩の前駆体を空気中、３００℃で１時間焼成してコバルト・セリウム複合酸化物を作製した。これを塩化白金酸の水溶液に浸漬させ、撹拌及び加温しながら、溶液を蒸発させた。白金の担持率は、コバルト・セリウム複合酸化物に対して重量比で２％とした。乾燥した試料を水素雰囲気下において４００℃で１時間還元することにより目的触媒を得た。 [Comparative Example 1]
Platinum-supported cobalt-cerium composite oxide (support using chloroplatinic acid)
<1> Production of Catalyst A cobalt-cerium composite oxide was produced by firing a precursor of cobalt carbonate and cerium carbonate in air at 300 ° C. for 1 hour. This was immersed in an aqueous solution of chloroplatinic acid, and the solution was evaporated while stirring and heating. The platinum loading was 2% by weight with respect to the cobalt-cerium composite oxide. The dried sample was reduced at 400 ° C. for 1 hour in a hydrogen atmosphere to obtain the target catalyst.

＜２＞触媒の性能評価
トルエン及び酢酸エチルに対するＣＯ２生成率（燃焼率）の温度依存性 図２のＤ（トルエン、白金（２％、塩化白金酸）担持コバルト・セリウム複合酸化物）、図３のＤ（酢酸エチル、白金（２％、塩化白金酸）担持コバルト・セリウム複合酸化物） <2> Performance Evaluation of Catalyst Temperature dependency of CO2 production rate (combustion rate) with respect to toluene and ethyl acetate FIG. 2D (toluene, platinum (2%, chloroplatinic acid) -supported cobalt-cerium composite oxide), FIG. D (ethyl acetate, platinum (2%, chloroplatinic acid) -supported cobalt-cerium composite oxide)

従来から広く用いられている典型的な原料である塩化白金酸を用いて白金を担持したコバルト・セリウム複合酸化物を用いた場合、後述するコバルト・セリウム複合酸化物（白金担持なし）を用いた場合と比して、トルエンの燃焼温度はほとんど変わらず（図２のＤ）、酢酸エチルのＣＯ２生成率が９０〜１００％に達する温度は２００〜２５０℃程度に上昇し（図３のＤ）、白金を担持することにより性能がむしろ悪くなった。これは、比表面積が小さい、表面との親和性が低い等の理由によりコバルト・セリウム複合酸化物上に白金が均一に分散されず、凝集してしまったため、性能が悪くなったと考えられる。 When a cobalt-cerium composite oxide supporting platinum using chloroplatinic acid, which is a typical raw material that has been widely used in the past, was used, a cobalt-cerium composite oxide (without platinum support) described later was used. Compared to the case, the combustion temperature of toluene hardly changed (D in FIG. 2), and the temperature at which the CO 2 production rate of ethyl acetate reached 90 to 100% increased to about 200 to 250 ° C. (D in FIG. 3). ) The performance was rather deteriorated by supporting platinum. This is probably because platinum was not uniformly dispersed and agglomerated on the cobalt-cerium composite oxide for reasons such as a small specific surface area and low affinity with the surface.

［比較例２］
コバルト・セリウム複合酸化物（白金担持なし）
＜１＞触媒の作製
コバルト炭酸塩とセリウムの炭酸塩の前駆体を空気中、３００℃で１時間焼成してコバルト・セリウム複合酸化物を作製した。 [Comparative Example 2]
Cobalt / cerium composite oxide (without platinum support)
<1> Production of Catalyst A cobalt-cerium composite oxide was produced by firing a precursor of cobalt carbonate and cerium carbonate in air at 300 ° C. for 1 hour.

＜２＞触媒の性能評価
トルエン及び酢酸エチルに対するＣＯ２生成率（燃焼率）の温度依存性 図２のＥ（トルエン、コバルト・セリウム複合酸化物（白金担持なし））、図３のＥ（酢酸エチル、コバルト・セリウム複合酸化物（白金担持なし）） <2> Performance evaluation of catalyst Temperature dependency of CO 2 production rate (combustion rate) with respect to toluene and ethyl acetate E in FIG. 2 (toluene, cobalt-cerium composite oxide (without platinum support)), E in FIG. Ethyl, cobalt-cerium composite oxide (without platinum support)

コバルト・セリウム複合酸化物（白金担持なし）を用いた場合、酢酸エチルのＣＯ２生成率が９０〜１００％に達する温度は約２５０℃付近であった（図３のＥ）が、トルエンでは３００℃程度を必要とした（図２のＥ）。 When the cobalt-cerium composite oxide (without platinum support) was used, the temperature at which the CO 2 production rate of ethyl acetate reached 90 to 100% was about 250 ° C. (E in FIG. 3), but 300 to 300 for toluene. About 0 ° C. was required (E in FIG. 2).

［比較例３］
白金担持アルミナ（日揮ユニバーサル株式会社製市販品）
＜１＞触媒
白金担持アルミナを適度な大きさに砕いて触媒充填管内を閉塞しないように充填した。 [Comparative Example 3]
Platinum-supported alumina (commercially available from JGC Universal Corporation)
<1> Catalyst The platinum-supported alumina was crushed to an appropriate size and filled so as not to close the inside of the catalyst filling tube.

＜２＞触媒の性能評価
トルエン及び酢酸エチルに対するＣＯ２生成率（燃焼率）の温度依存性 図２のＦ（トルエン、市販白金担持アルミナ）、図３のＦ（酢酸エチル、市販白金担持アルミナ） <2> Performance evaluation of catalyst Temperature dependency of CO2 production rate (combustion rate) with respect to toluene and ethyl acetate F in FIG. 2 (toluene, commercially available platinum-supported alumina), F in FIG. 3 (ethyl acetate, commercially-available platinum-supported alumina)

市販の白金担持アルミナ触媒を用いた場合、トルエンのＣＯ２生成率が９０〜１００％に達する温度は２００〜２５０℃程度であった（図２のＦ）が、酢酸エチルでは約３５０℃付近となった（図３のＦ）。 When a commercially available platinum-supported alumina catalyst was used, the temperature at which the CO 2 production rate of toluene reached 90 to 100% was about 200 to 250 ° C. (F in FIG. 2). (F in FIG. 3).

［比較例４］
白金担持コバルト・セリウム複合酸化物（粉砕した酸化セリウムを使用）
＜１＞触媒の作製
コバルト炭酸塩を空気中、３００℃で１時間焼成することにより酸化コバルトを作製した。 [Comparative Example 4]
Platinum-supported cobalt-cerium composite oxide (uses ground cerium oxide)
<1> Production of catalyst Cobalt oxide was produced by firing cobalt carbonate in air at 300 ° C for 1 hour.

セリウムの炭酸塩を空気中、３００℃で１時間焼成して酸化セリウムを作製し、湿式粉砕機（フリッチュ・ジャパン株式会社製遊星型ボールミル クラシックラインＰ−７）を用いて粉砕した。粉砕前のメディアン径は２３．３μｍ、粉砕後のメディアン径は０．４１５μ
ｍであった。粉砕前後の細孔分布はマイクロトラック・ベル株式会社製ＢＥＬＳＯＲＰ−ｍａｘを用いて測定した。粉砕後の試料をポリビニルピロリドンで保護された白金コロイド（田
中貴金属工業株式会社製）の水溶液に浸漬させ、撹拌及び加温しながら、溶液を蒸発、乾燥させた。乾燥させた試料と酸化コバルトを混合し、空気中で１分間に０．９℃ずつ徐々に昇温して最終的に３００℃で１時間焼成することにより目的触媒を得た。白金の担持率は、コバルト・セリウム複合酸化物に対して重量比で２％とした。 Cerium carbonate was baked in air at 300 ° C. for 1 hour to produce cerium oxide, which was pulverized using a wet pulverizer (French Japan Co., Ltd. planetary ball mill Classic Line P-7). The median diameter before crushing is 23.3 μm, and the median diameter after crushing is 0.415 μm.
m. The pore distribution before and after pulverization was measured using BELSORP-max manufactured by Microtrac Bell. The crushed sample was immersed in an aqueous solution of platinum colloid protected by polyvinylpyrrolidone (manufactured by Tanaka Kikinzoku Kogyo Co., Ltd.), and the solution was evaporated and dried while stirring and heating. The dried sample and cobalt oxide were mixed, gradually heated at a rate of 0.9 ° C. per minute in air, and finally calcined at 300 ° C. for 1 hour to obtain the target catalyst. The platinum loading was 2% by weight with respect to the cobalt-cerium composite oxide.

＜２＞触媒の性能評価
１５０℃で２４時間燃焼を継続した後のコーキング生成評価 図４のＣ（１５０℃、粉砕後の酸化セリウムを使用）
１７０℃で２４時間燃焼を継続した後のコーキング生成評価 図４のＤ（１７０℃、粉砕後の酸化セリウムを使用）
粉砕前の酸化セリウムの細孔分布 図５のＡ（粉砕前）
粉砕後の酸化セリウムの細孔分布 図５のＢ（粉砕後） <2> Performance evaluation of catalyst Evaluation of coking formation after continuation of combustion at 150 ° C. for 24 hours FIG. 4C (150 ° C., using cerium oxide after grinding)
Evaluation of coking formation after burning for 24 hours at 170 ° C D in Fig. 4 (170 ° C, using cerium oxide after grinding)
Distribution of pores of cerium oxide before grinding A in FIG. 5 (before grinding)
Pore distribution of cerium oxide after grinding B in Fig. 5 (after grinding)

トルエン燃焼により触媒表面に蓄積したコーキングの燃焼に伴うＣＯ２の発生に関して、酸化セリウムを粉砕後にコバルト・セリウム複合酸化物を合成し、ポリビニルピロリドンで保護された白金コロイドの水溶液を用いて白金を担持した触媒では、１５０℃・２４時間のトルエン燃焼後の触媒（図４のＣ）、１７０℃・２４時間のトルエン燃焼後の触媒（図４のＤ）ともにコーキングの存在が認められなかった。これは粉砕により細孔容積が減少し（図５のＡ、Ｂ）、白金を担持する際、分散剤で保護された白金コロイド（直径３３ｎｍ）の拡散性が向上し白金が表面により均一に分散するため、コーキング量が減少すると考えられる。 For the occurrence of CO 2 due to the combustion of coking accumulated on the catalyst surface by toluene burning, cerium oxide cobalt-cerium composite oxide synthesized after grinding, loading platinum using an aqueous solution of colloidal platinum-protected polyvinylpyrrolidone In the catalyst, coking was not observed in both the catalyst after toluene combustion at 150 ° C. for 24 hours (C in FIG. 4) and the catalyst after toluene combustion at 170 ° C. for 24 hours (D in FIG. 4). This is because the pore volume is reduced by grinding (A and B in FIG. 5), and when carrying platinum, the diffusibility of the platinum colloid (diameter 33 nm) protected by the dispersant is improved, and platinum is evenly dispersed on the surface. Therefore, the amount of coking is considered to decrease.

Claims (5)

ＶＯＣを含有するガス燃焼処理用の、白金をコバルト・セリウム系複合酸化物上に直接担持させたＶＯＣ処理用触媒であって、
触媒全体の質量に占めるコバルト・セリウム系複合酸化物の質量割合が８０％以上であり、コバルト・セリウム系複合酸化物の質量に占める白金の含有量をａ（単位：質量％）とすると、０＜ａ≦２０の範囲であることを特徴とするＶＯＣ処理用触媒。 A catalyst for VOC treatment in which platinum is directly supported on a cobalt-cerium composite oxide for gas combustion treatment containing VOC,
When the mass ratio of the cobalt-cerium composite oxide in the total mass of the catalyst is 80% or more and the platinum content in the mass of the cobalt-cerium composite oxide is a (unit: mass%), 0 A catalyst for VOC treatment, wherein <a ≦ 20. 前記白金は、分散剤で保護された白金コロイドの溶液を原料とすることを特徴とする請求項１に記載のＶＯＣ処理用触媒。   The catalyst for VOC treatment according to claim 1, wherein the platinum is made from a solution of a platinum colloid protected with a dispersant. 前記触媒は、バインダー成分とともに成型してなる、或いは
所望形状のステンレス鋼、鉄鋼、銅合金、アルミニウム合金、及びセラミックス材の何れか１つの担体に担持されていることを特徴とする請求項１または２記載のＶＯＣ処理用触媒。 2. The catalyst according to claim 1, wherein the catalyst is molded together with a binder component, or is supported on any one of stainless steel, steel, copper alloy, aluminum alloy, and ceramic material having a desired shape. 2. The catalyst for VOC treatment according to 2. 請求項１ないし３いずれか記載のＶＯＣ処理用触媒の製造方法であって、
前記コバルト・セリウム系複合酸化物は、コバルトとセリウムの炭酸塩を前駆体とする化合物を空気中３００〜５００℃で焼成し、その後粉砕処理して作製す
ることを特徴とするＶＯＣ処理用触媒の製造方法。 A method for producing a VOC treatment catalyst according to any one of claims 1 to 3,
The cobalt-cerium composite oxide is produced by calcining a compound having a cobalt and cerium carbonate precursor as a precursor at 300 to 500 ° C. in air, and then pulverizing the compound. Production method. 請求項１ないし３いずれか記載のＶＯＣ処理用触媒を用いたＶＯＣ処理方法であって、
運転温度が、１００〜３００℃であることを特徴とするＶＯＣ処理方法。 A VOC treatment method using the VOC treatment catalyst according to any one of claims 1 to 3,
An operating temperature is 100 to 300 ° C.
JP2017131884A 2017-07-05 2017-07-05 Method for producing VOC treatment catalyst, VOC treatment method, and VOC treatment catalyst Active JP7119256B2 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2017131884A JP7119256B2 (en) 2017-07-05 2017-07-05 Method for producing VOC treatment catalyst, VOC treatment method, and VOC treatment catalyst
CN201880029094.1A CN110621399A (en) 2017-07-05 2018-06-29 Catalyst for VOC treatment
PCT/JP2018/024929 WO2019009216A1 (en) 2017-07-05 2018-06-29 Catalyst for voc treatment

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2017131884A JP7119256B2 (en) 2017-07-05 2017-07-05 Method for producing VOC treatment catalyst, VOC treatment method, and VOC treatment catalyst

Publications (3)

Publication Number Publication Date
JP2019013871A true JP2019013871A (en) 2019-01-31
JP2019013871A5 JP2019013871A5 (en) 2020-03-19
JP7119256B2 JP7119256B2 (en) 2022-08-17

Family

ID=64950043

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2017131884A Active JP7119256B2 (en) 2017-07-05 2017-07-05 Method for producing VOC treatment catalyst, VOC treatment method, and VOC treatment catalyst

Country Status (3)

Country Link
JP (1) JP7119256B2 (en)
CN (1) CN110621399A (en)
WO (1) WO2019009216A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021029410A1 (en) * 2019-08-14 2021-02-18 地方独立行政法人東京都立産業技術研究センター Method for manufacturing catalyst for voc treatment
KR20210138881A (en) * 2020-05-13 2021-11-22 주식회사 신성이엔지 VOC removal system and its control method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011224546A (en) * 2010-03-31 2011-11-10 Tokyo Metropolitan Industrial Technology Research Institute Inorganic oxide molded catalyst and method for manufacturing the same
JP2013208621A (en) * 2013-07-01 2013-10-10 New Cosmos Electric Corp Carbon monoxide oxidation catalyst and method for producing the same
CN105013508A (en) * 2015-06-29 2015-11-04 浙江大学 Catalyst for low temperature catalytic combustion of chlorinated volatile organic compounds and preparation method
JP2015217324A (en) * 2014-05-15 2015-12-07 国立研究開発法人産業技術総合研究所 Combustion catalyst system
JP6140326B1 (en) * 2016-03-08 2017-05-31 株式会社流機エンジニアリング Method for regenerating adsorbent of volatile organic compound

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5578283A (en) * 1994-12-30 1996-11-26 Engelhard Corporation Catalytic oxidation catalyst and method for controlling VOC, CO and halogenated organic emissions
KR100416735B1 (en) * 1995-10-09 2004-03-26 삼성전기주식회사 Catalyst for purifying exhaust gas from car and method for preparing thereof
JP3799945B2 (en) * 1999-03-29 2006-07-19 株式会社豊田中央研究所 Room temperature purification catalyst and method of using the same
JP2002219363A (en) * 2001-01-26 2002-08-06 Matsushita Electric Ind Co Ltd Catalyst for cleaning volatile organic compound and method for preparing the same
JP2003225568A (en) * 2002-02-05 2003-08-12 Matsushita Electric Ind Co Ltd Catalyst for purifying volatile organic compound and production method therefor
US20080233039A1 (en) * 2005-06-02 2008-09-25 Symyx Technologies, Inc. Catalysts For Co Oxidation,Voc Combustion And Nox Reduction And Methods Of Making And Using The Same
CN1919455A (en) * 2005-08-25 2007-02-28 中国科学院生态环境研究中心 Process for eliminating volatile organic pollutant by catalytic oxidation
CN101400441B (en) * 2005-11-01 2014-12-31 日产自动车株式会社 Catalyst for exhaust-gas purification and process for producing the same
DE102006046884A1 (en) * 2006-10-04 2008-04-10 Christian Dr. Koch Process and apparatus for the catalytic oxidation and reduction of gases and vapors with crystalline compounds of heavy metals and rare earths
JP5503155B2 (en) * 2009-01-30 2014-05-28 新コスモス電機株式会社 Carbon monoxide removal filter
CN102247867B (en) * 2010-05-21 2013-06-19 中国石油化工股份有限公司 Catalytic oxidation catalyst for methyl acetate in organic waste gas and preparation method thereof
CN104053503B (en) * 2012-01-19 2016-11-02 丰田自动车株式会社 Exhaust emission control catalyst and manufacture method thereof
CN105964254A (en) * 2016-06-20 2016-09-28 西南化工研究设计院有限公司 Monolithic catalyst for catalyzing combustion of volatile organic compounds and preparation method of catalyst
CN106540714A (en) * 2016-11-07 2017-03-29 上海纳米技术及应用国家工程研究中心有限公司 A kind of cerium cobalt complex oxides loaded palladium catalyst and preparation and application for propane catalysis oxidation

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011224546A (en) * 2010-03-31 2011-11-10 Tokyo Metropolitan Industrial Technology Research Institute Inorganic oxide molded catalyst and method for manufacturing the same
JP2013208621A (en) * 2013-07-01 2013-10-10 New Cosmos Electric Corp Carbon monoxide oxidation catalyst and method for producing the same
JP2015217324A (en) * 2014-05-15 2015-12-07 国立研究開発法人産業技術総合研究所 Combustion catalyst system
CN105013508A (en) * 2015-06-29 2015-11-04 浙江大学 Catalyst for low temperature catalytic combustion of chlorinated volatile organic compounds and preparation method
JP6140326B1 (en) * 2016-03-08 2017-05-31 株式会社流機エンジニアリング Method for regenerating adsorbent of volatile organic compound

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021029410A1 (en) * 2019-08-14 2021-02-18 地方独立行政法人東京都立産業技術研究センター Method for manufacturing catalyst for voc treatment
JP2021030098A (en) * 2019-08-14 2021-03-01 地方独立行政法人東京都立産業技術研究センター Manufacturing method of voc treatment catalyst
JP7344505B2 (en) 2019-08-14 2023-09-14 地方独立行政法人東京都立産業技術研究センター Method for manufacturing catalyst for VOC treatment
KR20210138881A (en) * 2020-05-13 2021-11-22 주식회사 신성이엔지 VOC removal system and its control method thereof
KR102434675B1 (en) * 2020-05-13 2022-08-19 주식회사 신성이엔지 VOC removal system and its control method thereof

Also Published As

Publication number Publication date
WO2019009216A1 (en) 2019-01-10
JP7119256B2 (en) 2022-08-17
CN110621399A (en) 2019-12-27

Similar Documents

Publication Publication Date Title
Reddy et al. Structural characteristics and catalytic activity of nanocrystalline ceria− praseodymia solid solutions
Qu et al. 3D gold‐modified cerium and cobalt oxide catalyst on a graphene aerogel for highly efficient catalytic formaldehyde oxidation
EP3673992B1 (en) Methane oxidizing catalyst
JP7119256B2 (en) Method for producing VOC treatment catalyst, VOC treatment method, and VOC treatment catalyst
Durgasri et al. Facile synthesis of catalytically active CeO 2–Gd 2 O 3 solid solutions for soot oxidation
JP5703924B2 (en) Columnar ceria catalyst
Wang et al. Metal–Organic Framework (MOF) template based efficient Pt/ZrO2@ C catalysts for selective catalytic reduction of H2 below 90° C
Li et al. Insights into key parameters of MnO 2 catalyst toward high catalytic combustion performance
JP2010110697A (en) Ammonia decomposition catalyst
CN109289937B (en) Preparation method of high-dispersion supported metal catalyst
Dyachenko et al. Preparation and characterization of Ni–Co/SiO 2 nanocomposite catalysts for CO 2 methanation
CN106984318B (en) Bimetal cobalt-based catalyst, preparation method and application
JP6964448B2 (en) Mold carbon material for fuel cell catalyst carrier, catalyst layer for fuel cell, and fuel cell
Valechha et al. Effect of SO 2 on catalytic CO oxidation over nano-structured, mesoporous Au/Ce 1− x Zr x O 2 catalysts
EP3651898B1 (en) Catalysts based on pd/ceo2 and preparation method thereof
JP2015157236A (en) Catalyst material for purifying engine exhaust gas, and particulate filter
JP7344505B2 (en) Method for manufacturing catalyst for VOC treatment
KR102278420B1 (en) Method for manufacturing vehicle exhaust gas treatment catalyst and vehicle exhaust gas treatment catalyst prepared by the same
CN112584926A (en) Catalyst for exhaust gas purification
JP2019193913A (en) Hydrogen manufacturing catalyst
EP2870997A1 (en) Catalyst for emission gas purification and production method thereof
JP2013034937A (en) Method for producing platinum particle, method for producing platinum particle carrying catalyst, and purifying catalyst
JP2013118049A (en) Cathode catalyst for solid polymer fuel battery and manufacturing method thereof
JP2021126599A (en) Voc removal catalyst and method for producing the same
JP2010221091A (en) Composite oxide for exhaust gas cleaning catalyst, coating material for exhaust gas cleaning catalyst and diesel exhaust gas cleaning filter

Legal Events

Date Code Title Description
A521 Request for written amendment filed

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20200203

A621 Written request for application examination

Free format text: JAPANESE INTERMEDIATE CODE: A621

Effective date: 20200203

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20210226

A521 Request for written amendment filed

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20210420

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20210910

A521 Request for written amendment filed

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20211109

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20220329

A521 Request for written amendment filed

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20220530

TRDD Decision of grant or rejection written
A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

Effective date: 20220628

A61 First payment of annual fees (during grant procedure)

Free format text: JAPANESE INTERMEDIATE CODE: A61

Effective date: 20220707

R150 Certificate of patent or registration of utility model

Ref document number: 7119256

Country of ref document: JP

Free format text: JAPANESE INTERMEDIATE CODE: R150