JP2007175598A - Aldehydes gas removing agent - Google Patents

Aldehydes gas removing agent Download PDF

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JP2007175598A
JP2007175598A JP2005375786A JP2005375786A JP2007175598A JP 2007175598 A JP2007175598 A JP 2007175598A JP 2005375786 A JP2005375786 A JP 2005375786A JP 2005375786 A JP2005375786 A JP 2005375786A JP 2007175598 A JP2007175598 A JP 2007175598A
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manganese
zirconium
removing agent
aldehyde gas
removal
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Tadao Masumori
忠雄 増森
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Toyobo Co Ltd
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Toyobo Co Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To provide an aldehydes gas removing agent capable of exhibiting a satisfactory removal performance at a temperature/humidity area in a general life for a long period of time regarding removal of the aldehydes gas and having a low influence to environment pollution. <P>SOLUTION: The aldehydes gas removing agent contains at least a manganese-zirconium based removing agent, the manganese-zirconium based removing agent contains a manganese element (Mn) and a zirconium element (Zr) in a range of Mn/Zr (molar ratio) of 0.2-2.0, and a BET specific surface area of the manganese-zirconium based removing agent is 100 m<SP>2</SP>/g or more. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

本発明は、アルデヒド類ガス除去に優れたアルデヒド類ガス除去剤に関し、更に詳しくは、常温で長期にわたって除去性能を維持できるアルデヒド類ガス除去剤に関する。   The present invention relates to an aldehyde gas removing agent excellent in aldehyde gas removal, and more particularly to an aldehyde gas removing agent capable of maintaining removal performance at room temperature for a long period of time.

従来より、建物の室内や自動車の車内等におけるタバコ臭の除去を主目的として、空気清浄機や脱臭剤が広く用いられている。これらは、タバコ臭の主成分であるアセトアルデヒド、あるいは、シックハウスの原因物質であるホルムアルデヒド等の除去を目的とするものであり、多くの除去剤の検討がなされている。その中でも、活性炭は各種有機物質を吸着除去する材料として古くから知られているが、低分子で高極性の有機物(例えば、アセトアルデヒド、ホルムアルデヒド等)は十分吸着除去することができず、上述の用途に用いる場合は、活性炭にアミン類やアスコルビン酸等を担持させて吸着除去能を高めたものが用いられている。   Conventionally, air purifiers and deodorizing agents have been widely used mainly for the purpose of removing tobacco odors in the interior of buildings or in automobiles. These are intended to remove acetaldehyde, which is the main component of tobacco odor, or formaldehyde, which is a causative substance of sick house, and many removal agents have been studied. Among them, activated carbon has long been known as a material for adsorbing and removing various organic substances, but it cannot sufficiently adsorb and remove low-molecular and high-polarity organic substances (for example, acetaldehyde, formaldehyde, etc.). In the case of use in the present invention, an activated carbon having amines, ascorbic acid or the like supported thereon to enhance the adsorption removal ability is used.

このように、アミン類を担持させたものとしては、例えば、アニリンを用いたものや(例えば特許文献1参照)、エタノール系アミン等を用いたものが開示されている(例えば特許文献2参照)。
特開昭56−53744号公報 特開昭60−202735号公報
Thus, as what carried amines, what used aniline (for example, refer to patent documents 1), and what used ethanol system amine etc. are indicated (for example, refer to patent documents 2). .
JP 56-53744 A JP-A-60-202735

しかしながら、アミン類を担持させる技術は、担持アミン類の状態は不安定であることから、熱的および経時的な化学変化による失活が起こりやすく、長期にわたって満足すべき除去性能を発現することが困難であるという問題がある。また、アスコルビン酸においても、吸湿すると空気中で容易に酸化分解され、失活してしまい性能劣化が起こるという問題がある。   However, the technology for supporting amines is unstable in the state of the supported amines, and thus is easily deactivated due to thermal and chemical changes over time, and can exhibit satisfactory removal performance over a long period of time. There is a problem that it is difficult. In addition, ascorbic acid also has a problem that when it absorbs moisture, it is easily oxidized and decomposed in the air and deactivated, resulting in performance deterioration.

一方、アルデヒド類ガスの除去方法として、金属酸化物を用いる方法が近年注目を集めており、特に、酸化マンガンを用いる方法は数多く報告されている。(例えば非特許文献1〜2、および、特許文献3〜4参照)。   On the other hand, as a method for removing aldehyde gases, a method using a metal oxide has attracted attention in recent years, and in particular, many methods using manganese oxide have been reported. (For example, refer nonpatent literature 1-2 and patent literature 3-4.).

しかしながら、かかる酸化マンガンでは、一般生活における温湿度領域では、除去活性が低いという問題がある。また、マンガン酸化物は、PRTR第一種指定化学物質であり、環境汚染の懸念から、その量の低減が望まれている。
Applied Catalysis B: Environmental, Vol.8, pp.405-415(1996). Atmospheric Environment, Vol.36, pp.5543-5547(2002). 特開平11−276862号公報 特開2000−79157号公報
However, such manganese oxide has a problem that its removal activity is low in the temperature and humidity range in general life. Manganese oxide is a PRTR first-class designated chemical substance, and reduction of the amount thereof is desired because of concern about environmental pollution.
Applied Catalysis B: Environmental, Vol.8, pp.405-415 (1996). Atmospheric Environment, Vol.36, pp.5543-5547 (2002). JP-A-11-276862 JP 2000-79157 A

上述のとおり、一般生活における温湿度領域で、長期にわたってアルデヒド類ガスを除去するアルデヒド類ガス除去剤において、環境汚染への影響が低く、かつ、その除去性能を維持できるアルデヒド類ガス除去剤は見当たらないのが現状である。ここで言う、一般生活における温湿度領域とは、温度範囲でおおよそ−30〜50℃、湿度範囲でおおよそ20〜95RH%のことである。   As described above, in an aldehyde gas removal agent that removes aldehyde gas over a long period in the temperature and humidity range in general life, there is no aldehyde gas removal agent that has a low impact on environmental pollution and can maintain its removal performance. There is no current situation. The temperature / humidity region in general life referred to here is approximately −30 to 50 ° C. in the temperature range and approximately 20 to 95 RH% in the humidity range.

本発明は上記従来技術の課題を背景になされたものであり、アルデヒド類ガス除去に関して、一般生活における温湿度領域で長期にわたって満足すべき除去性能を発現することができ、かつ、環境汚染への影響が低いアルデヒド類ガス除去剤を提供することを目的とする。   The present invention has been made against the background of the above-described prior art. With regard to aldehyde gas removal, the present invention can exhibit satisfactory removal performance over a long period of time in the temperature and humidity range in general life, and is free from environmental pollution. An object of the present invention is to provide an aldehyde gas removing agent having a low influence.

本発明者らは上記課題を解決するため、鋭意研究した結果、遂に本発明を完成するに到った。すなわち本発明は、(1)アルデヒド類ガスを除去するアルデヒド類ガス除去剤において、前記アルデヒド類ガス除去剤が少なくともマンガン−ジルコニウム系除去剤を含有し、かつ、前記マンガン−ジルコニウム系除去剤が、マンガン元素(Mn)とジルコニウム元素(Zr)をMn/Zr(モル比)=0.2〜2.0の範囲で含有し、(2)前記マンガン−ジルコニウム系除去剤のBET比表面積が100m2/g以上であることを特徴とする(1)(2)のいずれかに記載のアルデヒド類ガス除去剤である。 As a result of intensive studies to solve the above problems, the present inventors have finally completed the present invention. That is, the present invention provides (1) an aldehyde gas removing agent that removes aldehyde gas, wherein the aldehyde gas removing agent contains at least a manganese-zirconium-based removing agent, and the manganese-zirconium-based removing agent comprises: Manganese element (Mn) and zirconium element (Zr) are contained in the range of Mn / Zr (molar ratio) = 0.2 to 2.0, and (2) the manganese-zirconium-based remover has a BET specific surface area of 100 m 2. (1) The aldehyde gas removing agent according to any one of (2), wherein the aldehyde gas removing agent is at least g.

本発明によるアルデヒド類ガス除去剤は、少なくともマンガン−ジルコニウム系除去剤を含有し、かつ、前記マンガン−ジルコニウム系除去剤が、マンガン元素(Mn)とジルコニウム元素(Zr)をMn/Zr(モル比)=0.2〜2.0の範囲で含有し、前記マンガン−ジルコニウム系除去剤のBET比表面積が100m2/g以上であるため、一般生活における温湿度領域での高い除去性能、かつ、長期にわたって満足すべき除去性能を発現することが可能であり、また、環境汚染への影響が少ないという利点を有する。 The aldehyde gas removing agent according to the present invention contains at least a manganese-zirconium-based removing agent, and the manganese-zirconium-based removing agent contains manganese element (Mn) and zirconium element (Zr) as Mn / Zr (molar ratio). ) = 0.2 to 2.0, and since the BET specific surface area of the manganese-zirconium-based removal agent is 100 m 2 / g or more, high removal performance in a temperature and humidity region in general life, and It is possible to exhibit satisfactory removal performance over a long period of time, and there is an advantage that the influence on environmental pollution is small.

以下、本発明を詳細に説明する。本発明におけるアルデヒド類ガス除去剤はマンガン−ジルコニウム系除去剤を少なくとも含有することが好ましい。アルデヒド類ガス除去剤におけるマンガン−ジルコニウム系除去剤の含有比率、および、マンガン−ジルコニウム系除去剤を除くその他の成分については特に限定しない。その他の成分としては、一般的な吸着剤、触媒等が適用できる。   Hereinafter, the present invention will be described in detail. The aldehyde gas removing agent in the present invention preferably contains at least a manganese-zirconium-based removing agent. The content ratio of the manganese-zirconium-based remover in the aldehyde gas remover and other components other than the manganese-zirconium-based remover are not particularly limited. As other components, general adsorbents, catalysts and the like can be applied.

本発明におけるマンガン−ジルコニウム系除去剤において、マンガン元素(Mn)とジルコニウム元素(Zr)をMn/Zr(モル比)=0.2〜2.0の範囲で含有することが好ましい。より好ましくは、1.0〜2.0である。マンガン元素のみ、もしくは、ジルコニウム元素のみを含有するアルデヒド類ガス除去剤では一般生活における温湿度領域において十分な除去性能は実現できない。しかしながら、マンガン元素(Mn)とジルコニウム元素(Zr)をMn/Zr(モル比)=0.2〜2.0の範囲で含有すると、その相乗効果により非常に高い除去性能を実現することができることを本発明者は見出した。相乗効果のメカニズムは明確ではないが、次の(1)〜(4)のように推測される。つまり、最初に、(1)アルデヒド類ガスがジルコニウム元素上に捕捉される、さらに、(2)ジルコニウム元素上に捕捉されたアルデヒド類ガスがジルコニウムの電子授受作用により活性化され分解されやすい状態になる、最後に、(3)そのごく近傍に位置するマンガン元素により、ジルコニウム元素上で活性化されたアルデヒド類ガスが分解される、その際、(4)近傍に位置するジルコニウム元素からの電子授受作用を受け、マンガン元素においても、その分解力が向上していると考えられる。もし、Mn/Zr(モル比)が2より大きいと、ジルコニウム元素がマンガン元素により被覆され、前記相乗効果のメカニズムおける(1)、および、(2)が阻害されてしまい、相乗効果が小さくなり、その結果、十分な除去性能が実現できなくなる。一方で、Mn/Zr(モル比)が0.2より小さいと、マンガン元素が少な過ぎるため、前記相乗効果のメカニズムにおける(3)の影響が小さくなり、結果として、十分な除去性能が実現できなくなる。   In the manganese-zirconium-based remover in the present invention, it is preferable to contain manganese element (Mn) and zirconium element (Zr) in the range of Mn / Zr (molar ratio) = 0.2 to 2.0. More preferably, it is 1.0-2.0. An aldehyde gas removal agent containing only manganese element or only zirconium element cannot realize sufficient removal performance in the temperature and humidity range in general life. However, when manganese element (Mn) and zirconium element (Zr) are contained in the range of Mn / Zr (molar ratio) = 0.2 to 2.0, very high removal performance can be realized by the synergistic effect. The inventor found out. The mechanism of the synergistic effect is not clear, but is presumed as the following (1) to (4). That is, first, (1) the aldehyde gas is trapped on the zirconium element, and (2) the aldehyde gas trapped on the zirconium element is activated and easily decomposed by the electron transfer action of zirconium. Finally, (3) the aldehyde gas activated on the zirconium element is decomposed by the manganese element located in the immediate vicinity thereof, and in this case, (4) electron transfer from the zirconium element located in the vicinity is performed. It is considered that the decomposition power of manganese element is improved. If Mn / Zr (molar ratio) is larger than 2, zirconium element is covered with manganese element, and (1) and (2) in the mechanism of the synergistic effect are inhibited, and the synergistic effect is reduced. As a result, sufficient removal performance cannot be realized. On the other hand, if Mn / Zr (molar ratio) is less than 0.2, the amount of manganese element is too small, so the influence of (3) in the mechanism of the synergistic effect is reduced, and as a result, sufficient removal performance can be realized. Disappear.

前記マンガン−ジルコニウム系除去剤におけるBET比表面積は、100m2/g以上であることが好ましい。BET比表面積が100m2/g以上であれば、低温での高い除去性能を実現することができることを本発明者は見出したからである。より好ましくは150m2/g以上である。BET比表面積の上限は特に限定するものではないが、1000m2/g以下であることが好ましい。この範囲を超えると、除去性能はほとんど変化しない一方で、製造が非常に困難になるという不都合が生じるからである。 The BET specific surface area in the manganese-zirconium-based removal agent is preferably 100 m 2 / g or more. This is because the present inventor has found that if the BET specific surface area is 100 m 2 / g or more, high removal performance at a low temperature can be realized. More preferably, it is 150 m 2 / g or more. The upper limit of the BET specific surface area is not particularly limited, but is preferably 1000 m 2 / g or less. If this range is exceeded, the removal performance is hardly changed, but the disadvantage is that manufacturing becomes very difficult.

本発明におけるマンガン−ジルコニウム系除去剤の製造方法は、マンガン塩、ジルコニウム塩を含有する溶液にアルカリを添加して沈殿を生成させた後、沈殿を濾別、乾燥、焼成して製造することが好ましい。マンガン、および、ジルコニウムの塩の種類に関しては、特に定めないが、塩化物、硝酸塩、硫酸塩等の一般的な塩を使用することができる。溶解度の面から、硝酸塩が好ましい。アルカリに関しては、アンモニア、炭酸アンモニウム等のアンモニウム塩が好ましい。溶液の溶媒の種類に関しては、特に定めないが、一般的な有機溶剤、水等を使用することができる。環境への負荷を考慮すると、水が好ましい。乾燥、焼成温度に関しては、500℃以下であることが好ましい。500℃以上であると、マンガン−ジルコニウム系除去剤の結晶化が進行し、結果として、十分な除去性能が実現できなくなる。   The method for producing a manganese-zirconium-based removal agent in the present invention may be produced by adding an alkali to a solution containing a manganese salt and a zirconium salt to form a precipitate, and then separating the precipitate by filtration, drying and baking. preferable. Although there are no particular restrictions on the types of manganese and zirconium salts, common salts such as chlorides, nitrates, sulfates, and the like can be used. Nitrate is preferred from the viewpoint of solubility. Regarding the alkali, ammonium salts such as ammonia and ammonium carbonate are preferred. The type of solvent in the solution is not particularly defined, but a general organic solvent, water, or the like can be used. Considering the environmental load, water is preferable. The drying and firing temperature is preferably 500 ° C. or lower. When the temperature is 500 ° C. or higher, crystallization of the manganese-zirconium-based removal agent proceeds, and as a result, sufficient removal performance cannot be realized.

以下、実施例によって本発明の作用効果をより具体的に示す。下記実施例は本発明方法を限定する性質のものではなく、前・後記の趣旨に沿って設計変更することはいずれも本発明の技術的範囲に含まれるものである。   Hereinafter, the effects of the present invention will be described more specifically by way of examples. The following examples are not intended to limit the method of the present invention, and any design changes in accordance with the gist of the preceding and following descriptions are included in the technical scope of the present invention.

(BET比表面積の測定方法)
除去剤サンプルを約100mg採取し、120℃で12時間真空乾燥した後、秤量した。自動比表面積装置ジェミニ2375(マイクロメリティックス社製)を使用し、液体窒素の沸点(−195.8℃)における窒素ガスの吸着量を相対圧が0.02〜0.95の範囲で徐々に高めながら40点測定し、上記サンプルの吸着等温線を作製した。相対圧0.02〜0.15での結果をBETプロットし、重量当りのBET比表面積[m2/g]を求めた。
(Measurement method of BET specific surface area)
About 100 mg of a remover sample was collected, vacuum-dried at 120 ° C. for 12 hours, and weighed. Using an automatic specific surface area device Gemini 2375 (manufactured by Micromeritics), the adsorption amount of nitrogen gas at the boiling point of liquid nitrogen (-195.8 ° C.) is gradually increased in a range of relative pressure of 0.02 to 0.95. The sample was measured at 40 points while increasing the temperature to obtain an adsorption isotherm of the sample. The results at a relative pressure of 0.02 to 0.15 were BET-plotted to determine the BET specific surface area [m 2 / g] per weight.

(アセトアルデヒド除去性能の測定方法)
5Lのテドラーバッグ中にアセトアルデヒド100ppmを含む温度25℃、湿度50RH%の空気、および、除去剤サンプル30mgを封入した。中に入っている除去剤サンプルとアセトアルデヒドを含む空気が十分に接触、反応するように、テドラーバッグを適宜振った。なお、テドラーバッグ周囲の雰囲気温度は25℃とした。3時間後のテドラーバッグ内のアセトアルデヒドガス濃度をFID付きガスクロマトグラフにて測定し、反応前後のアセトアルデヒドの濃度変化からアセトアルデヒド除去量[mg]を求め、これを試料の重量で割ることにより、除去容量[mg/g]を算出した。
(Method for measuring acetaldehyde removal performance)
In a 5 L Tedlar bag, air containing 100 ppm of acetaldehyde at a temperature of 25 ° C., humidity of 50 RH%, and a removal agent sample of 30 mg were enclosed. The Tedlar bag was shaken appropriately so that the sample containing the remover and the air containing acetaldehyde sufficiently contacted and reacted. The ambient temperature around the Tedlar bag was 25 ° C. The acetaldehyde gas concentration in the Tedlar bag after 3 hours was measured with a gas chromatograph with FID, the acetaldehyde removal amount [mg] was determined from the concentration change of the acetaldehyde before and after the reaction, and this was divided by the weight of the sample, thereby removing the volume [ mg / g] was calculated.

(実施例1)
硝酸マンガン(II)六水和物(ナカライテスク社製)5.12g、オキシ硝酸ジルコニウム(ナカライテスク社製)4.76gを50mlのイオン交換水に溶解させ、しばらく撹拌した。その後、炭酸アンモニウム(ナカライテスク社製)6.85gを含有する水溶液20mlをゆっくりと添加したところ、白色の沈殿が得られた。白色の沈殿を濾別し、120℃で乾燥させた後、300℃で1時間焼成処理を施したところアルデヒド類ガス除去剤が得られた。得られたアルデヒド類ガス除去剤について、BET比表面積、アセトアルデヒド除去性能を測定した。
Example 1
Manganese (II) nitrate hexahydrate (Nacalai Tesque) 5.12 g and zirconium oxynitrate (Nacalai Tesque) 4.76 g were dissolved in 50 ml of ion-exchanged water and stirred for a while. Thereafter, 20 ml of an aqueous solution containing 6.85 g of ammonium carbonate (manufactured by Nacalai Tesque) was slowly added to obtain a white precipitate. A white precipitate was filtered off, dried at 120 ° C., and then subjected to a baking treatment at 300 ° C. for 1 hour, whereby an aldehyde gas removing agent was obtained. About the obtained aldehyde gas removal agent, the BET specific surface area and the acetaldehyde removal performance were measured.

(実施例2)
硝酸マンガン(II)六水和物(ナカライテスク社製)1.02g、オキシ硝酸ジルコニウム(ナカライテスク社製)4.76gを25mlのイオン交換水に溶解させ、しばらく撹拌した。その後、炭酸アンモニウム(ナカライテスク社製)4.11gを含有する水溶液12mlをゆっくりと添加したところ、白色の沈殿が得られた。白色の沈殿を濾別し、120℃で乾燥させた後、300℃で1時間焼成処理を施したところアルデヒド類ガス除去剤が得られた。得られたアルデヒド類ガス除去剤について、BET比表面積、アセトアルデヒド除去性能を測定した。
(Example 2)
Manganese (II) nitrate hexahydrate (manufactured by Nacalai Tesque) 1.02 g and zirconium oxynitrate (manufactured by Nacalai Tesque) 4.76 g were dissolved in 25 ml of ion-exchanged water and stirred for a while. Thereafter, when 12 ml of an aqueous solution containing 4.11 g of ammonium carbonate (Nacalai Tesque) was slowly added, a white precipitate was obtained. A white precipitate was filtered off, dried at 120 ° C., and then subjected to a baking treatment at 300 ° C. for 1 hour, whereby an aldehyde gas removing agent was obtained. About the obtained aldehyde gas removal agent, the BET specific surface area and the acetaldehyde removal performance were measured.

(実施例3)
硝酸マンガン(II)六水和物(ナカライテスク社製)5.12g、オキシ硝酸ジルコニウム(ナカライテスク社製)2.38gを35mlのイオン交換水に溶解させ、しばらく撹拌した。その後、炭酸アンモニウム(ナカライテスク社製)5.14gを含有する水溶液15mlをゆっくりと添加したところ、白色の沈殿が得られた。白色の沈殿を濾別し、120℃で乾燥させた後、300℃で1時間焼成処理を施したところアルデヒド類ガス除去剤が得られた。得られたアルデヒド類ガス除去剤について、BET比表面積、アセトアルデヒド除去性能を測定した。
(Example 3)
Manganese (II) nitrate hexahydrate (Nacalai Tesque) 5.12 g and zirconium oxynitrate (Nacalai Tesque) 2.38 g were dissolved in 35 ml of ion-exchanged water and stirred for a while. Thereafter, when 15 ml of an aqueous solution containing 5.14 g of ammonium carbonate (manufactured by Nacalai Tesque) was slowly added, a white precipitate was obtained. A white precipitate was filtered off, dried at 120 ° C., and then subjected to a baking treatment at 300 ° C. for 1 hour, whereby an aldehyde gas removing agent was obtained. About the obtained aldehyde gas removal agent, the BET specific surface area and the acetaldehyde removal performance were measured.

(比較例1)
硝酸マンガン(II)六水和物(ナカライテスク社製)5.12gを25mlのイオン交換水に溶解させ、しばらく撹拌した。その後、炭酸アンモニウム(ナカライテスク社製)3.43gを含有する水溶液10mlをゆっくりと添加したところ、白色の沈殿が得られた。白色の沈殿を濾別し、120℃で乾燥させた後、300℃で1時間焼成処理を施したところアルデヒド類ガス除去剤が得られた。得られたアルデヒド類ガス除去剤について、BET比表面積、アセトアルデヒド除去性能を測定した。
(Comparative Example 1)
5.12 g of manganese (II) nitrate hexahydrate (manufactured by Nacalai Tesque) was dissolved in 25 ml of ion-exchanged water and stirred for a while. Thereafter, 10 ml of an aqueous solution containing 3.43 g of ammonium carbonate (manufactured by Nacalai Tesque) was slowly added to obtain a white precipitate. A white precipitate was filtered off, dried at 120 ° C., and then subjected to a baking treatment at 300 ° C. for 1 hour, whereby an aldehyde gas removing agent was obtained. About the obtained aldehyde gas removal agent, the BET specific surface area and the acetaldehyde removal performance were measured.

(比較例2)
オキシ硝酸ジルコニウム(ナカライテスク社製)4.76gを25mlのイオン交換水に溶解させ、しばらく撹拌した。その後、炭酸アンモニウム(ナカライテスク社製)3.43gを含有する水溶液10mlをゆっくりと添加したところ、白色の沈殿が得られた。白色の沈殿を濾別し、120℃で乾燥させた後、300℃で1時間焼成処理を施したところアルデヒド類ガス除去剤が得られた。得られたアルデヒド類ガス除去剤について、BET比表面積、アセトアルデヒド除去性能を測定した。
(Comparative Example 2)
4.76 g of zirconium oxynitrate (manufactured by Nacalai Tesque) was dissolved in 25 ml of ion exchange water and stirred for a while. Thereafter, 10 ml of an aqueous solution containing 3.43 g of ammonium carbonate (manufactured by Nacalai Tesque) was slowly added to obtain a white precipitate. A white precipitate was filtered off, dried at 120 ° C., and then subjected to a baking treatment at 300 ° C. for 1 hour, whereby an aldehyde gas removing agent was obtained. About the obtained aldehyde gas removal agent, the BET specific surface area and the acetaldehyde removal performance were measured.

(比較例3)
硝酸マンガン(II)六水和物(ナカライテスク社製)0.51g、オキシ硝酸ジルコニウム(ナカライテスク社製)4.76gを27mlのイオン交換水に溶解させ、しばらく撹拌した。その後、炭酸アンモニウム(ナカライテスク社製)3.77gを含有する水溶液11mlをゆっくりと添加したところ、白色の沈殿が得られた。白色の沈殿を濾別し、120℃で乾燥させた後、300℃で1時間焼成処理を施したところアルデヒド類ガス除去剤が得られた。得られたアルデヒド類ガス除去剤について、BET比表面積、アセトアルデヒド除去性能を測定した。
(Comparative Example 3)
Manganese (II) nitrate hexahydrate (Nacalai Tesque) 0.51 g and zirconium oxynitrate (Nacalai Tesque) 4.76 g were dissolved in 27 ml of ion-exchanged water and stirred for a while. Thereafter, 11 ml of an aqueous solution containing 3.77 g of ammonium carbonate (manufactured by Nacalai Tesque) was slowly added to obtain a white precipitate. A white precipitate was filtered off, dried at 120 ° C., and then subjected to a baking treatment at 300 ° C. for 1 hour, whereby an aldehyde gas removing agent was obtained. About the obtained aldehyde gas removal agent, the BET specific surface area and the acetaldehyde removal performance were measured.

(比較例4)
硝酸マンガン(II)六水和物(ナカライテスク社製)5.12g、オキシ硝酸ジルコニウム(ナカライテスク社製)0.95gを30mlのイオン交換水に溶解させ、しばらく撹拌した。その後、炭酸アンモニウム(ナカライテスク社製)4.11gを含有する水溶液12mlをゆっくりと添加したところ、白色の沈殿が得られた。白色の沈殿を濾別し、120℃で乾燥させた後、300℃で1時間焼成処理を施したところアルデヒド類ガス除去剤が得られた。得られたアルデヒド類ガス除去剤について、BET比表面積、アセトアルデヒド除去性能を測定した。
(Comparative Example 4)
Manganese (II) nitrate hexahydrate (manufactured by Nacalai Tesque) 5.12 g and zirconium oxynitrate (manufactured by Nacalai Tesque) 0.95 g were dissolved in 30 ml of ion-exchanged water and stirred for a while. Thereafter, when 12 ml of an aqueous solution containing 4.11 g of ammonium carbonate (Nacalai Tesque) was slowly added, a white precipitate was obtained. A white precipitate was filtered off, dried at 120 ° C., and then subjected to a baking treatment at 300 ° C. for 1 hour, whereby an aldehyde gas removing agent was obtained. About the obtained aldehyde gas removal agent, the BET specific surface area and the acetaldehyde removal performance were measured.

実施例1〜3、比較例1〜4のアルデヒド類ガス除去剤に関して、BET比表面積、アセトアルデヒド除去性能を測定した結果を表1に示す。表1より明らかなように、本発明である実施例1〜3は、マンガン元素(Mn)のみの場合(比較例1)、ジルコニウム元素(Zr)のみの場合(比較例2)、Mn/Zr(モル比)が0.2より小さい場合(比較例3)、2より大きい場合(比較例4)と比較して高除去性能であることが分かる。   Table 1 shows the results of measuring the BET specific surface area and acetaldehyde removal performance for the aldehyde gas removal agents of Examples 1 to 3 and Comparative Examples 1 to 4. As is clear from Table 1, Examples 1 to 3 according to the present invention have a manganese element (Mn) only (Comparative Example 1), a zirconium element (Zr) only (Comparative Example 2), and Mn / Zr. It can be seen that the removal performance is higher than when the (molar ratio) is smaller than 0.2 (Comparative Example 3) and larger than 2 (Comparative Example 4).

Figure 2007175598
Figure 2007175598

本発明のアルデヒド類ガス除去剤は、一般生活における温湿度領域で長期にわたって満足すべき除去性能を安価に発現することができ、かつ、環境汚染への影響が低いため、広い分野で用いることができ、産業界に寄与すること大である。   The aldehyde gas removal agent of the present invention can express a satisfactory removal performance over a long period of time in the temperature and humidity range in general life at a low cost, and has a low influence on environmental pollution, so it can be used in a wide range of fields. It is possible to contribute to the industry.

Claims (2)

マンガン−ジルコニウム系除去剤を含有し、かつ、前記マンガン−ジルコニウム系除去剤がマンガン元素(Mn)とジルコニウム元素(Zr)をMn/Zr(モル比)=0.2〜2.0の範囲で含有することを特徴とするアルデヒド類ガス除去剤。   A manganese-zirconium-based remover is contained, and the manganese-zirconium-based remover contains manganese element (Mn) and zirconium element (Zr) in a range of Mn / Zr (molar ratio) = 0.2 to 2.0. Aldehyde gas scavenger characterized by containing. 前記マンガン−ジルコニウム系除去剤のBET比表面積が100m2/g以上であることを特徴とする請求項1に記載のアルデヒド類ガス除去剤。 2. The aldehyde gas removing agent according to claim 1, wherein the manganese-zirconium-based removing agent has a BET specific surface area of 100 m 2 / g or more.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010104915A (en) * 2008-10-30 2010-05-13 Kobe Steel Ltd Deodorant for removing acetaldehyde and method for removing acetaldehyde
JP2014036949A (en) * 2012-07-18 2014-02-27 Denso Corp Air cleaning catalyst and method for manufacturing the same

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010104915A (en) * 2008-10-30 2010-05-13 Kobe Steel Ltd Deodorant for removing acetaldehyde and method for removing acetaldehyde
JP2014036949A (en) * 2012-07-18 2014-02-27 Denso Corp Air cleaning catalyst and method for manufacturing the same

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