JP2010172871A - Adsorbent of lower aldehydes and method for manufacturing the same - Google Patents
Adsorbent of lower aldehydes and method for manufacturing the same Download PDFInfo
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Abstract
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本発明は、ホルムアルデヒド、アセトアルデヒドなどの低級アルデヒド類に対し優れた吸着性能を有し、使用期間中に添着薬品臭のしない吸着剤に関する。 The present invention relates to an adsorbent that has excellent adsorption performance for lower aldehydes such as formaldehyde and acetaldehyde, and does not cause an odor of chemicals during use.
ホルムアルデヒド、アセトアルデヒドなどの低級アルデヒド類は、いずれも特異な刺激臭を発する有害なガスである。ホルムアルデヒドは、空気中の許容濃度が０．３ｐｐｍと低く、かつ発ガン性を有すると言われている。また、アセトアルデヒドをはじめとしてＣ１〜Ｃ４の脂肪族低級アルデヒド類は我が国では特定悪臭物質に指定され、いずれも嗅覚閾値が非常に低く悪臭公害を引き起こす物質である。
ホルムアルデヒドの発生源としては、ホルムアルデヒドの製造工場および尿素、メラミン、フェノールなどを原料とした樹脂の製造工場のほか、これらの樹脂の加工工場、さらにこれらの樹脂を使用した建材、家具など製造工場などが挙げられる。また、消毒剤としてのホルムアルデヒドや石油類の不完全燃焼排ガス、たばこの副流煙にも含まれている。最近では、室内においても新建材や家具などから発生するホルムアルデヒドが問題になっている。
アセトアルデヒドの発生源としては、アセトアルデヒドおよびその誘導体の製造工場のほか、下水汚泥の加熱処理時にも発生し、またたばこの主流煙中にも含まれている。
Lower aldehydes such as formaldehyde and acetaldehyde are harmful gases that emit unique irritating odors. Formaldehyde is said to have a carcinogenicity and an allowable concentration in air as low as 0.3 ppm. In addition, acetaldehyde and other C 1 -C 4 aliphatic lower aldehydes are designated as specific malodorous substances in Japan, and all of them are substances that have a very low olfactory threshold and cause odor pollution.
Formaldehyde generation sources include formaldehyde manufacturing plants, resin manufacturing plants made from urea, melamine, phenol, etc., processing plants for these resins, and manufacturing plants for building materials and furniture using these resins. Is mentioned. It is also contained in formaldehyde as a disinfectant, incomplete combustion exhaust gas of petroleum, and sidestream smoke of tobacco. Recently, formaldehyde generated from new building materials and furniture has become a problem even indoors.
As a source of acetaldehyde, it is generated at the time of heat treatment of sewage sludge in addition to the manufacturing plant of acetaldehyde and its derivatives, and is also contained in the mainstream smoke of cigarettes.
近年、これら低級アルデヒド類に対して、作業環境の改善および生活環境の向上などの観点から、有害物質や臭気などが問題視され、この観点から気体、特に空気中の低級アルデヒド類を効率よく除去する吸着剤の開発が強く要望されている。
従来から低級アルデヒド類の吸着剤としては、活性炭、活性アルミナ、シリカゲルなどが挙げられ、なかでも活性炭が広く使用されてきたが、これらの吸着剤自体は、その特性上、ホルムアルデヒド、アセトアルデヒドなどの低級アルデヒド類に対する吸着容量が小さく、寿命が短いという欠点がある。
この改善策として、前記の吸着剤などに低級アルデヒド類と反応する化合物、たとえば、尿素、脂肪族アミン類、芳香族アミン類などの有機化合物を担持させたものなどが提案されている。
In recent years, harmful substances and odors have been seen as problems with these lower aldehydes from the viewpoint of improving the working environment and living environment. From this viewpoint, gas, especially lower aldehydes in the air are efficiently removed. There is a strong demand for the development of adsorbents.
Conventionally, as adsorbents for lower aldehydes, activated carbon, activated alumina, silica gel and the like have been used, and among them, activated carbon has been widely used. However, these adsorbents themselves have lower properties such as formaldehyde and acetaldehyde. There are drawbacks in that the adsorption capacity for aldehydes is small and the lifetime is short.
As an improvement measure, a compound that reacts with the lower aldehydes, for example, an organic compound such as urea, aliphatic amines, aromatic amines, etc. supported on the adsorbent is proposed.
たとえば、尿素と炭酸ナトリウムを多孔性の無機焼結体に担持した吸着剤（特許文献１）、尿素と硫酸アンモニウムや尿素と水酸化ナトリウムなどを活性炭に担持した吸着剤（特許文献２）、尿素と塩化カルシウム、尿素と塩化マグネシウムを多孔性物質に担持した吸着剤（特許文献３）などが提案されている。
しかしながら、従来の技術による低級アルデヒド類吸着剤は、いずれも低級アルデヒド類の除去に対して満足できるものではなかった。
For example, an adsorbent in which urea and sodium carbonate are supported on a porous inorganic sintered body (Patent Document 1), an adsorbent in which urea and ammonium sulfate, urea and sodium hydroxide are supported on activated carbon (Patent Document 2), urea and An adsorbent (Patent Document 3) in which calcium chloride, urea and magnesium chloride are supported on a porous material has been proposed.
However, none of the conventional lower aldehyde adsorbents is satisfactory for the removal of lower aldehydes.
本発明は、熱的に安定で、環境に対して安全であり、かつ低級アルデヒド類を長時間にわたり効率よく吸着除去することができる優れた低級アルデヒド類の吸着剤を提供することを目的としている。 An object of the present invention is to provide an excellent adsorbent for lower aldehydes that is thermally stable, safe for the environment, and can efficiently adsorb and remove lower aldehydes over a long period of time. .
本発明者は、前記の点を鑑み鋭意研究して、活性炭１ｇ当たり尿素を１５０〜８００ｍｇと第一燐酸カルシウム及び／又は第一燐酸アンモニウムを１０〜３００ｍｇ添着させた吸着剤が、熱的に安定で、環境に対して安全であり、低級アルデヒド類を長期にわたり効率よく吸着除去することを見出した。また、活性炭に尿素と第一燐酸カルシウム及び／又は第一燐酸アンモニウムを添着させる際に、水溶液を４０〜９５℃に加温することで、活性炭１ｇ当たり１００〜８００μＬの極少量の水溶液で添着する薬品の全量を完全に溶解することができるので、所定量の尿素と第一燐酸カルシウム及び／又は第一燐酸アンモニウムを均一に、かつ、簡単に添着することができ、添着後特に乾燥することもなく、そのままの状態で低級アルデヒド類を非常によく吸着・除去剤とすることができる。なお、第一燐酸カルシウムを配合した吸着剤はより安定で、使用中の臭気は全くなく、特に好ましいものである。 The present inventor has intensively studied in view of the above points, and the adsorbent in which 150 to 800 mg of urea and 10 to 300 mg of monocalcium phosphate and / or monobasic ammonium phosphate are impregnated with 1 g of activated carbon is thermally stable. And found that it is safe for the environment and efficiently adsorbs and removes lower aldehydes over a long period of time. Further, when urea and monobasic calcium phosphate and / or monobasic ammonium phosphate are added to activated carbon, the aqueous solution is heated to 40 to 95 ° C., so that the aqueous solution is added in a very small amount of 100 to 800 μL per 1 g of activated carbon. Since the entire amount of the chemical can be completely dissolved, a predetermined amount of urea and monobasic calcium phosphate and / or monobasic ammonium phosphate can be uniformly and easily added, and can be dried particularly after the addition. In this state, the lower aldehydes can be used as adsorption / removal agents very well. An adsorbent containing monocalcium phosphate is more stable, has no odor during use, and is particularly preferable.
本発明で使用される活性炭としては、木炭、コークス、石炭、ヤシ殻、樹脂などを原料として通常の方法により賦活されたものであれば、いかなるものでもよい。その形状は、破砕状、円柱状、球状、ハニカム状、繊維状などいかなるものでもよい。また、これらの活性炭の比表面積は、５０ｍ２／ｇ以上、好ましくは１００〜２，５００ｍ２／ｇのものである。
活性炭を予め表面酸化処理することで低級アルデヒド類の吸着性能が著しく向上する。活性炭を酸化する方法としては、たとえば、硝酸、窒素酸化物（ＮＯｘ）、硫酸、硫黄酸化物（ＳＯｘ）、三酸化硫黄、二酸化塩素、過酸化水素、オゾン、酸素含有ガス（たとえば、空気、燃焼排ガスなど）などの酸化剤で、液相あるいは気相で酸化するなどの方法が挙げられる。ＮＯｘやＳＯｘなどの場合は、活性炭にＮＯｘやＳＯｘ含有ガスの吸着、脱着を繰り返すなど方法で活性炭を酸化してもよい。また、酸素含有ガスによる気相酸化などのように活性炭に対する酸化力が弱い場合などでは、ガス中の酸素濃度にもよるが、常温以上の温度、たとえば、２００℃以上、好ましくは２００〜８００℃、さらに好ましくは２５０〜６００℃の温度で行うのが効率的である。また、大都市などの浄水場で行われているオゾン法高度浄水場で長年使用された使用済み活性炭は、液相におけるオゾン酸化でその表面に酸素含有基が多量に生成されており、このような活性炭は、本発明に有効に利用できる。
As the activated carbon used in the present invention, any activated carbon may be used as long as it is activated by a normal method using charcoal, coke, coal, coconut shell, resin, or the like as a raw material. The shape may be any shape such as a crushed shape, a columnar shape, a spherical shape, a honeycomb shape, and a fiber shape. The specific surface area of the activated carbons include, 50 m 2 / g or more, preferably 100~2,500m 2 / g.
By subjecting activated carbon to surface oxidation treatment in advance, the adsorption performance of lower aldehydes is remarkably improved. Examples of the method for oxidizing activated carbon include nitric acid, nitrogen oxide (NOx), sulfuric acid, sulfur oxide (SOx), sulfur trioxide, chlorine dioxide, hydrogen peroxide, ozone, oxygen-containing gas (for example, air, combustion) For example, oxidation may be performed in a liquid phase or a gas phase with an oxidizing agent such as exhaust gas. In the case of NOx, SOx, etc., the activated carbon may be oxidized by a method such as repeated adsorption and desorption of NOx and SOx-containing gas on the activated carbon. In addition, when the oxidizing power for activated carbon is weak, such as gas phase oxidation with an oxygen-containing gas, the temperature is higher than room temperature, for example, 200 ° C. or higher, preferably 200 to 800 ° C., depending on the oxygen concentration in the gas. More preferably, it is efficient to carry out at a temperature of 250 to 600 ° C. In addition, spent activated carbon used for many years at ozone treatment plants in water treatment plants in large cities has produced a large amount of oxygen-containing groups on its surface due to ozone oxidation in the liquid phase. Such activated carbon can be effectively used in the present invention.
このような酸化処理によって活性炭表面に酸素含有基が生成する。本発明での酸化処理において、活性炭に対するこれらの酸化剤使用量は、処理方法や酸化条件（たとえば、処理温度、時間など）などにもよるが、通常、活性炭１ｇ当り酸素原子換算量で１０ｍｇ以上、好ましくは、２０ｍｇ以上、より好ましくは、３０〜２，０００ｍｇである。
これらの酸化処理により、活性炭表面に、例えばカルボニル基、カルボキシル基、フェノール性水酸基などの酸素含有基が生成される。この表面酸素含有基は、酸素原子として活性炭全体の１重量％以上、好ましくは、２重量％以上より好ましくは３〜８０重量％である。
Such an oxidation treatment produces oxygen-containing groups on the activated carbon surface. In the oxidation treatment of the present invention, the amount of these oxidizing agents used for activated carbon depends on the treatment method and oxidation conditions (for example, treatment temperature, time, etc.), but is usually 10 mg or more in terms of oxygen atom per gram of activated carbon. The amount is preferably 20 mg or more, more preferably 30 to 2,000 mg.
By these oxidation treatments, for example, oxygen-containing groups such as a carbonyl group, a carboxyl group, and a phenolic hydroxyl group are generated on the activated carbon surface. This surface oxygen-containing group is 1% by weight or more, preferably 2% by weight or more, more preferably 3 to 80% by weight of the activated carbon as oxygen atoms.
本発明では、活性炭１ｇ当たり尿素を１５０〜８００ｍｇ、好ましくは２００〜５００ｍｇと第一燐酸カルシウム及び／又は第一燐酸アンモニウムを１０〜３００ｍｇ、好ましくは１０〜２００ｍｇを添着するのが特徴の１つである。このように添着することによって、低級アルデヒド類の吸着性能が飛躍的に向上する。
また、活性炭に尿素と第一燐酸カルシウム及び／又は第一燐酸アンモニウムを添着する際にこれらを含む水溶液を４０〜９５℃に加温することも本発明の大きな特徴の一つである。この加温によって活性炭１ｇ当たりに吸着させる薬品の全量を溶解した１００〜８００μＬの極少量の水溶液とすることができるので、この加温下で活性炭に接触させることによって、多量の尿素と第一燐酸カルシウム及び／又は第一燐酸アンモニウムを瞬時に活性炭に均一に添着でき、かつ添着後に乾燥しなくともそのままで低級アルデヒド類を非常によく吸着する吸着剤を得ることができる。なお、尿素と第一燐酸カルシウム及び／又は第一燐酸アンモニウムを水に溶解する場合に燐酸、硫酸などの酸を用いることによってできるだけ少量の水溶液でより多量の尿素と第一燐酸カルシウム及び／又は第一燐酸アンモニウムを溶解することができる。
One feature of the present invention is that 150 to 800 mg, preferably 200 to 500 mg of urea and 10 to 300 mg, preferably 10 to 200 mg of monocalcium phosphate and / or monobasic ammonium phosphate are added per 1 g of activated carbon. is there. By so adhering, the adsorption performance of lower aldehydes is dramatically improved.
In addition, when adding urea and monobasic calcium phosphate and / or monobasic ammonium phosphate to the activated carbon, it is one of the major features of the present invention that the aqueous solution containing these is heated to 40 to 95 ° C. This heating makes it possible to obtain a very small amount of an aqueous solution of 100 to 800 μL in which the total amount of the chemical adsorbed per gram of activated carbon is dissolved. By contacting the activated carbon with this heating, a large amount of urea and primary phosphoric acid are obtained. It is possible to obtain an adsorbent that can uniformly and uniformly adsorb calcium and / or ammonium monophosphate to activated carbon instantaneously and adsorbs the lower aldehydes as they are without drying. When urea and monobasic calcium phosphate and / or monobasic ammonium phosphate are dissolved in water, by using an acid such as phosphoric acid and sulfuric acid, a larger amount of urea and monobasic calcium phosphate and / or dilute in an aqueous solution as small as possible. Ammonium monophosphate can be dissolved.
本発明の低級アルデヒド類吸着剤は、尿素と第一燐酸カルシウム及び／又は第一燐酸アンモニウムを含む水溶液を４０〜９５℃に加温して活性炭にこれらの薬品を添着することによって容易に得られる。尿素と第一燐酸カルシウム及び／又は第一燐酸アンモニウムを含む水溶液の加温は直接的あるいは間接的に通常の方法で行うことができる。尿素と第一燐酸カルシウム及び／又は第一燐酸アンモニウムを含む水溶液を４０〜９５℃に加温する時間は、特に限定されるものではなく、尿素と第一燐酸カルシウム及び／又は第一燐酸アンモニウムが完全に溶解して水溶液になればよい。尿素と第一燐酸カルシウム及び／又は第一燐酸アンモニウムを含む水溶液の加温を９５℃以上にすると、これらの薬品が変質したり、多量の水蒸気が発生したりするので好ましくない。 The lower aldehyde adsorbent of the present invention can be easily obtained by heating an aqueous solution containing urea and monobasic calcium phosphate and / or monobasic ammonium phosphate to 40 to 95 ° C. and adhering these chemicals to activated carbon. . Warming of an aqueous solution containing urea and monocalcium phosphate and / or monobasic ammonium phosphate can be performed directly or indirectly by a usual method. The time for heating the aqueous solution containing urea and monobasic calcium phosphate and / or monobasic ammonium phosphate to 40 to 95 ° C. is not particularly limited, and urea, monobasic calcium phosphate and / or monobasic ammonium phosphate are not limited. It only needs to be completely dissolved to form an aqueous solution. When the temperature of the aqueous solution containing urea and monobasic calcium phosphate and / or monobasic ammonium phosphate is 95 ° C. or higher, these chemicals are deteriorated and a large amount of water vapor is generated, which is not preferable.
本発明における除去対象の低級アルデヒド類は、炭素数が６以下で沸点が１００℃以下のアルデヒド、例えばホルムアルデヒド、アセトアルデヒド、プロピオンアルデヒド、アクロレイン、３−メチル−ブチルアルデヒドを指すが、代表的なものはホルムアルデヒドとアセトアルデヒドである。
本発明においては、上記のようにして得られたアルデヒド類吸着剤を空間内、装置内などに存在させて、アルデヒド類を効率よく除去する方法なども含まれる。アルデヒド類吸着剤を空間内に存在させる場合には、たとえば、アルデヒド類吸着剤をシート状などにしたり、建材に含ませたり、通常よく行われる方法などが挙げられる。また、装置内などに存在させる場合は、塔、容器などに充填したりして、これらにアルデヒド類を含むガスを通気する方法などが考えられる。
The lower aldehydes to be removed in the present invention refer to aldehydes having 6 or less carbon atoms and a boiling point of 100 ° C. or less, such as formaldehyde, acetaldehyde, propionaldehyde, acrolein, and 3-methyl-butyraldehyde. Formaldehyde and acetaldehyde.
The present invention also includes a method for efficiently removing aldehydes by allowing the aldehyde adsorbent obtained as described above to exist in a space or in an apparatus. In the case where the aldehyde adsorbent is present in the space, for example, the aldehyde adsorbent may be formed into a sheet form, included in a building material, or a method that is usually performed. Moreover, when it exists in an apparatus etc., the method etc. which fill a tower, a container, etc., and ventilate the gas containing aldehydes to these are considered.
本発明のアルデヒド吸着剤は、それを使用する常温付近では、無臭で、かつ化学的及び熱的に安定な固体薬品である、尿素と第一燐酸カルシウム及び／又は第一燐酸アンモニウムを活性炭に添着するので、熱的に安定で、環境に対して安全であり、かつ低級アルデヒド類を長時間にわたり効率よく吸着除去することができ、従来の低級アルデヒド吸着剤に比べて非常に優れた低級アルデヒド類の吸着剤である。 The aldehyde adsorbent of the present invention impregnates activated carbon with urea and monobasic calcium phosphate and / or monobasic ammonium phosphate, which are solid chemicals that are odorless and chemically and thermally stable at around room temperature. Therefore, lower aldehydes that are thermally stable, safe for the environment, and can efficiently adsorb and remove lower aldehydes over a long period of time, which are superior to conventional lower aldehyde adsorbents. Adsorbent.
以下に実施例をあげて、本発明を具体的に説明する。 The present invention will be specifically described with reference to the following examples.
８〜３２メッシュの瀝青炭系活性炭Ａ（ＢＥＴ比表面積１１５０ｍ２／ｇ）に対して下記のような処理を施して尿素と各種の無機塩を均一に添着した試料を作成した。
試料Ｎｏ．１：水４００μＬに尿素１５０ｍｇと第一燐酸アンモニウム２００ｍｇを入れ、４０℃に加温してこれらを完全に溶解し、活性炭Ａの１ｇに均一に添着し、大気中で１２時間放置した。
試料Ｎｏ．２：Ｎｏ．１において、尿素５００ｍｇと第一燐酸カルシウム１０ｍｇを用い、９５℃に加温して調製した。
試料Ｎｏ．３：試料Ｎｏ．１において、尿素３００ｍｇと第一燐酸アンモニウム４０ｍｇを用い、６０℃に加温して調製した。
試料Ｎｏ．４：試料Ｎｏ．１において、尿素３００ｍｇと第一燐酸カルシウム４０ｍｇを用い、８０℃に加温して調製した。
試料Ｎｏ．５：試料Ｎｏ．１において、尿素２００ｍｇと第一燐酸アンモニウム５０ｍｇを用い、７０℃に加温して調製した。
試料Ｎｏ．６：試料Ｎｏ．１において、尿素４００ｍｇと第一燐酸カルシウム５０ｍｇを用い、８０℃に加温して調製した。
試料Ｎｏ．７：試料Ｎｏ．１において、尿素３００ｍｇと硫酸アンモニウム４０ｍｇを用い、６０℃に加温して調製した。
試料Ｎｏ．８：試料Ｎｏ．１において、尿素３００ｍｇと炭酸ナトリウム４０ｍｇを用い、６０℃に加温して調製した。
試料Ｎｏ．９：試料Ｎｏ．１において、尿素３００ｍｇと塩化カルシウム４０ｍｇを用い、６０℃に加温して調製した。
試料Ｎｏ．１０：試料Ｎｏ．１において、尿素３００ｍｇと塩化マグネシウム４０ｍｇを用い、６０℃に加温して調製した。
試料Ｎｏ．１１：試料Ｎｏ．１において、尿素３００ｍｇと重炭酸アンモニウ４０ｍｇを用い、６０℃に加温して調製した。
試料Ｎｏ．１２：試料Ｎｏ．１において、尿素３００ｍｇと塩化アンモニウム４０ｍｇを用い、６０℃に加温して調製した。
これらの各試料２００ｍｇを３Ｌのテトラバッグに量り込み、空気で満たした。各テトラバッグに所定量のアセトアルデヒド水溶液を注入して、各テトラバッグ中のアセトアルデヒド濃度（Ｃ０）を６５０ｐｐｍとした。２４時間後の各テトラバッグ中のアセトアルデヒド濃度（Ｃ）を測定した。アセトアルデヒド除去性能として次式で求めた値を表１に示した。
アセトアルデヒド除去性能＝（１−Ｃ／Ｃ０）×１００（％）
The following treatment was applied to 8-32 mesh bituminous coal-based activated carbon A (BET specific surface area 1150 m 2 / g) to prepare a sample in which urea and various inorganic salts were uniformly added.
Sample No. 1: 150 mg of urea and 200 mg of primary ammonium phosphate were added to 400 μL of water, heated to 40 ° C. to completely dissolve them, uniformly attached to 1 g of activated carbon A, and left in the atmosphere for 12 hours.
Sample No. 2: No. In No. 1, 500 mg of urea and 10 mg of monobasic calcium phosphate were used and heated to 95 ° C.
Sample No. 3: Sample No. In No. 1, 300 mg of urea and 40 mg of ammonium monophosphate were used and heated to 60 ° C.
Sample No. 4: Sample No. In No. 1, 300 mg of urea and 40 mg of monobasic calcium phosphate were used and heated to 80 ° C.
Sample No. 5: Sample No. 1 was prepared by heating to 70 ° C. using 200 mg of urea and 50 mg of ammonium monophosphate.
Sample No. 6: Sample No. In No. 1, 400 mg of urea and 50 mg of monobasic calcium phosphate were used and heated to 80 ° C.
Sample No. 7: Sample No. In No. 1, 300 mg of urea and 40 mg of ammonium sulfate were used and heated to 60 ° C.
Sample No. 8: Sample No. 1 was prepared by heating to 60 ° C. using 300 mg of urea and 40 mg of sodium carbonate.
Sample No. 9: Sample No. No. 1 was prepared by heating to 60 ° C. using 300 mg of urea and 40 mg of calcium chloride.
Sample No. 10: Sample No. 1 was prepared by heating to 60 ° C. using 300 mg of urea and 40 mg of magnesium chloride.
Sample No. 11: Sample No. 1 was prepared by heating to 60 ° C. using 300 mg of urea and 40 mg of ammonium bicarbonate.
Sample No. 12: Sample No. In No. 1, 300 mg of urea and 40 mg of ammonium chloride were used and heated to 60 ° C.
200 mg of each of these samples was weighed into a 3 L tetrabag and filled with air. A predetermined amount of acetaldehyde aqueous solution was injected into each tetrabag to adjust the acetaldehyde concentration (C 0 ) in each tetrabag to 650 ppm. The acetaldehyde concentration (C) in each tetrabag after 24 hours was measured. The values obtained by the following formula as acetaldehyde removal performance are shown in Table 1.
Acetaldehyde removal performance = (1-C / C 0 ) × 100 (%)
これに対して、対照の吸着剤（Ｎｏ．７〜１２）は、尿素３００ｍｇと各種の無機塩４０ｍｇを入れ、６０℃に加温してこれらを完全に溶解し、活性炭Ａの１ｇに均一に添着し、大気中で１２時間放置して得られたものであるが、アセトアルデヒドの除去性能は、５５〜８５％で非常に悪い。
On the other hand, the control adsorbent (No. 7-12) contains 300 mg of urea and 40 mg of various inorganic salts, heated to 60 ° C. to completely dissolve them, and uniformly into 1 g of activated carbon A. The acetaldehyde removal performance was very poor at 55 to 85%, although it was obtained after being attached and left in the atmosphere for 12 hours.
実施例１の各試料５０ｍｇを３Ｌのテトラバッグに量り込み、空気で満たした。各テトラバッグに所定量のホルムアルデヒド水溶液を注入して、各テトラバッグ中のホルムアルデヒド濃度（Ｃ０）を３００ｐｐｍとした。２４時間後の各テトラバッグ中のホルムアルデヒド濃度（Ｃ）を測定した。ホルムアルデヒド除去性能として次式で求めた値を表２に示した。
ホルムアルデヒド除去性能＝（１−Ｃ／Ｃ０）×１００（％）
50 mg of each sample of Example 1 was weighed into a 3 L tetra bag and filled with air. A predetermined amount of an aqueous formaldehyde solution was injected into each tetra bag to adjust the formaldehyde concentration (C 0 ) in each tetra bag to 300 ppm. The formaldehyde concentration (C) in each tetrabag after 24 hours was measured. Table 2 shows the value obtained by the following formula as the formaldehyde removal performance.
Formaldehyde removal performance = (1-C / C 0 ) × 100 (%)
実施例１の瀝青炭系活性炭Ａの各３０ｇを５５ｍｍφの石英ガラス管に充填して、それぞれ２５０、４００、５００、および６００℃の各温度でＯ２−１０.０ｖｏｌ％含有のＮ２ガスを線流速５ｃｍ／秒で２０分間流通した後、Ｎ２ガス中で常温まで冷却して、活性炭Ｂ、Ｃ、ＤおよびＥを得た。
酸化処理をした活性炭Ｂ、Ｃ、ＤおよびＥについて、次の方法で測定した表面酸化物又は酸素含有基に起因する表面酸素量は、それぞれ５．５重量％、８．９重量％、１２．３重量％および１６．１重量％であった。なお、酸化処理をしない活性炭Ａの酸素量は０．７重量％であった。
「活性炭の表面酸素量の測定法」
直径２０ｍｍ×長さ１,０００ｍｍの石英カラムに試料活性炭３ｇを入れ、試料の前後は十分に乾燥させた石英ガラスウールに固定し、電気環状炉にセットした。また石英カラムにはゴム栓で前後に蓋をして窒素を導入するための孔と排出するための孔を空ける。１００ｍｌ／分の流速で窒素を石英カラムに流しながら、１００℃まで加熱昇温し、次いで、出口ガスをテトラバックに接続し、４００℃／時間の昇温速度で９００℃まで加熱昇温した。９００℃になってから、さらに３０分間９００℃で保持した後、テトラバックを外し、捕集したガス量を測定するとともに、捕集されたガスにおけるＣＯとＣＯ2の総濃度を、メタンコンバータ付きのＦＩＤ検出器付ガスクロマトグラフィーで測定し、表面酸素量を算出した。
水４００μＬに尿素２５０ｍｇと第一燐酸カルシウム６０ｍｇを入れ、８０℃に加温してこれらを完全に溶解し、活性炭ＡおよびＢ、Ｃ、ＤおよびＥの各１ｇに対して均一に添着し、大気中で１２時間放置した。
これらの各試料１００ｍｇを３Ｌのテトラバッグに量り込み、空気で満たした。各テトラバッグに所定量のアセトアルデヒド水溶液を注入して、各テトラバッグ中のアセトアルデヒド濃度（Ｃ０）を６５０ｐｐｍとした。２４時間後の各テトラバッグ中のアセトアルデヒド濃度（Ｃ）を測定した。アセトアルデヒド除去性能として次式で求めた値を表３に示した。
アセトアルデヒド除去性能＝（１−Ｃ／Ｃ０）×１００（％）
By filling each 30g of bituminous coal-based activated carbon A Example 1 in a quartz glass tube 55Mmfai, lines the O 2 -10.0vol% content of N 2 gas at each temperature, respectively 250,400,500, and 600 ° C. After flowing for 20 minutes at a flow rate of 5 cm / sec, the mixture was cooled to room temperature in N 2 gas to obtain activated carbon B, C, D, and E.
For the activated carbons B, C, D and E subjected to oxidation treatment, the surface oxygen amounts attributable to the surface oxides or oxygen-containing groups measured by the following method were 5.5% by weight, 8.9% by weight, and 12. 3 wt% and 16.1 wt%. The oxygen content of the activated carbon A that was not oxidized was 0.7% by weight.
"Measurement method of surface oxygen content of activated carbon"
3 g of sample activated carbon was placed in a quartz column having a diameter of 20 mm and a length of 1,000 mm, and the sample was fixed on quartz glass wool that had been sufficiently dried before and after the sample and set in an electric annular furnace. In addition, the quartz column has a hole for introducing nitrogen and a hole for discharging nitrogen by capping the front and back with rubber stoppers. While flowing nitrogen through the quartz column at a flow rate of 100 ml / min, the temperature was raised to 100 ° C., and then the outlet gas was connected to a tetra-buck and heated to 900 ° C. at a rate of 400 ° C./hour. After reaching 900 ° C., hold at 900 ° C. for another 30 minutes, then remove the tetraback, measure the amount of gas collected, and add the total concentration of CO and CO 2 in the collected gas with a methane converter. The amount of surface oxygen was calculated by gas chromatography with a FID detector.
In 400 μL of water, 250 mg of urea and 60 mg of monobasic calcium phosphate were added, heated to 80 ° C. to completely dissolve them, and uniformly attached to 1 g of each of activated carbon A and B, C, D and E, Left in it for 12 hours.
100 mg of each of these samples was weighed into a 3 L tetrabag and filled with air. A predetermined amount of acetaldehyde aqueous solution was injected into each tetrabag to adjust the acetaldehyde concentration (C 0 ) in each tetrabag to 650 ppm. The acetaldehyde concentration (C) in each tetrabag after 24 hours was measured. Table 3 shows values obtained by the following formula as acetaldehyde removal performance.
Acetaldehyde removal performance = (1-C / C 0 ) × 100 (%)
内径９４ｍｍφのアクリル製カラムに８〜３２メッシュのヤシ殻系活性炭Ｆ（ＢＥＴ比表面積１，２００ｍ２／ｇ）１００ｍｌをステンレス金網容器に入れて、活性炭充填層を形成した。この活性炭層にオゾン約１８０ｐｐｍ含有の空気を流量５Ｌ／分で２５日間流通し、気相でのオゾン酸化処理活性炭Ｇを得た。活性炭ＦおよびＧの表面酸素量は、それぞれ０．５重量％および１２．５重量％であった。
活性炭ＦおよびＧについて実施例３と同様な方法で、水４００μＬに尿素２５０ｍｇと第一燐酸アンモニウム３０ｍｇを入れ、８０℃に加温してこれらを完全に溶解し、活性炭ＦおよびＧの各１ｇに対して均一に添着し、大気中で１２時間放置した。
このようにして得られた各試料１００ｍｇを３Ｌのテトラバッグに量り込み、空気で満たした。各テトラバッグに所定量のアセトアルデヒド水溶液を注入して、各テトラバッグ中のアセトアルデヒド濃度（Ｃ０）を６５０ｐｐｍとした。２４時間後の各テトラバッグ中のアセトアルデヒド濃度（Ｃ）を測定した。アセトアルデヒド除去性能として次式で求めた値を表４に示した。
アセトアルデヒド除去性能＝（１−Ｃ／Ｃ０）×１００（％）
100 ml of 8-32 mesh coconut shell activated carbon F (BET specific surface area 1,200 m 2 / g) was placed in an acrylic column having an inner diameter of 94 mmφ in a stainless wire mesh container to form an activated carbon packed bed. Air containing about 180 ppm of ozone was circulated through the activated carbon layer at a flow rate of 5 L / min for 25 days to obtain ozone-oxidized activated carbon G in the gas phase. The surface oxygen amounts of the activated carbons F and G were 0.5% by weight and 12.5% by weight, respectively.
For activated carbon F and G, in the same manner as in Example 3, 250 mg of urea and 30 mg of monobasic ammonium phosphate were added to 400 μL of water and heated to 80 ° C. to completely dissolve them. On the other hand, it was uniformly applied and left in the atmosphere for 12 hours.
100 mg of each sample thus obtained was weighed into a 3 L tetra bag and filled with air. A predetermined amount of acetaldehyde aqueous solution was injected into each tetrabag to adjust the acetaldehyde concentration (C 0 ) in each tetrabag to 650 ppm. The acetaldehyde concentration (C) in each tetrabag after 24 hours was measured. Table 4 shows the values obtained by the following formula as the acetaldehyde removal performance.
Acetaldehyde removal performance = (1-C / C 0 ) × 100 (%)
５００ｍＬのビーカーに５重量％の過酸化水素水１００ｍＬを入れ、８０℃の水浴中で８０℃に加熱した。この過酸化水素水に実施例１の瀝青炭系活性炭Ａの１０ｇを入れて攪拌しながら３０分間酸化した。酸化後の活性炭をろ過して１００℃で乾燥した。酸化処理をした活性炭Ｈの表面酸素量は、８．５重量％であった。
活性炭ＦおよびＧについて実施例３と同様な方法で、水４００μＬに尿素３００ｍｇと第一燐酸カルシウム４０ｍｇを入れ、８０℃に加温してこれらを完全に溶解し、活性炭ＡおよびＨの各１ｇに対して均一に添着し、大気中で１２時間放置した。
このようにして得られた各試料１００ｍｇを３Ｌのテトラバッグに量り込み、空気で満たした。各テトラバッグに所定量のアセトアルデヒド水溶液を注入して、各テトラバッグ中のアセトアルデヒド濃度（Ｃ０）を６５０ｐｐｍとした。２４時間後の各テトラバッグ中のアセトアルデヒド濃度（Ｃ）を測定した。アセトアルデヒド除去性能として次式で求めた値を表５に示した。
アセトアルデヒド除去性能＝（１−Ｃ／Ｃ０）×１００（％）
A 500 mL beaker was charged with 100 mL of 5 wt% hydrogen peroxide and heated to 80 ° C in an 80 ° C water bath. In this hydrogen peroxide solution, 10 g of the bituminous coal-based activated carbon A of Example 1 was added and oxidized for 30 minutes while stirring. The oxidized activated carbon was filtered and dried at 100 ° C. The surface oxygen amount of the activated carbon H subjected to the oxidation treatment was 8.5% by weight.
For activated carbons F and G, in the same manner as in Example 3, 300 mg of urea and 40 mg of monobasic calcium phosphate were placed in 400 μL of water and heated to 80 ° C. to completely dissolve them. On the other hand, it was uniformly applied and left in the atmosphere for 12 hours.
100 mg of each sample thus obtained was weighed into a 3 L tetra bag and filled with air. A predetermined amount of acetaldehyde aqueous solution was injected into each tetrabag to adjust the acetaldehyde concentration (C 0 ) in each tetrabag to 650 ppm. The acetaldehyde concentration (C) in each tetrabag after 24 hours was measured. Table 5 shows the values obtained by the following formula as acetaldehyde removal performance.
Acetaldehyde removal performance = (1-C / C 0 ) × 100 (%)
実施例１の８〜３２メッシュの瀝青炭系活性炭Ａをオゾン法高度浄水処理場で３年間使用し、液相でオゾン酸化された活性炭を１１０℃で１時間乾燥した。この使用済み活性炭Ｉの表面酸素量は２５．６重量％であった。
活性炭Ａおよび活性炭Ｉについて実施例３と同様な方法で、水４００μＬに尿素３００ｍｇと第一燐酸カルシウム４０ｍｇを入れ、８０℃に加温してこれらを完全に溶解し、活性炭Ａおよび活性炭Ｉの各１ｇに対して均一に添着し、大気中で１２時間放置した。
このようにして得られた各試料１００ｍｇを３Ｌのテトラバッグに量り込み、空気で満たした。各テトラバッグに所定量のアセトアルデヒド水溶液を注入して、各テトラバッグ中のアセトアルデヒド濃度（Ｃ０）を６５０ｐｐｍとした。２４時間後の各テトラバッグ中のアセトアルデヒド濃度（Ｃ）を測定した。アセトアルデヒド除去性能として次式で求めた値を表６に示した。
アセトアルデヒド除去性能＝（１−Ｃ／Ｃ０）×１００（％）
The 8-32 mesh bituminous coal-based activated carbon A of Example 1 was used in an ozone process advanced water purification plant for 3 years, and the activated carbon that was ozone-oxidized in the liquid phase was dried at 110 ° C. for 1 hour. The surface oxygen content of this used activated carbon I was 25.6% by weight.
For activated carbon A and activated carbon I, in the same manner as in Example 3, 300 mg of urea and 40 mg of monobasic calcium phosphate were placed in 400 μL of water and heated to 80 ° C. to completely dissolve them. It was uniformly applied to 1 g and left in the atmosphere for 12 hours.
100 mg of each sample thus obtained was weighed into a 3 L tetra bag and filled with air. A predetermined amount of acetaldehyde aqueous solution was injected into each tetrabag to adjust the acetaldehyde concentration (C 0 ) in each tetrabag to 650 ppm. The acetaldehyde concentration (C) in each tetrabag after 24 hours was measured. Table 6 shows values obtained by the following formula as acetaldehyde removal performance.
Acetaldehyde removal performance = (1-C / C 0 ) × 100 (%)
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012230096A (en) * | 2011-04-13 | 2012-11-22 | Eiko:Kk | Method of adsorbing radioactive cesium |
| JP2013539413A (en) * | 2010-08-30 | 2013-10-24 | アルベマール・コーポレーシヨン | Improved adsorbent for removing mercury from emissions generated during fuel combustion |
| CN110339810A (en) * | 2018-04-02 | 2019-10-18 | 广西大学 | A kind of activated carbon for formaldehyde adsorption and preparation method thereof |
| JP6607422B1 (en) * | 2019-02-06 | 2019-11-20 | 孝章 下原 | Formaldehyde scavenger |
| WO2020162091A1 (en) * | 2019-02-06 | 2020-08-13 | 孝章 下原 | Formaldehyde scavenger |
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- 2009-02-02 JP JP2009021408A patent/JP2010172871A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013539413A (en) * | 2010-08-30 | 2013-10-24 | アルベマール・コーポレーシヨン | Improved adsorbent for removing mercury from emissions generated during fuel combustion |
| JP2012230096A (en) * | 2011-04-13 | 2012-11-22 | Eiko:Kk | Method of adsorbing radioactive cesium |
| CN110339810A (en) * | 2018-04-02 | 2019-10-18 | 广西大学 | A kind of activated carbon for formaldehyde adsorption and preparation method thereof |
| JP6607422B1 (en) * | 2019-02-06 | 2019-11-20 | 孝章 下原 | Formaldehyde scavenger |
| WO2020162091A1 (en) * | 2019-02-06 | 2020-08-13 | 孝章 下原 | Formaldehyde scavenger |
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