JP2001137703A - Adsorbent for gas and its preparing method - Google Patents
Adsorbent for gas and its preparing methodInfo
- Publication number
- JP2001137703A JP2001137703A JP32312999A JP32312999A JP2001137703A JP 2001137703 A JP2001137703 A JP 2001137703A JP 32312999 A JP32312999 A JP 32312999A JP 32312999 A JP32312999 A JP 32312999A JP 2001137703 A JP2001137703 A JP 2001137703A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- porous body
- metal
- pores
- gas
- 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.)
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、気体吸着材料及び
その製造方法に関する。詳細には、本発明は、多孔質体
の細孔内において酸と金属塩を反応させることにより形
成された金属錯体を、この細孔内に担持している多孔質
体からなり、メタン、水素等を吸着し、効率的に貯蔵す
ることのできる気体吸着材料に関する。The present invention relates to a gas adsorbing material and a method for producing the same. In detail, the present invention comprises a porous body that supports a metal complex formed by reacting an acid and a metal salt in the pores of the porous body, and the methane, hydrogen The present invention relates to a gas adsorbing material that can adsorb and the like and can be stored efficiently.
【０００２】[0002]
【従来の技術】メタンを主成分とする天然ガスは一般に
高圧にしてタンクに貯蔵されている。このメタンは多孔
質体の細孔内に吸着するため、多孔質体を用いれば、常
圧付近においてより多くのメタンを貯蔵することができ
る。また、ある種の金属錯体はメタンに対して吸着能を
有するため、多孔質体内部にこの金属錯体を導入すれ
ば、多孔質体のメタン吸着能を向上させることができる
と考えられる。2. Description of the Related Art Natural gas mainly composed of methane is generally stored in a tank at a high pressure. Since this methane is adsorbed in the pores of the porous body, the use of the porous body allows more methane to be stored near normal pressure. In addition, since a certain metal complex has an adsorption ability for methane, it is considered that the introduction of this metal complex into the porous body can improve the methane adsorption ability of the porous body.
【０００３】ところで、多孔質体の細孔内に錯体を担持
させた吸着剤としては、現在各種のものが知られてい
る。例えば、特開平２−２８３６０８号公報には、活性
炭に四塩化アルミニウム錯体を担持させたものを用いて
一酸化炭素を吸着させる方法が記載されている。また、
特開平９−２９０１５３号公報には、ジアミン化合物と
ハロゲン化銅からなる錯体を活性炭に担持してなる、一
酸化炭素吸着剤が記載されている。さらに、特開昭６３
−２２９１１８号公報には、塩化第一銅と塩化アルミニ
ウムとからなる錯体を多孔質担体に担持してなる、エチ
レン吸着剤が記載されている。By the way, various adsorbents having a complex supported in the pores of a porous body are known at present. For example, JP-A-2-283608 describes a method of adsorbing carbon monoxide using an activated carbon having an aluminum tetrachloride complex supported thereon. Also,
JP-A-9-290153 describes a carbon monoxide adsorbent comprising a complex comprising a diamine compound and a copper halide supported on activated carbon. Further, Japanese Unexamined Patent Publication
Japanese Patent No. 229118 describes an ethylene adsorbent in which a complex comprising cuprous chloride and aluminum chloride is supported on a porous carrier.
【０００４】ところがこれらの錯体は、メタンを吸着さ
せるには適していない。またこれらの吸着剤は、錯体を
形成後、この錯体を有機溶媒に溶解させ、この溶液を活
性炭等の多孔質材料に含浸させ、最後に溶媒を蒸発させ
て製造している。ところが、メタンに対して吸着能を有
することが知られている錯体、例えばジカルボン酸金属
塩は分子量が大きく、有機溶媒に対して難溶であるた
め、上記のような従来の手段によってはこの錯体を多孔
質体内に導入することができない。またこの錯体は塩の
形態であるため水溶性であるが、溶媒として水を用いる
と、構造が壊れ、メタン吸着能を失ってしまう。[0004] However, these complexes are not suitable for adsorbing methane. These adsorbents are produced by forming a complex, dissolving the complex in an organic solvent, impregnating the solution with a porous material such as activated carbon, and finally evaporating the solvent. However, a complex known to have an adsorption ability to methane, for example, a metal dicarboxylate has a large molecular weight and is hardly soluble in an organic solvent. Cannot be introduced into the porous body. Further, this complex is water-soluble because it is in the form of a salt, but when water is used as a solvent, the structure is broken and the methane adsorption ability is lost.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、上記の従来
の問題点を解消し、気体、特にメタンの吸着能にすぐれ
た金属錯体を細孔内に有する多孔質体からなる気体吸着
材料、及びその製造方法を提供する。SUMMARY OF THE INVENTION The present invention solves the above-mentioned conventional problems and provides a gas adsorbing material comprising a porous material having pores containing a metal complex having an excellent ability to adsorb gas, particularly methane. And a method for producing the same.
【０００６】[0006]
【課題を解決するための手段】本発明によれば、上記問
題点を解決するために、酸と金属塩を反応させてなる金
属錯体を、細孔内に担持している多孔質体からなる気体
吸着材料が提供される。この気体吸着材料において、前
記酸は好ましくはジカルボン酸であり、前記金属塩は好
ましくはカルボン酸金属塩であり、被吸着気体はメタン
である。According to the present invention, in order to solve the above-mentioned problems, the present invention comprises a porous body which carries a metal complex obtained by reacting an acid and a metal salt in pores. A gas sorbent material is provided. In this gas adsorption material, the acid is preferably a dicarboxylic acid, the metal salt is preferably a metal carboxylate, and the gas to be adsorbed is methane.
【０００７】さらに本発明によれば、酸と金属塩の混合
溶液中に多孔質体を含浸し、多孔質体の細孔内に前記混
合溶液を侵入させた後、この細孔内で前記酸と金属塩を
反応させて金属錯体を成長析出させ、多孔質体を回収し
て乾燥する工程からなる、上記気体吸着材料の製造方法
が提供される。Further, according to the present invention, the porous body is impregnated in a mixed solution of an acid and a metal salt, and the mixed solution is made to penetrate into the pores of the porous body. And a metal salt to react and grow a metal complex, recovering and drying the porous body, and providing the method for producing the gas adsorbing material.
【０００８】[0008]
【発明の実施の形態】図１に多孔質体の細孔の構造を示
す。この図１に示すように、多孔質体の細孔は、細孔径
が25nm以上であるマクロ細孔、細孔径が１〜25nmである
メソ細孔、及び細孔径が0.4 〜１nmであるミクロ細孔か
らなっていると考えられている。これらの細孔のうち、
メソ細孔が気体、特にメタンの吸着に寄与するが、マク
ロ細孔はほとんど寄与しないと考えられる。またミクロ
細孔については不明である。すなわち、吸着材として多
孔質体を用いた場合、導入された気体は、この多孔質体
のメソ細孔においては毛管凝縮現象により凝集し液体状
態となって保持されるが、マクロ細孔においては細孔径
が大きいため気体状態のままであり、このマクロ細孔に
おいては気体は吸着されない。FIG. 1 shows the structure of the pores of a porous body. As shown in FIG. 1, the pores of the porous body include macropores having a pore diameter of 25 nm or more, mesopores having a pore diameter of 1 to 25 nm, and microfine pores having a pore diameter of 0.4 to 1 nm. It is thought to consist of holes. Of these pores,
It is believed that the mesopores contribute to the adsorption of gases, especially methane, while the macropores contribute little. The micropore is unknown. That is, when a porous body is used as the adsorbent, the introduced gas is aggregated by the capillary condensation phenomenon in the mesopores of the porous body and held in a liquid state, but is held in the macropore. Since the pore diameter is large, it remains in a gaseous state, and no gas is adsorbed in the macropores.
【０００９】そこで、この多孔質体のマクロ細孔に、気
体吸着能を有する金属錯体を設ければ、多孔質体のマク
ロ細孔においても有効に気体を吸着することができ、吸
着能を向上させることができる。Therefore, if a metal complex having a gas adsorbing ability is provided in the macropores of the porous body, the gas can be effectively adsorbed even in the macropores of the porous body, and the adsorbing ability is improved. Can be done.
【００１０】この金属錯体は、酸と金属塩を反応させる
ことにより形成されるものである。この酸としては、ジ
カルボン酸、例えばシュウ酸、マロン酸、コハク酸、グ
ルタル酸、アジピン酸、アジピン酸、ピメリン酸、スベ
リン酸、アゼライン酸、セバシン酸等の脂肪族ジカルボ
ン酸、及びテレフタル酸等の芳香族ジカルボン酸を用い
ることが好ましい。また金属塩としては、酸としてジカ
ルボン酸を用いる場合、カルボン酸金属塩、例えば蟻酸
金属塩、酢酸金属塩を用いることが好ましい。さらに、
金属としては錯体を形成する遷移金属、特に４配位の金
属、例えば銅を用いることが好ましい。[0010] The metal complex is formed by reacting an acid with a metal salt. Examples of the acid include dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, aliphatic dicarboxylic acids such as sebacic acid, and terephthalic acid. It is preferred to use aromatic dicarboxylic acids. When a dicarboxylic acid is used as the acid, it is preferable to use a metal carboxylate, for example, a metal formate or a metal acetate. further,
As the metal, it is preferable to use a transition metal that forms a complex, particularly a four-coordinate metal, for example, copper.
【００１１】この金属錯体は、有機溶媒に対して難溶で
あるため、有機溶媒に溶解させて多孔質体の細孔内に導
入することができない。またこの錯体は水溶性ではある
が、水に溶解させると、錯体の構造が壊れてしまい、気
体吸着能を失うため、錯体を形成後に水に溶解させて多
孔質体の細孔に導入することもできない。そこで本発明
では、錯体を形成後に多孔質体の細孔に導入するのでは
なく、酸の溶液と金属塩の溶液を混合後、細孔内に導入
し、この細孔内で反応させることによって、細孔内にお
いて錯体を形成する。Since this metal complex is hardly soluble in an organic solvent, it cannot be dissolved in the organic solvent and introduced into the pores of the porous body. Also, although this complex is water-soluble, dissolving it in water will break the structure of the complex and lose its gas adsorption ability.Therefore, dissolve it in water after forming the complex and introduce it into the pores of the porous body. I can't do that either. Therefore, in the present invention, instead of introducing the complex into the pores of the porous body after forming the complex, a solution of the acid and the metal salt are mixed, then introduced into the pores, and reacted in the pores. Forms a complex in the pores.
【００１２】具体的には、まず金属塩、例えば蟻酸銅塩
をメタノールに溶解し、残さを濾過によって除去する。
溶媒としてメタノールを用いるのは、水を用いると、金
属塩の溶解度が高いため、形成した錯体の析出が困難で
あるからである。これとは別に、酸、例えばテレフタル
酸をメタノールに溶解し、蟻酸を添加後、残さを濾過に
よって除去する。そしてこの金属塩溶液と酸溶液を混合
する。この金属塩と酸は単に混合したのみでは反応はほ
とんど進行せず、室温においては錯体の形成には数カ月
を要する。Specifically, first, a metal salt, for example, a copper formate salt is dissolved in methanol, and the residue is removed by filtration.
The reason why methanol is used as the solvent is that when water is used, the solubility of the metal salt is high, so that it is difficult to precipitate the formed complex. Separately, an acid, for example terephthalic acid, is dissolved in methanol, the formic acid is added, and the residue is removed by filtration. Then, the metal salt solution and the acid solution are mixed. The reaction hardly proceeds by merely mixing the metal salt and the acid, and it takes several months to form a complex at room temperature.
【００１３】次いでこの混合溶液に多孔質体を含浸させ
る。多孔質体としては各種の材料、例えば活性炭、ゼオ
ライト、シリカ、アルミナ、チタニア等を用いることが
できる。含浸後、溶液を60〜80℃に加熱し、還流加熱を
20〜40時間行い、マクロ細孔内で金属錯体を析出させ
る。最後に多孔質体を溶液から取り出し、乾燥させる。Next, a porous body is impregnated with the mixed solution. As the porous body, various materials, for example, activated carbon, zeolite, silica, alumina, titania and the like can be used. After impregnation, heat the solution to 60-80 ° C and heat to reflux.
Perform for 20 to 40 hours to precipitate the metal complex in the macropores. Finally, the porous body is taken out of the solution and dried.
【００１４】以上のようにして形成される金属錯体の反
応及び構造式を図２に示す。テレフタル酸と蟻酸銅を反
応させることにより、格子状の構造を有する金属錯体
（テレフタル酸銅）が得られる。この格子間の距離は用
いる酸によってきまり、１nm以下にすることができ、吸
着しようとする気体、例えばメタン、水素等に応じて適
宜設定することができる。そして気体はこの格子間にト
ラップされ吸着されることになる。この金属錯体は、図
３に示すように、多孔質体のマクロ細孔に形成されてい
るため、気体の吸着に寄与していなかったマクロ細孔
も、このマクロ細孔内に形成された金属錯体の格子内に
おいて、導入された気体が毛管凝縮され吸着されるた
め、気体の吸着に大きく寄与することになる。FIG. 2 shows the reaction and the structural formula of the metal complex formed as described above. By reacting terephthalic acid and copper formate, a metal complex having a lattice structure (copper terephthalate) is obtained. The distance between the lattices is determined by the acid used and can be set to 1 nm or less, and can be appropriately set according to the gas to be adsorbed, such as methane and hydrogen. Then, gas is trapped and adsorbed between the lattices. As shown in FIG. 3, this metal complex is formed in the macropores of the porous body. In the complex lattice, the introduced gas is capillary-condensed and adsorbed, which greatly contributes to gas adsorption.
【００１５】[0015]
【発明の効果】多孔質体のマクロ細孔に金属錯体を設け
ることにより、このマクロ細孔をも気体吸着能を有する
ことになり、多孔質体全体の気体吸着能が向上する。こ
の金属錯体は、多孔質体の細孔内における反応により形
成されるため、より多くの金属錯体を担持させることが
できる。By providing a metal complex in the macropores of the porous body, the macropores also have a gas adsorbing ability, and the gas adsorbing ability of the entire porous body is improved. Since this metal complex is formed by a reaction in the pores of the porous body, more metal complexes can be supported.
【図１】多孔質体の細孔構造を示す略断面図である。FIG. 1 is a schematic sectional view showing a pore structure of a porous body.
【図２】金属錯体の反応・構造を示す式である。FIG. 2 is a formula showing a reaction / structure of a metal complex.
【図３】金属錯体を設けた多孔質体の細孔内の概念図で
ある。FIG. 3 is a conceptual diagram of the inside of a pore of a porous body provided with a metal complex.
Claims (3)
を、細孔内に担持している多孔質体からなる気体吸着材
料。1. A gas adsorbing material comprising a porous body that carries a metal complex formed by reacting an acid and a metal salt in pores.
塩がカルボン酸金属塩であり、被吸着気体がメタンであ
る、請求項１記載の気体吸着材料。2. The gas adsorbing material according to claim 1, wherein the acid is a dicarboxylic acid, the metal salt is a metal carboxylate, and the gas to be adsorbed is methane.
浸し、多孔質体の細孔内に前記混合溶液を侵入させた
後、この細孔内で前記酸と金属塩を反応させて金属錯体
を成長析出させ、多孔質体を回収して乾燥する工程から
なる、請求項１記載の気体吸着材料の製造方法。3. A porous body is impregnated in a mixed solution of an acid and a metal salt, and the mixed solution is allowed to penetrate into pores of the porous body. 2. The method for producing a gas adsorbing material according to claim 1, comprising a step of growing and depositing a metal complex, collecting and drying the porous body.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32312999A JP2001137703A (en) | 1999-11-12 | 1999-11-12 | Adsorbent for gas and its preparing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32312999A JP2001137703A (en) | 1999-11-12 | 1999-11-12 | Adsorbent for gas and its preparing method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001137703A true JP2001137703A (en) | 2001-05-22 |
Family
ID=18151421
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32312999A Pending JP2001137703A (en) | 1999-11-12 | 1999-11-12 | Adsorbent for gas and its preparing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2001137703A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006297278A (en) * | 2005-04-20 | 2006-11-02 | Kuraray Co Ltd | Gas absorbent, its manufacturing method and gas-absorbing method using it |
| US8163069B2 (en) | 2009-11-24 | 2012-04-24 | Corning Incorporated | Carboxylic acid salt articles and methods of making and using them |
| JP2014036935A (en) * | 2012-08-17 | 2014-02-27 | National Institute Of Advanced Industrial & Technology | Composite porous body and method of manufacturing the same |
| JP2014528822A (en) * | 2011-08-15 | 2014-10-30 | エンパイア テクノロジー ディベロップメント エルエルシー | Oxalate sorbent for mercury removal |
| WO2019181185A1 (en) * | 2018-03-22 | 2019-09-26 | 株式会社大阪ソーダ | Metal treatment agent and method for treating metal in liquid phase |
-
1999
- 1999-11-12 JP JP32312999A patent/JP2001137703A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006297278A (en) * | 2005-04-20 | 2006-11-02 | Kuraray Co Ltd | Gas absorbent, its manufacturing method and gas-absorbing method using it |
| JP4603926B2 (en) * | 2005-04-20 | 2010-12-22 | 株式会社クラレ | Gas absorbent, method for producing the same, and method for absorbing gas using the same |
| US8163069B2 (en) | 2009-11-24 | 2012-04-24 | Corning Incorporated | Carboxylic acid salt articles and methods of making and using them |
| JP2014528822A (en) * | 2011-08-15 | 2014-10-30 | エンパイア テクノロジー ディベロップメント エルエルシー | Oxalate sorbent for mercury removal |
| JP2014036935A (en) * | 2012-08-17 | 2014-02-27 | National Institute Of Advanced Industrial & Technology | Composite porous body and method of manufacturing the same |
| WO2019181185A1 (en) * | 2018-03-22 | 2019-09-26 | 株式会社大阪ソーダ | Metal treatment agent and method for treating metal in liquid phase |
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