JP2009292670A - Method for producing high specific surface area activated carbon - Google Patents

Method for producing high specific surface area activated carbon Download PDF

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JP2009292670A
JP2009292670A JP2008146287A JP2008146287A JP2009292670A JP 2009292670 A JP2009292670 A JP 2009292670A JP 2008146287 A JP2008146287 A JP 2008146287A JP 2008146287 A JP2008146287 A JP 2008146287A JP 2009292670 A JP2009292670 A JP 2009292670A
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activated carbon
surface area
specific surface
metal
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JP5288592B2 (en
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Toshinori Kokubu
俊則 國府
Takashi Kogin
孝 古吟
Sojiro Kimura
壮次郎 木村
Kotaro Hirayama
鋼太郎 平山
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Dai Ichi High Frequency Co Ltd
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    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/32—Hydrogen storage

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing an activated carbon with a high specific surface area and a high micropore volume. <P>SOLUTION: The method comprises a first step of treating a porous organic material or a porous carbon material with superheated steam to produce a raw material activated carbon having a specific surface area of 400 m<SP>2</SP>/g or more, a second step of impregnating the resulting raw material activated carbon with at least one metal selected from alkali metals (Li, Na, K), alkaline earth metals (Mg, Ca), and transition metals (Ti, Fe, Co, Ni, Mo, Pt) to produce a metal-impregnated raw material activated carbon, and a third step of heat-treating the resulting metal-impregnated raw material activated carbon at 900 to 1,000°C in a reduced condition to increase the specific surface area thereof. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

本発明は、高比表面積活性炭の製造方法に関する。   The present invention relates to a method for producing high specific surface area activated carbon.

例えば、水素吸蔵、電気二重層コンデンサ、揮発性有機化合物（ＶＯＣ）等のガス吸着などの用途に使用される活性炭において、良好な吸着性能を発現させるためには、高い比表面積を有することが肝要である。また、比較的小さい分子または原子を吸着するための活性炭には、孔径が２ｎｍ以下のマイクロ孔の細孔容積が高いことが要求される。   For example, activated carbon used for applications such as hydrogen storage, electric double layer capacitors, gas adsorption of volatile organic compounds (VOC), etc. must have a high specific surface area in order to develop good adsorption performance. It is. Further, activated carbon for adsorbing relatively small molecules or atoms is required to have a high pore volume of micropores having a pore diameter of 2 nm or less.

従来、黒鉛系水素吸蔵材料を製造する方法として、原料黒鉛を粉砕処理して黒鉛の結晶子の大きさを小さくした後、賦活処理することにより、比表面積が４００ｍ2 ／ｇ以上で、半径５ｎｍ以下の細孔の容積が０．３ｃｍ3 ／ｇ以上になるよう調整して黒鉛系材料を得る方法が紹介されている（特許文献１参照）。また、特許文献１には、Ｐｔ、Ｐｄ、Ｎｉ、Ｋ、Ｌｉ、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｚｒ、Ｎｂの何れかを黒鉛系材料に含有させることによって水素吸蔵の向上を図ることが記載されている。 Conventionally, as a method for producing a graphite-based hydrogen storage material, the specific surface area is 400 m 2 / g or more and the radius is 5 nm by pulverizing the raw material graphite to reduce the size of the crystallites of the graphite and then performing the activation treatment. A method for obtaining a graphite-based material by adjusting the volume of the following pores to 0.3 cm 3 / g or more has been introduced (see Patent Document 1). Patent Document 1 discloses that hydrogen storage is improved by including any of Pt, Pd, Ni, K, Li, Ti, V, Cr, Mn, Fe, Co, Zr, and Nb in a graphite-based material. It is described that it is planned.

また、電気二重層コンデンサ材料を構成する多孔質炭素を製造する方法として、ディレードコーカーによる生コークス製造工程で、原料油中にアルカリ金属（Ｋ，Ｎａ，Ｌｉ）／アルカリ土類金属（Ｃａ，Ｍｇ，Ｚｎ）／遷移金属（Ｆｅ，Ｎｉ，Ｃｏ）元素のうちの１種以上からなる賦活剤を添加したのち、賦活成分が分散した生コークスを水蒸気、二酸化炭素および酸素から選択される少なくとも一種を有効成分とする酸化性ガスで賦活又はアルカリ賦活処理する方法が開示されている（特許文献２参照）。   Moreover, as a method for producing porous carbon constituting the electric double layer capacitor material, in the raw coke production process by a delayed coker, alkali metal (K, Na, Li) / alkaline earth metal (Ca, Mg) , Zn) / transition metal (Fe, Ni, Co) element, and after adding an activator, at least one selected from steam, carbon dioxide and oxygen is used as raw coke in which the activator is dispersed. A method of activation or alkali activation treatment using an oxidizing gas as an active ingredient is disclosed (see Patent Document 2).

また、細孔分布のマイクロ孔領域にメディアン値を有する分子ふるい活性炭を製造する方法として、アルカリ金属の水酸化物と、縮合型タンニンと、アルデヒド水溶液またはヘキサメチレンテトラミンとを含有するゲル状組成物を乾燥し、不活性ガス雰囲気下で炭化させた後、炭酸ガスまたは水蒸気を含む不活性ガスにより活性化させる方法が記載されている（特許文献３参照）。   Further, as a method for producing a molecular sieve activated carbon having a median value in the micropore region of the pore distribution, a gel composition containing an alkali metal hydroxide, condensed tannin and an aldehyde aqueous solution or hexamethylenetetramine Is dried, carbonized in an inert gas atmosphere, and then activated by an inert gas containing carbon dioxide or water vapor (see Patent Document 3).

しかしながら、特許文献１に記載の方法で得られた活性炭は、その比表面積が４００〜１１００と、精々１１００ｍ2 ／ｇ程度であり、また、マイクロ孔の細孔容積も十分に高いものにはならない。 However, the activated carbon obtained by the method described in Patent Document 1 has a specific surface area of 400 to 1100, at most about 1100 m 2 / g, and the pore volume of the micropores is not sufficiently high. .

また、特許文献２に記載の方法で得られた多孔質炭素は、賦活剤を添加せずに賦活処理して得られた多孔質炭素と比較して、ある程度高い比表面積を有しているものの、１１００〜１３００ｍ2 ／ｇ程度であり十分に高いものではない。 Moreover, although the porous carbon obtained by the method described in Patent Document 2 has a certain high specific surface area as compared with porous carbon obtained by activation treatment without adding an activator. 1100-1300 m 2 / g, which is not sufficiently high.

また、特許文献３に記載の方法で得られた活性炭は、細孔分布のマイクロ孔領域にシャープなピークを有するものの、その比表面積は８００ｍ2 ／ｇ程度に止まる。 Moreover, although the activated carbon obtained by the method described in Patent Document 3 has a sharp peak in the micropore region of the pore distribution, its specific surface area is only about 800 m 2 / g.

上記のように、特許文献１〜３に記載のものを含めて従来公知の方法では、比表面積が高く、マイクロ孔の細孔容積が高い活性炭を製造するまでには至っていない。
特開２００３−３２１２１６ 特開２００５−１９６８ 特開２００３−２８６０２２ As described above, conventionally known methods including those described in Patent Documents 1 to 3 have not yet produced activated carbon having a high specific surface area and a high micropore volume.
JP 2003-321216 A JP2005-1968 JP 2003-286022 A

本発明は以上のような事情に基いてなされたものである。
本発明の目的は、比表面積が高くて、マイクロ孔の細孔容積の高い活性炭を確実に製造することのできる製造方法を提供することにある。 The present invention has been made based on the above situation.
An object of the present invention is to provide a production method capable of reliably producing activated carbon having a high specific surface area and a high pore volume of micropores.

上記の目的を達成するために本発明者らが鋭意検討を重ねた結果、賦活処理を経て得られる活性炭（原料活性炭）に対して特定種類の金属を含浸させた後、この活性炭（金属含浸原料活性炭）を、還元状態において、特定の温度で加熱処理することにより、当該活性炭の比表面積およびマイクロ孔の細孔容積が効果的に増大し、比表面積が高く、マイクロ孔の細孔容積が高い活性炭（高比表面積活性炭）が得られることを見出し、かかる知見に基いて本発明を完成した。   As a result of intensive studies by the present inventors to achieve the above object, activated carbon (raw material activated carbon) obtained through activation treatment is impregnated with a specific type of metal, and then this activated carbon (metal impregnated raw material) When the activated carbon is heated at a specific temperature in a reduced state, the specific surface area of the activated carbon and the pore volume of the micropores are effectively increased, the specific surface area is high, and the pore volume of the micropores is high. It discovered that activated carbon (high specific surface area activated carbon) was obtained, and completed this invention based on this knowledge.

本発明の高比表面積活性炭の製造方法は、多孔質有機材料または多孔質炭素材料を過熱水蒸気を用いて処理することにより、比表面積が４００ｍ2 ／ｇ以上の原料活性炭を製造する第１工程と、
得られた原料活性炭に、アルカリ金属（Ｌｉ，Ｎａ，Ｋ）、アルカリ土類金属（Ｍｇ，Ｃａ）および遷移金属（Ｔｉ，Ｆｅ，Ｃｏ，Ｎｉ，Ｍｏ，Ｐｔ）から選ばれた少なくとも１種の金属を含浸させて金属含浸原料活性炭を製造する第２工程と、
得られた金属含浸原料活性炭を、還元状態において９００〜１０００℃で加熱処理することにより、その比表面積を増大させる第３工程と
を含むことを特徴とする。 The high specific surface area activated carbon production method of the present invention includes a first step of producing a raw material activated carbon having a specific surface area of 400 m 2 / g or more by treating a porous organic material or a porous carbon material with superheated steam. ,
The obtained activated carbon is at least one selected from alkali metals (Li, Na, K), alkaline earth metals (Mg, Ca) and transition metals (Ti, Fe, Co, Ni, Mo, Pt). A second step of impregnating a metal to produce a metal-impregnated raw material activated carbon;
The obtained metal-impregnated raw material activated carbon is subjected to heat treatment at 900 to 1000 ° C. in a reduced state, thereby including a third step of increasing the specific surface area.

本発明の製造方法においては、下記の形態が好ましい。
（ａ）第１工程において、過熱水蒸気とともに二酸化炭素を用いて処理すること。
（ｂ）第１工程において、過熱水蒸気による処理を７００〜９５０℃で１時間以上行うこと。
（ｃ）第１工程において、過熱水蒸気による処理を、１回あたり１〜３時間で、２回以上繰り返して行うこと。
（ｄ）第２工程において、金属としてＬｉおよび／またはＴｉを含浸させること。
（ｅ）第２工程において、原料活性炭に金属塩の水溶液を含浸させて乾燥することにより、当該金属を含浸させること。
（ｆ）第３工程において、加熱処理を９２５〜９７５℃で３６時間以上行うこと。 In the production method of the present invention, the following modes are preferred.
(A) In the first step, carbon dioxide is used together with superheated steam.
(B) In the first step, treatment with superheated steam is performed at 700 to 950 ° C. for 1 hour or longer.
(C) In the first step, the treatment with superheated steam is repeated twice or more in 1 to 3 hours per time.
(D) In the second step, impregnation with Li and / or Ti as a metal.
(E) In the second step, impregnation with the metal by impregnating the raw material activated carbon with an aqueous solution of a metal salt and drying.
(F) In the third step, heat treatment is performed at 925 to 975 ° C. for 36 hours or more.

また、本発明の製造方法は、アルカリ金属（Ｌｉ，Ｎａ，Ｋ）、アルカリ土類金属（Ｍｇ，Ｃａ）および遷移金属（Ｔｉ，Ｆｅ，Ｃｏ，Ｎｉ，Ｍｏ，Ｐｔ）から選ばれた少なくとも１種の金属を含浸する金属含浸原料活性炭を、還元状態において９００〜１０００℃で加熱処理する工程を含むことを特徴とする。   The production method of the present invention is at least one selected from alkali metals (Li, Na, K), alkaline earth metals (Mg, Ca), and transition metals (Ti, Fe, Co, Ni, Mo, Pt). It includes a step of heat-treating a metal-impregnated raw material activated carbon impregnated with a seed metal at 900 to 1000 ° C. in a reduced state.

本発明の高比表面積活性炭は、本発明の製造方法により得られる、比表面積が２０００ｍ2 ／ｇ以上の活性炭である。
本発明の水素吸蔵材料は、本発明の高比表面積活性炭からなる。
本発明の電気二重層コンデンサ材料は、本発明の高比表面積活性炭からなる。 The high specific surface area activated carbon of the present invention is activated carbon having a specific surface area of 2000 m 2 / g or more obtained by the production method of the present invention.
The hydrogen storage material of the present invention comprises the high specific surface area activated carbon of the present invention.
The electric double layer capacitor material of the present invention comprises the high specific surface area activated carbon of the present invention.

本発明の製造方法によれば、高い比表面積および高い細孔容積を有し、特にマイクロ孔の細孔容積が高い活性炭を確実に製造することができる。   According to the production method of the present invention, it is possible to reliably produce activated carbon having a high specific surface area and a high pore volume, in particular, a high pore volume of micropores.

＜第１工程＞
本発明の製造方法における第１工程は、多孔質有機材料または多孔質炭素材料を過熱水蒸気を用いて処理することにより原料活性炭を製造する工程である。
第１工程において処理される「多孔質有機材料」としては、活性炭の原料として従来公知の有機材料を使用することができ、コーヒー粕、ヤシ殻、木材、竹などを例示することができる。これらのうち、均一で微細な多孔質構造を持つために金属を含浸させやすい活性炭を得ることができること、成分抽出のためにほぼ均一の粒子径に粉砕されていること、および産業廃棄物の有効利用という観点からコーヒー粕を使用することが好ましい。
また、使用する多孔質有機材料は、予め乾燥処理しておくことが好ましい。 <First step>
The 1st process in the manufacturing method of this invention is a process of manufacturing raw material activated carbon by processing a porous organic material or a porous carbon material using superheated steam.
As the “porous organic material” to be treated in the first step, a conventionally known organic material can be used as a raw material of activated carbon, and examples include coffee candy, coconut shell, wood, bamboo and the like. Among these, it is possible to obtain activated carbon that is easy to impregnate metal because it has a uniform and fine porous structure, that it is pulverized to a nearly uniform particle size for component extraction, and effective industrial waste From the viewpoint of utilization, it is preferable to use coffee mash.
The porous organic material to be used is preferably previously dried.

第１工程において処理される「多孔質炭素材料」としては、上記の多孔質有機材料の炭化生成物（炭）を挙げることができ、多孔質有機材料を４００〜５００℃で加熱することにより炭化させて得られるものが好ましい。このように比較的低い温度で多孔質有機材料を炭化させることにより、アモルファス状態の炭化生成物を高い収率で得ることができる。そして、これを過熱水蒸気により処理して得られる原料活性炭は、アモルファス状態が維持され、後の工程（第３工程）で行われる加熱処理により、その比表面積を効果的に増大させることができる。
多孔質炭素材料を過熱水蒸気を用いて処理する場合において、多孔質炭素材料の形成（多孔質有機材料の炭化）は、後述する過熱水蒸気による処理装置の処理室内において、過熱水蒸気による処理に先立って行われることが好ましい。
以下、多孔質有機材料および多孔質炭素材料の両者をあわせて「多孔質材料」ということがある。 Examples of the “porous carbon material” to be treated in the first step include carbonized products (charcoal) of the porous organic material described above, and carbonized by heating the porous organic material at 400 to 500 ° C. What is obtained is preferably obtained. Thus, by carbonizing the porous organic material at a relatively low temperature, a carbonized product in an amorphous state can be obtained in a high yield. And the raw material activated carbon obtained by processing this with superheated steam is maintained in an amorphous state, and the specific surface area can be effectively increased by the heat treatment performed in the subsequent step (third step).
In the case where the porous carbon material is treated with superheated steam, the formation of the porous carbon material (carbonization of the porous organic material) is performed prior to the treatment with superheated steam in the treatment chamber of the superheated steam treatment apparatus described later. Preferably, it is done.
Hereinafter, both the porous organic material and the porous carbon material may be collectively referred to as “porous material”.

過熱水蒸気による処理装置としては、例えば、過熱水蒸気発生装置と、当該過熱水蒸気発生装置からの過熱水蒸気が導入される処理室とを備えている。ここに、過熱水蒸気発生装置としては、急速な昇温・降温操作を行うことができることなどから、誘導加熱方式によるものが好ましい。   As a processing apparatus using superheated steam, for example, a superheated steam generator and a processing chamber into which superheated steam from the superheated steam generator is introduced are provided. Here, the superheated steam generator is preferably an induction heating system because it can perform a rapid temperature increase / decrease operation.

炭の燃焼消失を抑制して原料活性炭の収量を確保するためには、処理室内における多孔質材料への酸素の接触を極力避ける必要がある。このため、処理室内への多孔質材料の充填方法として、例えば、多孔質材料を金網製容器内に充填し、当該金網製容器をステンレス容器内に載置し、このステンレス容器と金網製容器との隙間に市販の粉炭を充填した後、ステンレス容器を処理室内に収容する方法を挙げることができる。   In order to suppress the combustion disappearance of charcoal and ensure the yield of the raw material activated carbon, it is necessary to avoid the oxygen contact with the porous material in the processing chamber as much as possible. Therefore, as a method for filling the processing chamber with the porous material, for example, the porous material is filled in a metal mesh container, and the metal mesh container is placed in a stainless steel container. A method of accommodating the stainless steel container in the processing chamber after filling the gaps with commercially available pulverized coal can be mentioned.

第１工程における過熱水蒸気による処理温度としては、７００〜９５０℃であることが好ましく、更に好ましくは７５０〜８５０℃、特に好ましくは７７５〜８２５℃とされる。
過熱水蒸気による処理温度を７００℃以上とすることにより、多孔質材料において、吸熱反応である水蒸気賦活反応（炭素の消耗反応）が進行して比表面積が増大し、比表面積が４００以上の原料活性炭を効率的に得ることができる。
また、この処理温度が９５０℃以下であることにより、得られる原料活性炭（第２工程を経て得られる金属含浸原料活性炭）の比表面積を、後の工程（第３工程）において確実に増大させることができる。処理温度が９５０℃を超える場合には、第３工程による比表面積の増大効果が十分に発揮されないことがある。 The treatment temperature with superheated steam in the first step is preferably 700 to 950 ° C, more preferably 750 to 850 ° C, and particularly preferably 775 to 825 ° C.
By setting the treatment temperature with superheated steam to 700 ° C. or higher, a raw material activated carbon having a specific surface area of 400 or more increases in the porous material by a water vapor activation reaction (carbon consumption reaction) that is an endothermic reaction and increases in specific surface area. Can be obtained efficiently.
In addition, when the treatment temperature is 950 ° C. or lower, the specific surface area of the obtained raw material activated carbon (metal impregnated raw material activated carbon obtained through the second step) is surely increased in the subsequent step (third step). Can do. When the processing temperature exceeds 950 ° C., the effect of increasing the specific surface area by the third step may not be sufficiently exhibited.

処理室の単位断面積当たりの過熱水蒸気の流量としては、５００〜２５００ｇ／ｍ2 ・分であることが好ましく、更に好ましくは１７００〜２３００ｇ／ｍ2 ・分とされる。
過熱水蒸気の流量が過少である場合には、水蒸気賦活反応を十分に進行させることができず、得られる原料活性炭の比表面積を十分に高くすることができない。
一方、過熱水蒸気の流量が過剰である場合には原料活性炭の燃焼消失が促進されて過熱水蒸気処理活性炭の収量が著しく減少する。 The flow rate of the superheated steam per unit cross-sectional area of the processing chamber is preferably 500~2500g / m 2 · min, more preferably are 1700~2300g / m 2 · min.
When the flow rate of the superheated steam is too small, the steam activation reaction cannot sufficiently proceed, and the specific surface area of the obtained raw material activated carbon cannot be sufficiently increased.
On the other hand, when the flow rate of superheated steam is excessive, combustion disappearance of the raw activated carbon is promoted, and the yield of the superheated steam-treated activated carbon is significantly reduced.

第１工程においては、過熱水蒸気とともに二酸化炭素を用いて、多孔質材料を処理することが好ましい。ここに、処理室の単位断面積当たりの二酸化炭素の流量としては０〜７５０Ｌ／ｍ2 ・分であることが好ましく、更に好ましくは２５０〜５００Ｌ／ｍ2 ・分とされる。
二酸化炭素の流量が過剰である場合には、過剰に生成される一酸化炭素によって炭素消耗が阻害され、比表面積を増大させることができなくなる。 In the first step, it is preferable to treat the porous material using carbon dioxide together with superheated steam. Here, it is preferable that as the carbon dioxide flow rate per unit cross-sectional area of the processing chamber is a 2-minute 0~750L / m, more preferably are 250~500L / m 2 · min.
When the flow rate of carbon dioxide is excessive, carbon consumption is inhibited by excessively generated carbon monoxide, and the specific surface area cannot be increased.

過熱水蒸気による処理時間としては、１時間以上であることが好ましく、更に好ましくは１〜３時間とされる。処理時間は水蒸気の流量と反比例の関係にあり、流量が多いと燃焼による炭素消耗が多くなって処理後の炭の収量が減少し、一方、１時間未満では、多孔質材料の比表面積を十分に増大させることができない場合がある。   The treatment time with superheated steam is preferably 1 hour or longer, more preferably 1 to 3 hours. The treatment time is inversely proportional to the flow rate of water vapor, and if the flow rate is high, the carbon consumption due to combustion increases and the yield of charcoal after treatment decreases, while if less than 1 hour, the specific surface area of the porous material is sufficient. In some cases, it cannot be increased.

また、過熱水蒸気による処理を複数回に分けて実施する（一定時間経過後に処理を中断する）ことができ、これにより、同じ時間で連続的に処理したときよりも、比表面積を増大させることができる。ここに、１回あたりの処理時間は、１時間以上、例えば１〜３時間であることが好ましい。また、処理回数としては、１回あたりの処理時間によっても異なるが、例えば２〜４回とされる。また、処理の中断時間としては、特に限定されるものではない。   In addition, the treatment with superheated steam can be carried out in a plurality of times (the treatment is interrupted after a lapse of a certain time), thereby increasing the specific surface area compared to the case where the treatment is continuously carried out at the same time. it can. Here, the treatment time per time is preferably 1 hour or more, for example, 1 to 3 hours. The number of times of processing is, for example, 2 to 4 times, although it varies depending on the processing time per time. Further, the processing interruption time is not particularly limited.

過熱水蒸気による処理を複数回に分けて実施する具体的方法としては、例えば、８００℃で２時間の処理（１回目）を行った後、放冷し、処理室から試料（多孔質材料および／または活性炭を含む試料）を取り出し、ふるい分けにより灰分等を分離除去した後、処理室内に再度充填し、８００℃で２時間の処理（２回目）を行う。その後、再度放冷し、処理室から試料を取り出し、ふるい分けにより灰分を分離除去した後、処理室内に再度充填し、８００℃で２時間の処理（３回目）を行う方法を挙げることができる。   As a specific method for carrying out the treatment with superheated steam in a plurality of times, for example, a treatment (first time) is performed at 800 ° C. for 2 hours, and then allowed to cool, and a sample (porous material and / or Or a sample containing activated carbon) is taken out, and ash and the like are separated and removed by sieving, and then filled again into the treatment chamber, followed by treatment at 800 ° C. for 2 hours (second time). Thereafter, it is allowed to cool again, and a sample is taken out from the processing chamber, and after ash is separated and removed by sieving, it is filled again in the processing chamber, and a treatment is performed at 800 ° C. for 2 hours (third time).

第１工程における過熱水蒸気による処理により、多孔質材料の比表面積が増大し、原料活性炭が得られる。
多孔質材料の比表面積が増大するプロセスとしては明らかではないが、水蒸気賦活反応により、既存の孔隙を形成していた炭素が消耗して細孔径が増大するとともに、多数の細孔が新たに形成されることによるものと推測される。 By the treatment with the superheated steam in the first step, the specific surface area of the porous material is increased, and raw material activated carbon is obtained.
Although it is not clear as a process that increases the specific surface area of the porous material, the steam activation reaction consumes the carbon that had formed the existing pores, increasing the pore size, and creating a large number of new pores It is presumed that this is due to

第１工程により得られる原料活性炭の比表面積としては、４００ｍ2 ／ｇ以上とされ、好ましくは４００〜１５００ｍ2 ／ｇ、更に好ましくは８００〜１５００ｍ2 ／ｇとされる。比表面積が４００ｍ2 ／ｇ未満の活性炭によっては、後の工程（第２工程および第３工程）を経て得られる活性炭の比表面積を２０００ｍ2 ／ｇ以上にすることは困難である。 The specific surface area of the base activated carbon obtained by the first step, is a 400 meters 2 / g or more, preferably 400~1500m 2 / g, more preferably a 800~1500m 2 / g. By activated carbon having a specific surface area of less than 400 meters 2 / g, making the specific surface area after the step (second and third steps) menstrual to obtain activated carbon or 2000 m 2 / g is difficult.

第１工程により得られる原料活性炭の細孔容積としては０．３ｃｍ3 ／ｇ以上であることが好ましく、更に好ましくは０．４〜０．６ｃｍ3 ／ｇとされる。
原料活性炭におけるマイクロ孔の細孔容積としては０．２５ｃｍ3 ／ｇ以上であることが好ましく、更に好ましくは０．３〜０．５ｃｍ3 ／ｇとされる。 The pore volume of the raw material activated carbon obtained by the first step is preferably 0.3 cm 3 / g or more, and more preferably 0.4 to 0.6 cm 3 / g.
The pore volume of the micropores in the raw activated carbon is preferably 0.25 cm 3 / g or more, more preferably 0.3 to 0.5 cm 3 / g.

＜第２工程＞
本発明の製造方法における第２工程は、第１工程で得られた原料活性炭に、特定種類の金属を含浸させて金属含浸原料活性炭を製造する工程である。
本発明においては、賦活処理（活性化処理）を経て得られる原料活性炭に対して金属を含浸させるものである。多孔質有機材料に金属を含浸させ、その後これを炭化・賦活処理する場合には、後の第３工程での加熱処理によって、活性炭（原料活性炭）の比表面積を増大させることができない（後述する比較例４参照）。 <Second step>
The second step in the production method of the present invention is a step of producing a metal-impregnated raw material activated carbon by impregnating the raw material activated carbon obtained in the first step with a specific type of metal.
In the present invention, a raw material activated carbon obtained through an activation treatment (activation treatment) is impregnated with a metal. When the porous organic material is impregnated with metal and then carbonized and activated, the specific surface area of the activated carbon (raw material activated carbon) cannot be increased by heat treatment in the subsequent third step (described later). (See Comparative Example 4).

原料活性炭に含浸させる金属としては、アルカリ金属であるＬｉ，Ｎａ，Ｋ、アルカリ土類金属であるＭｇ，Ｃａ、遷移金属であるＴｉ，Ｆｅ，Ｃｏ，Ｎｉ，Ｍｏ，Ｐｔを挙げることができ、これらは単独でまたは２種類以上組み合わされて使用することができる。 これらのうち、後の第３工程での加熱処理による活性炭の比表面積を増大させる効果に優れていることからＬｉおよびＴｉが好ましく、特に好ましくはＬｉである。
これらの金属は、金属（元素）の形態で活性炭に含浸されていてもよいし、金属化合物の形態で活性炭に含浸されていてもよい。 Examples of the metal impregnated in the raw material activated carbon include Li, Na, K, which are alkali metals, Mg, Ca, which are alkaline earth metals, and Ti, Fe, Co, Ni, Mo, and Pt, which are transition metals. These can be used alone or in combination of two or more. Among these, Li and Ti are preferable, and Li is particularly preferable because it is excellent in the effect of increasing the specific surface area of the activated carbon by the heat treatment in the subsequent third step.
These metals may be impregnated in activated carbon in the form of a metal (element), or may be impregnated in activated carbon in the form of a metal compound.

原料活性炭に金属を含浸させる（金属含浸原料活性炭を製造する）方法としては、特に限定されるものではないが、好適な方法として、金属塩の水溶液に原料活性炭を浸漬することにより、原料活性炭に金属塩の水溶液を含浸させ、これを脱水・乾燥する方法を挙げることができる。
ここに、金属塩としては、上記の金属（Ｌｉ，Ｎａ，Ｋ，Ｍｇ，Ｃａ，Ｔｉ，Ｆｅ，Ｃｏ，Ｎｉ，Ｍｏ，Ｐｔ）の塩酸塩、硫酸塩、硝酸塩、炭酸塩、リン酸塩などを例示することができる。 The method of impregnating the raw material activated carbon with the metal (manufacturing the metal-impregnated raw material activated carbon) is not particularly limited, but as a preferred method, the raw material activated carbon is immersed in the aqueous solution of the metal salt. A method of impregnating an aqueous solution of a metal salt and dehydrating and drying it can be mentioned.
Here, as the metal salt, hydrochloride, sulfate, nitrate, carbonate, phosphate, etc. of the above metals (Li, Na, K, Mg, Ca, Ti, Fe, Co, Ni, Mo, Pt), etc. Can be illustrated.

＜第３工程＞
本発明の製造方法における第３工程は、第２工程で得られた金属含浸原料活性炭を、還元状態において９００〜１０００℃で加熱処理することにより、その比表面積を増大させて高比表面積活性炭を製造する工程である。 <Third step>
In the third step of the production method of the present invention, the metal-impregnated raw material activated carbon obtained in the second step is heat-treated at 900 to 1000 ° C. in a reduced state, thereby increasing its specific surface area to obtain a high specific surface area activated carbon. It is a manufacturing process.

金属含浸原料活性炭の加熱処理は、電気炉などにより行うことができる。
金属含浸原料活性炭の加熱処理は、還元状態で行われる。ここに、「還元状態」とは、酸素との接触が実質的に遮断された状態をいう。
還元状態とすることにより、金属含浸原料活性炭の燃焼消失を防止することができる。還元状態に維持する方法としては、特に限定されるものではないが、好適な方法として、例えば、金属含浸原料活性炭をシート（好ましくは耐火性のもの）に包み、金属含浸原料活性炭を内包する当該シートを、市販の粉炭が底部に敷きつめられている蓋付の容器（るつぼ）内に載置し、当該容器内の隙間を粉炭で充填した後に蓋をし、この容器を電気炉内に収容する方法を挙げることができる。 The heat treatment of the metal-impregnated raw material activated carbon can be performed by an electric furnace or the like.
The heat treatment of the metal-impregnated raw material activated carbon is performed in a reduced state. Here, the “reduced state” means a state in which contact with oxygen is substantially cut off.
By making it into a reduced state, it is possible to prevent the combustion loss of the metal-impregnated raw material activated carbon. The method for maintaining the reduced state is not particularly limited, but as a suitable method, for example, the metal-impregnated raw material activated carbon is wrapped in a sheet (preferably refractory), and the metal-impregnated raw material activated carbon is included. The sheet is placed in a container with a lid (crucible) in which commercially available pulverized coal is placed at the bottom, the gap in the container is filled with pulverized coal, the lid is closed, and the container is accommodated in an electric furnace. A method can be mentioned.

第３工程における加熱処理温度としては、通常９００〜１０００℃とされ、好ましくは９２５〜９７５℃とされる。
処理温度が９００℃未満では、活性炭の比表面積を十分に増大させることができない。一方、１０００℃を超える場合には、細孔の収縮が起こり、比表面積の経時的減少が生じる。 The heat treatment temperature in the third step is usually 900 to 1000 ° C., preferably 925 to 975 ° C.
When the treatment temperature is less than 900 ° C., the specific surface area of the activated carbon cannot be increased sufficiently. On the other hand, when it exceeds 1000 ° C., the pores shrink and the specific surface area decreases with time.

加熱処理時間としては、通常３６時間以上とされ、好ましくは３６〜４８時間とされる。
処理時間が３６時間未満では活性炭の比表面積を十分に増大させることができず、３６時間以上加熱することにより活性炭の比表面積が急激に増大する。 The heat treatment time is usually 36 hours or longer, preferably 36 to 48 hours.
If the treatment time is less than 36 hours, the specific surface area of the activated carbon cannot be sufficiently increased, and the specific surface area of the activated carbon increases rapidly by heating for 36 hours or more.

第３工程における加熱処理によれば、金属含浸原料活性炭の比表面積および細孔容積を著しく増大させることができる。これは、炭素消耗による細孔径の拡大および新規な細孔の形成によるものと推測される。
また、この加熱処理よれば、金属含浸原料活性炭におけるマイクロ孔の細孔容積が顕著に増大する。これは、新たなマイクロ孔が多数形成されるからであると推測される。 According to the heat treatment in the third step, the specific surface area and pore volume of the metal-impregnated raw material activated carbon can be remarkably increased. This is presumed to be due to the expansion of the pore diameter due to carbon consumption and the formation of new pores.
Further, according to this heat treatment, the pore volume of the micropores in the metal-impregnated raw material activated carbon is remarkably increased. This is presumed to be because many new micropores are formed.

細孔径の拡大および新規な細孔（特にマイクロ孔）の形成、延いては、これらによる比表面積および細孔容積の増大は、活性炭に含浸されている金属により促進される。すなわち、活性炭に含浸されている金属は、比表面積および細孔容積を増大させる反応の触媒として作用する。
金属を含浸しない活性炭に対して、第３工程と同様の加熱処理を行っても、比表面積や細孔容積を十分に増大させることはできない（後述する比較例２〜３参照）。 The enlargement of the pore diameter and the formation of new pores (especially micropores), and thus the increase of the specific surface area and the pore volume are promoted by the metal impregnated in the activated carbon. That is, the metal impregnated in the activated carbon acts as a catalyst for the reaction that increases the specific surface area and pore volume.
Even if the same heat treatment as in the third step is performed on the activated carbon not impregnated with metal, the specific surface area and pore volume cannot be sufficiently increased (see Comparative Examples 2 to 3 described later).

また、多孔質有機材料の段階で金属を含浸させ、その後、炭化・賦活処理して活性炭（原料活性炭）を製造した場合には、そのような原料活性炭に対して第３工程と同様の加熱処理を行っても、比表面積や細孔容積を十分に増大させることはできない（後述する比較例４参照）。   In addition, when activated carbon (raw activated carbon) is produced by impregnating metal at the porous organic material stage and then carbonized and activated, the same heat treatment as in the third step is performed on such activated carbon. However, the specific surface area and pore volume cannot be increased sufficiently (see Comparative Example 4 described later).

上記の第１工程乃至第３工程を経て得られる高比表面積活性炭は、比表面積が高く、マイクロ孔の細孔容積が高いものである。
高比表面積活性炭の比表面積としては、通常２０００ｍ2 ／ｇ以上とされ、好ましくは２５００ｍ2 ／ｇ以上、更に好ましくは３０００ｍ2 ／ｇ以上とされる。
高比表面積活性炭の細孔容積としては１．０ｃｍ3 ／ｇ以上であることが好ましく、更に好ましくは１．５ｃｍ3 ／ｇ以上とされる。
高比表面積活性炭におけるマイクロ孔の細孔容積としては０．５ｃｍ3 ／ｇ以上であることが好ましく、更に好ましくは１．０ｃｍ3 ／ｇ以上とされる。
高比表面積活性炭の粒径は、ふるい分けなどによって適宜調整することができる。 The high specific surface area activated carbon obtained through the first to third steps has a high specific surface area and a high micropore volume.
The specific surface area of the high specific surface area activated carbon is usually 2000 m 2 / g or more, preferably 2500 m 2 / g or more, more preferably 3000 m 2 / g or more.
The pore volume of the high specific surface area activated carbon is preferably 1.0 cm 3 / g or more, more preferably 1.5 cm 3 / g or more.
The pore volume of the micropores in the high specific surface area activated carbon is preferably 0.5 cm 3 / g or more, more preferably 1.0 cm 3 / g or more.
The particle size of the high specific surface area activated carbon can be appropriately adjusted by sieving or the like.

以下、本発明の実施例について説明するが、本発明はこれらの実施例に限定されるものではない。なお、以下において、多孔質有機材料であるコーヒー粕は、コーヒー豆を焙煎・粉砕し、飲料用成分を抽出した後の残留物を３日間天日干しした後、乾燥機により１２０℃で２４時間乾燥したものを使用した。   Examples of the present invention will be described below, but the present invention is not limited to these examples. In the following, the coffee candy, which is a porous organic material, is obtained by roasting and pulverizing coffee beans, extracting the beverage ingredients, and sun-drying them for 3 days, followed by drying at 120 ° C. for 24 hours. The dried one was used.

過熱水蒸気処理装置としては、誘導加熱方式の過熱水蒸気発生装置と、当該過熱水蒸気発生装置からの過熱水蒸気が導入される処理室とを備えている装置（第一高周波工業（株）製）を使用した。
活性炭の比表面積および細孔分布の測定には「マイクロメリテックス Ｇｅｍｉｎｉ ２３７５型」（（株）島津製作所製）を使用した。比表面積はＢＥＴ３点法により、細孔分布はＢＪＨ法に従って測定した。 As the superheated steam treatment apparatus, an apparatus (manufactured by Daiichi High-Frequency Industry Co., Ltd.) having an induction heating type superheated steam generation apparatus and a treatment chamber into which superheated steam from the superheated steam generation apparatus is introduced is used. did.
“Micromeritex Gemini 2375 type” (manufactured by Shimadzu Corporation) was used for measurement of the specific surface area and pore distribution of the activated carbon. The specific surface area was measured by the BET 3-point method, and the pore distribution was measured by the BJH method.

＜実施例１＞
（第１工程）
コーヒー粕１．０Ｋｇを金網製容器内に充填した。
次いで、コーヒー粕が充填された金網製容器を耐熱ステンレス容器内に載置し、耐熱ステンレス容器と金網製容器との隙間に竹炭を充填した。
次いで、この耐熱ステンレス容器を、過熱水蒸気処理装置の処理室（断面積０．０２０ｍ2 ）に収容した。
処理室内を５００℃で９０分間保持してコーヒー粕を炭化させた後、処理室内に、過熱水蒸気（流量＝２０００ｇ／ｍ2 ・分）および二酸化炭素（流量＝５００Ｌ／ｍ2 ・分）を導入し、７７５℃で２時間にわたり過熱水蒸気を用いて処理することにより、約１５０ｇの活性炭を得た。
このようにして得られた活性炭について、電磁式ふるい振とう器により粒径ごとにふるい分け、粒径３００〜５００μｍの粒子を採取した。これを「原料活性炭（ａ）」とする。
原料活性炭（ａ）の比表面積は８５２ｍ2 ／ｇ、細孔容積は０．４９ｃｍ3 ／ｇ、マイクロ孔（孔径≦２ｎｍ）の細孔容積は０．４２ｃｍ3 ／ｇであった。 <Example 1>
(First step)
A coffee mesh container (1.0 kg) was filled into a wire mesh container.
Next, the wire mesh container filled with the coffee grinder was placed in a heat resistant stainless steel container, and bamboo charcoal was filled in the gap between the heat resistant stainless steel container and the wire mesh container.
Subsequently, this heat-resistant stainless steel container was accommodated in the processing chamber (cross-sectional area 0.020 m 2 ) of the superheated steam processing apparatus.
After holding the treatment chamber at 500 ° C for 90 minutes to carbonize the coffee grounds, superheated steam (flow rate = 2000 g / m 2 · min) and carbon dioxide (flow rate = 500 L / m 2 · min) are introduced into the treatment chamber Then, the mixture was treated with superheated steam at 775 ° C. for 2 hours to obtain about 150 g of activated carbon.
The activated carbon thus obtained was sieved for each particle size using an electromagnetic sieve shaker, and particles having a particle size of 300 to 500 μm were collected. This is referred to as “raw activated carbon (a)”.
The specific surface area of the raw material activated carbon (a) was 852 m 2 / g, the pore volume was 0.49 cm 3 / g, and the pore volume of the micropores (pore diameter ≦ 2 nm) was 0.42 cm 3 / g.

（第２工程）
第１工程により得られた原料活性炭（ａ）１０ｇを塩化リチウム水溶液（１ｍｍｏｌ／Ｌ）６０ｍＬに浸漬し、これを１時間加熱煮沸して脱気することにより、原料活性炭（ａ）に塩化リチウム水溶液を含浸させた。冷却後、塩化リチウム水溶液を含浸している活性炭を脱水し、乾燥機を使用して１２０℃で２４時間乾燥することにより、リチウムを含浸する金属含浸原料活性炭を得た。これを「金属含浸原料活性炭（Ｌ１）」とする。 (Second step)
The raw material activated carbon (a) 10g obtained by the 1st process is immersed in 60 mL of lithium chloride aqueous solution (1 mmol / L), and this is heated and boiled for 1 hour, It deaerates to raw material activated carbon (a), lithium chloride aqueous solution Was impregnated. After cooling, the activated carbon impregnated with the lithium chloride aqueous solution was dehydrated, and dried at 120 ° C. for 24 hours using a dryer to obtain a metal-impregnated raw material activated carbon impregnated with lithium. This is referred to as “metal-impregnated activated carbon (L1)”.

（第３工程）
第２工程で得られた金属含浸原料活性炭（Ｌ１）をセラミック繊維「カオウール（登録商標）」からなる耐火性シートに包み、金属含浸原料活性炭（Ｌ１）を内包する当該耐火性シートを、市販の粉炭（粒径５００μｍ）を底部に敷きつめた蓋付の容器（ＳｉＣ製のるつぼ）内に載置するとともに、当該容器内の隙間（耐火性シートの周囲）を粉炭で充填して耐火性シートを粉炭中に埋め込み、その後、容器に蓋をして、金属含浸原料活性炭（Ｌ１）の空気（酸素）との接触を遮断した。次いで、この容器を電気マッフル炉内に収容し、還元状態において９５０℃で３６時間加熱処理した。 (Third step)
The metal impregnated raw material activated carbon (L1) obtained in the second step is wrapped in a fire resistant sheet made of ceramic fiber “Kao wool (registered trademark)”, and the fire resistant sheet containing the metal impregnated raw material activated carbon (L1) is commercially available. Place the powdered charcoal (particle size 500 μm) in a covered container (SiC crucible) with the bottom part, and fill the gap (around the refractory sheet) in the container with pulverized coal. After embedding in pulverized coal, the container was covered and the contact of the metal-impregnated raw material activated carbon (L1) with air (oxygen) was blocked. Subsequently, this container was accommodated in an electric muffle furnace and heat-treated at 950 ° C. for 36 hours in a reduced state.

＜実施例２＞ 第３工程において、金属含浸原料活性炭（Ｌ１）の処理時間を４８時間に延長したこと以外は実施例１と同様にして、加熱処理された活性炭を得た。 <Example 2> In the third step, heat-treated activated carbon was obtained in the same manner as in Example 1 except that the treatment time of the metal-impregnated raw material activated carbon (L1) was extended to 48 hours.

＜実施例３＞
塩化リチウム水溶液に代えて、硫酸チタン水溶液（１．０ｍｍｏｌ／Ｌ）６０ｍＬに原料活性炭（ａ）１０ｇを浸漬したこと以外は実施例１の第２工程と同様にして、チタンを含浸する金属含浸原料活性炭を得た。これを「金属含浸原料活性炭（Ｔ１）」とする。
次いで、金属含浸原料活性炭（Ｌ１）に代えて金属含浸原料活性炭（Ｔ１）を使用したこと以外は実施例１の第３工程と同様にして加熱処理（還元状態において９５０℃で３６時間の加熱処理）を行った。 <Example 3>
A metal-impregnated raw material impregnated with titanium in the same manner as in the second step of Example 1, except that 10 g of the raw material activated carbon (a) was immersed in 60 mL of an aqueous solution of titanium sulfate (1.0 mmol / L) instead of the aqueous lithium chloride solution. Activated carbon was obtained. This is referred to as “metal-impregnated raw material activated carbon (T1)”.
Subsequently, heat treatment (heat treatment at 950 ° C. for 36 hours in the reduced state) was performed in the same manner as in the third step of Example 1 except that the metal-impregnated raw material activated carbon (T1) was used instead of the metal-impregnated raw material activated carbon (L1). )

＜実施例４＞ 第３工程において、金属含浸原料活性炭（Ｔ１）の処理時間を４８時間に延長したこと以外は実施例３と同様にして、加熱処理された活性炭を得た。 <Example 4> In the third step, heat-treated activated carbon was obtained in the same manner as in Example 3 except that the treatment time of the metal-impregnated raw material activated carbon (T1) was extended to 48 hours.

＜実施例５＞
実施例１の第１工程と同様の処理により得られた活性炭（原料活性炭（ａ）に相当するもの）に対して、再度、過熱水蒸気による処理（７７５℃で２時間）を行った。
このようにして得られた活性炭について、ふるい分けにより粒径３００〜５００μｍの粒子を採取した。これを「原料活性炭（ｂ）」とする。
原料活性炭（ｂ）の比表面積は１０３６ｍ2 ／ｇ、細孔容積は０．８７ｃｍ3 ／ｇ、マイクロ孔（孔径≦２ｎｍ）の細孔容積は０．３０ｃｍ3 ／ｇであった。 <Example 5>
The activated carbon obtained by the same treatment as in the first step of Example 1 (corresponding to the raw material activated carbon (a)) was again treated with superheated steam (at 775 ° C. for 2 hours).
With respect to the activated carbon thus obtained, particles having a particle size of 300 to 500 μm were collected by sieving. This is referred to as “raw activated carbon (b)”.
The specific surface area of the raw material activated carbon (b) was 1036 m 2 / g, the pore volume was 0.87 cm 3 / g, and the pore volume of the micropores (pore diameter ≦ 2 nm) was 0.30 cm 3 / g.

原料活性炭（ａ）に代えて原料活性炭（ｂ）１０ｇを使用したこと以外は実施例１の第２工程と同様にして、リチウムを含浸する金属含浸原料活性炭を得た。これを「金属含浸原料活性炭（Ｌ２）」とする。
次いで、金属含浸原料活性炭（Ｌ１）に代えて金属含浸原料活性炭（Ｌ２）を使用したこと以外は実施例２の第３工程と同様にして加熱処理（還元状態において９５０℃で４８時間の加熱処理）を行った。 A metal-impregnated raw material activated carbon impregnated with lithium was obtained in the same manner as in the second step of Example 1, except that 10 g of the raw material activated carbon (b) was used instead of the raw material activated carbon (a). This is referred to as “metal-impregnated raw material activated carbon (L2)”.
Next, heat treatment was performed in the same manner as in the third step of Example 2 except that metal impregnated raw material activated carbon (L2) was used instead of metal impregnated raw material activated carbon (L1) (heat treatment at 950 ° C. for 48 hours in the reduced state). )

＜比較例１＞
実施例１の第１工程と同様の処理により活性炭（原料活性炭（ａ）に相当するもの）を製造した。
この比較例１は、金属の含浸処理および還元状態における加熱処理を行わない比較例である。 <Comparative Example 1>
Activated carbon (corresponding to the raw material activated carbon (a)) was produced by the same treatment as in the first step of Example 1.
Comparative Example 1 is a comparative example in which the metal impregnation treatment and the heat treatment in the reduced state are not performed.

＜比較例２＞
実施例１の第１工程と同様の処理により活性炭（原料活性炭（ａ）に相当するもの）を製造した。
次いで、金属含浸原料活性炭（Ｌ１）に代えて上記の活性炭を使用したこと以外は実施例１の第３工程と同様にして加熱処理（還元状態において９５０℃で３６時間の加熱処理）を行った。
この比較例２は、金属が含浸されていない活性炭を還元状態で加熱処理した比較例である。 <Comparative Example 2>
Activated carbon (corresponding to the raw material activated carbon (a)) was produced by the same treatment as in the first step of Example 1.
Next, heat treatment (heat treatment at 950 ° C. for 36 hours in a reduced state) was performed in the same manner as in the third step of Example 1 except that the above activated carbon was used instead of the metal-impregnated raw material activated carbon (L1). .
Comparative Example 2 is a comparative example in which activated carbon not impregnated with metal is heat-treated in a reduced state.

＜比較例３＞
活性炭（原料活性炭（ａ）に相当するもの）の加熱処理時間を４８時間に延長したこと以外は比較例２と同様にして、加熱処理された活性炭を得た。
この比較例３は、金属が含浸されていない活性炭を還元状態で加熱処理した比較例である。 <Comparative Example 3>
Heat-treated activated carbon was obtained in the same manner as in Comparative Example 2 except that the heat treatment time of activated carbon (corresponding to the raw material activated carbon (a)) was extended to 48 hours.
Comparative Example 3 is a comparative example in which activated carbon not impregnated with metal is heat-treated in a reduced state.

＜比較例４＞
硝酸リチウム水溶液（１．０ｍｍｏｌ／Ｌ）２Ｌに、７５０ｇのコーヒー粕を１週間浸漬することにより、コーヒー粕に硝酸リチウム水溶液を含浸させた。
次いで、硝酸リチウム水溶液を含浸しているコーヒー粕を、オートクレーブを使用して１２１℃で３０分間加熱蒸煮した後に天日乾燥し、更に乾燥機を使用して１２０℃で２４時間乾燥することにより、リチウムが含浸されているコーヒー粕を得た。これを「金属含浸コーヒー粕」とする。
次いで、金属含浸コーヒー粕７５０ｇを過熱水蒸気処理装置を用いて、５００℃で６０分間の炭化処理および７７５℃で２時間の過熱水蒸気による処理（過熱水蒸気の流量＝４０ｇ／分、二酸化炭素の流量＝１０Ｌ／分）を行うことにより、１００ｇの活性炭を得た。このようにして得られた活性炭について、電磁式ふるい振とう器により粒径ごとにふるい分けた。これを「原料活性炭（ｃ）」とする。この原料活性炭（ｃ）の比表面積は６７５ｍ2 ／ｇであった。
次いで、金属含浸原料活性炭（Ｌ１）に代えて上記の原料活性炭（ｃ）を使用したこと以外は実施例２の第３工程と同様にして加熱処理（還元状態において９５０℃で４８時間の加熱処理）を行った。
このようにして加熱処理された活性炭の比表面積は５２７ｍ2 ／ｇであった。
この比較例４は、多孔質有機材料の段階で金属を含浸させ、その後、炭化・賦活処理して得られた活性炭を加熱処理した比較例である。 <Comparative example 4>
By immersing 750 g of coffee candy in 2 L of an aqueous lithium nitrate solution (1.0 mmol / L) for 1 week, the coffee candy was impregnated with an aqueous lithium nitrate solution.
Next, the coffee cake impregnated with the aqueous lithium nitrate solution is heated and steamed at 121 ° C. for 30 minutes using an autoclave and then dried in the sun, and further dried at 120 ° C. for 24 hours using a dryer. A coffee cake impregnated with lithium was obtained. This is referred to as a “metal impregnated coffee bowl”.
Next, 750 g of metal-impregnated coffee cake was treated with carbonization for 60 minutes at 500 ° C. and with superheated steam for 2 hours at 775 ° C. using a superheated steam treatment apparatus (flow rate of superheated steam = 40 g / min, flow rate of carbon dioxide = 10 L / min), 100 g of activated carbon was obtained. The activated carbon thus obtained was sieved for each particle size using an electromagnetic sieve shaker. This is referred to as “raw activated carbon (c)”. The specific surface area of this raw material activated carbon (c) was 675 m 2 / g.
Next, heat treatment was performed in the same manner as in the third step of Example 2 except that the above-described raw material activated carbon (c) was used instead of the metal-impregnated raw material activated carbon (L1) (heat treatment at 950 ° C. for 48 hours in the reduced state). )
The specific surface area of the activated carbon thus heat-treated was 527 m 2 / g.
The comparative example 4 is a comparative example in which activated carbon obtained by impregnating a metal at the stage of the porous organic material and then carbonizing and activating is heat-treated.

実施例１〜５で得られた高比表面積活性炭および比較例１〜４で得られた活性炭の各々について、比表面積、細孔容積、マイクロ孔（孔径≦２ｎｍ）の細孔容積を測定した。結果を下記表１に示す。
また、実施例１、実施例２および比較例１に得られた活性炭の各々について、測定した細孔分布曲線を図１に示す。 For each of the high specific surface area activated carbon obtained in Examples 1 to 5 and the activated carbon obtained in Comparative Examples 1 to 4, the specific surface area, pore volume, and pore volume of micropores (pore diameter ≦ 2 nm) were measured. The results are shown in Table 1 below.
Moreover, the pore distribution curve measured about each of the activated carbon obtained in Example 1, Example 2, and Comparative Example 1 is shown in FIG.


Figure 2009292670
Figure 2009292670

表１に示すように、実施例１〜５で得られた高比表面積活性炭は、比表面積および細孔容積が高く、特に、マイクロ孔の細孔容積が高いものであり、金属含浸原料活性炭の加熱処理によれば、比表面積および細孔容積（特にマイクロ孔の細孔容積）が大幅に増大することが理解される。
また、図１に示された細孔分布曲線から、加熱処理（９５０℃×３６時間または４８時間）によってマイクロ孔の細孔容積が顕著に増加していることが認められる。 As shown in Table 1, the high specific surface area activated carbon obtained in Examples 1 to 5 has high specific surface area and fine pore volume, in particular, high micropore pore volume. It is understood that the heat treatment greatly increases the specific surface area and pore volume (especially the pore volume of micropores).
Further, from the pore distribution curve shown in FIG. 1, it is recognized that the pore volume of the micropores is remarkably increased by the heat treatment (950 ° C. × 36 hours or 48 hours).

これに対して、加熱処理がなされていない比較例１に係る活性炭は、比表面積および細孔容積が低い。
また、金属を含浸しない原料活性炭を加熱処理して得られた比較例２〜３に係る活性炭は、その比表面積および細孔容積が十分に高いものではなく、金属を含浸させない場合には、加熱処理しても、比表面積および細孔容積を十分に増大させることはできない。
また、金属含浸コーヒー粕を過熱水蒸気によって処理して得られる原料活性炭（ｃ）は比表面積および細孔容積が低く、更に、原料活性炭（ｃ）を加熱処理して得られた比較例４に係る活性炭は、加熱処理によって比表面積が減少している。 On the other hand, the activated carbon according to Comparative Example 1 that has not been heat-treated has a low specific surface area and pore volume.
Moreover, the activated carbon according to Comparative Examples 2 to 3 obtained by heat-treating the raw material activated carbon not impregnated with the metal is not sufficiently high in specific surface area and pore volume. Even if it processes, a specific surface area and a pore volume cannot fully be increased.
Further, the raw material activated carbon (c) obtained by treating the metal-impregnated coffee cake with superheated steam has a low specific surface area and pore volume, and further relates to Comparative Example 4 obtained by heat-treating the raw material activated carbon (c). The specific surface area of activated carbon is reduced by heat treatment.

実施例１、実施例２および比較例１で得られた活性炭の各々を吸着剤としたときの水素の吸着等温線（水素平衡圧力−水素吸蔵量）を測定した。結果を図２の（１）〜（３）に示す。また、活性炭の比表面積と、水素平衡圧力が１１ＭＰａであるときの水素吸蔵量との関係を図３に示す。
図２に示すように、実施例１および実施例２で得られた活性炭は、高圧条件（１１ＭＰａ）で高い水素吸蔵量の値を示し、低圧条件で水素を放出していることから、水素の吸着・脱着を繰り返して行うことが可能である。
また、図３に示すように、水素平衡圧力が１１ＭＰａであるときの水素吸蔵値量の値は、活性炭の比表面積に依存していることが確認された。 Hydrogen adsorption isotherms (hydrogen equilibrium pressure-hydrogen storage amount) were measured when each of the activated carbons obtained in Example 1, Example 2 and Comparative Example 1 was used as an adsorbent. The results are shown in (1) to (3) of FIG. FIG. 3 shows the relationship between the specific surface area of the activated carbon and the hydrogen storage amount when the hydrogen equilibrium pressure is 11 MPa.
As shown in FIG. 2, the activated carbon obtained in Example 1 and Example 2 shows a high hydrogen storage amount value under high pressure conditions (11 MPa), and releases hydrogen under low pressure conditions. It is possible to repeat adsorption and desorption.
Moreover, as shown in FIG. 3, it was confirmed that the value of the hydrogen storage value when the hydrogen equilibrium pressure is 11 MPa depends on the specific surface area of the activated carbon.

本発明の製造方法により得られる高比表面積活性炭は、比表面積および細孔容積が高く、特にマイクロ孔の細孔容積が高いという、優れた吸着特性を有するので、水素吸蔵材料、電気二重層コンデンサ材料、揮発性有機化合物（ＶＯＣ）等のガス吸着剤などの用途に好適に利用することができる。   The high specific surface area activated carbon obtained by the production method of the present invention has an excellent adsorption characteristic that the specific surface area and the pore volume are high, especially the micropore pore volume is high. Therefore, the hydrogen storage material, the electric double layer capacitor It can utilize suitably for uses, such as materials, gas adsorbents, such as a volatile organic compound (VOC).

実施例１、実施例２および比較例１に得られた活性炭の各々について測定した細孔分布曲線である。2 is a pore distribution curve measured for each of the activated carbons obtained in Example 1, Example 2 and Comparative Example 1. 実施例１、実施例２および比較例１で得られた活性炭の各々を吸着剤とする水素の吸着等温線である。2 is an adsorption isotherm of hydrogen using each of the activated carbons obtained in Example 1, Example 2 and Comparative Example 1 as an adsorbent. 活性炭の比表面積と、水素平衡圧力が１１ＭＰａであるときの水素吸蔵値量との関係を示す説明である。It is description which shows the relationship between the specific surface area of activated carbon, and the hydrogen storage value amount when hydrogen equilibrium pressure is 11 Mpa.

Claims (11)

多孔質有機材料または多孔質炭素材料を過熱水蒸気を用いて処理することにより、比表面積が４００ｍ2 ／ｇ以上の原料活性炭を製造する第１工程と、
得られた原料活性炭に、アルカリ金属（Ｌｉ，Ｎａ，Ｋ）、アルカリ土類金属（Ｍｇ，Ｃａ）および遷移金属（Ｔｉ，Ｆｅ，Ｃｏ，Ｎｉ，Ｍｏ，Ｐｔ）から選ばれた少なくとも１種の金属を含浸させて金属含浸原料活性炭を製造する第２工程と、
得られた金属含浸原料活性炭を、還元状態において９００〜１０００℃で加熱処理することにより、その比表面積を増大させる第３工程と
を含む高比表面積活性炭の製造方法。 A first step of producing a raw material activated carbon having a specific surface area of 400 m 2 / g or more by treating a porous organic material or a porous carbon material with superheated steam;
The obtained activated carbon is at least one selected from alkali metals (Li, Na, K), alkaline earth metals (Mg, Ca) and transition metals (Ti, Fe, Co, Ni, Mo, Pt). A second step of impregnating a metal to produce a metal-impregnated raw material activated carbon;
A method for producing a high specific surface area activated carbon comprising: a third step of increasing the specific surface area of the obtained metal-impregnated raw material activated carbon by heat treatment at 900 to 1000 ° C. in a reduced state. 第１工程において、過熱水蒸気とともに二酸化炭素を用いて処理する請求項１に記載の高比表面積活性炭の製造方法。   The manufacturing method of the high specific surface area activated carbon of Claim 1 processed in a 1st process using a carbon dioxide with superheated steam. 第１工程において、過熱水蒸気による処理を７００〜９５０℃で１時間以上行う請求項１または請求項２に記載の高比表面積活性炭の製造方法。   The manufacturing method of the high specific surface area activated carbon of Claim 1 or Claim 2 which performs a process by superheated steam at 700-950 degreeC for 1 hour or more in a 1st process. 第１工程において、過熱水蒸気による処理を、１回あたり１〜３時間で、２回以上繰り返して行う請求項１乃至３の何れかに記載の高比表面積活性炭の製造方法。   The method for producing a high specific surface area activated carbon according to any one of claims 1 to 3, wherein in the first step, the treatment with superheated steam is repeated twice or more for 1 to 3 hours per time. 第２工程において、金属としてＬｉおよび／またはＴｉを含浸させる請求項１乃至４の何れかに記載の高比表面積活性炭の製造方法。   The method for producing high specific surface area activated carbon according to any one of claims 1 to 4, wherein Li and / or Ti are impregnated as a metal in the second step. 第２工程において、原料活性炭に金属塩の水溶液を含浸させて乾燥する請求項１乃至５の何れかに記載の高比表面積活性炭の製造方法。   The method for producing high specific surface area activated carbon according to any one of claims 1 to 5, wherein, in the second step, the raw material activated carbon is impregnated with an aqueous solution of a metal salt and dried. 第３工程において、加熱処理を９２５〜９７５℃で３６時間以上行う請求項１乃至６の何れかに記載の高比表面積活性炭の製造方法。   The method for producing a high specific surface area activated carbon according to any one of claims 1 to 6, wherein in the third step, the heat treatment is performed at 925 to 975 ° C for 36 hours or more. アルカリ金属（Ｌｉ，Ｎａ，Ｋ）、アルカリ土類金属（Ｍｇ，Ｃａ）および遷移金属（Ｔｉ，Ｆｅ，Ｃｏ，Ｎｉ，Ｍｏ，Ｐｔ）から選ばれた少なくとも１種の金属を含浸する金属含浸原料活性炭を、還元状態において９００〜１０００℃で加熱処理する工程を含む高比表面積活性炭の製造方法。   Metal impregnation raw material impregnated with at least one metal selected from alkali metals (Li, Na, K), alkaline earth metals (Mg, Ca) and transition metals (Ti, Fe, Co, Ni, Mo, Pt) A method for producing high specific surface area activated carbon comprising a step of heat-treating activated carbon at 900 to 1000 ° C. in a reduced state. 請求項１乃至８の何れかの製造方法により得られる、比表面積が２０００ｍ2 ／ｇ以上の高比表面積活性炭。 A high specific surface area activated carbon having a specific surface area of 2000 m 2 / g or more, obtained by the production method according to claim 1. 請求項９に記載の高比表面積活性炭からなる水素吸蔵材料。   A hydrogen storage material comprising the high specific surface area activated carbon according to claim 9. 請求項９に記載の高比表面積活性炭からなる電気二重層コンデンサ材料。   An electric double layer capacitor material comprising the high specific surface area activated carbon according to claim 9.
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Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011046001A1 (en) * 2009-10-15 2011-04-21 Ｊｘ日鉱日石エネルギー株式会社 Hydrogen storage material
WO2011117657A3 (en) * 2010-03-26 2012-01-12 Shanghai Jiao Tong University Carbon materials comprising nano structures
WO2012070573A1 (en) * 2010-11-22 2012-05-31 Ｊｘ日鉱日石エネルギー株式会社 Composite container for storage of hydrogen, and hydrogen-filling method
JP2012106883A (en) * 2010-11-17 2012-06-07 Jx Nippon Oil & Energy Corp Hydrogen storage material
JP2012106179A (en) * 2010-11-17 2012-06-07 Jx Nippon Oil & Energy Corp Hydrogen storage material
CN102859625A (en) * 2010-04-21 2013-01-02 康宁股份有限公司 Electrochemical capacitor having lithium containing electrolyte
JP2013220963A (en) * 2012-04-13 2013-10-28 Toshinori Kokubu Functional ceramics and method for manufacturing the same
CN104108713A (en) * 2014-07-25 2014-10-22 哈尔滨工业大学深圳研究生院 Preparation methods and application of porous carbon from towel gourd vegetable sponge and composite material of porous carbon
CN105645408A (en) * 2016-03-09 2016-06-08 湘潭大学 Process using date pits to prepare nitrogen-doped porous carbon material and preparation method of super-capacitor electrode
CN105788885A (en) * 2016-03-09 2016-07-20 湘潭大学 Process for preparing camellia petal based sulfur and nitrogen co-doping draped nanosheet by explosion method and fabrication method of supercapacitor electrode
CN105788876A (en) * 2016-03-09 2016-07-20 湘潭大学 Process for preparing biomass porous nitrogen-doped carbon material and fabrication method of supercapacitor electrode
CN105958041A (en) * 2016-07-18 2016-09-21 扬州大学 Method for preparing hollow microporous carbon sphere coated nanometer sulfur molecular material
JP2017075068A (en) * 2015-10-14 2017-04-20 大阪ガスケミカル株式会社 Active carbon
CN108063057A (en) * 2017-12-28 2018-05-22 宁波中车新能源科技有限公司 A kind of preparation method of compound porous carbon material and its high-capacity super capacitor
KR101921694B1 (en) 2017-03-21 2018-11-26 한국기계연구원 Method for production of activated carbon structure using carbothermic reduction and the activated carbon structure
WO2019172225A1 (en) * 2018-03-07 2019-09-12 サンコール株式会社 Method for producing activated carbon
WO2019172226A1 (en) * 2018-03-07 2019-09-12 サンコール株式会社 Method for producing activated carbon
US10511029B2 (en) 2016-08-31 2019-12-17 Hyundai Motor Company Method for manufacturing catalyst support, catalyst support manufactured thereby, and catalyst for fuel cell including the same
CN111689494A (en) * 2020-06-23 2020-09-22 新疆大学 Non-corrosive catalyst and method for preparing activated carbon by catalytic activation
CN112919466A (en) * 2021-03-02 2021-06-08 北海艾米碳材料技术研发有限公司 Active carbon graphene modification method for preparing super capacitor
CN115282947A (en) * 2022-03-11 2022-11-04 常州大学 Method for preparing high-specific-surface-area metal/activated carbon composite material by using isosorbide residual tar

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104843803B (en) * 2015-04-09 2017-03-15 江西师范大学 A kind of method that Co3O4 spiral nanometer bands are prepared as template with three-dimensional porous mestha bar carbon

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0883736A (en) * 1994-09-09 1996-03-26 Nippon Sanso Kk Active carbon electrode of electronic double-layer capacitor and manufacture thereof
JPH08119614A (en) * 1994-10-18 1996-05-14 Mitsubishi Chem Corp Activated carbon, its production and electrode for electric-double-layer capacitor
JP2001122608A (en) * 1999-10-26 2001-05-08 Tokyo Gas Co Ltd Activated carbon controlled in fine pore structure and method of manufacturing the same
JP2002087808A (en) * 2000-09-14 2002-03-27 Showa Denko Kk Adsorbent for purifying perfluorocarbon, manufacturing method thereof, high purity octafluorocyclobutane, method of purifying and manufacturing the same and utilization thereof
JP2007320799A (en) * 2006-05-31 2007-12-13 Nippon Oil Corp Hydrogen occluding carbon
JP2008007387A (en) * 2006-06-30 2008-01-17 Kansai Coke & Chem Co Ltd Method and apparatus for highly purifying activated carbon

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0883736A (en) * 1994-09-09 1996-03-26 Nippon Sanso Kk Active carbon electrode of electronic double-layer capacitor and manufacture thereof
JPH08119614A (en) * 1994-10-18 1996-05-14 Mitsubishi Chem Corp Activated carbon, its production and electrode for electric-double-layer capacitor
JP2001122608A (en) * 1999-10-26 2001-05-08 Tokyo Gas Co Ltd Activated carbon controlled in fine pore structure and method of manufacturing the same
JP2002087808A (en) * 2000-09-14 2002-03-27 Showa Denko Kk Adsorbent for purifying perfluorocarbon, manufacturing method thereof, high purity octafluorocyclobutane, method of purifying and manufacturing the same and utilization thereof
JP2007320799A (en) * 2006-05-31 2007-12-13 Nippon Oil Corp Hydrogen occluding carbon
JP2008007387A (en) * 2006-06-30 2008-01-17 Kansai Coke & Chem Co Ltd Method and apparatus for highly purifying activated carbon

Cited By (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011084432A (en) * 2009-10-15 2011-04-28 Jx Nippon Oil & Energy Corp Hydrogen storage material
US8980788B2 (en) 2009-10-15 2015-03-17 Jx Nippon Oil & Energy Corporation Hydrogen storage material
WO2011046001A1 (en) * 2009-10-15 2011-04-21 Ｊｘ日鉱日石エネルギー株式会社 Hydrogen storage material
WO2011117657A3 (en) * 2010-03-26 2012-01-12 Shanghai Jiao Tong University Carbon materials comprising nano structures
CN102859625A (en) * 2010-04-21 2013-01-02 康宁股份有限公司 Electrochemical capacitor having lithium containing electrolyte
JP2012106883A (en) * 2010-11-17 2012-06-07 Jx Nippon Oil & Energy Corp Hydrogen storage material
JP2012106179A (en) * 2010-11-17 2012-06-07 Jx Nippon Oil & Energy Corp Hydrogen storage material
JP2012112409A (en) * 2010-11-22 2012-06-14 Jx Nippon Oil & Energy Corp Composite container for storage of hydrogen and hydrogen-filling method
WO2012070573A1 (en) * 2010-11-22 2012-05-31 Ｊｘ日鉱日石エネルギー株式会社 Composite container for storage of hydrogen, and hydrogen-filling method
JP2013220963A (en) * 2012-04-13 2013-10-28 Toshinori Kokubu Functional ceramics and method for manufacturing the same
CN104108713A (en) * 2014-07-25 2014-10-22 哈尔滨工业大学深圳研究生院 Preparation methods and application of porous carbon from towel gourd vegetable sponge and composite material of porous carbon
CN104108713B (en) * 2014-07-25 2016-04-27 哈尔滨工业大学深圳研究生院 A kind ofly come from the porous carbon of Vegetable Sponge of Luffa and the preparation method of matrix material thereof and application
JP2017075068A (en) * 2015-10-14 2017-04-20 大阪ガスケミカル株式会社 Active carbon
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JP2019156649A (en) * 2018-03-07 2019-09-19 サンコール株式会社 Manufacturing method of active charcoal
JP2019156650A (en) * 2018-03-07 2019-09-19 サンコール株式会社 Manufacturing method of active charcoal
WO2019172226A1 (en) * 2018-03-07 2019-09-12 サンコール株式会社 Method for producing activated carbon
WO2019172225A1 (en) * 2018-03-07 2019-09-12 サンコール株式会社 Method for producing activated carbon
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