JP5563239B2 - Method for producing porous carbon material - Google Patents

Method for producing porous carbon material Download PDF

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JP5563239B2
JP5563239B2 JP2009116941A JP2009116941A JP5563239B2 JP 5563239 B2 JP5563239 B2 JP 5563239B2 JP 2009116941 A JP2009116941 A JP 2009116941A JP 2009116941 A JP2009116941 A JP 2009116941A JP 5563239 B2 JP5563239 B2 JP 5563239B2
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porous carbon
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尚一 竹中
純一 安丸
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Kansai Coke and Chemicals 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
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    • Y02E60/13—Energy storage using capacitors

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Description

本発明は多孔質炭素材料の製造方法に関するものであり、特に高比表面積化を達成し、かつ、細孔径を制御することができる多孔質炭素材料の製造方法に関するものである。   The present invention relates to a method for producing a porous carbon material, and more particularly to a method for producing a porous carbon material capable of achieving a high specific surface area and controlling the pore diameter.

従来、多孔質炭素材料、特に活性炭はその優れた吸着能から電気二重層キャパシタ用電極や吸着剤として広く使用されている。このような用途で効果的に機能するために、活性炭には高比表面積、かつ、適切な細孔径を有することが要求される。   Conventionally, porous carbon materials, particularly activated carbon, have been widely used as electrodes and adsorbents for electric double layer capacitors because of their excellent adsorption ability. In order to function effectively in such applications, activated carbon is required to have a high specific surface area and an appropriate pore size.

そして、多孔質炭素材料の製造方法は種々提案されており、例えば、特許文献１には、１）炭化処理した活性炭材料を一次賦活する工程、２）９０％以上の粒子が０．２５ｍｍ以下の粒径となるように一次賦活後の当該材料を細粒化する工程、及び３）当該細粒粒子を二次賦活する工程、を含んで成ること特徴とする蓄電デバイス電極用炭素材料の製造方法が開示されている。   Various methods for producing a porous carbon material have been proposed. For example, in Patent Document 1, 1) a step of primary activation of a carbonized carbon material, and 2) 90% or more of particles are 0.25 mm or less. A method for producing a carbon material for an electricity storage device electrode, comprising: a step of finely pulverizing the material after primary activation so as to have a particle size; and 3) a step of secondary activating the fine particle Is disclosed.

特許文献２には、既知の電気二重層用活性炭（通常の水蒸気賦活あるいはＫＯＨ賦活法等による）を金属塩共存下で、炭酸ガス雰囲気中７００〜１０００℃で加熱して改質することを特徴とする電気二重層キャパシタ用活性炭の改質方法が開示されている。   Patent Document 2 is characterized in that a known activated carbon for electric double layer (by a normal steam activation or KOH activation method) is modified by heating at 700 to 1000 ° C. in a carbon dioxide atmosphere in the presence of a metal salt. A method for modifying activated carbon for electric double layer capacitors is disclosed.

特許文献３には、炭素化合物を炭化処理して得た炭化物を活性化処理した後に粉砕して活性炭基材とし、該活性炭基材にバインダーを加え板状に成形して成形体とし、該成形体を炭化処理して板状活性炭を製造する方法において、前記活性炭基材の平均粒径が１０μｍ以下であることを特徴とする電気二重層コンデンサー用活性炭電極の製造方法が開示されている。   In Patent Document 3, a carbide obtained by carbonizing a carbon compound is activated and then pulverized to obtain an activated carbon base material, and a binder is added to the activated carbon base material to form a plate to obtain a molded body. In a method for producing plate-like activated carbon by carbonizing a body, a method for producing an activated carbon electrode for an electric double layer capacitor is disclosed, wherein the activated carbon substrate has an average particle size of 10 μm or less.

特許文献４には、賦活状態にある炭素質材料および／または賦活処理が施された炭素質材料を黒鉛化したのち、さらにこの黒鉛化物に対して賦活処理を施すことを特徴とする、導電性多孔質炭素材の製造方法が開示されている。   Patent Document 4 discloses a conductive material characterized by graphitizing a carbonaceous material in an activated state and / or a carbonaceous material subjected to activation treatment, and further subjecting the graphitized material to activation treatment. A method for producing a porous carbon material is disclosed.

特開２００８−２７０４２７号公報JP 2008-270427 A 特開２００３−３０９０４６号公報JP 2003-309046 A 特開平８−１１５８５６号公報JP-A-8-115856 特開平５−１３９７１２号公報JP-A-5-139712

従来、多孔質炭素材料の製造に用いられている水蒸気賦活法では、水蒸気による炭素質の分解により多孔質化が行われるため、賦活反応が進行するにつれて比表面積、細孔径が共に大きくなる。このような大きな細孔径を有する多孔質炭素材料は、吸着物質の移動抵抗が小さいといった利点がある。しかしながら、吸着物質の分子サイズや電解液中のイオンサイズによって、多孔質炭素材料に求められる細孔径が異なる。そのため、単に高比表面積化を達成するだけでなく、形成される細孔径を制御することができれば、要求に応じた多孔質炭素材料の製造が容易になる。   Conventionally, in the steam activation method used for the production of porous carbon materials, the carbonaceous material is decomposed by water vapor, so that the specific surface area and the pore diameter are increased as the activation reaction proceeds. The porous carbon material having such a large pore diameter has an advantage that the migration resistance of the adsorbent is small. However, the pore diameter required for the porous carbon material differs depending on the molecular size of the adsorbent and the ion size in the electrolytic solution. Therefore, if it is possible not only to achieve a high specific surface area but also to control the pore diameter to be formed, it becomes easy to produce a porous carbon material according to requirements.

本発明は上記事情に鑑みてなされたものであって、高比表面積化を達成し、かつ、細孔径を制御することができる多孔質炭素材料の製造方法を提供することを目的とする。   This invention is made | formed in view of the said situation, Comprising: It aims at providing the manufacturing method of the porous carbon material which can achieve high specific surface area and can control a pore diameter.

上記課題を解決することができた本発明の多孔質炭素材料の製造方法は、炭素原料をガス賦活することにより多孔質炭素材料を製造する方法であって、前記ガス賦活処理中に、一時的に炉内の賦活ガスを不活性ガスで置換する操作を挟むことを特徴とする。具体的には、本発明の製造方法は、炉に炭素原料を収容し、炉内を加熱する昇温工程；加熱された炉内に、賦活ガスを供給する第１賦活工程；第１賦活工程後、炉内を加熱したまま賦活ガスを不活性ガスに置換する置換工程；及び、前記置換工程後、炉内を加熱したまま再び炉内に賦活ガスを供給する第２賦活工程；を含むことを特徴とする。前記置換工程においては、炉の容積に対して、体積比で２倍〜１００倍の不活性ガスを流入させることが好ましい。   The method for producing a porous carbon material of the present invention that has solved the above-described problem is a method for producing a porous carbon material by gas activating a carbon raw material, and temporarily during the gas activation treatment. An operation for replacing the activation gas in the furnace with an inert gas is sandwiched between the two. Specifically, the production method of the present invention includes a temperature raising step of storing a carbon raw material in a furnace and heating the inside of the furnace; a first activation step of supplying an activation gas into the heated furnace; a first activation step Thereafter, a replacement step of replacing the activation gas with an inert gas while the inside of the furnace is heated; and a second activation step of supplying the activation gas into the furnace again while the inside of the furnace is heated after the replacement step; It is characterized by. In the replacement step, it is preferable to introduce an inert gas having a volume ratio of 2 to 100 times the volume of the furnace.

本発明には、前記製造方法により得られた多孔質炭素材料を含有する電気二重層キャパシタ用電極および該電気二重層キャパシタ用電極を用いた電気二重層キャパシタ、並びに、前記製造方法により得られた多孔質炭素材料を含有する吸着剤も包含される。   In the present invention, an electric double layer capacitor electrode containing the porous carbon material obtained by the production method, an electric double layer capacitor using the electric double layer capacitor electrode, and the production method obtained Adsorbents containing porous carbon materials are also included.

本発明によれば、得られる多孔質炭素材料の高比表面積化を達成し、かつ、形成される細孔径を制御することができる。   ADVANTAGE OF THE INVENTION According to this invention, the high specific surface area increase of the porous carbon material obtained can be achieved, and the pore diameter formed can be controlled.

製造例１，２，５で得られた多孔質炭素材料の細孔径分布を示す図である。It is a figure which shows the pore diameter distribution of the porous carbon material obtained by manufacture example 1,2,5.

本発明の多孔質炭素材料の製造方法は、炭素原料をガス賦活することにより多孔質炭素材料を製造する方法であって、前記ガス賦活処理中に、一時的に炉内の賦活ガスを不活性ガスで置換する操作を挟むことを特徴とする。   The method for producing a porous carbon material of the present invention is a method for producing a porous carbon material by gas activating a carbon raw material, wherein the activation gas in the furnace is temporarily deactivated during the gas activation treatment. It is characterized by sandwiching an operation of replacing with gas.

ガス賦活処理中に不活性ガスで置換する操作を挟むことにより、得られる多孔質炭素材料の細孔径を制御することができる理由は必ずしも明らかでないが、以下のように考えることができる。すなわち、１段階賦活処理では、賦活が進行するにつれて、形成された細孔内部に賦活ガスによる炭素質の分解によって生じたＣＯ、ＣＯ2などのガスが充満し、細孔深部に賦活ガスが接触しづらくなる。そのため、１段階賦活処理では、賦活が進行するにつれて、細孔径を増大させる方向（径方向）に賦活反応が進行してしまう。これに対して、本発明製法のようにガス賦活処理中に不活性ガスで置換する操作を挟んだ多段階賦活処理では、賦活が進行するにつれて細孔内部に充満したＣＯ、ＣＯ2などのガスが置換工程において除去される。従って、置換工程後に行われる賦活処理は、細孔内部に発生ガスがない状態から開始されるため、細孔深部に賦活ガスが到達しやすくなり、細孔の深さ方向へと賦活反応が進行する。そのため、本発明製法では、賦活反応が細孔の深さ方法へと進行しやすくなり、細孔径の増大を抑制することができると考えられる。 The reason why the pore diameter of the obtained porous carbon material can be controlled by inserting an operation of substituting with an inert gas during the gas activation treatment is not necessarily clear, but can be considered as follows. That is, in the one-step activation process, as the activation proceeds, the formed pores are filled with gases such as CO and CO 2 generated by the decomposition of the carbonaceous material by the activation gas, and the activation gas contacts deep pores. It becomes difficult. Therefore, in the one-step activation process, the activation reaction proceeds in the direction (diameter direction) in which the pore diameter is increased as the activation proceeds. On the other hand, in the multi-stage activation process with an operation of replacing with an inert gas during the gas activation process as in the production method of the present invention, the gas such as CO and CO 2 filled in the pores as the activation proceeds. Are removed in the replacement step. Therefore, since the activation process performed after the replacement step is started from a state in which no generated gas is present inside the pores, the activation gas easily reaches the deep pores, and the activation reaction proceeds in the depth direction of the pores. To do. For this reason, in the production method of the present invention, it is considered that the activation reaction easily proceeds to the pore depth method, and the increase in the pore diameter can be suppressed.

本発明の製造方法は、具体的には、炉に炭素原料を収容し、炉内を加熱する昇温工程；加熱された炉内に、賦活ガスを供給する第１賦活工程；第１賦活工程後、炉内を加熱したまま賦活ガスを不活性ガスに置換する置換工程；及び、前記置換工程後、炉内を加熱したまま再び炉内に賦活ガスを供給する第２賦活工程；を含むことを特徴とする。   Specifically, the production method of the present invention includes a temperature raising step of storing a carbon raw material in a furnace and heating the inside of the furnace; a first activation step of supplying an activation gas into the heated furnace; a first activation step Thereafter, a replacement step of replacing the activation gas with an inert gas while the inside of the furnace is heated; and a second activation step of supplying the activation gas into the furnace again while the inside of the furnace is heated after the replacement step; It is characterized by.

以下、本発明の多孔質炭素材料の製造方法について詳しく説明する。   Hereinafter, the manufacturing method of the porous carbon material of this invention is demonstrated in detail.

前記昇温工程は、炉に炭素原料を収容し、炉内を加熱する工程である。なお、本工程には、常温の炉内に炭素原料を収容した後、炉内を加熱する態様；予め加熱しておいた炉内に炭素原料を収容した後、引き続き炉内を加熱する態様；いずれも含まれる。本発明の製造方法に用いられる炉としては、ロータリーキルン、流動床炉、撹拌混合炉などの原料を均質に加熱できる装置などが挙げられる。   The temperature raising step is a step of storing the carbon raw material in a furnace and heating the inside of the furnace. In this step, after the carbon raw material is stored in a furnace at room temperature, the furnace is heated; after the carbon raw material is stored in a preheated furnace, the furnace is subsequently heated; Both are included. Examples of the furnace used in the production method of the present invention include apparatuses that can uniformly heat raw materials such as a rotary kiln, a fluidized bed furnace, and a stirring and mixing furnace.

本発明に用いられる炭素原料としては、炭素質物質の炭化物を用いることができる。前記炭素質物質としては、例えば、ヤシガラ、木材、おが屑、木炭、セルロース系繊維、合成樹脂（例えば、フェノール樹脂、フラン樹脂）などの難黒鉛化性炭素；ピッチ（例えば、メソフェーズピッチ）、コークス（例えば、ピッチコークス、ニードルコークス、フリュードコークス）、ポリ塩化ビニル、ポリイミド、ポリアクリルニトリル（ＰＡＮ）などの易黒鉛化性炭素；およびこれらの混合物が挙げられる。これらの炭素質物質は、単独で使用してもよいし、２種以上を併用してもよい。これらの中でも、ヤシガラ、フェノール樹脂などの難黒鉛化性炭素が好適である。ここで、「難黒鉛化性炭素」とは、熱処理によっても黒鉛構造に至らない非晶質炭素をいい、「易黒鉛化性炭素」とは、絶対温度が３３００Ｋ前後の高温処理により黒鉛に変換できる非晶質炭素をいう。   As the carbon raw material used in the present invention, a carbonaceous material carbide can be used. Examples of the carbonaceous material include non-graphitizable carbon such as coconut shell, wood, sawdust, charcoal, cellulosic fiber, synthetic resin (eg, phenol resin, furan resin); pitch (eg, mesophase pitch), coke ( Examples thereof include graphitizable carbon such as pitch coke, needle coke, and fluid coke), polyvinyl chloride, polyimide, polyacrylonitrile (PAN); and mixtures thereof. These carbonaceous materials may be used alone or in combination of two or more. Among these, non-graphitizable carbon such as coconut shell and phenol resin is preferable. Here, “non-graphitizable carbon” refers to amorphous carbon that does not reach a graphite structure even by heat treatment. “Graphitizable carbon” is converted to graphite by high-temperature treatment at an absolute temperature of about 3300K. This refers to amorphous carbon that can be produced.

なお、前記炭素質物質の炭化処理は、通常、不活性ガス雰囲気下で加熱処理することによりなされる。該炭化処理の温度は、５００℃以上が好ましく、より好ましくは５５０℃以上であり、８５０℃以下が好ましく、より好ましくは８００℃以下である。   The carbonaceous material is usually carbonized by heat treatment in an inert gas atmosphere. The carbonization temperature is preferably 500 ° C. or higher, more preferably 550 ° C. or higher, preferably 850 ° C. or lower, more preferably 800 ° C. or lower.

炭素原料の平均粒子径は１μｍ以上が好ましく、より好ましくは３μｍ以上、さらに好ましくは５μｍ以上であり、１０ｃｍ以下が好ましく、より好ましくは７ｃｍ以下、さらに好ましくは５ｃｍ以下である。ここで、本願において平均粒子径とは、水に分散させた試料を、レーザ回折式粒度分布測定装置（例えば、島津製作所製の「ＳＡＬＤ（登録商標）−２０００」）により測定して、求められる体積平均粒子径である。なお、炭素原料の平均粒子径は粉砕により調整すればよい。また、炭素原料の平均粒子径が２００μｍ以上の場合は、篩を用いて整粒すればよい。   The average particle diameter of the carbon raw material is preferably 1 μm or more, more preferably 3 μm or more, further preferably 5 μm or more, preferably 10 cm or less, more preferably 7 cm or less, and further preferably 5 cm or less. Here, in the present application, the average particle size is obtained by measuring a sample dispersed in water with a laser diffraction particle size distribution measuring device (for example, “SALD (registered trademark) -2000” manufactured by Shimadzu Corporation). Volume average particle size. The average particle size of the carbon raw material may be adjusted by pulverization. Moreover, what is necessary is just to size-size using a sieve, when the average particle diameter of a carbon raw material is 200 micrometers or more.

炉内を加熱する際には、不活性ガスを流入させる。不活性ガスの流入量は、炉の容積や炭素原料の仕込み量に応じて適宜調整すればよいが、通常、炉の容積に対する空間速度（ＳＶ）を０．０１Ｌ／Ｌ／分以上１．０Ｌ／Ｌ／分以下とすることが好ましい。なお、不活性ガスとしては、窒素、アルゴン、ヘリウムなどを用いることができる。炉を加熱する際の昇温速度は、１℃／分以上が好ましく、より好ましくは５℃／分以上である。なお、昇温速度の上限は特になく、予め加熱した炉に炭素原料を投入してもよい。   When the inside of the furnace is heated, an inert gas is introduced. The inflow amount of the inert gas may be appropriately adjusted according to the furnace volume and the amount of the carbon raw material charged. Usually, the space velocity (SV) with respect to the furnace volume is 0.01 L / L / min or more and 1.0 L. / L / min or less is preferable. Note that nitrogen, argon, helium, or the like can be used as the inert gas. The heating rate when heating the furnace is preferably 1 ° C./min or more, more preferably 5 ° C./min or more. There is no particular upper limit on the rate of temperature increase, and the carbon raw material may be charged into a preheated furnace.

前記第１賦活工程は、加熱された炉内に賦活ガスを供給することにより、炭素原料に賦活処理を行う工程である。ここで、「賦活処理」とは、固体残渣の表面に細孔を形成して、比表面積および細孔容積を大きくする処理である。本発明製法において賦活ガスとしては、水蒸気、空気、炭酸ガス、酸素、燃焼ガスおよびこれらの混合ガスを用いることができる。これらの中でも、低コストであり、賦活に対して高い反応性を有することから、賦活ガスとしては水蒸気が好適である。賦活ガスを供給する態様としては、賦活ガスを希釈せずに供給する態様、賦活ガスを不活性ガスで希釈して供給する態様のいずれも可能であるが、賦活反応を効率良く進行させるために、不活性ガスで希釈して供給する態様が好ましい。   The first activation step is a step of performing activation treatment on the carbon raw material by supplying an activation gas into the heated furnace. Here, the “activation process” is a process for forming pores on the surface of the solid residue to increase the specific surface area and the pore volume. In the production method of the present invention, water vapor, air, carbon dioxide gas, oxygen, combustion gas, and a mixed gas thereof can be used as the activation gas. Among these, water vapor is suitable as the activation gas because it is low-cost and has high reactivity with respect to activation. As an aspect for supplying the activation gas, either an aspect in which the activation gas is supplied without dilution or an aspect in which the activation gas is diluted with an inert gas and supplied is possible, but in order to advance the activation reaction efficiently. A preferred mode is one that is diluted with an inert gas and supplied.

第１賦活工程において供給する賦活ガスの総量は、炭素原料１００質量部に対して、５０質量部以上とすることが好ましく、より好ましくは１００質量部以上、さらに好ましくは２００質量部以上であり、１００００質量部以下とすることが好ましく、より好ましくは５０００質量部以下、さらに好ましくは３０００質量部以下である。供給する賦活ガスの総量が炭素原料１００質量部に対して５０質量部以上であれば、賦活反応による細孔形成がより良好となり、１００００質量部以下であれば、賦活反応がより効率良く進行し、生産性を向上できる。   The total amount of activation gas supplied in the first activation step is preferably 50 parts by mass or more, more preferably 100 parts by mass or more, further preferably 200 parts by mass or more, with respect to 100 parts by mass of the carbon raw material. The amount is preferably 10,000 parts by mass or less, more preferably 5000 parts by mass or less, and still more preferably 3000 parts by mass or less. If the total amount of activation gas to be supplied is 50 parts by mass or more with respect to 100 parts by mass of the carbon raw material, pore formation by the activation reaction becomes better, and if it is 10000 parts by mass or less, the activation reaction proceeds more efficiently. , Improve productivity.

賦活処理を行う際の温度（炉内温度）は４００℃以上が好ましく、より好ましくは４５０℃以上であり、１５００℃以下が好ましく、より好ましくは１３００℃以下である。また、賦活処理を行う際の加熱時間は０．１時間以上が好ましく、より好ましくは０．５時間以上であり、５０時間以下が好ましく、より好ましくは３０時間以下である。なお、賦活ガスの供給方法の好適態様、ならびに供給される賦活ガスの総量、賦活温度および賦活時間の好適範囲は、所望する多孔質炭素材料の物性に応じて適宜変更すればよい。   The temperature at the time of activation treatment (furnace temperature) is preferably 400 ° C. or higher, more preferably 450 ° C. or higher, preferably 1500 ° C. or lower, more preferably 1300 ° C. or lower. In addition, the heating time in performing the activation treatment is preferably 0.1 hour or longer, more preferably 0.5 hour or longer, 50 hours or shorter, more preferably 30 hours or shorter. In addition, what is necessary is just to change suitably the suitable aspect of the supply method of activation gas, and the suitable range of the total amount of activation gas supplied, activation temperature, and activation time according to the physical property of the desired porous carbon material.

前記置換工程は、第１賦活工程後、炉内を加熱したまま炉内の賦活ガスを不活性ガスに置換する工程である。置換工程は、第１賦活工程後、炉内温度を常温まで冷却したり、第１賦活工程を経た炭素原料を炉から取り出したりすることなく、第１賦活工程に連続して行われる。   The replacement step is a step of replacing the activation gas in the furnace with an inert gas while the inside of the furnace is heated after the first activation step. After the first activation step, the replacement step is performed continuously to the first activation step without cooling the furnace temperature to room temperature or taking out the carbon raw material that has passed through the first activation step from the furnace.

置換工程において、炉内に流入させる不活性ガスの総量（体積）は、炉の容積に対して２倍以上とすることが好ましく、より好ましくは３倍以上、さらに好ましくは４倍以上であり、１００倍以下とすることが好ましく、より好ましくは８０倍以下、さらに好ましくは５０倍以下である。流入させる不活性ガスの総量を炉の容積に対して２倍以上とすることにより、炉内を十分に不活性ガスに置換することができ、細孔径増大の抑制効果がより向上し、１００倍以下とすることにより、置換工程の作業時間を短縮することができ、生産性がより高くなる。なお、不活性ガスの体積とは、流入する炉内温度における体積である。   In the replacement step, the total amount (volume) of the inert gas that flows into the furnace is preferably at least twice the volume of the furnace, more preferably at least three times, even more preferably at least four times, It is preferably 100 times or less, more preferably 80 times or less, and still more preferably 50 times or less. By making the total amount of the inert gas to flow into more than twice the volume of the furnace, the inside of the furnace can be sufficiently replaced with the inert gas, and the effect of suppressing the increase in pore diameter is further improved. By making it below, the work time of the replacement process can be shortened, and the productivity becomes higher. The volume of the inert gas is the volume at the in-furnace temperature.

不活性ガスによる置換を行う際の温度（炉内温度）は４００℃以上が好ましく、より好ましくは４５０℃以上であり、１５００℃以下が好ましく、より好ましくは１３００℃以下である。なお、作業を簡便にする観点から、置換を行う際の温度は、前記第１賦活工程における賦活処理温度と同じ温度とすることが好ましい。   The temperature (furnace temperature) at the time of substitution with an inert gas is preferably 400 ° C or higher, more preferably 450 ° C or higher, preferably 1500 ° C or lower, more preferably 1300 ° C or lower. In addition, from the viewpoint of simplifying the work, it is preferable that the temperature at the time of replacement is the same as the activation treatment temperature in the first activation step.

前記第２賦活工程は、前記置換工程後、炉内を加熱したまま再び炉内に賦活ガスを供給することにより、炭素原料に賦活処理を行う工程である。第２賦活工程は、置換工程後、連続して行われる。   The second activation step is a step of performing an activation process on the carbon raw material by supplying an activation gas into the furnace again while the inside of the furnace is heated after the replacement step. The second activation process is performed continuously after the replacement process.

第２賦活工程における賦活ガスの供給方法の好適態様、ならびに供給される賦活ガスの総量、賦活温度および賦活時間の好適範囲は、前記第１賦活工程と同様であり、所望する多孔質炭素材料の物性に応じて適宜変更すればよい。第２賦活工程における賦活温度は、第１賦活工程における賦活温度と同一でも異なっていてもよい。なお、より作業性を向上させるために、第１賦活工程における賦活温度、置換工程における置換する際の温度、第２賦活工程における賦活温度を一定にすることが好ましい。   The preferred embodiment of the supply method of the activation gas in the second activation step and the preferred range of the total amount of activation gas to be supplied, the activation temperature and the activation time are the same as those in the first activation step, and the desired porous carbon material What is necessary is just to change suitably according to a physical property. The activation temperature in the second activation step may be the same as or different from the activation temperature in the first activation step. In addition, in order to improve workability | operativity more, it is preferable to make constant the activation temperature in a 1st activation process, the temperature at the time of substitution in a substitution process, and the activation temperature in a 2nd activation process.

本発明の製造方法は、少なくとも昇温工程、第１賦活工程、置換工程および第２賦活工程を含むが、置換工程と賦活工程を一対とする操作を、さらに一対以上繰り返し行ってもよい。置換工程を挟んで、賦活工程を繰返し行うことにより、得られる多孔質炭素材料の平均細孔径の増大を抑制しつつ、さらなる高比表面積化を図ることができる。繰返し行われる置換工程および賦活工程における置換条件および賦活条件は、前記条件と同様である。   The production method of the present invention includes at least a temperature raising step, a first activation step, a substitution step, and a second activation step, but the operation of pairing the substitution step and the activation step may be repeated one or more pairs. By repeating the activation process with the replacement process in between, it is possible to further increase the specific surface area while suppressing an increase in the average pore diameter of the obtained porous carbon material. Substitution conditions and activation conditions in repeated substitution steps and activation steps are the same as those described above.

なお、置換工程および賦活工程を繰り返す回数は、特に制限されないが、繰返し回数を増加させると作業が煩雑になる。そのため、本発明の製造方法は、第１賦活工程、置換工程および第２賦活工程を含む態様；第１賦活工程、第１置換工程、第２賦活工程、第２置換工程および第３賦活工程を含む態様；が好適である。   In addition, the number of times of repeating the replacement step and the activation step is not particularly limited, but the work becomes complicated when the number of repetitions is increased. Therefore, the manufacturing method of the present invention includes an aspect including a first activation process, a replacement process, and a second activation process; a first activation process, a first replacement process, a second activation process, a second replacement process, and a third activation process. Including embodiments are preferred.

本発明の製造方法には、前記賦活工程および置換工程に加えて、洗浄工程、熱処理工程、粉砕工程を含ませてもよい。   The production method of the present invention may include a washing step, a heat treatment step, and a pulverization step in addition to the activation step and the replacement step.

洗浄工程では、賦活工程後の多孔質炭素材料を洗浄し、乾燥させる。洗浄に用いる溶媒としては、水、酸、有機溶剤などが挙げられる。多孔質炭素材料を洗浄することにより、金属不純物、灰分、有機溶剤可溶成分などを除去することができる。   In the washing step, the porous carbon material after the activation step is washed and dried. Examples of the solvent used for washing include water, an acid, and an organic solvent. By washing the porous carbon material, metal impurities, ash, organic solvent soluble components, and the like can be removed.

熱処理工程では、賦活工程後あるいは洗浄工程後の多孔質炭素材料を、さらに不活性ガス雰囲気下で熱処理する。多孔質炭素材料を熱処理することにより、多孔質炭素材料の表面の官能基量を調整することができる。   In the heat treatment step, the porous carbon material after the activation step or the cleaning step is further heat-treated in an inert gas atmosphere. By heat-treating the porous carbon material, the amount of functional groups on the surface of the porous carbon material can be adjusted.

粉砕工程では、多孔質炭素材料の粒径を調整する。多孔質炭素材料の粉砕方法は、特に限定されるものでなく、ディスクミル、ボールミル、ビーズミルなどを用いて行えばよい。なお、多孔質炭素材料の粒子径は、用途に応じて適宜調整すればよい。   In the pulverization step, the particle size of the porous carbon material is adjusted. The method for pulverizing the porous carbon material is not particularly limited, and may be performed using a disk mill, a ball mill, a bead mill, or the like. In addition, what is necessary is just to adjust the particle diameter of a porous carbon material suitably according to a use.

本発明の製造方法によれば、高比表面積を有するにもかかわらず、細孔径の小さい多孔質炭素材料が得られる。具体的には、例えば、炭素原料として、炭化ヤシガラを用いた場合、比表面積が１０００ｍ2／ｇ〜２０００ｍ2／ｇであり、平均細孔径が１．４０ｎｍ〜１．６５ｎｍである多孔質炭素材料；炭素原料として、炭化フェノール樹脂を用いた場合には、比表面積が１０００ｍ2／ｇ〜２０００ｍ2／ｇであり、平均細孔径が１．５０ｎｍ〜２．００ｎｍである多孔質炭素材料が得られる。 According to the production method of the present invention, a porous carbon material having a small pore diameter can be obtained despite having a high specific surface area. Specifically, for example, as a carbon raw material, the use of carbonized coconut shell, specific surface area of 1000m 2 / g~2000m 2 / g, the porous carbon material average pore diameter of 1.40nm~1.65nm ; as the carbon material, when a carbonized phenolic resin is a specific surface area of 1000m 2 / g~2000m 2 / g, the porous carbon material average pore diameter of 1.50nm~2.00nm obtain .

本発明の製造方法により得られる多孔質炭素材料は、電気二重層キャパシタ用電極材料として用いることができ、当該電極材料を使用して、電気二重層キャパシタ用電極や電気二重層キャパシタを製造することが可能である。本発明の製造方法によれば、多孔質炭素材料の高比表面積化を図りつつ形成される細孔径を制御することができる。換言すれば、所望の細孔径を維持したまま、さらなる高比表面積化が可能となる。従って、電解液中のイオンサイズに適した細孔径を有する細孔を形成しつつ、さらなる高比表面積化が可能となる。そのため、本発明の製造方法により得られた多孔質炭素材料を電気二重層キャパシタに用いることにより、静電容量に優れる電気二重層キャパシタが得られる。   The porous carbon material obtained by the production method of the present invention can be used as an electrode material for an electric double layer capacitor, and an electrode for an electric double layer capacitor or an electric double layer capacitor is produced using the electrode material. Is possible. According to the production method of the present invention, the pore diameter formed while increasing the specific surface area of the porous carbon material can be controlled. In other words, it is possible to further increase the specific surface area while maintaining the desired pore diameter. Therefore, it is possible to further increase the specific surface area while forming pores having a pore diameter suitable for the ion size in the electrolytic solution. Therefore, by using the porous carbon material obtained by the production method of the present invention for an electric double layer capacitor, an electric double layer capacitor having excellent capacitance can be obtained.

次に、本発明の電気二重層キャパシタについて説明する。本発明の電気二重層キャパシタは、前記の製造方法により得られた多孔質炭素材料を用いたことを特徴とする。   Next, the electric double layer capacitor of the present invention will be described. The electric double layer capacitor of the present invention is characterized by using the porous carbon material obtained by the above production method.

電気二重層キャパシタ用電極としては、例えば、多孔質炭素材料、導電性付与剤、およびバインダーを混練し、さらに溶媒を添加してペーストを調製し、このペーストをアルミ箔などの集電板に塗布した後、溶媒を乾燥除去したものが挙げられる。   As an electrode for an electric double layer capacitor, for example, a porous carbon material, a conductivity imparting agent, and a binder are kneaded, a solvent is added to prepare a paste, and this paste is applied to a current collector plate such as an aluminum foil Then, the solvent is removed by drying.

前記電気二重層キャパシタ用電極に使用されるバインダーとしては、ポリテトラフルオロエチレン、ポリフッ化ビニリデンなどのフッ素系高分子化合物や、カルボキシメチルセルロース、スチレン−ブタジエンゴム、石油ピッチ、フェノール樹脂などを使用できる。また、導電性付与剤としては、アセチレンブラック、ケッチェンブラックなどを使用できる。   As the binder used for the electrode for the electric double layer capacitor, fluorine-based polymer compounds such as polytetrafluoroethylene and polyvinylidene fluoride, carboxymethyl cellulose, styrene-butadiene rubber, petroleum pitch, phenol resin, and the like can be used. As the conductivity imparting agent, acetylene black, ketjen black, or the like can be used.

電気二重層キャパシタは、一般的には、電極、電解液、およびセパレータを主要構成とし、一対の電極間にセパレータを配置した構造となっている。前記電解液としては、例えば、プロピレンカーボネート、エチレンカーボネート、メチルエチルカーボネートなどの有機溶剤に、アミジン塩を溶解した電解液；過塩素酸の４級アンモニウム塩を溶解した電解液；４級アンモニウムやリチウムなどのアルカリ金属の四フッ化ホウ素塩や六フッ化リン塩を溶解した電解液；４級ホスホニウム塩を溶解した電解液などが挙げられる。また、前記セパレータとしては、例えば、セルロース、ガラス繊維、または、ポリエチレンやポリプロピレンなどのポリオレフィンを主成分とした不織布、クロス、微孔フィルムが挙げられる。   An electric double layer capacitor generally has a structure in which an electrode, an electrolytic solution, and a separator are main components, and a separator is disposed between a pair of electrodes. Examples of the electrolytic solution include an electrolytic solution in which an amidine salt is dissolved in an organic solvent such as propylene carbonate, ethylene carbonate, and methyl ethyl carbonate; an electrolytic solution in which a quaternary ammonium salt of perchloric acid is dissolved; quaternary ammonium or lithium An electrolytic solution in which an alkali metal boron tetrafluoride salt or phosphorous hexafluoride salt is dissolved; an electrolytic solution in which a quaternary phosphonium salt is dissolved may be mentioned. Examples of the separator include cellulose, glass fiber, or a nonwoven fabric, cloth, or microporous film mainly composed of polyolefin such as polyethylene or polypropylene.

また、本発明の製造方法により得られる多孔質炭素材料は、吸着剤としても好適に用いることができる。前記吸着剤としては、ガス吸着剤、浄水用吸着剤、排水浄化用吸着剤などが挙げられる。   Moreover, the porous carbon material obtained by the production method of the present invention can also be suitably used as an adsorbent. Examples of the adsorbent include a gas adsorbent, an adsorbent for water purification, and an adsorbent for wastewater purification.

以下に実施例を挙げて本発明をより具体的に説明するが、本発明は、下記実施例によって限定されるものではなく、前・後記の趣旨に適合しうる範囲で適宜変更して実施することも可能であり、それらはいずれも本発明の技術的範囲に包含される。   The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to the following examples, and may be appropriately modified and implemented within a range that can meet the purpose described above and below. All of which are within the scope of the present invention.

比表面積、全細孔容積および平均細孔径の測定方法
窒素吸着装置（Ｍｉｃｒｏｍｅｒｉｔｉｃｓ社製、「ＡＳＡＰ−２４００」）を用いてＮ2ガス吸着法による吸着等温線を求め、ＢＥＴ法により比表面積および全細孔容積を求めた。また、同装置を使用して吸着等温線を求め、ＢＪＨ法により解析することで細孔径分布を求めた。さらに、細孔径１．０ｎｍ〜３０ｎｍの範囲における細孔容積と比表面積に基づき、平均細孔径を求めた。 Method for measuring specific surface area, total pore volume and average pore diameter An adsorption isotherm obtained by an N 2 gas adsorption method is obtained using a nitrogen adsorption apparatus (manufactured by Micromeritics, “ASAP-2400”). The pore volume was determined. Moreover, the adsorption isotherm was calculated | required using the same apparatus, and the pore diameter distribution was calculated | required by analyzing by BJH method. Furthermore, the average pore diameter was determined based on the pore volume and specific surface area in the pore diameter range of 1.0 nm to 30 nm.

製造例１
炭化ヤシガラ原料１００ｇ（平均粒子径：５ｍｍ〜１５ｍｍ）をロータリーキルン（タナカテック社製（容積：２．５Ｌ））内に投入し、窒素流通下（１Ｌ／分）で、炉内温度を９００℃まで昇温した（昇温速度：１０℃／分）。炉内温度が９００℃に達してから、ロータリーキルン内に水蒸気と窒素との混合気体（水蒸気分圧：７１．２ｋＰａ、全圧：１０１．３ｋＰａ）を流量１Ｌ／分で供給し、１時間３０分水蒸気賦活処理を行った（第１賦活工程）。この時、水蒸気の総使用量は１８０ｇ、すなわち炭素原料１００質量部に対して１８０質量部とした。 Production Example 1
100 g (average particle diameter: 5 mm to 15 mm) of carbonized coconut shell material is put into a rotary kiln (manufactured by Tanaka Tech Co., Ltd. (volume: 2.5 L)), and the furnace temperature is increased to 900 ° C. under nitrogen flow (1 L / min). The temperature was raised (heating rate: 10 ° C./min). After the furnace temperature reaches 900 ° C., a mixed gas of water vapor and nitrogen (water vapor partial pressure: 71.2 kPa, total pressure: 101.3 kPa) is supplied into the rotary kiln at a flow rate of 1 L / min for 1 hour 30 minutes. A steam activation treatment was performed (first activation step). At this time, the total amount of steam used was 180 g, that is, 180 parts by mass with respect to 100 parts by mass of the carbon raw material.

その後、水蒸気の供給を止め、窒素流量を炉容積に対する空間速度で０．４Ｌ／Ｌ／分として、１時間３０分流通させてロータリーキルン内を置換した（置換工程）。このとき、炉に流入させた窒素の総体積は９０Ｌ、すなわち、炉の容積に対して３６倍であった。   Thereafter, the supply of water vapor was stopped, the flow rate of nitrogen was 0.4 L / L / min with respect to the furnace volume, and the inside of the rotary kiln was replaced for 1 hour and 30 minutes (replacement step). At this time, the total volume of nitrogen introduced into the furnace was 90 L, that is, 36 times the volume of the furnace.

再びロータリーキルン内に水蒸気と窒素との混合気体（水蒸気分圧７１．２ｋＰａ、全圧：１０１．３ｋＰａ）を流量１Ｌ／分で供給しながら、１時間３０分水蒸気賦活を行った（第２賦活工程）。この時、水蒸気の総使用量は１８０ｇ、すなわち炭素原料１００質量部に対して１８０質量部とした。得られた多孔質炭素材料を評価し、結果を表１に示した。   Water vapor activation was performed for 1 hour 30 minutes while supplying a mixed gas of water vapor and nitrogen (water vapor partial pressure 71.2 kPa, total pressure: 101.3 kPa) at a flow rate of 1 L / min into the rotary kiln again (second activation step). ). At this time, the total amount of water vapor used was 180 g, that is, 180 parts by mass with respect to 100 parts by mass of the carbon raw material. The obtained porous carbon material was evaluated, and the results are shown in Table 1.

製造例２
炭化ヤシガラ原料１００ｇ（平均粒子径：５ｍｍ〜１５ｍｍ）をロータリーキルン（タナカテック社製（容積：２．５Ｌ））内に投入し、窒素流通下（１Ｌ／分）で、炉内温度を９００℃まで昇温した（昇温速度：１０℃／分）。炉内温度が９００℃に達してから、ロータリーキルン内に水蒸気と窒素との混合気体（水蒸気分圧：７１．２ｋＰａ、全圧：１０１．３ｋＰａ）を流量１Ｌ／分で供給し、１時間水蒸気賦活処理を行った（第１賦活工程）。この時、水蒸気の総使用量は１２０ｇ、すなわち炭素原料１００質量部に対して１２０質量部とした。 Production Example 2
100 g (average particle diameter: 5 mm to 15 mm) of carbonized coconut shell material is put into a rotary kiln (manufactured by Tanaka Tech Co., Ltd. (volume: 2.5 L)), and the furnace temperature is increased to 900 ° C. under nitrogen flow (1 L / min). The temperature was raised (heating rate: 10 ° C./min). After the furnace temperature reaches 900 ° C., a mixed gas of water vapor and nitrogen (water vapor partial pressure: 71.2 kPa, total pressure: 101.3 kPa) is supplied into the rotary kiln at a flow rate of 1 L / min, and steam activation is performed for 1 hour. Processing was performed (first activation step). At this time, the total amount of water vapor used was 120 g, that is, 120 parts by mass with respect to 100 parts by mass of the carbon raw material.

その後、水蒸気の供給を止め、窒素流量を炉容積に対する空間速度で０．４Ｌ／Ｌ／分として、１時間流通させてロータリーキルン内を置換した（第１置換工程）。このとき、炉に流入させた窒素の総体積は６０Ｌすなわち、炉の容積に対して２４倍であった。   Thereafter, the supply of water vapor was stopped, the nitrogen flow rate was set to 0.4 L / L / min in space velocity with respect to the furnace volume, and the inside of the rotary kiln was replaced for 1 hour (first replacement step). At this time, the total volume of nitrogen introduced into the furnace was 60 L, that is, 24 times the volume of the furnace.

再びロータリーキルン内に水蒸気と窒素との混合気体（水蒸気分圧７１．２ｋＰａ、全圧：１０１．３ｋＰａ）を流量１Ｌ／分で供給しながら、１時間水蒸気賦活を行った（第２賦活工程）。この時、水蒸気の総使用量は１２０ｇ、すなわち炭素原料１００質量部に対して１２０質量部とした。   Water vapor activation was performed for 1 hour while supplying a mixed gas of water vapor and nitrogen (water vapor partial pressure: 71.2 kPa, total pressure: 101.3 kPa) at a flow rate of 1 L / min into the rotary kiln again (second activation step). At this time, the total amount of water vapor used was 120 g, that is, 120 parts by mass with respect to 100 parts by mass of the carbon raw material.

その後、再度水蒸気の供給を止め、窒素流量を炉容積に対する空間速度で０．４Ｌ／Ｌ／分として、１時間流通させてロータリーキルン内を置換した（第２置換工程）。このとき、炉に流入させた窒素の総体積は６０Ｌすなわち、炉の容積に対して２４倍であった。   Thereafter, the supply of water vapor was stopped again, the nitrogen flow rate was set to 0.4 L / L / min in space velocity with respect to the furnace volume, and the inside of the rotary kiln was replaced for 1 hour (second replacement step). At this time, the total volume of nitrogen introduced into the furnace was 60 L, that is, 24 times the volume of the furnace.

続いて、ロータリーキルン内に水蒸気と窒素との混合気体（水蒸気分圧７１．２ｋＰａ、全圧：１０１．３ｋＰａ）を流量１Ｌ／分で供給しながら、１時間水蒸気賦活を行った（第３賦活工程）。この時、水蒸気の総使用量は１２０ｇ、すなわち炭素原料１００質量部に対して１２０質量部とした。得られた多孔質炭素材料を評価し、結果を表１に示した。   Subsequently, steam activation was performed for 1 hour while supplying a mixed gas of water vapor and nitrogen (water vapor partial pressure: 71.2 kPa, total pressure: 101.3 kPa) in the rotary kiln at a flow rate of 1 L / min (third activation step). ). At this time, the total amount of water vapor used was 120 g, that is, 120 parts by mass with respect to 100 parts by mass of the carbon raw material. The obtained porous carbon material was evaluated, and the results are shown in Table 1.

製造例３
炭化ヤシガラ原料１００ｇを、炭化フェノール樹脂原料（フェノール樹脂（住友ベークライト社製）を処理温度７００℃で炭化したもの（平均粒子径：５ｍｍ〜１５ｍｍ））に換えたこと以外は製造例１と同様にして、連続２段階水蒸気賦活処理を行った。得られた多孔質炭素材料を評価し、結果を表１に示した。 Production Example 3
The same procedure as in Production Example 1 except that 100 g of the carbonized coconut shell material was replaced with a carbonized phenol resin material (phenol resin (manufactured by Sumitomo Bakelite Co., Ltd.) carbonized at a processing temperature of 700 ° C. (average particle size: 5 mm to 15 mm)). Then, a continuous two-stage steam activation treatment was performed. The obtained porous carbon material was evaluated, and the results are shown in Table 1.

製造例４
炭化ヤシガラ原料１００ｇを、炭化フェノール樹脂原料（フェノール樹脂（住友ベークライト社製）を処理温度７００℃で炭化したもの（平均粒子径：５ｍｍ〜１５ｍｍ））に換えたこと以外は製造例２と同様にして、連続３段階水蒸気賦活処理を行った。得られた多孔質炭素材料を評価し、結果を表１に示した。 Production Example 4
The same procedure as in Production Example 2 except that 100 g of the carbonized coconut shell material was replaced with a carbonized phenol resin material (phenol resin (manufactured by Sumitomo Bakelite Co., Ltd.) carbonized at a treatment temperature of 700 ° C. (average particle size: 5 mm to 15 mm)). Then, a continuous three-stage steam activation treatment was performed. The obtained porous carbon material was evaluated, and the results are shown in Table 1.

製造例５
炭化ヤシガラ原料１００ｇ（平均粒子径：５ｍｍ〜１５ｍｍ）をロータリーキルン（タナカテック社製（容積：２．５Ｌ））内に投入し、窒素流通下（１Ｌ／分）で９００℃まで昇温した（昇温速度：１０℃／分）。 Production Example 5
100 g (average particle size: 5 mm to 15 mm) of carbonized coconut shell material was put into a rotary kiln (manufactured by Tanaka Tech Co., Ltd. (volume: 2.5 L)) and heated to 900 ° C. under nitrogen flow (1 L / min) (rising) (Temperature rate: 10 ° C./min).

９００℃に達してからロータリーキルン内に水蒸気（水蒸気分圧：７１．２ｋＰａ）を窒素とともに供給し、３時間水蒸気賦活処理を行った。この時、水蒸気の総使用量は３６０ｇ、すなわち炭素原料１００質量部に対して３６０質量部とした。得られた多孔質炭素材料を評価し、結果を表１に示した。   After reaching 900 ° C., steam (steam partial pressure: 71.2 kPa) was supplied together with nitrogen into the rotary kiln, and steam activation treatment was performed for 3 hours. At this time, the total amount of water vapor used was 360 g, that is, 360 parts by mass with respect to 100 parts by mass of the carbon raw material. The obtained porous carbon material was evaluated, and the results are shown in Table 1.

製造例６
炭化ヤシガラ原料１００ｇを、炭化フェノール樹脂原料（フェノール樹脂（住友ベークライト社製）を処理温度７００℃で炭化したもの（平均粒子径：５ｍｍ〜１５ｍｍ））に換えたこと以外は製造例５と同様にして、水蒸気賦活処理を行った。得られた多孔質炭素材料を評価し、結果を表１に示した。 Production Example 6
The same procedure as in Production Example 5 except that 100 g of the carbonized coconut shell material was replaced with a carbonized phenol resin material (phenol resin (manufactured by Sumitomo Bakelite) carbonized at a processing temperature of 700 ° C. (average particle size: 5 mm to 15 mm)). Then, steam activation treatment was performed. The obtained porous carbon material was evaluated, and the results are shown in Table 1.

製造例Ｎｏ．１，２，５は、炭素原料として炭化ヤシガラを使用し、賦活温度を９００℃、賦活処理の合計時間を３時間として、置換工程の回数のみを変更したものである。これらの多孔質炭素材料を比較すると、いずれも賦活処理の合計時間が３時間であるためほぼ同様の比表面積、細孔容積が得られているにもかかわらず、置換工程を挟んだ回数が多いほど、得られる平均細孔径が小さくなっていることがわかる。   Production Example No. Nos. 1, 2, and 5 are obtained by using carbonized coconut shell as a carbon raw material, with an activation temperature of 900 ° C., and a total activation process time of 3 hours, with only the number of replacement steps being changed. Comparing these porous carbon materials, since the total time of activation treatment is 3 hours, the number of times that the substitution step is interposed is large even though almost the same specific surface area and pore volume are obtained. It can be seen that the average pore diameter obtained is smaller.

同様に、製造例Ｎｏ．３，４，６は、炭素原料として炭化フェノール樹脂を使用し、賦活温度を９００℃、賦活処理の合計時間を３時間として、置換工程の回数のみを変更したものである。これらの多孔質炭素材料を比較しても、いずれも賦活処理の合計時間が３時間であるためほぼ同様の比表面積、細孔容積が得られているにもかかわらず、置換工程を挟んだ回数が多いほど、得られる平均細孔径が小さくなっていることがわかる。   Similarly, Production Example No. Nos. 3, 4 and 6 use a carbonized phenol resin as a carbon raw material, change the activation temperature to 900 ° C., set the total activation process time to 3 hours, and change only the number of substitution steps. Even when these porous carbon materials are compared, since the total time of activation treatment is 3 hours, the same number of specific surface areas and pore volumes are obtained, but the number of times the substitution process is sandwiched. It can be seen that the larger the amount of, the smaller the average pore diameter obtained.

図１に炭素原料として炭化ヤシガラを用いた製造例Ｎｏ．１，２，５で得られた多孔質炭素材料の細孔径分布を示す。図１に示すように、置換工程を挟んだ回数が多いほど、細孔径のピーク位置が小径側に移動していることがわかる。この細孔径分布図からも、置換工程を挟むことにより細孔径の増大を抑制できていることがわかる。   FIG. 1 shows a production example No. 1 using carbonized coconut shell as a carbon raw material. The pore diameter distribution of the porous carbon material obtained in 1, 2, 5 is shown. As shown in FIG. 1, it can be understood that the peak position of the pore diameter moves to the smaller diameter side as the number of times the replacement step is interposed is increased. From this pore size distribution chart, it can be seen that the increase in pore size can be suppressed by interposing the substitution step.

本発明は、高比表面積を有し、かつ、平均細孔径が小さい多孔質炭素材料の製造に有用である。   The present invention is useful for producing a porous carbon material having a high specific surface area and a small average pore diameter.

Claims (6)

炭素原料をガス賦活することにより多孔質炭素材料を製造する方法であって、
前記ガス賦活処理中に、一時的に炉内の賦活ガスを不活性ガスで置換する操作を挟むと共に、
前記不活性ガスで置換する操作の前後で同じ賦活ガスを用いてガス賦活処理することを特徴とする多孔質炭素材料の製造方法。 A method for producing a porous carbon material by gas activation of a carbon raw material,
During the gas activation process, while temporarily sandwiching the operation of replacing the activation gas in the furnace with an inert gas ,
A method for producing a porous carbon material, comprising performing a gas activation treatment using the same activation gas before and after the operation of replacing with the inert gas . 炉に炭素原料を収容し、炉内を加熱する昇温工程、
加熱された炉内に、賦活ガスを供給する第１賦活工程、
第１賦活工程後、炉内を加熱したまま賦活ガスを不活性ガスに置換する置換工程、及び、
前記置換工程後、炉内を加熱したまま再び炉内に前記第１賦活工程と同じ賦活ガスを供給する第２賦活工程、
を含むことを特徴とする多孔質炭素材料の製造方法。 A temperature raising step of storing the carbon raw material in the furnace and heating the inside of the furnace,
A first activation step of supplying an activation gas into the heated furnace;
After the first activation step, a replacement step of replacing the activation gas with an inert gas while heating the inside of the furnace, and
A second activation step of supplying the same activation gas as that of the first activation step to the furnace again while the furnace is heated after the replacement step;
A method for producing a porous carbon material, comprising: 前記置換工程において、炉の容積に対して、体積比で２倍〜１００倍の不活性ガスを流入させる請求項２に記載の多孔質炭素材料の製造方法。   3. The method for producing a porous carbon material according to claim 2, wherein in the replacement step, an inert gas having a volume ratio of 2 to 100 times is introduced with respect to the volume of the furnace. 請求項１〜３のいずれか一項に記載の製造方法により得られた多孔質炭素材料を含有することを特徴とする電気二重層キャパシタ用電極。   An electrode for an electric double layer capacitor, comprising the porous carbon material obtained by the production method according to claim 1. 請求項４に記載の電気二重層キャパシタ用電極を用いたことを特徴とする電気二重層キャパシタ。   An electric double layer capacitor comprising the electrode for an electric double layer capacitor according to claim 4. 請求項１〜３のいずれか一項に記載の製造方法により得られた多孔質炭素材料を含有することを特徴とする吸着剤。   An adsorbent comprising the porous carbon material obtained by the production method according to claim 1.
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