JPH0543345A - Production of active carbon porous body - Google Patents
Production of active carbon porous bodyInfo
- Publication number
- JPH0543345A JPH0543345A JP3196891A JP19689191A JPH0543345A JP H0543345 A JPH0543345 A JP H0543345A JP 3196891 A JP3196891 A JP 3196891A JP 19689191 A JP19689191 A JP 19689191A JP H0543345 A JPH0543345 A JP H0543345A
- Authority
- JP
- Japan
- Prior art keywords
- powder
- weight
- parts
- activated carbon
- porous body
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/0022—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof obtained by a chemical conversion or reaction other than those relating to the setting or hardening of cement-like material or to the formation of a sol or a gel, e.g. by carbonising or pyrolysing preformed cellular materials based on polymers, organo-metallic or organo-silicon precursors
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00844—Uses not provided for elsewhere in C04B2111/00 for electronic applications
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は活性炭素多孔体の製造方
法に関する。本発明は特に電気二重層コンデンサの電極
として好適な高密度ブロック状活性炭素多孔体の製造方
法に関する。TECHNICAL FIELD The present invention relates to a method for producing an activated carbon porous material. The present invention particularly relates to a method for producing a high-density block-shaped activated carbon porous body suitable as an electrode of an electric double layer capacitor.
【０００２】[0002]
【従来の技術】活性炭は排水処理や脱臭処理等の用途に
広く使用されている。更に最近では電気二重層コンデン
サの電極として使用されはじめている。この用途に使用
される活性炭は、コンデンサの性能向上、特に高静電容
量と低内部抵抗の２つの性能向上の要求を満たすため、
高密度、ブロック状、かつ電解液の含浸性の良いことが
要求されている。2. Description of the Related Art Activated carbon is widely used for applications such as wastewater treatment and deodorization treatment. More recently, they have begun to be used as electrodes of electric double layer capacitors. The activated carbon used for this purpose satisfies the requirements for improved performance of capacitors, especially high performance and low internal resistance.
It is required to have high density, block shape, and good impregnation property with an electrolytic solution.
【０００３】従来より活性炭素多孔体の製造方法として
は、幾つかの方法が知られている。例えば、レゾール型
フェノール樹脂にフロン等の蒸発型発泡剤を配合後、同
蒸発型発泡剤を気化せしめてフェノール樹脂多孔体を製
造することは公知であり、更にそのフェノール樹脂発泡
体を炭化、賦活することにより活性炭素多孔体が得られ
ることも特開昭６２−１３２７１５号等により公知であ
る。このような方法で得られた活性炭素多孔体は無数の
気泡と気泡を取り囲む炭素薄膜とで形成される細胞構造
を有しており、細胞間には炭化時に生じるガスを系外に
放出するための通路として通常炭素薄膜に小さな穴が形
成されている。しかし、この方法で形成される活性炭素
多孔体の穴はガスまたは水等の液体が自由に出入りする
には不十分であり、特に嵩密度が０．４ｇ／cm3 を越す
樹脂発泡体を炭化、賦活する場合、炭化中に発生する分
解ガスの抜けが困難になり、しばしば炭化物がこなごな
に砕ける現象を生じた。Conventionally, several methods have been known as methods for producing activated carbon porous materials. For example, it is known to prepare a phenol resin porous body by mixing an evaporative foaming agent such as Freon into a resol type phenolic resin, and then vaporizing the evaporative foaming agent to carbonize and activate the phenol resin foam. It is also known from JP-A-62-132715 that an activated carbon porous material can be obtained by doing so. The activated carbon porous material obtained by such a method has a cell structure formed of innumerable bubbles and a carbon thin film surrounding the bubbles, and the gas generated during carbonization is released between the cells to the outside of the system. A small hole is usually formed in the carbon thin film as a passage for the. However, the pores of the activated carbon porous body formed by this method are not sufficient for the free entry and exit of liquids such as gas or water, and in particular, carbonization of resin foam having a bulk density of 0.4 g / cm 3 or more, When activated, it became difficult for the decomposition gas generated during carbonization to escape, and the phenomenon that the carbide was often broken into small pieces occurred.
【０００４】より連続気泡率の高い炭素多孔体を製造す
る方法についても、既に多くの提案がある。特開昭５８
−１７２２０９号、６１−１８６２０９号、６１−１８
６２１１号公報には液状フェノール樹脂、粒状フェノー
ル樹脂、ポリビニルアルコール、および澱粉等の気孔形
成剤とを混合して、樹脂成形物を形成したのち炭化し、
炭素多孔体を製造する技術が開示されている。しかし、
この方法では樹脂の硬化工程で時間を要するという問題
があり、かつ得られる多孔体の孔径が大き過ぎて嵩密度
を大きくできないこと、更に賦活して活性炭にした場合
に性能が充分でないという問題があった。Many proposals have already been made for a method of producing a carbon porous body having a higher open cell ratio. JP 58
-172209, 61-186209, 61-18
In JP 6211, a liquid phenol resin, a granular phenol resin, polyvinyl alcohol, and a pore-forming agent such as starch are mixed to form a resin molded product, which is then carbonized.
A technique for producing a carbon porous body is disclosed. But,
In this method, there is a problem that it takes time in the curing step of the resin, and that the pore size of the obtained porous body is too large to increase the bulk density, and further there is a problem that the performance is not sufficient when activated to activated carbon. there were.
【０００５】本発明者らは先にレゾール型フェノール樹
脂(a) １００重量部、親油性で１００℃以上の沸点を有
する常温で液状の化合物(b) １ないし１００重量部、及
び親水性で１００℃以上の沸点を有する液状の化合物
(c) １ないし１００重量部とからなる組成物を炭化、賦
活して得られる活性炭素多孔体は、高密度でかつ細かい
気孔が形成されていることを見いだし先に提案した。
（特願平２−３０４８９７号）The present inventors have previously prepared 100 parts by weight of a resol type phenolic resin (a), 1 to 100 parts by weight of a lipophilic compound (b) which is liquid at room temperature and has a boiling point of 100 ° C. or higher, and 100% by weight of a hydrophilic compound. Liquid compounds with boiling point above ℃
(c) An activated carbon porous body obtained by carbonizing and activating a composition comprising 1 to 100 parts by weight was found to have high density and fine pores, and was proposed earlier.
(Japanese Patent Application No. 2-304897)
【０００６】[0006]
【発明が解決しようとする問題点】しかし、この方法で
得られた活性炭素多孔体の孔は嵩密度に上限があり、活
性炭の吸着性能の指標であるヘンゼン吸着度において３
５％以上の活性炭素多孔体では、嵩密度が０．５g/cm3
以下になことが判明した。親油性化合物や親水性化合物
の配合量を減らして高密度品を得るという試みは、たい
ていの場合、炭化工程時に硬化物の爆裂を生じた。ま
た、先に提案した組成物から得られる活性炭素多孔体の
平均細孔直径は比較的小さいため、この活性炭構造物を
電気二重層コンデンサの電極として用いた場合、コンデ
ンサの充放電の際の電解質イオンの移動時の抵抗に起因
する内部抵抗がやや大きいという欠点があった。However, the pores of the activated carbon porous material obtained by this method have an upper limit in the bulk density, and the Hensen adsorption degree, which is an index of the adsorption performance of activated carbon, is 3
With activated carbon porous material of 5% or more, the bulk density is 0.5 g / cm3.
It turned out that: Attempts to obtain high-density products by reducing the amounts of lipophilic compounds and hydrophilic compounds often resulted in the explosion of the cured product during the carbonization process. In addition, since the activated carbon porous body obtained from the composition proposed above has a relatively small average pore diameter, when this activated carbon structure is used as an electrode of an electric double layer capacitor, an electrolyte for charging and discharging the capacitor is used. There was a drawback that the internal resistance due to the resistance during movement of ions was rather large.
【問題を解決するための手段】本発明は、上記問題を解
決するため、レゾール型フェノール樹脂(a) １００重量
部、親油性で１００℃以上の沸点を有する常温で液状の
化合物(b) １ないし１００重量部、親水性で１００℃以
上の沸点を有する液状の化合物(c) １ないし１００重量
部、及び残炭率の高い粉体１ないし２００重量部とから
なる混合物の硬化物を形成後、５００℃以上の温度で炭
化、賦活することを特徴とする活性炭素多孔体の製造方
法を提供するものである。In order to solve the above problems, the present invention provides 100 parts by weight of a resol type phenolic resin (a), a lipophilic compound (b) 1 which is liquid at room temperature and has a boiling point of 100 ° C. or higher. To 100 parts by weight, 1 to 100 parts by weight of a liquid compound (c) which is hydrophilic and has a boiling point of 100 ° C. or more, and 1 to 200 parts by weight of a powder having a high residual carbon rate, after forming a cured product. The present invention provides a method for producing an activated carbon porous body, which comprises carbonizing and activating at a temperature of 500 ° C or higher.
【０００７】本発明を更に詳しく説明する。本発明で用
いられるレゾール型フェノール樹脂(a) とは、例えばフ
ェノール１モルとホルマリン１〜３モルをアルカリ性触
媒、例えばＮａＯＨ、ＫＯＨ、Ｃａ（ＯＨ）2、Ｂａ
（ＯＨ）2、ＮＨ2（ＣＨ2ＣＨ3） 等の存在下で８０〜
１００℃に加熱することにより縮合させ、次いで固形分
が６０〜８０％になるまで減圧下で水を留去して得られ
た常温での粘度が１０００〜２００００ｃｐｓの液体で
ある。本発明における親油性で１００℃以上の沸点を有
する常温で液状の化合物とは、例えば、オクタン、ノナ
ン、デカン、ウンデカン、ドデカン、灯油、鉱物油、流
動パラフィン等の直鎖状、または分岐状アルキル化合
物、トルエン、キシレン等の環状アルキレン化合物等を
挙げることができる。これらのうちでは、流動パラフィ
ンがレゾールとの粘度が近似し、混合した際安定な水中
油型分散系を作ることが出来るため、好ましい。The present invention will be described in more detail. The resol type phenolic resin (a) used in the present invention means, for example, 1 mol of phenol and 1 to 3 mol of formalin as an alkaline catalyst such as NaOH, KOH, Ca (OH) 2, Ba.
In the presence of (OH) 2, NH2 (CH2CH3), etc.
It is a liquid having a viscosity of 1000 to 20000 cps at room temperature, which is obtained by condensing by heating at 100 ° C. and then distilling off water under reduced pressure until the solid content becomes 60 to 80%. In the present invention, the lipophilic compound having a boiling point of 100 ° C. or higher and being liquid at room temperature includes, for example, straight chain or branched alkyl such as octane, nonane, decane, undecane, dodecane, kerosene, mineral oil, liquid paraffin, and the like. Examples thereof include compounds and cyclic alkylene compounds such as toluene and xylene. Among these, liquid paraffin is preferable because it has a viscosity similar to that of resole and a stable oil-in-water dispersion system can be prepared when mixed.
【０００８】この親油性化合物(b) のレゾール型フェノ
ール樹脂(a) １００重量部に対する配合量は通常１〜１
００重量部、好ましくは、１０〜６０重量部の範囲であ
る。親油性化合物(b) の量が少なすぎると、活性炭素多
孔体の多孔構造が少なくなって、吸着性能、液含浸性が
劣るようになる。また、炭化、賦活中に爆裂を生じ、活
性炭を製造しずらくなる。一方上記量を越えると、レゾ
ールの硬化特性が劣るようになる。また、炭化時に硬化
物の収縮が大きく、割れを生じ易くなる。The lipophilic compound (b) is usually added in an amount of 1 to 1 with respect to 100 parts by weight of the resol type phenol resin (a).
00 parts by weight, preferably 10 to 60 parts by weight. If the amount of the lipophilic compound (b) is too small, the porous structure of the activated carbon porous body will be small, resulting in poor adsorption performance and liquid impregnation property. In addition, explosion occurs during carbonization and activation, making it difficult to produce activated carbon. On the other hand, when the amount exceeds the above range, the curing property of the resole becomes poor. In addition, the shrinkage of the cured product is large during carbonization, and cracking is likely to occur.
【０００９】本発明における親水性で１００℃以上の沸
点を有する液状の化合物(c) とは、例えば、重合度２以
上のオキシアルキレン化合物、例えば、ジエチレングリ
コール、トリエチレングリコール、分子量１０００未満
のポリエチレングリコール、ジプロピレングリコール、
分子量１０００未満のポリプロピレングリコール、ある
いはグリセリン等を挙げることが出来る。これらのうち
では、レゾールの粘度に比較的近く、かつ適度な相溶性
がある点から分子量が４００〜６００のポリエチレング
リコール、または、ジプロピレングリコールが好まし
い。The liquid compound (c) having a boiling point of 100 ° C. or higher in the present invention means, for example, an oxyalkylene compound having a degree of polymerization of 2 or higher, such as diethylene glycol, triethylene glycol, polyethylene glycol having a molecular weight of less than 1000. , Dipropylene glycol,
Examples thereof include polypropylene glycol having a molecular weight of less than 1000, glycerin and the like. Among these, polyethylene glycol having a molecular weight of 400 to 600 or dipropylene glycol is preferable because it is relatively close to the viscosity of the resole and has a suitable compatibility.
【００１０】この親水性で１００℃以上の沸点を有する
液状の化合物(c) のレゾール型フェノール樹脂(a) １０
０重量部に対する配合量は、通常１ないし１００重量
部、好ましくは１０〜６０重量部の範囲である。親水性
化合物(c) の量が少なすぎると、親油性化合物(b) の分
散安定性が劣り、相分離を生じ易くなり、一方上記量を
越えるとレゾールの硬化特性が損なわれること、及び親
水性化合物とレゾールとが相分離しやすくなる。Resol type phenolic resin (a) 10 of this liquid compound (c) having a boiling point of 100 ° C. or higher
The compounding amount with respect to 0 part by weight is usually 1 to 100 parts by weight, preferably 10 to 60 parts by weight. If the amount of the hydrophilic compound (c) is too small, the dispersion stability of the lipophilic compound (b) is inferior, and phase separation easily occurs. On the other hand, if the amount exceeds the above amount, the curing property of the resole is impaired, and Of the organic compound and the resole are likely to occur in phase separation.
【００１１】本発明では親油性化合物(b) と、親水性化
合物(c) との配合比は、０．３〜３の範囲にすることが
好ましく、この範囲を外れると混合物が相分離し易くな
る。In the present invention, the compounding ratio of the lipophilic compound (b) and the hydrophilic compound (c) is preferably in the range of 0.3 to 3, and when it is out of this range, the mixture is likely to undergo phase separation. Become.
【００１２】本発明では、第４成分として、残炭率の高
い粉末をレゾール型フェノール樹脂１００重量部に対
し、１ないし２００重量部配合する。残炭率の高い粉末
とは、例えば、炭化した際重量残存率の高い樹脂、例え
ば、ポリビニルクロライド、ポリアクリロニトリル、ポ
リイミド等の残炭率の高いプラスチックの粉末、石油の
高沸点分、あるいは抽出残分、例えば、コールタールピ
ッチを４５０℃付近まで加熱して結晶化を促進させた
後、キノリンで抽出して得られる１μ程度の粉末である
メソフェーズピッチの粉末、石炭やコークスを粉砕して
得た粉末、炭素の粉末、例えば黒鉛粉末、カーボンブラ
ック、活性炭粉末、炭素繊維粉末等を言う。これらのう
ちでは水への親和性がなく、かつ形状が円形で径が均一
であり、かつ凝集がないため、組成物の粘度上昇が少な
いメソフェーズピッチ粉末が最も好ましい。In the present invention, as the fourth component, 1 to 200 parts by weight of powder having a high residual carbon ratio is mixed with 100 parts by weight of the resol type phenol resin. The powder having a high residual carbon rate means, for example, a resin having a high residual weight ratio when carbonized, for example, a powder of a plastic having a high residual carbon rate such as polyvinyl chloride, polyacrylonitrile, or polyimide, a high boiling point component of petroleum, or an extraction residue. Min, for example, coal tar pitch was heated to around 450 ° C. to promote crystallization, and then extracted with quinoline to obtain a powder of mesophase pitch of about 1 μ, which was obtained by pulverizing coal or coke. Powder, carbon powder, for example, graphite powder, carbon black, activated carbon powder, carbon fiber powder and the like. Of these, the mesophase pitch powder, which has no affinity for water, has a circular shape and a uniform diameter, and has no agglomeration, is the most preferable because the viscosity increase of the composition is small.
【００１３】残炭率の高い粉末の配合量は、レゾール型
フェノール樹脂１００重量部に対し１〜２００重量部，
好ましくは１０〜１００重量部の範囲である。粉末の量
が多すぎると混合物の粘度が上昇し、攪拌時に大きな気
泡を巻き込み、均一な活性炭素多孔体が得られなくな
る。一方、１重量部より少ないと、本発明の目的とした
効果が得られなくなる。The amount of the powder having a high residual carbon content is 1 to 200 parts by weight based on 100 parts by weight of the resol type phenol resin,
It is preferably in the range of 10 to 100 parts by weight. If the amount of the powder is too large, the viscosity of the mixture increases and large bubbles are entrained during stirring, so that a uniform activated carbon porous material cannot be obtained. On the other hand, if the amount is less than 1 part by weight, the effect of the present invention cannot be obtained.
【００１４】本発明でレゾール型フェノール樹脂(a) の
硬化に用いられる硬化剤としては、公知の種々の強酸性
化合物、例えば塩酸、硫酸、硝酸、リン酸、ピロリン
酸、ポリリン酸等の無機酸、フェノールスルホン酸、ベ
ンゼンスルホン酸、トルエンスルホン酸、メタクレゾー
ルスルホン酸等の有機酸、あるいはこれらの混合物を挙
げることが出来る。硬化剤の使用量は、通常レゾール型
フェノール樹脂１００重量部に対し通常１〜３０重量部
の範囲である。As the curing agent used for curing the resol type phenolic resin (a) in the present invention, various known strongly acidic compounds, for example, inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, pyrophosphoric acid and polyphosphoric acid are used. , Organic acids such as phenolsulfonic acid, benzenesulfonic acid, toluenesulfonic acid, and metacresolsulfonic acid, or a mixture thereof. The amount of the curing agent used is usually in the range of 1 to 30 parts by weight with respect to 100 parts by weight of the resol type phenol resin.
【００１５】本発明では、例えば、上記レゾール型フェ
ノール樹脂(a)親油性で１００℃以上の沸点を有する常
温で液状の化合物(b) 、親水性で１００℃以上の沸点を
有する液状の化合物(c) 、及び残炭率の高いい粉体(d)
必要に応じて更に界面活性剤、他の充填剤等を配合した
ものを攪拌、混合後重合体混合物を加熱して硬化させ
る。硬化は、常温ないし１００℃の範囲、好ましくは、
５０ないし９０℃の範囲で実施される。In the present invention, for example, the resol type phenolic resin (a) is a lipophilic compound having a boiling point of 100 ° C. or more and a liquid compound at room temperature (b), and a hydrophilic compound having a boiling point of 100 ° C. or more ( c), and fine powder with a high residual coal rate (d)
If necessary, a mixture of a surfactant and other filler is stirred and mixed, and then the polymer mixture is heated to cure. Curing is in the range of room temperature to 100 ° C, preferably
It is carried out in the range of 50 to 90 ° C.
【００１６】上記成分を混合する方法としては、好まし
くは、高速で回転する攪拌翼を持ったミキサー等で連続
的にまたは、回分的に逐次、または同時に混合する方法
を採用することができる。本発明の製造方法において、
攪拌、混合された直後の樹脂組成物の粘度は通常１０万
ｃｐｓ以下の粘度となる。このような低粘度のために攪
拌時に気泡を混入せず、嵩密度等の点で均質な活性炭素
多孔体を得ることができる。As a method of mixing the above-mentioned components, preferably, a method of mixing continuously, batchwise or simultaneously with a mixer having a stirring blade rotating at a high speed can be adopted. In the manufacturing method of the present invention,
The viscosity of the resin composition immediately after stirring and mixing is usually 100,000 cps or less. Due to such a low viscosity, bubbles can not be mixed in during stirring, and a homogeneous activated carbon porous material can be obtained in terms of bulk density and the like.
【００１７】本発明ではこのようにして得た樹脂硬化物
をそのまま、もしくは切削して板状体とした後、非酸化
性雰囲気下で炭化して炭素多孔体とする。非酸化性雰囲
気とは、例えば、Ａｒガス、Ｈｅガス、Ｎ2 ガス、ハロ
ゲンガス、アンモニアガス、ＣＯガス、水素ガス、ある
いはこれらの混合ガス、水性ガス等をいう。炭化のため
の温度は、好ましくは、５００℃〜１２００℃、特に６
００〜９００℃の範囲が好ましい。In the present invention, the resin cured product thus obtained is used as it is, or after being cut into a plate-like body, it is carbonized in a non-oxidizing atmosphere to form a carbon porous body. The non-oxidizing atmosphere means, for example, Ar gas, He gas, N2 gas, halogen gas, ammonia gas, CO gas, hydrogen gas, a mixed gas thereof, a water gas or the like. The temperature for carbonization is preferably 500 ° C to 1200 ° C, especially 6
The range of 00 to 900 ° C is preferable.
【００１８】以上のようにして得られた炭素多孔体は、
更に賦活処理を施して活性化する。賦活工程は、炭化工
程に連続していてもよいし、炭化工程と別個の工程とし
てもよい。炭素多孔体の賦活は炭素多孔体を酸化性ガ
ス、または酸化性ガスと不活性ガスとの混合気体の雰囲
気下で加熱して行われる。The carbon porous body obtained as described above is
Further, activation treatment is applied to activate. The activation step may be continuous with the carbonization step or may be a step separate from the carbonization step. Activation of the carbon porous body is performed by heating the carbon porous body in an atmosphere of an oxidizing gas or a mixed gas of an oxidizing gas and an inert gas.
【００１９】加熱温度は６００℃〜１２００℃、好まし
くは７５０〜１０００℃がよい。酸化性ガスとしては、
公知の酸化性ガス、例えば、水蒸気、二酸化炭素、酸
素、空気等が用いられる。これらは通常調節しやすいよ
うに不活性ガスＮ2 等と混合して用いる。The heating temperature is 600 ° C to 1200 ° C, preferably 750 to 1000 ° C. As oxidizing gas,
Known oxidizing gases such as steam, carbon dioxide, oxygen and air are used. These are usually mixed with an inert gas such as N2 for easy control.
【００２０】[0020]
【実施例】以下、実施例及び比較例により発明を更に具
体的に説明するが、本発明はその要旨を越えない限りこ
れらの実施例になんら制約されるものではない。 実施例１ ２５℃における粘度が４８００ｃｐｓのレゾール型フェ
ノール樹脂（略称レゾール）１００重量部に界面活性剤
として、ヒマシ油のポリオキシエチレン２モル付加物の
硫酸エステルナトリウム塩５重量部、高沸点親水性化合
物として、分子量が６００のポリエチレングリコール
（略称ＰＥＧ）２５重量部、高沸点親油性化合物とし
て、流動パラフィン（略称流パラ）２５重量部、及びメ
ソフェーズピッチ粉末（略称ＭＰ粉末）４０重量部と
を、３段のピン羽根を有する攪拌器で６０００回転／分
の速度で５分間充分に攪拌した。この混合物の粘度は８
３００ｃｐｓであった。この混合物に、硬化剤としてパ
ラトルエンスルホン酸２０重量部を加えて同様の攪拌速
度で１分間攪拌、混合後７０℃エアーオーブン中に１時
間放置して重合体硬化物を製造した。The present invention will be described in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples unless it exceeds the gist. Example 1 100 parts by weight of a resole-type phenol resin (abbreviation: resole) having a viscosity of 4800 cps at 25 ° C., as a surfactant, 5 parts by weight of a sodium salt of a sulfuric acid ester of a polyoxyethylene 2 mol adduct of castor oil, a high boiling hydrophilicity 25 parts by weight of polyethylene glycol (abbreviated as PEG) having a molecular weight of 600 as a compound, 25 parts by weight of liquid paraffin (abbreviated as flow para) as a high-boiling lipophilic compound, and 40 parts by weight of mesophase pitch powder (abbreviated as MP powder), The mixture was thoroughly stirred for 5 minutes at a speed of 6000 rpm with a stirrer having three stages of pin blades. The viscosity of this mixture is 8
It was 300 cps. To this mixture, 20 parts by weight of para-toluenesulfonic acid was added as a curing agent, the mixture was stirred at the same stirring speed for 1 minute, mixed and left in an air oven at 70 ° C. for 1 hour to prepare a polymer cured product.
【００２１】この重合体硬化物を電気炉に入れてＮ2 雰
囲気で１．５℃／分の速度で７００℃まで昇温し、同温
度で１時間保持後冷却した。以上の方法で得られた炭素
多孔体の重量、寸法を測定することにより嵩密度を算出
した。この炭素多孔体を厚さ５ｍｍのセラミックファイ
バーボードの箱に入れ、更にこの箱を電気炉に入れてＮ
2 雰囲気３℃／分の速度で９００℃まで昇温し、ついで
Ｎ2／Ｈ2Ｏ＝９／１の割合で賦活ガスを７時間導入後、
冷却して取り出した。The cured product of this polymer was placed in an electric furnace, heated to 700 ° C. at a rate of 1.5 ° C./min in an N 2 atmosphere, kept at the same temperature for 1 hour, and then cooled. The bulk density was calculated by measuring the weight and dimensions of the carbon porous body obtained by the above method. This carbon porous body was placed in a ceramic fiber board box having a thickness of 5 mm, and this box was placed in an electric furnace for N
2 The temperature was raised to 900 ° C. at a rate of 3 ° C./min, and then an activating gas was introduced at a ratio of N2 / H2O = 9/1 for 7 hours,
It was cooled and taken out.
【００２２】このようにして得た活性炭素多孔体のベン
ゼン吸着度を測定した。なお、ベンゼン吸着度は熱天秤
を用い、試料約１００mg、２５℃飽和蒸気下の吸着によ
る重量増加量を試料の重量で割った値（％）として求め
た。また、平均細孔径は自動比表面積。細孔分布測定装
置を用い、試料の低温におけるＮ2 の等温脱着曲線から
ＣＩ法により求めた。結果を表．１に示す。The benzene adsorption degree of the activated carbon porous material thus obtained was measured. The benzene adsorption degree was determined by using a thermobalance as a value (%) obtained by dividing the weight increase due to adsorption under a saturated vapor of 25 ° C. at about 100 mg of the sample by the weight of the sample. The average pore size is the automatic specific surface area. It was determined from the isothermal desorption curve of N2 at low temperature of the sample by the CI method using a pore distribution measuring device. The results are shown in the table. Shown in 1.
【００２３】実施例２ 実施例１において用いたＭＰ粉末の配合量を８０重量部
とする以外は、実施例１と同様に行った。結果を表．１
に示す。Example 2 Example 2 was repeated except that the amount of MP powder used in Example 1 was 80 parts by weight. The results are shown in the table. 1
Shown in.
【００２４】実施例３ 実施例１において用いたＭＰ粉末の代わりに３００メッ
シュパスの黒鉛粉末を用いる以外は、実施例１と同様に
行った。結果を表．１に示す。Example 3 The procedure of Example 1 was repeated, except that the MP powder used in Example 1 was replaced with a graphite powder having a 300-mesh pass. The results are shown in the table. Shown in 1.
【００２５】実施例４ 実施例１において用いたＭＰ粉末の代わりに１５０メッ
シュパスの籾殻粉末を用い、かつ賦活時間を６時間とす
る以外は、実施例１と同様に行った。結果を表１に示
す。Example 4 The procedure of Example 1 was repeated, except that the rice husk powder of 150 mesh pass was used in place of the MP powder used in Example 1 and the activation time was 6 hours. The results are shown in Table 1.
【００２６】実施例５ 実施例１において用いたＭＰ粉末の代わりにパルプ粉末
（山陽国策パルプ社製）を用いる以外は、実施例４と同
様に行った。結果を表．１に示す。Example 5 Example 4 was repeated except that pulp powder (manufactured by Sanyo Kokusaku Pulp Co., Ltd.) was used instead of the MP powder used in Example 1. The results are shown in the table. Shown in 1.
【００２７】比較例１ 実施例１において用いたＭＰ粉末を用いない以外は、実
施例１と同様に行った。結果を表．１に示す。Comparative Example 1 Example 1 was repeated except that the MP powder used in Example 1 was not used. The results are shown in the table. Shown in 1.
【００２８】比較例２ 実施例１において用いたＭＰ粉末の代わりにポリエチレ
ン粉末（略称ＰＥ粉末）を用いる以外は、実施例１と同
様に行った。結果を表．１に併記する。Comparative Example 2 The procedure of Example 1 was repeated except that polyethylene powder (abbreviated as PE powder) was used instead of the MP powder used in Example 1. The results are shown in the table. Also described in 1.
【００２９】比較例３ 実施例１において用いたＭＰ粉末の代わりに小麦粉を用
いる以外は、実施例１と同様に行った。結果を表．１に
示す。Comparative Example 3 The procedure of Example 1 was repeated except that wheat flour was used instead of the MP powder used in Example 1. The results are shown in the table. Shown in 1.
【００３０】比較例４ 比較例１においてＰＥＧを配合しない処方とする以外は
実施例１と同様に行った。この組成の硬化物は炭化時に
割れを生じた。Comparative Example 4 The same procedure as in Example 1 was carried out except that the formulation in Comparative Example 1 was not added with PEG. The cured product of this composition cracked during carbonization.
【００３１】[0031]
【表１】 [Table 1]
【００３２】[0032]
【発明の効果】本発明の製造方法に依れば、原料樹脂組
成物としてレゾール／親油性化合物／親水性化合物から
なる組成物に更に残炭率の高い粉体を配合することによ
り、配合しない組成物から得られる炭素多孔体に比べて
より高密度な活性炭素多孔体構造物を得ることができ
る。この本発明の製造方法で得られた活性炭構造物を二
重層コンデンサの電極として用いた場合、単位体積あた
りの静電容量を大きくできる。このため、コンデンサの
コンパクト化が図れる。また、より高密度の活性炭構造
物が得られることから、活性炭構造物自体の内部抵抗が
小さくなること、及び活性炭構造物の平均細孔直径を大
きくすることができることから、電解液の充放電時の移
動抵抗が小さくなり、コンデンサの内部抵抗をより小さ
くできる。その結果、より大電流の充放電が可能にな
る。EFFECTS OF THE INVENTION According to the production method of the present invention, the composition of resol / lipophilic compound / hydrophilic compound as a raw material resin composition is further compounded with a powder having a high residual carbon ratio, so that it is not compounded. It is possible to obtain an activated carbon porous material structure having a higher density than that of the carbon porous material obtained from the composition. When the activated carbon structure obtained by the manufacturing method of the present invention is used as an electrode of a double layer capacitor, the capacitance per unit volume can be increased. Therefore, the capacitor can be made compact. In addition, since a higher density activated carbon structure can be obtained, the internal resistance of the activated carbon structure itself can be reduced, and the average pore diameter of the activated carbon structure can be increased. The movement resistance of the capacitor becomes small and the internal resistance of the capacitor can be made smaller. As a result, a larger current can be charged and discharged.
Claims (2)
量部、親油性で１００℃以上の沸点を有する常温で液状
の化合物(b) １ないし１００重量部、親水性で１００℃
以上の沸点を有する液状の化合物(c) １ないし１００重
量部、及び残炭率の高い粉体(d) １ないし２００重量部
とからなる混合物の硬化物を形成した後、５００℃以上
の温度で炭化、賦活することを特徴とする活性炭素多孔
体の製造方法。1. Resol type phenolic resin (a) 100 parts by weight, lipophilic compound (b) 1 to 100 parts by weight which is liquid at room temperature and has a boiling point of 100 ° C. or more, hydrophilic 100 ° C.
After forming a cured product of a mixture of 1 to 100 parts by weight of a liquid compound (c) having the above boiling point and 1 to 200 parts by weight of a powder (d) having a high residual carbon content, a temperature of 500 ° C. or higher A method for producing an activated carbon porous body, which comprises carbonizing and activating with.
ェーズピッチ粉末、木粉、籾殻粉砕物、あるいは椰子殻
粉砕物であることを特徴とする請求項１記載の製造方
法。2. The method according to claim 1, wherein the powder having a high residual carbon rate is activated carbon powder, mesophase pitch powder, wood powder, crushed rice husks, or crushed coconut shells.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3196891A JPH0543345A (en) | 1991-08-06 | 1991-08-06 | Production of active carbon porous body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3196891A JPH0543345A (en) | 1991-08-06 | 1991-08-06 | Production of active carbon porous body |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0543345A true JPH0543345A (en) | 1993-02-23 |
Family
ID=16365370
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3196891A Pending JPH0543345A (en) | 1991-08-06 | 1991-08-06 | Production of active carbon porous body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0543345A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1027716A1 (en) * | 1996-12-12 | 2000-08-16 | Corning Incorporated | Activated carbon electrodes for electrical double layer capacitors |
| WO2004019356A1 (en) * | 2002-08-23 | 2004-03-04 | Nisshinbo Industries, Inc. | Electric double-layer capacitor |
| JP2008239391A (en) * | 2007-03-27 | 2008-10-09 | Sumitomo Bakelite Co Ltd | Carbon material, method for manufacturing the same, negative electrode material for secondary cell and nonaqueous electrolyte secondary cell |
-
1991
- 1991-08-06 JP JP3196891A patent/JPH0543345A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1027716A1 (en) * | 1996-12-12 | 2000-08-16 | Corning Incorporated | Activated carbon electrodes for electrical double layer capacitors |
| JP2001506059A (en) * | 1996-12-12 | 2001-05-08 | コーニング インコーポレイテッド | Active carbon electrode for electric double layer capacitor |
| EP1027716A4 (en) * | 1996-12-12 | 2004-12-01 | Corning Inc | Activated carbon electrodes for electrical double layer capacitors |
| WO2004019356A1 (en) * | 2002-08-23 | 2004-03-04 | Nisshinbo Industries, Inc. | Electric double-layer capacitor |
| US7342769B2 (en) | 2002-08-23 | 2008-03-11 | Nisshinbo Industries, Inc. | Electric double-layer capacitor |
| JP2008239391A (en) * | 2007-03-27 | 2008-10-09 | Sumitomo Bakelite Co Ltd | Carbon material, method for manufacturing the same, negative electrode material for secondary cell and nonaqueous electrolyte secondary cell |
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