JPH0543349A - Production of porous active carbon structure - Google Patents

Abstract

PURPOSE:To provide a method for readily producing a porous active carbon structure by forming a structure composed of a raw material polymer of the active carbon by using a simple method and subsequently carbonizing and activating it. CONSTITUTION:In a processing for curing a mixture composed of 100 pts.wt. resol-type phenol resin (a), 1-100 pts.wt. hydrophobic compound (b) having >=100 deg.C boiling point and showing a liquid state at normal temperatures and 1-100 pts.wt. hydrophilic liquid compound (c) low in actual carbon ratio and having >=100 deg.C boiling point, a resin composition structure is formed by forcedly shaping the mixture by a shaping member at a stage capable of plastic deformation after the fluidity of the mixture is lost. Carbonization and activation are subsequently carried out at >=500 deg.C. The method for producing the porous active carbon structure in this invention is characterized thereby.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a structure of activated carbon porous material. More specifically, it relates to a method for producing an activated carbon porous material structure suitable for use in an electrode of an electric double layer capacitor, ozone decomposition, a deodorizing filter and the like.

[0002]

2. Description of the Related Art Conventionally, a structure containing activated carbon as a main component has been used for applications such as electrodes of electric double layer capacitors, ozone decomposition and deodorizing filters. A method known so far as a method for producing such an activated carbon structure is, for example, JP-A-58-84180. In this method, excess activated carbon powder or carbon powder is mixed with a small amount of a binder resin, which is vigorously stirred with a device having a large horsepower such as an extruder, poured into a mold under pressure, and solidified by heating. It was something that caused it.

[0003]

In such a method, the viscosity of the resin composition is high, and it is difficult to add a large amount of a curing agent to the resin composition. As a result, the curing rate becomes slower and the curing hardly progresses at a temperature of 100 ° C. or lower, and therefore, a method of treating at a high temperature in a mold is adopted. As a result, there are problems that the process becomes complicated and many molds are required. The present invention provides a method for easily producing an activated carbon porous body structure by molding a structure of a raw material resin composition of activated carbon by a simple method and then carbonizing and activating the structure.

[0004]

Means for Solving the Problems That is, the present invention is based on 100 parts by weight of a resol type phenolic resin (a) and 10 parts by lipophilicity.
Consists of 1 to 100 parts by weight of a compound (b) having a boiling point of 0 ° C or higher at room temperature and 1 to 100 parts by weight of a liquid compound (c) which is hydrophilic and has a low residual carbon rate and a boiling point of 100 ° C or higher. In the step of hardening the mixture, after the mixture stops flowing, it is forcibly shaped by a shaping member at a stage where it can be plastically deformed to form a structure of the resin composition, and then a temperature of 500 ° C. or higher. The method for producing an activated carbon porous body structure is characterized in that carbonization and activation are carried out.

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 at room temperature of 1000 to 20000 cps, 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 liquid at room temperature is, for example, a straight chain compound such as octane, nonane, decane, undecane, dodecane, kerosene, mineral oil, liquid paraffin, or the like. Examples thereof include branched alkyl 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.

The amount of the lipophilic compound (b) to be blended per 100 parts by weight of the resol type phenol resin (a) is usually 1 to 1.
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.

The liquid compound (c) having a boiling point of 100 ° C. or higher in the present invention is, for example, an oxyalkylene compound having a degree of polymerization of 2 or higher, such as diethylene glycol, triethylene glycol or 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 or glycerin. 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.

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. When the amount of the hydrophilic compound (c) is too small, the dispersion stability of the lipophilic compound (b) is poor, and phase separation easily occurs. On the other hand, when the amount exceeds the above range, the curing property of the resole is impaired, and the hydrophilicity is high. The compound and the resole are easily phase separated.

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.

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.

In the present invention, the resol type phenolic resin (a) is a lipophilic compound having a boiling point of 100 ° C. or higher and is liquid at room temperature (b), and a hydrophilic liquid compound having a boiling point of 100 ° C. or higher (c) is used. If necessary, a mixture of a surfactant, other filler, etc. is stirred and mixed, and / or at the same time, a curing agent is mixed. As a method of mixing the above components, a method of continuously, batchwise, or simultaneously using a mixer having a stirring blade that rotates at high speed can be preferably used.

In the production method of the present invention, in the step of curing the resin composition, after the mixture stops flowing, it is forcibly shaped by a shaping member at a stage where it can be plastically deformed to form a polymer structure. To do. The shaping member does not have to have a particularly strong material, and may be a material such as rubber or plastic. Of course, hard materials such as metals and ceramics can also be effectively used. The shape of the shaping member is not particularly limited, but a roll shape is preferable if continuous productivity is important. This operation is preferably performed immediately after the resin composition starts to cure and loses fluidity.

According to the method of using such a roll, which is one aspect of the present invention, if the surface of the roll is smooth, a sheet having a smooth surface, and thus a smooth sheet-like activated carbon porous material can be obtained. Further, by using a roll having an embossed pattern formed on the surface, an activated carbon porous material having an embossed pattern can be obtained. Furthermore, if you use a roll with pins,
It is possible to obtain a sheet of activated carbon porous material in which numerous holes are formed.

In the production method of the present invention, the polymer mixture is subsequently cured. Curing is carried out at room temperature to 100 ° C, preferably at 50 to 90 ° C.

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.

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. Heating temperature is 600 ° C-120
The temperature is 0 ° C, preferably 750 to 1000 ° C. As the oxidizing gas, known oxidizing gases such as water vapor, carbon dioxide, oxygen, air and the like are used. These are usually mixed with an inert gas such as N2 for easy control.

[0018]

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 hydrophilic 3 parts by weight of 25 parts by weight of polyethylene glycol (abbreviation PEG) having a molecular weight of 600 as a compound and 25 parts by weight of liquid paraffin (abbreviated flow para) as a high-boiling lipophilic compound
The mixture was thoroughly stirred for 5 minutes at a speed of 6000 rpm by means of a stirrer having a stepped pin blade. The viscosity of this mixture is 3500
It was cps.

To this mixture was added 20 parts by weight of paratoluenesulfonic acid as a curing agent, and the mixture was stirred at the same stirring speed for 1 minute. This mixture was placed on a 0.5 mm thick Teflon-coated glass fiber woven belt. After 5 minutes of stirring, the resin composition started to cure and completely stopped flowing.
At this time, while moving the belt, the resin composition was passed through the gap between the two nitrile rubber rolls adjusted to 4 mm to prepare a sheet having a thickness of 3.5 mm. This sheet was left in an air oven at 70 ° C. for 30 minutes to produce a plate of a polymer cured product.

The plate of the cured product of this polymer was placed in an electric furnace to obtain N
2 In an atmosphere, raise the temperature to 700 ° C at a rate of 1.5 ° C / min,
After holding at the same temperature for 1 hour, it was cooled. The carbon porous plate obtained by the above method was manufactured. This carbon porous sheet is 5m thick
m ceramic fiber board box, and then put this box in an electric furnace and N2 atmosphere at a rate of 3 ° C / min for 900
The temperature is raised to ℃, and then an activating gas is introduced at a ratio of N2 / H2O = 9/1 for 4 hours and then cooled to a length of 75 mm × width of 75 m.
A plate of activated carbon porous material having an mx thickness of 3 mm was produced.

Comparative Example 1 50 parts by weight of the liquid resol type phenol resin used in Example 1 in place of the composition used in Example 1 and 50 parts by weight of a resole type phenol resin powder (trade name: Bell Pearl, manufactured by Kanebo Co., Ltd.) A mixture consisting of parts was prepared. The viscosity of this mixture was high and could not be measured by a normal viscometer. This resin mixture had no flowability. Therefore,
Even if the curing agent was added, it could not be stirred uniformly. Then, the mixture containing no curing agent was passed between the rolls after the same time as in Example 1, but the resin composition adhered to the rolls and did not form a good sheet. Also, when this composition was left in an air oven for 10 hours, the resin did not cure.

Comparative Example 2 Comparative Example 1 was carried out in the same manner as Comparative Example 1 except that the temperature of the air oven was 110 ° C. The plate began to cure after 5 hours, but bubbles formed on the plate surface.

Comparative Example 3 30 parts by weight of the liquid resol type phenolic resin used in Example 1 in place of the composition used in Example 1, and 1
A mixture consisting of 70 parts by weight of 00 mesh pass coke powder was prepared using a kneader. The viscosity of this mixture was high and could not be measured by a normal viscometer. This resin mixture had no flowability. A sheet was formed from the mixture in the same manner as in Example 1. The presence of large bubbles was observed in this sheet. The sheet was left in an air oven at 80 ° C. for 10 hours, but it did not cure.

Comparative Example 4 The procedure of Example 1 was repeated, except that the flow paraffin was not added in Comparative Example 1. A sheet of this composition was cracked during carbonization and a carbon porous plate could not be obtained.

Comparative Example 5 The same procedure as in Example 1 was carried out except that the formulation in Comparative Example 1 did not contain PEG. In this composition, liquid paraffin separated before curing, and a sheet having a good appearance could not be obtained.

[0026]

EFFECTS OF THE INVENTION According to the production method of the present invention, a thin resin sheet can be formed by utilizing the excellent fluidity of the composition of resol / lipophilic compound / hydrophilic compound used as the raw material resin composition. It can be molded. For example, a thin activated carbon porous body having a thickness of about 1 mm can be easily manufactured. Further, since the curing agent can be easily mixed, the molding speed can be increased as compared with the conventional method. In addition, since the composition used in the method of the present invention has excellent releasability from other resins after curing, any material can be used as the shaping material. Also, the production speed can be increased. From the above, according to the manufacturing method of the present invention, a thin activated carbon porous material required as an electrode of an electric double layer capacitor can be efficiently manufactured in a large amount. Further, by using a roll having irregularities or pins, an activated carbon porous body having holes and an activated carbon porous body having irregularities can be obtained. The activated carbon porous material having such a shape can be effectively used for applications such as a deodorizing filter and ozone decomposition.

Claims (1)

[Claims] 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 higher, hydrophilic and low residual carbon ratio 100 ° C. In the step of curing the mixture consisting of 1 to 100 parts by weight of the liquid compound (c) having the above boiling point, the mixture is forcibly shaped by the shaping member at the stage where it can be plastically deformed after the mixture stops flowing. Form a structure of the resin composition, and then carbonize at a temperature of 500 ° C. or higher,
A method for producing an activated carbon porous body structure, which comprises activating.