JP5988075B2 - Carbon material manufacturing method - Google Patents

Description

The present invention relates to a method for producing an organic polymer gel used as an adsorbent material, a catalyst carrier, and a carbon gel raw material used for sewage treatment, waste liquid treatment, an electric double layer capacitor electrode, a gas sensor electrode, and exhaust gas treatment. In addition, the present invention relates to a carbon gel that is a carbonized product thereof and a method for producing the same.

Carbon materials such as activated carbon are preferably used as adsorbents and various electrode materials used for water and sewage treatment and exhaust gas treatment because fine pores develop and the pore surface area is large. In order to further develop the fine pores of carbon materials, normally, porous carbon materials having fine pores generated by carbonization treatment are further heated in an oxidizing gas atmosphere or alkali. An activation treatment is performed such as heating in a non-oxidizing gas atmosphere after mixing with a metal hydroxide or the like.

However, in recent years, interest in the environment has increased, and at the same time, there has been an increase in interest in carbon materials that have developed more highly microscopic pores. Porous carbon materials that can be produced without activation treatment, or highly porous There is a demand for a porous carbon material with controlled slag, and carbon gel is attracting attention as such a porous carbon material. A carbon gel is produced by drying an organic hydroxygel obtained by polymerizing a phenolic compound and an aldehyde compound in a water solvent by a sol-gel reaction to obtain an organic dry gel, and carbonizing the organic dry gel. It is a porous carbon material that can be obtained, and a high pore surface area can be obtained without performing activation treatment. Furthermore, since this carbon gel has highly developed relatively large micropores, high performance can be obtained as an adsorbent or electrode material used in water and sewage treatment. Here, the organic hydroxy gel is composed of an organic dry gel having a three-dimensional network structure and water stored in the organic dry gel. Examples of the organic dry gel forming the three-dimensional network include gelatin by helix formation. , Polyacrylic acid that forms crosslinks by coordination bonds with alkaline earth metal ions, fully saponified polyvinyl alcohol that crosslinks by hydrogen bonds, and aromatic compounds having a plurality of phenolic OH groups (hereinafter referred to as polyhydric phenol compounds) Polyhydric phenol resins that are formed by crosslinking aldehyde compounds are known.

For example, as described in Patent Document 1, the organic hydroxygel is obtained by gelling resorcinol (1,3-dihydroxybenzene), which is a kind of polyhydric phenols, and formaldehyde, using water as a solvent. Can be obtained. Thereafter, the organic hydroxygel can be dried in supercritical carbon dioxide or supercritical water to obtain an organic aerogel. However, there is an economic problem that the cost of resorcinol is high and the production cost is very high, for example, an expensive facility with excellent pressure resistance is required because the fluid is processed at a critical pressure.

On the other hand, Patent Document 2 discloses a technique of polymerizing phenol (monohydroxybenzene) and formaldehyde, which have lower raw material costs than polyhydric phenol compounds, in an aqueous solvent. In this technique, an organic hydroxygel is obtained by increasing the amount of catalyst as compared with the conventional method in order to polymerize phenol, which is less reactive than resorcinol, with formaldehyde. However, in this technique, since a large amount of catalyst is always required, there is a problem that the effect of reducing the raw material cost is small even though inexpensive phenol is used.

On the other hand, Patent Document 3 discloses a technique relating to a method for producing a carbon xerogel in which a wet gel obtained by polymerizing phenol and formaldehyde under a strong acid or strong base catalyst such as hydrochloric acid or sodium hydroxide is convectively dried. In this technique, an organic solvent is added at the time of initial solution preparation, thereby omitting a solvent replacement step with an organic solvent which is indispensable at the time of drying and simplifying the operation. However, in the examples disclosed in the art, since an acid catalyst and a strong base catalyst are used, the obtained carbon xerogel is microporous and the degree of development of mesopores is low. In addition to this, an acid catalyst with a very high concentration is used, and equipment with high corrosion resistance is indispensable. At the same time, a large amount of catalyst remains without solvent replacement, and the original carbon gel is highly concentrated. There were problems such as loss of purity, and evaporation of highly volatile hydrochloric acid to adversely affect the environment and people. Furthermore, in this method, an excess organic solvent relative to the amount of raw material phenol or formaldehyde is used in the polymerization reaction in order to omit solvent substitution at the time of drying, and as such, it is described in the examples under such conditions. The carbon materials produced by acid-catalyzed polymerization reaction according to the conventional method have sufficient mesopore volume, mesopore diameter, surface area, and bulk density inherent in carbon gel obtained using an aqueous solvent. There wasn't.

JP2002-3211 JP2005-15649 Special table 2011-526634

As described above, the conventional technology is very small in production cost due to raw materials and capital investment, or cannot produce organic hydroxy gel with fine pores efficiently due to problems such as raw material reactivity. It did not provide organic hydroxy gel or carbon gel with highly developed pores.

In such a situation, the present inventors have intensively studied. As a result, in the step of polymerizing a phenol compound and an aldehyde compound to obtain an organic hydroxy gel, the polymerization catalyst is a weakly basic catalyst, and a water-organic solvent is used. It has been found that the carbon material obtained by carbonizing the organic hydroxygel obtained by adjusting the proportion (mass percent) of the organic solvent therein has the desired fine pores.

That is, the present invention includes the following (1) to (6).
(1) A carbon material obtained by polymerizing a phenolic compound and an aldehyde compound in a water-organic solvent mixed solution and then carbonizing after drying. The polymerization catalyst is a weakly basic catalyst, and water-organic The carbon material characterized by carbonizing the organic hydroxygel obtained by superposing | polymerizing at 60-120 degreeC whose ratio of the organic solvent in a solvent is 25-55 mass%.
(2) The carbon material according to claim 1, wherein the phenolic compound is phenol and the aldehyde compound is formaldehyde.
(3) The carbon material according to (1) or (2), wherein the BET surface area is 500 to 1000 m ² / g.
(4) The carbon material according to any one of (1) to (3) above, having an average pore diameter of 2 to 50 nm.
(5) The carbon material according to any one of (1) to (4) above, wherein the mesopore volume is 0.5 to 2 ml / g.
(6) The carbon material according to any one of (1) to (5) above, wherein the density is 0.5 to 2 g / cm ³ .

According to the present invention, both micropores and mesopores can be developed, and a high-density organic dry gel or carbon material can be provided at low cost.

The carbon material of the present invention comprises a gelation step of synthesizing an organic hydroxygel by polymerizing a phenolic compound and an aldehyde compound by a sol-gel reaction using a mixed solvent of water and a hydrophilic organic solvent, an organic hydroxygel The drying step and the step of carbonizing the organic hydroxygel are produced. Each process will be described below.

The gelation step of the present invention is a step of synthesizing an organic hydroxy gel by polymerizing a phenol compound and an aldehyde compound in a mixed solvent of water and an organic solvent by a sol-gel method. As the phenol compounds used in the present invention, those having any valence can be used. Phenol, o-cresol, m-cresol, p-cresol, thymol, naphthol for monohydric phenol compounds, resorcinol, catechol, hydroquinone, dihydroxynaphthalene for dihydric phenol compounds, pyrogallol, phloroglucylol for trihydric phenol compounds Etc. Of these, the use of a monohydric phenol compound, more preferably phenol, is preferable for increasing productivity.

Examples of the aldehyde compound used in the present invention include formaldehyde, acetaldehyde, butyraldehyde, salicylaldehyde, benzaldehyde and the like. Among these, it is preferable to use formaldehyde because of its high reactivity. Aldehydes may be a raw material previously dissolved in an aqueous solvent or the like.

The organic solvent used in the present invention is preferably a hydrophilic organic solvent miscible with water, such as methanol, ethanol, 1-propanol, 2-propanol, formic acid, 1-butanol, acetic acid, acetone, tetrahydrofuran, N, N -Dimethylformamide and the like. Among these, it is easy to prepare a water-organic solvent mixed solution in which lower alcohols such as ethanol, 1-propanol, and 2-propanol, which are excellent in versatility and economy, efficiently perform a sol-gel reaction.

In the present invention, the reaction rate of the phenol compound (hereinafter also referred to as P) and the aldehyde compound (hereinafter also referred to as F) in the raw material solution is not particularly limited, but the aldehyde compound (F) relative to the phenol compound (P) is not limited. ) Molar ratio (F / P) is usually 1 to 3, preferably 1.5 to 2.5, more preferably 1.75 to 2.25. If the molar ratio is less than 1, the amount of aldehyde compounds that play a role of crosslinking to form a three-dimensional structure is reduced, making it difficult to produce an organic hydroxygel having the desired microstructure. On the other hand, if it exceeds 3, the amount of the aldehyde compound becomes excessive and the target addition / condensation reaction tends to be inhibited, and at the same time, it tends to remain inside the microstructure and become an impurity.

The present invention is characterized in that a phenol compound and an aldehyde compound are polymerized in a water-organic solvent mixed solution in which the ratio of the organic solvent in the total solvent is 25 to 55% by mass. Preferably, it is adjusted to a specific ratio in this range depending on the kind of the organic solvent. In the case of ethanol, it is 40 to 55% by mass, in the case of 1-propanol, 37 to 53% by mass, in the case of 2-propanol, 27%. A range of ~ 37% by weight can be mentioned. When the proportion of the organic solvent is higher than 55% by mass, the proportion of the organic solvent is increased, so that the reactivity of the aldehyde compound is lowered and it is difficult to obtain desired pores. On the other hand, when the solvent ratio is lower than the specified value, the ratio of the aqueous solvent is increased, so that the reactivity of the phenol compound is lowered and it is difficult to obtain desired pores. Since the optimum value of the solvent ratio varies depending on the type and amount of the phenol compound used, the preparation conditions are appropriately adjusted. Further, the type of organic solvent mixed with water is not limited to one.

The present invention improves the reactivity of the phenolic compound and the aldehyde compound by adding a weakly basic catalyst to the raw material solution during the reaction of the phenolic compound and the aldehyde compound in the gelation step, if necessary. This is preferable because the formation of a three-dimensional network structure can be promoted. Examples of the weakly basic catalyst used in the present invention include sodium carbonate, potassium carbonate, lithium carbonate, sodium hydrogen carbonate, calcium carbonate and the like. Among these, sodium carbonate is preferable from the viewpoint of high safety and economical aspect. When an acidic catalyst is used, molecules are bonded linearly to the phenolic compound, so that a three-dimensional network structure is not constructed and a no-porous novolak resin is obtained, making it difficult to obtain desired pores. In addition, when a strong alkali such as sodium hydroxide is used, the reactivity is extremely higher than that of a weak base catalyst, so that it hardens before a three-dimensional network structure is formed, and it is difficult to obtain desired pores.

In the case of using a weakly basic catalyst, the blending amount thereof can be appropriately selected in consideration of the type of weakly basic catalyst and the solubility of the catalyst in a solvent. And the catalyst has a molar ratio (P / C) of 1 to 200, more preferably 30 to 80. When the amount of the catalyst is within this range, a large number of colloidal particles are generated in a short time, which is preferable because a desired three-dimensional structure is easily constructed.

In the gelation step, the reaction conditions for the sol-gel reaction are not particularly limited, but the reaction temperature is usually 60 to 120 ° C, preferably 80 to 100 ° C. When the reaction temperature is less than 60 ° C., the sol-gel reaction takes too much time, and the productivity tends to be greatly reduced. On the other hand, when the reaction temperature exceeds 100 ° C., the boiling point of the solvent is exceeded, so that the pressure in the reaction vessel rapidly increases and an expensive pressure vessel needs to be used, which is economically undesirable. Moreover, reaction time is 7 to 240 hours normally, Preferably it is 24 to 120 hours. If the reaction time is less than 7 hours, the progress of the sol-gel reaction is insufficient, so that the structure of the organic hydroxygel tends to become unstable and the strength tends to decrease. In addition, when the reaction time exceeds 240 hours, the cumulative evaporation amount of the solvent in the reaction system increases, and the organic hydroxy gel contracts accordingly, and the unique structure of the organic hydroxy gel tends to be lost.

The organic hydroxy gel can be dried to obtain an organic dry gel. A drying method capable of removing the solvent remaining in the three-dimensional network structure can be appropriately selected while maintaining the three-dimensional network structure of the fine particles constituting the organic hydroxygel. Examples of the drying method used in the present invention include hot air drying, vacuum drying, freeze drying, supercritical drying, and microwave drying. Among these, lyophilization, warm air drying, and microwave drying are preferable in terms of economy.

In the freeze-drying in the present invention, the freezing temperature is not particularly limited, but is usually −30 to −5 ° C., and preferably −15 to −10 ° C. It is preferable that the freezing temperature is within this range because a commonly used freeze-drying apparatus can be used and the drying speed can be relatively increased. Moreover, when performing microwave drying, it is although it does not specifically limit as an output of a microwave, Usually, 0.1-10 kW / kg, Preferably it is 0.5-5 kW / kg. It is preferable that the output of the microwave be within this range because structural destruction of the organic hydroxygel due to rapid vaporization of the solvent can be suppressed and the drying rate can be relatively increased. Moreover, when performing warm air drying, although it does not specifically limit as preset temperature, Usually, 20-150 degreeC, Preferably, it is 30-90 degreeC. It is preferable for the set temperature to fall within this range because a commonly used hot air or dryer can be used and the drying rate can be relatively increased.

The carbonization step in the present invention is a step of producing a carbon material having fine pores by heating and pyrolyzing the organic dry gel in a non-oxidizing gas atmosphere. Although it does not specifically limit as carbonization temperature used by this invention, Usually, 200-1200 degreeC, Preferably it is 300-1000 degreeC. If the carbonization temperature is too low, it is not preferable because the organic dry gel is not sufficiently pyrolyzed and carbonized. On the contrary, if the carbonization temperature is higher than 1200 ° C., the thermal decomposition proceeds excessively, the structure of the organic dry gel tends to collapse, and the structure is easily broken or the strength is lowered. The treatment time is not particularly limited, but is usually 1 to 20 hours, preferably 2 to 10 hours. A treatment time of less than 1 hour is not preferable because the organic dry gel is not sufficiently pyrolyzed and carbonized. On the other hand, if the treatment time is longer than 20 hours, the thermal decomposition proceeds excessively and the structure of the organic dry gel is liable to be destroyed, and the structure is easily broken and the strength is reduced.

The present invention can remove the solvent remaining in the three-dimensional network structure while the three-dimensional network structure of the fine particles constituting the organic hydroxygel is substantially maintained by the above method, and the structure at the time of drying. An organic dry gel is obtained in which no breakage occurs. Further, by carbonizing the organic dry gel, it is possible to obtain a carbon gel in which micropores are developed while maintaining a three-dimensional network structure. In the present invention, the organic dry gel or carbon gel has micropores and mesopores developed. The organic dry gel or carbon gel obtained in the present invention can be used as an adsorbent, various electrode materials, and a catalyst carrier used for water and sewage treatment, exhaust gas treatment, and the like.

The carbon material obtained from the present invention is preferably a carbon material having a BET surface area of 500 to 1000 m ² / g. The meso average pore diameter is preferably 2 to 50 nm. Further, a carbon material having a mesopore volume of 0.5 to 2 ml / g is preferable. Further, a carbon material having a density of 0.5 to 2 g / cm ³ is preferable. Thus, the carbon material of the present invention is a porous material having a high mesopore volume, a small average pore diameter, and a high surface area. Therefore, the carbon material of the present invention is suitable for use as an adsorbent, an electrode material, and a catalyst carrier.

EXAMPLES Hereinafter, although an Example demonstrates this invention in more detail, this invention is not limited to the following Example at all.

(Example 1) 188 parts by mass of phenol (P) as a phenol compound, 325 parts by mass of a 37% by weight formaldehyde aqueous solution (F / P molar ratio = 2) as an aldehyde compound (F), 100 parts by mass of water as a solvent, organic 334 parts by mass of ethanol as a solvent and 4 parts by mass of sodium carbonate as a catalyst were placed in a 20 ml glass bottle, and after moderate stirring, a polymerization reaction was performed at 90 ° C. for 72 hours to obtain 950 parts by mass of an organic hydroxygel. The mixed solvent remaining in the organic hydroxygel was replaced with tert-butyl alcohol, and then lyophilized at a freezing temperature of −10 ° C. for 72 hours to obtain an organic dry gel. The carbon material of the present invention was obtained by pyrolyzing the organic dry gel at 1000 ° C. in an inert gas atmosphere for 4 hours.

(Example 2) 188 parts by mass of phenol (P) as a phenol compound, 325 parts by mass of a 37% by weight formaldehyde aqueous solution (F / P molar ratio = 2) as an aldehyde compound (F), 154 parts by mass of water as a solvent, organic 298 parts by mass of 1-propanol as a solvent and 4 parts by mass of sodium carbonate as a catalyst were placed in a 20 ml glass bottle, and after moderate stirring, a polymerization reaction was performed at 90 ° C. for 72 hours to obtain 950 parts by mass of an organic hydroxygel. The mixed solvent remaining in the organic hydroxygel was replaced with tert-butyl alcohol, and then lyophilized at a freezing temperature of −10 ° C. for 72 hours to obtain an organic dry gel. The carbon material of the present invention was obtained by pyrolyzing the organic dry gel at 1000 ° C. in an inert gas atmosphere for 4 hours.

(Example 3) 188 parts by mass of phenol (P) as a phenolic compound, 325 parts by mass of a 37% by weight aqueous formaldehyde solution (F / P molar ratio = 2) as an aldehyde compound (F), 184 parts by mass of water as a solvent, organic 289 parts by mass of 2-propanol as a solvent and 4 parts by mass of sodium carbonate as a catalyst were placed in a 20 ml glass bottle, and after moderate stirring, a polymerization reaction was carried out at 90 ° C. for 72 hours to obtain 950 parts by mass of an organic hydroxygel. The mixed solvent remaining in the organic hydroxygel was replaced with tert-butyl alcohol, and then lyophilized at a freezing temperature of −10 ° C. for 72 hours to obtain an organic dry gel. The carbon material of the present invention was obtained by pyrolyzing the organic dry gel at 1000 ° C. in an inert gas atmosphere for 4 hours.

(Comparative Example 1) 188 parts by mass of phenol (P) as a phenol compound, 325 parts by mass of a 37% by weight aqueous formaldehyde solution (F / P molar ratio = 2) as an aldehyde compound (F), 329 parts by mass of water as a solvent, organic 153 parts by mass of ethanol as a solvent and 4 parts by mass of sodium carbonate as a catalyst were placed in a 20 ml glass bottle, and after moderate stirring, a polymerization reaction was carried out at 90 ° C. for 72 hours to obtain 950 parts by mass of an organic hydroxygel. The mixed solvent remaining in the organic hydroxygel was replaced with tert-butyl alcohol, and then lyophilized at a freezing temperature of −10 ° C. for 72 hours to obtain an organic dry gel. A carbon material was obtained by pyrolyzing the organic dry gel at 1000 ° C. in an inert gas atmosphere for 4 hours.

(Comparative Example 2) 188 parts by mass of phenol (P) as a phenol compound, 325 parts by mass of a 37% by weight formaldehyde aqueous solution (F / P molar ratio = 2) as an aldehyde compound (F), 58 parts by mass of water as a solvent, organic 375 parts by mass of 1-propanol as a solvent and 4 parts by mass of sodium carbonate as a catalyst were placed in a 20 ml glass bottle, and after moderate stirring, a polymerization reaction was carried out at 90 ° C. for 72 hours to obtain 950 parts by mass of an organic hydroxygel. The mixed solvent remaining in the organic hydroxygel was replaced with tert-butyl alcohol, and then lyophilized at a freezing temperature of −10 ° C. for 72 hours to obtain an organic dry gel. A carbon material was obtained by pyrolyzing the organic dry gel at 1000 ° C. in an inert gas atmosphere for 4 hours.

(Comparative Example 3) 188 parts by mass of phenol (P) as a phenol compound, 325 parts by mass of a 37% by weight aqueous formaldehyde solution (F / P molar ratio = 2) as an aldehyde compound (F), 54 parts by mass of water as a solvent, organic 368 parts by mass of 2-propanol as a solvent and 4 parts by mass of sodium carbonate as a catalyst were put in a 20 ml glass bottle, and after moderate stirring, a polymerization reaction was performed at 90 ° C. for 72 hours to obtain 900 parts by mass of an organic hydroxygel. The mixed solvent remaining in the organic hydroxygel was replaced with tert-butyl alcohol, and then lyophilized at a freezing temperature of −10 ° C. for 72 hours to obtain an organic dry gel. A carbon material was obtained by pyrolyzing the organic dry gel at 1000 ° C. in an inert gas atmosphere for 4 hours.

(Comparative Example 4) 188 parts by mass of phenol (P) as a phenol compound, 325 parts by mass of a 37% by weight aqueous formaldehyde solution (F / P molar ratio = 2) as an aldehyde compound (F), 522 parts by mass of water as a solvent, catalyst As follows, 4 parts by mass of sodium carbonate was put in a 20 ml glass bottle, and after moderate stirring, a polymerization reaction was carried out at 90 ° C. for 72 hours to obtain 1000 parts by mass of an organic hydroxygel. The mixed solvent remaining in the organic hydroxygel was replaced with tert-butyl alcohol, and then lyophilized at a freezing temperature of −10 ° C. for 72 hours to obtain an organic dry gel. A carbon material was obtained by pyrolyzing the organic dry gel at 1000 ° C. in an inert gas atmosphere for 4 hours.

(Comparative Example 5) 188 parts by mass of phenol (P) as a phenol compound, 325 parts by mass of a 37% by weight formaldehyde aqueous solution (F / P molar ratio = 2) as an aldehyde compound (F), 34 parts by mass of water as a solvent, organic 323 parts by mass of ethanol as a solvent and 66 parts by mass of 37% by mass hydrochloric acid solution as a catalyst were placed in a 20 ml glass bottle, and after moderate stirring, a polymerization reaction was performed at 90 ° C. for 72 hours to obtain 900 parts by mass of an organic hydroxygel. . The mixed solvent remaining in the organic hydroxygel was replaced with tert-butyl alcohol, and then lyophilized at a freezing temperature of −10 ° C. for 72 hours to obtain an organic dry gel. A carbon material was obtained by pyrolyzing the organic dry gel at 1000 ° C. in an inert gas atmosphere for 4 hours.

(Comparative Example 6) 188 parts by mass of phenol (P) as a phenol compound, 325 parts by mass of a 37% by weight formaldehyde aqueous solution (F / P molar ratio = 2) as an aldehyde compound (F), 87 parts by mass of water as a solvent, organic 323 parts by weight of ethanol as a solvent and 3.9 parts by weight of a 37% by weight aqueous hydrochloric acid solution as a catalyst were placed in a 20 ml glass bottle, and after moderate stirring, a polymerization reaction was carried out at 90 ° C. for 72 hours to obtain 900 parts by weight of an organic hydroxygel. . The mixed solvent remaining in the organic hydroxygel was replaced with tert-butyl alcohol, and then lyophilized at a freezing temperature of −10 ° C. for 72 hours to obtain an organic dry gel. A carbon material was obtained by pyrolyzing the organic dry gel at 1000 ° C. in an inert gas atmosphere for 4 hours.

(Comparative Example 7) 188 parts by mass of phenol (P) as a phenol compound, 325 parts by mass of a 37% by weight formaldehyde aqueous solution (F / P molar ratio = 2) as an aldehyde compound (F), 36 parts by mass of water as a solvent, organic 323 parts by weight of ethanol as a solvent and 27 parts by weight of 50 w / v% aqueous sodium hydroxide solution as a catalyst are placed in a 20 ml glass bottle, and after moderate stirring, a polymerization reaction is carried out at 90 ° C. for 72 hours, and 850 parts by weight of an organic hydroxygel Got. The mixed solvent remaining in the organic hydroxygel was replaced with tert-butyl alcohol, and then lyophilized at a freezing temperature of −10 ° C. for 72 hours to obtain an organic dry gel. A carbon material was obtained by pyrolyzing the organic dry gel at 1000 ° C. in an inert gas atmosphere for 4 hours.

(Comparative Example 8) 188 parts by mass of phenol (P) as a phenol compound, 325 parts by mass of a 37% by weight formaldehyde aqueous solution (F / P molar ratio = 2) as an aldehyde compound (F), 90 parts by mass of water as a solvent, organic 323 parts by weight of ethanol as a solvent and 2 parts by weight of 50 w / v% aqueous sodium hydroxide solution as a catalyst are placed in a 20 ml glass bottle, and after moderate stirring, a polymerization reaction is carried out at 90 ° C. for 72 hours, and 900 parts by weight of organic hydroxy gel Got. The mixed solvent remaining in the organic hydroxygel was replaced with tert-butyl alcohol, and then lyophilized at a freezing temperature of −10 ° C. for 72 hours to obtain an organic dry gel. A carbon material was obtained by pyrolysis of an organic dry gel at 1000 ° C. for 4 hours in an inert gas atmosphere.

About the carbon gel obtained by the Example and the comparative example, the BET surface area and the mesopore diameter volume were measured with the following method. The results are shown in Table 1.
-BET surface area: N ₂ adsorption / desorption isotherm was measured with a fully automatic gas adsorption device (77K), and calculated by BET method.
-Mesopore volume: N ₂ adsorption / desorption isotherm was measured with a fully automatic gas adsorption device (77K), and calculated by the Dollimore-Heal method.

The carbon materials obtained in Examples 1 to 3 exhibited excellent characteristics in both BET surface area and mesopore pore volume. In particular, in Examples 1 and 3, since the polymerization reaction is performed using a weak base catalyst under conditions where the solvent composition is in a preferable range, the reaction of hydrophobic phenol and hydrophilic formaldehyde smoothly proceeds, resulting in a three-dimensional network. The structure was formed, and the carbon material finally obtained was a preferable material in terms of surface area, mesopore volume and density. While having a three-dimensional network structure, Comparative Example 1 to
In No. 3, the solvent composition was outside the optimum range, so the reactivity was remarkably lowered, and it was difficult to produce a carbon material with both micropores and mesopores. In Comparative Example 4, the desired carbon material could not be obtained because the reactivity of hydrophobic phenol was remarkably lowered when the solvent was only water. In addition, Comparative Examples 5 to 8 use high-concentration hydrochloric acid and high-concentration sodium hydroxide, which are more reactive than weak base catalysts, as the catalyst, so that they harden before becoming the desired structure and become non-porous. The desired structure was not obtained.

Claims (3)

A phenolic compound and an aldehyde compound are polymerized in a water-organic solvent mixed solution (provided that the organic solvent is a hydrophilic organic solvent and the mixed solution does not contain a surfactant) and is organically Obtaining a hydroxy gel,
The obtained organic hydroxy gel includes a step of carbonizing after drying to obtain a carbon material , having a three-dimensional network, having a BET surface area of 500 to 1000 m ² / g, and an average mesopore diameter of 2 A method for producing a carbon material having a mesopore volume of 0.5 to 2 ml / g, which is ˜50 nm ,
The ratio of the organic solvent in the water-organic solvent mixed solution is 25 to 55% by mass,
The catalyst during the polymerization is a weakly basic catalyst,
The polymerization temperature is in the range of 60 to 120 ° C. ,
A method for producing a carbon material, wherein the molar ratio (F / P) of the aldehyde compound (F) to the phenol compound (P) is in the range of 1.5 to 2.5 . The production method according to claim 1, wherein the phenol compound is phenol and the aldehyde compound is formaldehyde. The manufacturing method according to claim 1, wherein the carbon material has a density of 0.5 to 2 g / cm ³ .