JP5947585B2 - Method for producing spherical phenol resin granulated product, method for producing carbon material, and method for producing activated carbon material - Google Patents

Description

  The present invention relates to a method for producing a spherical phenol resin granulated product, a method for producing a carbon material, and a method for producing an activated carbon material.

Lithium ion secondary batteries, which are a type of non-aqueous electrolyte secondary battery, are lightweight and have high energy density, and can be used as power sources for power sources such as portable small electronic devices, hybrid cars, and electric vehicles. Increasingly. As these power supplies become more sophisticated, their power consumption is increasing, and lithium ion secondary batteries used as the power supplies are required to have higher capacities. In addition to the high capacity, the power supply is also required to have excellent rapid charge / discharge characteristics and excellent cycle characteristics. Thus, with the demand for higher performance for lithium ion secondary batteries, higher performance is also required for the negative electrode material that is a constituent member thereof.
In general, in order to increase the output of a lithium ion secondary battery, it is effective to shorten the diffusion path of lithium ions in order to increase the doping / undoping rate. There is a method of reducing the particle size of the carbon material which is an active material.

Apart from lithium ion secondary batteries, electric double layer capacitors have been widely used as small backup power sources with excellent charge / discharge cycle characteristics and rapid charging. This electric double layer capacitor is currently used in a wide range of small-sized capacitors mainly for memory backup applications in communication equipment. Recently, with the expansion of applications, it has come to be expected as a device suitable for a hybrid car, a motor of a fuel cell vehicle, a storage of regenerative energy, and the like that require a higher capacity and a larger current. However, at present, it cannot be said that an excellent electric double layer capacitor has been obtained from the viewpoint of energy density and output, or from the viewpoint of reduction of output in a low temperature range, and further improvement is required.
In general, in an electric double layer capacitor, there is a close relationship between the specific surface area of an activated carbon material, which is an active material, and the capacity and output. As the specific surface area of the activated carbon material increases, the amount of electrolyte ions stored on the surface increases and the capacity increases. However, when the specific surface area is increased by opening deep pores in the activated carbon material, the movement path of the electrolyte ions passing through the active material becomes longer and the electrolyte ions interfere with each other when entering and leaving the pores. As a result, the charge cannot be transferred quickly, and the output characteristics deteriorate. Therefore, a method for reducing the particle diameter of the active material has been proposed as a method for improving the capacity and output of the electric double layer capacitor. When the particle diameter of the active material is reduced, the surface area per unit mass of the active material increases. For this reason, many pores are vacated over the entire surface under normal activation treatment conditions, and the pores become shallow although they have a high specific surface area. Thereby, the movement path | route of electrolyte ion is restrained short, As a result, it leads to high capacity | capacitance and high output. Moreover, even in a low temperature range where the viscosity of the electrolytic solution increases, the electrolyte ion movement path is short, which leads to an improvement in output reduction.

  The lithium ion secondary battery has a high energy density and can be driven for a long time. In addition, the electric double layer capacitor can be rapidly charged and discharged, and has a long use life. In recent years, lithium ion capacitors have been developed as power storage devices that combine the advantages of such lithium ion secondary batteries and electric double layer capacitors. This is to store energy by using the electric double layer capacity on the surface of the activated carbon material on the positive electrode side and the intercalation capacity of lithium ion to the carbon material on the negative electrode side, and it has large capacity and high-speed charge / discharge performance. It is an energy storage device that is to be realized in a balanced manner. The electric double layer capacity used on the positive electrode side is the same as in the case of the electric double layer capacitor, and the increase in capacity as a lithium ion capacitor is related to the physical properties of the activated carbon material that is the positive electrode active material. Yes. Therefore, also in the lithium ion capacitor, by reducing the particle size of the positive electrode active material, the surface area per unit mass increases, and the pores become shallow, so that the movement path of the electrolyte ions can be kept short, and as a result, High capacity and high output.

As described above, the active material for the negative electrode of the lithium ion secondary battery, the active material for the electric double layer capacitor electrode, and the active material for the positive electrode of the lithium ion capacitor (hereinafter, these may be collectively referred to as “electrode material”). Is required to reduce the particle size. As the electrode material, a phenol resin is preferable from the viewpoint of solid-phase carbonization during carbonization, amorphous carbon, high carbonization yield, and easy activation.
However, even if the conventional phenol resin or its carbide (carbon material) or its activated carbon material is pulverized to reduce the particle size, there is a limit to the particle size that can be reduced, and the shape thereof is not uniform. . Moreover, even if the particle size can be reduced to a desired particle size by pulverization, voids increase when the electrode is filled, and the packing density per unit volume is lowered. In addition, since the inside of the particle that does not reach the activation treatment appears on the surface, there is a problem that the effect as the electrode material cannot be sufficiently obtained.

On the other hand, for example, the following method has been proposed as a method for obtaining a phenol resin having a small particle size regardless of pulverization.
(1) Reaction of a compound having two or more phenolic hydroxyl groups per benzene ring and an aldehyde in the presence of water without using a surfactant or under a basic catalyst. A slurry is prepared, and an acetone solution of a dried product of the slurry is centrifuged to finally obtain spherical resin fine particles (see Patent Document 1).
(2) A method of obtaining spherical resin fine particles by reacting resorcin and an aldehyde source in water to prepare a fine particle aqueous dispersion, centrifuging the fine particle aqueous dispersion, and drying and crushing (patent) Reference 2).
(3) A method for obtaining a spherical phenol resin by subjecting a phenol and an aldehyde to a condensation reaction in an aqueous medium in the presence of a condensation reaction catalyst and an emulsifying dispersant under conditions of a predetermined temperature and pressure (patent) Reference 3).

Japanese Patent No. 3655183 Japanese Patent No. 3724789 Japanese Patent No. 3576433

However, in the methods described in Patent Documents 1 and 2, in order to separate and recover the spherical resin fine particles, it is necessary to perform a separation operation using a centrifuge, but industrially a large centrifuge is used. Is inefficient and impractical. In addition, the spherical phenol resin separated and recovered by centrifugation is likely to be a hard and tight lump, and it is not rational from the viewpoint of workability such that crushing is indispensable to prevent poor cleaning.
Moreover, in the method described in Patent Document 3, the particle size of the obtained spherical phenol resin is about 1 μm to 1 mm, which is the range of particle size distribution of general suspension polymerization, and a particle having a smaller particle size is produced. Difficult to do. In addition, since an emulsifying dispersant is used, the smaller the particle size of the spherical phenol resin, the more difficult it is to settle, and it takes a long time to separate and recover. In addition, since the emulsifying dispersant, the catalyst, and the unreacted raw material remain in the reaction liquid containing the spherical phenol resin, it is difficult to recover and to recover only the spherical phenol resin when the reaction liquid is dried as it is. When carbonization or activation is performed, there is a problem that it is difficult to obtain a fine spherical carbon material or activated carbon material.

  The present invention has been made in view of the above circumstances, and a spherical phenol resin capable of controlling the average particle diameter of fine spherical phenol resin particles and efficiently recovering the spherical phenol resin particles without performing centrifugation. It is an object to provide a method for producing a granulated product, a method for producing a carbon material using a spherical phenol resin granulated product obtained by the production method, and a method for producing an activated carbon material.

The present inventors synthesize a phenol resin by a condensation reaction of phenols containing polyhydric phenols and aldehydes, and in addition, by separating and recovering the phenol resin using an organic coagulant, The inventors have found that the above problems can be solved and have completed the present invention.
That is, the present onset Ming, in an aqueous medium in the presence of a condensation reaction catalyst of a phenol and an aldehyde containing a polyhydric phenol by a condensation reaction, spherical spherical phenol resin is dispersed phenolic resin dispersion The step (1) of obtaining a coagulated product by adding an organic coagulant to the spherical phenol resin dispersion, the step (3) of separating and collecting the coagulated product, and the separation and recovery The step (4) of obtaining a dried product by drying the aggregate, the step (5) of obtaining a mixture by mixing the dried product and a binder, and the step of obtaining a granulated product by granulating the mixture (6). ) and have a includes phenols containing the polyvalent phenols, and one or more polyhydric phenols selected from dihydric phenols and trivalent phenols, and monohydric phenols, wherein step (1 ) At the temperature of 10 To 200 DEG ° C., and carrying out under a pressure 0.13～1.5MPa, a method for producing a spherical phenol resin granules for carbonization, activation.

In the method for producing a spherical phenol resin granulated product of the present invention, the condensation reaction catalyst is preferably a basic catalyst .
In the method for producing a spherical phenol resin granulated product of the present invention, it is preferable that an average particle size of the spherical phenol resin dispersed in the spherical phenol resin dispersion is 0.05 to 10 μm.

The carbon material production method of the present invention is characterized by carbonizing the spherical phenol resin granulated product produced by the spherical phenol resin granulated product production method of the present invention.
In the method for producing a carbon material of the present invention, it is preferable to crush after the carbonization.

Moreover, the manufacturing method of the activated carbon material of this invention is activated after carbonizing the spherical phenol resin granulated material manufactured by the manufacturing method of the spherical phenol resin granulated material of the said invention, It is characterized by the above-mentioned.
In the manufacturing method of the activated carbon material of this invention, it is preferable to crush after the said activation.

With the method for producing a spherical phenol resin granulated product of the present invention, fine spherical phenol resin particles can be efficiently recovered without performing centrifugation. In addition, the average particle diameter of the spherical phenol resin particles can be easily controlled. In addition, a spherical phenol resin granulated product capable of maintaining a fine particle shape can be obtained even when carbonization is performed, despite containing a binder.
Moreover, the fine spherical carbon material and the fine spherical activated carbon material can be obtained by the carbon material production method and the activated carbon material production method of the present invention, respectively.

1A is a scanning electron micrograph of the dried product obtained in step (4) in Example 1. FIG. FIG. 1B is a scanning electron micrograph of a spherical activated carbon material obtained after activation in Example 1. FIG. 2 is a scanning electron micrograph of the dried product obtained in step (4) in Example 3. It is sectional drawing of the coin-type electric double layer capacitor used in the present Example. It is a graph which shows the result of having measured the discharge capacity at the time of repeating charge / discharge of 100 cycles about the electric double layer capacitor. It is a graph which shows the result of having calculated | required the initial stage discharge capacity maintenance factor when changing an electric current about the electric double layer capacitor. It is sectional drawing of the coin-type lithium ion secondary battery used in the present Example. It is a graph which shows the result of having measured the discharge capacity at the time of repeating charge / discharge of 20 cycles about the lithium ion secondary battery. It is a graph which shows the result of having calculated | required the initial discharge capacity maintenance factor when changing an electric current about the lithium ion secondary battery.

<Method for producing spherical phenol resin granulated product>
In the method for producing a spherical phenol resin granule according to the present invention, a spherical phenol resin is dispersed in an aqueous medium by subjecting a phenol containing a polyhydric phenol and an aldehyde to a condensation reaction in the presence of a condensation reaction catalyst. A step (1) of obtaining a spherical phenol resin dispersion, a step (2) of obtaining a coagulated product by adding an organic coagulant to the spherical phenol resin dispersion, and a step of separating and recovering the coagulated product (3) ), Drying the separated and recovered coagulated product to obtain a dried product (4), mixing the dried product and a binder to obtain a mixture (5), and granulating the mixture to produce a mixture. (6) which obtains a granule.

[Step (1)]
In step (1), a spherical phenol resin dispersion in which a spherical phenol resin is dispersed is obtained by subjecting a phenol containing polyhydric phenols and an aldehyde to a condensation reaction in an aqueous medium in the presence of a condensation reaction catalyst. obtain.

(Phenols)
In the method for producing a spherical phenol resin granulated product of the present invention, phenols containing polyhydric phenols are used.
As used herein, “polyhydric phenol” refers to an aromatic hydroxy compound having two or more hydroxy groups bonded to one aromatic ring. The aromatic ring means a conjugated unsaturated ring structure in which the number of electrons contained in the π-electron system on the ring is 4n + 2 (n = 0 or natural number), and includes both monocyclic and polycyclic rings. Examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, phenanthrene, indene and fluorene. Therefore, in the present invention, bisphenol is included in monohydric phenol.

The polyhydric phenols in the present invention are preferably dihydric phenols or trihydric phenols.
Examples of the dihydric phenols include catechol, resorcinol, hydroquinone, dihydroxynaphthalene and the like, and resorcinol is particularly preferable.
Examples of the trihydric phenol include pyrogallol and phloroglucinol.
Phenols may be used alone or in combination of two or more.

In the present invention, by using those containing polyhydric phenols as phenols, the condensation reaction rate is increased and fine spherical phenol resin particles are easily obtained.
As phenols, it is preferable to use monohydric phenols together with polyhydric phenols. Among these, it is particularly preferable to include one or more polyhydric phenols selected from dihydric phenols and trihydric phenols and monohydric phenols.
As monohydric phenols, phenol, o-cresol, m-cresol, p-cresol, styrenated phenol, alkylphenol substituted with an alkyl group having 2 to 9 carbon atoms, o-phenylphenol, m-phenylphenol, p -Phenylphenol, xylenol, 1-naphthol, 2-naphthol, bisphenol A and the like. Of these, phenol is preferred.

According to the reaction between polyhydric phenols and aldehydes, a fine spherical phenol resin centered on a particle size of 0.1 μm can be obtained in a short time, but it is difficult to control the particle size in this reaction. By containing one or more polyhydric phenols selected from polyhydric phenols, particularly dihydric phenols and trihydric phenols, and monohydric phenols, a fine spherical phenol resin (about 0.05 to 1 μm) Can be easily obtained, and the particle size can be easily controlled.
The mixing ratio of the monohydric phenol and the polyhydric phenol is preferably a monohydric phenol / polyhydric phenol = 0.5 / 9.5 to 5/5, and 1/9 to 5/5 in terms of molar ratio. Is more preferable, and 2/8 to 5/5 is more preferable. When this molar ratio is at least the preferred lower limit, a spherical phenol resin having a smaller particle size can be easily obtained. On the other hand, when the molar ratio is less than or equal to the preferable upper limit value, the particle size can be easily controlled.
The “molar ratio” as used herein means a ratio obtained by converting each usage amount (preparation amount) of monohydric phenols and polyhydric phenols used in the condensation reaction in the step (1) into moles.

(Aldehydes)
Examples of aldehydes include formaldehyde, acetaldehyde, benzaldehyde, terephthalaldehyde, hydroxybenzaldehyde, furfural, paraformaldehyde and the like. Of these, formaldehyde and paraformaldehyde are preferable.
Aldehydes may be used alone or in combination of two or more.

(Condensation reaction catalyst)
As the condensation reaction catalyst, ammonia, hexamethylenetetramine, monoethanolamine, ethylenediamine, diethylenetriamine, triethylenetetraamine, tetraethylenepentamine, pentaethylenehexamine, N- (2-aminoethyl) ethanolamine, N- (2- An amine compound having one or more amino groups (—NH ₂ ) such as aminoethyl) propanolamine; and metal salts such as sodium carbonate and calcium carbonate. Among them, an amine compound having amino groups (-NH ₂₎ 1 or more.
Among amine compounds having 1 or more amino group (-NH _2), ethylenediamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, an alkyl amine compound having 2 or more pentaethylenehexamine an amino group (-NH ₂₎ Is particularly preferred.
A condensation reaction catalyst may be used individually by 1 type, and may use 2 or more types together.
The condensation reaction between phenols and aldehydes is preferably performed in the presence of a basic catalyst. By using a basic catalyst as the condensation reaction catalyst, a suitable thermosetting resin (resole resin) can be obtained from the viewpoint of heat resistance in carbonization.

(Condensation reaction between phenols and aldehydes)
The condensation reaction of phenols and aldehydes is performed by mixing phenols and aldehydes in an aqueous medium in the presence of a condensation reaction catalyst.
The aqueous medium is a medium containing water, and the condensation reaction is preferably carried out in a medium containing 50% by mass or more, more preferably 80% by mass or more of water in the system. The aqueous medium may contain alcohol or the like as a solvent other than water. Solvents other than water may be used alone or in combination of two or more.
The condensation reaction between phenols and aldehydes is carried out, for example, by charging phenols, aldehydes, condensation reaction catalyst, and water in a pressure-resistant reaction vessel (autoclave, etc.) that can be sealed, and sealing the reaction tank. While mixing under high pressure.

  The mixing ratio of phenols and aldehydes is preferably 0.6 to 4 mol, and more preferably 1 to 3 mol, per mol of phenol. If the molar ratio of aldehydes to 1 mol of phenol is equal to or greater than the preferred lower limit, the condensation reaction proceeds sufficiently. On the other hand, unreacted aldehydes are further reduced when the molar ratio is not more than the preferred upper limit. The “molar ratio” referred to here means a ratio in terms of the respective amounts used (charges) of phenols and aldehydes used in the condensation reaction in step (1) in terms of moles.

  The amount of the condensation reaction catalyst used is preferably 0.01 to 1 part by mass and more preferably 0.05 to 0.3 part by mass with respect to 100 parts by mass of the phenols. When the amount of condensation reaction catalyst used is not less than the preferred lower limit, the condensation reaction proceeds favorably. On the other hand, when the amount of condensation reaction catalyst used is less than or equal to the preferred upper limit, the time for removing the condensation reaction catalyst is short. Therefore, it is possible to suppress a decrease in productivity.

The method for mixing phenols and aldehydes is not particularly limited, and the Reynolds number representing the mixing conditions is preferably 0 to 10 ⁵ , more preferably 10 ² to 10 ⁴ . When the Reynolds number is within this range, a uniform spherical phenol resin dispersion is easily obtained.

The condensation reaction between phenols and aldehydes is preferably carried out under high temperature and pressure. Thereby, since the condensation reaction proceeds efficiently, unreacted substances such as phenols and aldehydes hardly remain in the spherical phenol resin dispersion. In addition, a high-density, high-molecular weight spherical phenol resin is easily obtained.
“Under high temperature and high pressure” here means a temperature exceeding 100 ° C. and a pressure exceeding atmospheric pressure.
The reaction temperature in the condensation reaction is preferably 105 to 200 ° C, more preferably 110 to 170 ° C. When the condensation reaction is carried out under this reaction temperature condition, the reaction rate is increased, a sufficient degree of curing is easily obtained, and a carbon material having a certain physical property is less likely to cause melt agglomeration during subsequent carbonization. Can be obtained stably.
The condensation reaction is preferably performed under a pressure condition of 0.13 to 1.5 MPa, and more preferably 0.2 to 1 MPa.
By controlling the reaction temperature and pressure within the above preferred ranges, the condensation reaction proceeds efficiently, and unreacted products such as phenols and aldehydes are reduced, resulting in fine, high-density, high molecular weight spherical phenols. Resin is easily obtained. In addition, curing is likely to proceed sufficiently in a short time.
The pressure here means the pressure at the time when a predetermined reaction temperature (the above-mentioned preferable reaction temperature) is reached by temperature adjustment such as temperature increase.

In addition, the condensation reaction of phenols and aldehydes in the step (1) is carried out under normal pressure, with the phenols, aldehydes, condensation reaction catalyst, water and It is preferable to start heating from room temperature while mixing and to continue the mixing for a certain time at around 100 ° C., preferably under reflux.
Thus, before mixing under high temperature and high pressure, by mixing at around 100 ° C., uncured spherical phenol resin particles are prevented from fusing with each other, and a single spherical particle is stable. It becomes easy to obtain.

  As for the pH conditions for carrying out the condensation reaction, the pH is preferably in the range of 4 to 9, and more preferably in the range of 5 to 7. If it is this range, a single spherical phenol resin is easy to be obtained. When the pH is 4 or more, the phenol resin particles are less likely to aggregate with each other, and a single spherical shape is easily obtained. On the other hand, if the pH is 9 or less, it becomes difficult to form an agar-like material called aerogel, and it is easy to obtain fine particles.

In the step (1), a spherical phenol resin dispersion in which a spherical phenol resin having a small particle size is dispersed is obtained.
Specifically, a spherical phenol resin dispersion in which a spherical phenol resin having an average particle size of 0.05 to 10 μm, preferably 0.1 to 5 μm, more preferably 0.1 to 3 μm is dispersed is easily obtained.
In the present invention, the “average particle size” means that a spherical phenol resin and activated carbon material of interest are observed with a scanning electron microscope, and about 50 to 200 particles are photographed in one sheet. The average value calculated | required by measuring the ferret diameter (The average of an X-axis direction and a Y-axis direction or an X-axis direction) of ten particles at random from the inside is shown.
In addition, about the spherical phenol resin in a dispersion liquid, an average particle diameter can be calculated | required using the scanning electron micrograph of the dried material obtained after the below-mentioned process (4). This is because the particle size of the spherical phenol resin in the dispersion obtained in the step (1) does not change depending on the operations in the steps (2), (3) and (4).

[Step (2)]
In step (2), an organic coagulant is added to the spherical phenol resin dispersion obtained in step (1) to obtain a coagulated product.
(Organic coagulant)
Organic coagulants include polyethyleneimine, polycondensate of dicyandiamide and formalin, polycondensation of dimethylamine and epichlorohydrin, copolymer of dimethylaminoethyl methacrylate and styrene, polycondensate of melamine and formalin, Examples thereof include polydimethyldiacrylammonium salt, polydiallyldimethylammonium salt, and a copolymer of diallyldimethylammonium salt and acrylamide.
Among these, polydiallyldimethylammonium salt is preferable and polydiallyldimethylammonium chloride is particularly preferable because it easily forms a coagulated product with the spherical phenol resin.
An organic coagulant may be used individually by 1 type, and may use 2 or more types together.

  Since the spherical phenol resin dispersion obtained in the step (1) is usually 100 ° C. or higher, it is first cooled to room temperature to 60 ° C. prior to the step (2). The organic coagulant and water are added and mixed there, and then the mixture is allowed to stand for 30 minutes to 12 hours, preferably 2 to 6 hours, so that the coagulated product settles.

  What is necessary is just to determine the usage-amount of an organic type coagulant suitably according to the kind of organic type coagulant, the spherical phenol resin density | concentration in a dispersion liquid, etc. 0.1-10 mass parts is preferable with respect to a total of 100 mass parts of phenols and aldehydes used at a process (1), and 0.5-5 mass parts is more preferable. When the amount of the organic coagulant used is equal to or more than the preferred lower limit, it becomes easy to obtain a spherical phenol resin as a coagulated product. On the other hand, if it is below the preferable upper limit value, the sedimentation of the aggregate is further promoted.

5-100 mass parts is preferable with respect to 100 mass parts of spherical phenol resin dispersions, and, as for the quantity of the water added with an organic type coagulant | flocculant, 10-50 mass parts is more preferable. When the amount of water used is equal to or more than the preferred lower limit, it becomes easy to obtain a spherical phenol resin as a condensed product. On the other hand, if it is below the preferable upper limit value, the sedimentation of the aggregate is further promoted.
The temperature condition for adding the organic coagulant is preferably 60 ° C. or less, and more preferably from room temperature to 40 ° C. By setting the temperature condition to be equal to or less than the preferable upper limit value, sedimentation of the aggregate is likely to occur. On the other hand, by setting the temperature condition to be equal to or more than the preferable lower limit value, the sedimentation of the aggregate is further promoted.

[Step (3)]
In step (3), the aggregate obtained in step (2) is separated and recovered.
Separation and collection of the aggregate is performed, for example, by decantation that removes the supernatant after the aggregate has settled. During the separation and recovery, it is preferable to wash the condensed matter. Washing is carried out by removing the supernatant, adding new water, and stirring at 60 to 90 ° C. Thereby, unreacted phenols, unreacted aldehydes, condensation reaction catalysts and the like can be removed. Preferably, this washing operation (removal of the supernatant liquid to stirring) is repeated several times until the washing liquid does not become cloudy.

[Step (4)]
In step (4), the condensate separated and recovered in step (3) is dried to obtain a dried product.
As a method of drying the aggregate, a method of drying with hot air is preferable. It is also preferable to perform air drying prior to hot air drying.
The drying device is not particularly limited and is a powder dryer such as a spray dryer or a slurry dryer, which can be used industrially; applying heated air to prevent the spherical phenol resin particles from agglomerating An oscillating fluid dryer that blows and dries from the surface; a hot-air circulating oven or the like can be used.
50-120 degreeC is preferable and the temperature conditions which dry a condensed material have more preferable 60-100 degreeC. The drying time of the aggregate is preferably 1 to 10 hours, more preferably 3 to 6 hours.
The dried product obtained after the step (4) has a form in which spherical phenol resin particles are gathered while maintaining the spherical shape, as shown in FIG.

  If the spherical phenol resin dispersion after the step (1) is directly dried, unreacted phenols, unreacted aldehydes, condensation reaction catalysts, etc. remaining in the spherical phenol resin dispersion are fixed during drying. Then it becomes a lump. In addition, when the carbon material or the activated carbon material is used due to the influence of impurities, problems such as poor quality are likely to occur. In addition, since the aldehydes are evaporated during drying, the working environment is deteriorated.

[Step (5)]
In step (5), the dried product obtained in step (4) and a binder are mixed to obtain a mixture.
When a fine carbon material is activated, the carbon material may flow out of the furnace together with the activation gas continuously introduced into the furnace. Therefore, in the present invention, by mixing and granulating the binder, outflow of the carbon material to the outside of the furnace is suppressed during activation.
In addition, since a binder lose | disappears in the case of carbonization, the shape of the fine phenol resin particle can be maintained even after carbonization.

(Binder)
As the binder, liquid phenol resin, pitch, polyvinyl alcohol, carboxymethyl cellulose, lignin, sugar liquid, and the like are preferable.
A binder may be used individually by 1 type and may use 2 or more types together.

Mixing of the dried product and the binder is performed, for example, by adding a binder and water to the dried product and kneading.
0.5-10 mass parts is preferable with respect to 100 mass parts of dried products, and, as for the usage-amount of a binder, 1-5 mass parts is more preferable. When the amount of the binder used is equal to or more than the preferable lower limit value, the granulated product can be easily generated. On the other hand, if it is below the preferable upper limit, each operation of kneading and granulation can be performed more stably.
3-30 mass parts is preferable with respect to 100 mass parts of dried products, and, as for the usage-amount of water, 5-15 mass parts is more preferable. When the usage-amount of water is more than the preferable lower limit, it can have sufficient viscosity for kneading. On the other hand, if it is below the preferable upper limit, each operation of kneading and granulation can be performed more stably.

[Step (6)]
In step (6), the mixture obtained in step (5) is granulated to obtain a granulated product. In this way, it is possible to continuously perform carbonization and activation by granulating a spherical phenol resin instead of granulating after carbonization.
The granulation method of the mixture is not particularly limited, and rolling granulation, fluidized bed granulation, ejection layer granulation, pulverization granulation, compression granulation, extrusion granulation, and the like are applicable. Specifically, a spherical phenol resin granulated product is obtained by granulating the mixture of the dried product and the binder obtained in step (4) by any of the granulation methods.
Step (6) can be performed simultaneously with step (5). That is, a spherical phenol resin granulated product can be obtained by simultaneously kneading and granulating while adding a binder and water to the dried product obtained in the step (4). Even in this case, any of the granulation methods can be applied.

The method for producing a spherical phenol resin granulated product of the present invention may have other steps in addition to the steps (1) to (6).
As other steps, for example, a step of dehydrating and concentrating the spherical phenol resin dispersion under reduced pressure to obtain a slurry may be provided before and after step (2).

According to the method for producing a spherical phenol resin granulated product of the present invention, in the condensation reaction in the step (1), the use of polyhydric phenols having an increased reaction rate makes it possible to form fine spherical particles of micron to submicron order. Phenolic resin particles can be obtained. In addition, the average particle size of the spherical phenol resin particles can be easily controlled.
In addition, according to the method for producing a spherical phenol resin granulated product of the present invention, the aggregate produced by adding an organic coagulant to the spherical phenol resin dispersion obtained in step (1) can be easily separated and recovered. Therefore, spherical phenol resin particles can be efficiently recovered without performing centrifugation.

  Moreover, the spherical phenol resin granulated product manufactured by the manufacturing method of the spherical phenol resin granulated product of the present invention is composed of a crosslinked phenol resin. Since the spherical phenol resin granulated product does not obtain a significant measurement value in the gelation time (150 ° C.) and flow (125 ° C.) defined in JIS K 6910, it does not melt in the subsequent carbonization, Carbonization treatment is easy.

<Method for producing carbon material>
The method for producing a carbon material of the present invention is characterized in that the spherical phenol resin granulated product produced by the method for producing a spherical phenol resin granulated product of the present invention is carbonized.
For the carbonization of the spherical phenol resin granulated product, a method of carbonizing in a non-oxidizing gas atmosphere using a multi-stage furnace, a rotary kiln furnace, a fluidized bed furnace or the like can be used.
Examples of the non-oxidizing gas include a gas substantially free of oxygen, such as nitrogen, helium, argon, hydrogen, carbon monoxide and the like.
500-2000 degreeC is preferable and the temperature conditions of carbonization have more preferable 700-1500 degreeC. If the carbonization temperature is at least the preferred lower limit, a spherical carbon material having the desired conductivity and mechanical strength can be easily obtained. When it is at least a preferable lower limit, particularly 700 ° C. or higher, a spherical carbon material having high conductivity is easily obtained. Energy consumption is likely to be suppressed if it is not more than a preferred upper limit, particularly 1500 ° C. or less.

In the method for producing a carbon material of the present invention, it is preferable to crush after carbonization. By crushing, the particle size is made uniform and the dispersibility of the particles is also increased. The method for crushing is not particularly limited, and can be performed using a hammer mill, a ball mill, a jet mill, an atomizer or the like.
Moreover, after carbonization or after crushing, classification may be performed as necessary. By performing classification, it is possible to easily control the particle size within a desired range. In particular, in the carbon material after crushing, the crushed material derived from the binder can be removed by this classification. As a classification method, an air classifier, a vibration sieve, or the like can be used.

  According to the method for producing a carbon material of the present invention, a fine spherical carbon material having practical value as an electrode material can be produced industrially.

<Method for producing activated carbon material>
The method for producing an activated carbon material of the present invention is characterized in that the spherical phenol resin granulated product produced by the method for producing a spherical phenol resin granulated product of the present invention is carbonized and then activated.
In order to activate the spherical phenol resin granulated product after carbonization, a conventionally known activation method may be performed using a multistage furnace, a rotary kiln furnace, a fluidized bed furnace, or the like.
Specific examples of the activation method include gas activation methods in which water vapor, carbon dioxide (combustion gas), oxygen (air), and other oxidizing gases are brought into contact with each other at a temperature of 700 to 1200 ° C .; zinc chloride, phosphate, potassium hydroxide, etc. After impregnating the alkali metal compound or acid such as sulfuric acid, a chemical activation method of heating at a temperature of preferably 300 to 800 ° C. in an inert gas atmosphere can be used. In the case of a chemical activation method, after activation, the product and the chemical used can be neutralized with an acid or alkali, or removed by washing with water or the like.
Among the above activation methods, the gas activation method is preferable, and the gas activation method using water vapor is particularly preferable in terms of simplicity of equipment and the point that no special treatment is required after activation.

In the manufacturing method of the activated carbon material of this invention, it is preferable to crush after activation. By crushing, the particle size is made uniform and the dispersibility of the particles is also increased. The method for crushing is not particularly limited, and can be performed using a hammer mill, a ball mill, a jet mill, an atomizer or the like.
Moreover, after activation or after crushing, classification may be performed as necessary. By performing classification, it is possible to easily control the particle size within a desired range. In particular, in the activated carbon material after pulverization, crushed material derived from the binder can be removed by this classification. As a classification method, an air classifier, a vibration sieve, or the like can be used.

The spherical activated carbon material obtained by the present invention has a small particle size and a narrow particle size distribution, and therefore has a low porosity when filled. When the porosity is low, the contact point between the particles increases, which leads to an improvement in electrical conductivity when used as an electrode material. In addition, since the movement path of the electrolyte ions can be kept short, the output is increased, and the output characteristics in the low temperature region where the viscosity of the electrolytic solution increases is also improved. Furthermore, since it has a high sphericity, the porosity is low and the capacity per volume is high.
Thus, according to the manufacturing method of the activated carbon material of this invention, the spherical activated carbon material which has practical value as an electrode material can be manufactured industrially.

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto. In this example, “%” indicates “% by mass” unless otherwise specified.
In this example, as described above, the average particle size was determined by observing the target spherical phenol resin and activated carbon material with a scanning electron microscope (JSM-6390, manufactured by JEOL), and 50 to 200 in one sheet. About the photograph in which the particle | grains are reflected, the ferret diameter (X-axis direction) of 10 particle | grains was measured at random, and it calculated | required by calculating these average values.
The specific surface area of the activated carbon material was measured by a BET method using nitrogen adsorption under liquid nitrogen temperature conditions using a BET specific surface area meter.

<Production example>
Example 1
Step (1):
In a 5 liter autoclave equipped with a thermometer and stirrer, 55 g (0.58 mol) of phenol, 220 g (2.00 mol) of resorcinol, 300 g of 50% formalin (5.00 mol of formaldehyde), as a condensation reaction catalyst Sodium carbonate 0.28 g and water 2613 g were charged, and the temperature was raised from room temperature to 90 ° C. over 30 minutes while rotating the stirring blade at 100 rpm, and then stirring was continued at 90 ° C. for 4.0 hours. did. Next, the autoclave was sealed, and a phenol resin dispersion was obtained by reacting at 130 ° C. for 1.0 hour (condensation reaction) while rotating the stirring blade at 100 rpm. At this time (when the temperature reached 130 ° C. due to temperature increase), the pressure of the system became 0.25 to 0.33 MPa.
Step (2):
Next, this phenol resin dispersion was cooled to 50 ° C. or less, 1000 g of water and 10 g of polydiallyldimethylammonium chloride were added with stirring, and after 10 minutes, stirring was stopped and the mixture was allowed to stand. After about 2 hours, the coagulated product and the reaction residue (supernatant) were separated.
Step (3):
The supernatant was then removed by decantation. Thereafter, 2500 g of water was added to the condensate, washing was carried out by heating to 60 ° C. and stirring for 10 minutes, and then stirring was stopped and the mixture was allowed to stand for 120 minutes. The above washing treatment (operation from decantation to stirring and standing at 60 ° C. for 10 minutes) was further carried out 5 times to remove phenolic monomers, formaldehyde and sodium carbonate. Thereafter, the aggregate was separated and recovered from the liquid after the washing treatment by decantation.
Step (4):
The coagulated product separated and recovered was air-dried and then dried at 100 ° C. for 1 hour in a hot air circulating oven to obtain a dried product.
Step (5):
Next, 3 parts by mass of polyvinyl alcohol (completely saponified type) and 10 parts by mass of water are added as a binder to 100 parts by mass of the obtained dried product, and kneaded for 10 minutes at a rotational speed of 80 rpm with a universal mixing stirrer. A mixture was obtained.
Step (6):
Next, the obtained mixture was extruded into a strand shape by a pellet mill and cut to obtain a pellet-shaped extruded product (spherical phenol resin granulated product) having a diameter of 1.6 mm and a length of 2 to 5 mm.
Carbonization:
Next, the obtained extrusion-molded product was heat-treated at 290 ° C., and then carbonized by using a rotary kiln (diameter: 600 mm) and raising the temperature to 800 ° C. in 90 minutes under a nitrogen speed of 4 rpm. A carbon material was obtained.
Activation:
Furthermore, the carbon material obtained was continuously activated with nitrogen gas and steam (steam partial pressure 49%) at 900 ° C. for 65 minutes, with an average diameter of 1.4 mm and a length of 1 to 4 mm. A pellet-like activated carbon material was obtained.
Next, this activated carbon material was put in a ball mill and crushed.

(Example 2)
A spherical phenol resin and a spherical activated carbon material were obtained in the same manner as in Example 1 except that the phenols in Example 1 were changed to 110 g (1.17 mol) of phenol and 165 g (1.50 mol) of resorcinol. It was.

Example 3
A spherical phenol resin and a spherical activated carbon material were obtained in the same manner as in Example 1 except that the condensation reaction catalyst (sodium carbonate 0.28 g) in Example 1 was changed to 0.28 g of triethylenetetramine.

Example 4
A spherical phenol resin and a spherical activated carbon material were obtained in the same manner as in Example 1 except that the condensation reaction catalyst (0.28 g of sodium carbonate) in Example 1 was changed to 0.28 g of hexamethylenetetramine.

(Comparative Example 1)
Only monohydric phenols were used as phenols.
Step (1):
In a 5-liter autoclave equipped with a thermometer and stirrer, 275 g (2.92 mol) of phenol, 300 g of 50% formalin (5.00 mol of formaldehyde), 0.28 g of triethylenetetramine as a condensation reaction catalyst, and 2613 g of water The temperature was raised from room temperature to 90 ° C. over 30 minutes while rotating the stirring blade at 100 rpm.
At this point, the reaction solution was cloudy, but most of the resin components were in a lump and entangled with the vessel wall and stirring blade, making it difficult to carry out the subsequent operation and stopping the reaction. did. In the lump, the resin components were integrated and no spherical resin was produced. That is, a phenol resin dispersion could not be prepared.

(Comparative Example 2)
Step of obtaining a phenol resin dispersion:
In a 5-liter autoclave equipped with a thermometer and a stirrer, 1100 g (11.7 mol) of phenol, 1262.5 g of 50% formalin (21.0 mol of formaldehyde), 99 g of triethylenetetramine as a condensation reaction catalyst, 550 g of an aqueous solution in which 11 g of ethyl cellulose was dissolved and 660 of water were charged, and the temperature was raised from room temperature to 90 ° C. over 30 minutes while rotating the stirring blade at 500 rpm. Continued for hours. Next, the autoclave was sealed, and a phenol resin dispersion was obtained by reacting at 130 ° C. for 1.0 hour while rotating the stirring blade at 500 rpm. At this time (when the temperature reached 130 ° C. due to temperature increase), the pressure of the system became 0.25 to 0.33 MPa.
Separation and recovery process:
Next, this phenol resin dispersion was cooled to 50 ° C. or lower, and 1150 g of water was added with stirring, and after 10 minutes, stirring was stopped and the mixture was allowed to stand. The supernatant was removed by decantation. Thereafter, 2500 g of water was added to the product separated and collected by decantation, and the mixture was washed with an operation of heating to 80 ° C. and stirring for 10 minutes, and then hydroxyethylcellulose was removed by decantation. Further, the above washing treatment (operation from decantation to stirring at 80 ° C. for 10 minutes) had to be repeated twice until the supernatant liquid was not colored by the anthrone reagent.
Drying process:
Next, the material separated and recovered by decantation was air-dried and then dried at 100 ° C. for 1 hour in a hot air circulation oven to obtain a dried product.
Carbonization:
Next, after heat-treating the obtained dried material at 290 ° C., using a rotary kiln (diameter: 600 mm), carbonization was performed by heating to 800 ° C. in 90 minutes under a rotation speed of 4 rpm and a nitrogen atmosphere, A carbon material was obtained.
Activation:
Furthermore, the carbon material obtained was continuously activated with nitrogen gas and steam (steam partial pressure 49%) at 900 ° C. for 65 minutes, with an average diameter of 1.4 mm and a length of 1 to 4 mm. A pellet-like activated carbon material was obtained.
Next, this activated carbon material was put in a ball mill and crushed.

(Comparative Example 3)
The phenol resin solution (liquid in which a resol type phenol resin manufactured by Gunei Chemical Industry Co., Ltd. was dispersed) was subjected to a curing treatment at 180 ° C. for 4 hours with a hot air dryer to obtain a cured resin product.
The obtained cured resin was pulverized to a size of about 100 μm with a cutter mill. The pulverized product obtained here was not spherical but had a non-uniform shape.
Carbonization:
The pulverized product of the obtained cured resin is heat-treated at 290 ° C., and then heated to 800 ° C. in 90 minutes under a nitrogen atmosphere using a rotary kiln (diameter 600 mm) for carbonization. Carbon material was obtained. The carbon material obtained here was not spherical but had a non-uniform shape.
Activation:
Furthermore, the carbon material obtained was continuously activated with nitrogen gas and steam (steam partial pressure 49%) at 900 ° C. for 65 minutes, with an average diameter of 1.4 mm and a length of 1 to 4 mm. A pellet-like activated carbon material was obtained.
Next, the activated carbon material was pulverized with a jet mill and classified with an airflow classifier. The activated carbon material obtained here was not spherical but had a non-uniform shape.

FIG. 1 shows a scanning electron micrograph of the dried product obtained in Example 1 and a spherical activated carbon material. FIG. 2 shows a scanning electron micrograph of the dried product obtained in Example 3.
1A is a scanning electron micrograph of the dried product obtained in step (4) in Example 1. FIG. Spherical phenol resin particles 61 having a high sphericity can be confirmed.
FIG. 1B is a scanning electron micrograph of a spherical activated carbon material obtained after activation in Example 1. Fine spherical activated carbon particles 70 can be confirmed.
FIG. 2 is a scanning electron micrograph of the dried product obtained in step (4) in Example 3. Spherical phenol resin particles 63 having a high sphericity can be confirmed.

  Table 1 shows the average particle diameter of the spherical phenol resin obtained in Examples and Comparative Examples, the average particle diameter of the activated carbon material, and the specific surface area. In addition, "-" in a table | surface shows not measuring.

<Use for electric double layer capacitors>
The characteristics when the spherical activated carbon material obtained in Example 1 and the conventional activated carbon material (powder carbon material AC: average particle size 5.0 μm) are used as the active material of the electrode in the electric double layer capacitor are shown. evaluated.
FIG. 3 is a cross-sectional view of the coin-type electric double layer capacitor used in this example.
In the electric double layer capacitor 10 shown in FIG. 3, an electrode 2a adjacent to the current collector 1a and an electrode 2b adjacent to the current collector 1b are connected to each other through the separator 3 in the storage container 5. , 1b is arranged facing the storage container 5 side. The storage container 5 is filled with the electrolytic solution 4.
Suspension mesh was used for the current collector 1a and the current collector 1b.
As the separator 3, glass wool punched into a predetermined shape was used.
As the electrolytic solution 4, an electrolytic solution in which tetraethylammonium tetrafluoroborate (Et ₄ NBF ₄ ) was dissolved in propylene carbonate (PC) to a concentration of 1 molar was used.
In both electrodes 2a and 2b, the electrode mixture was prepared by mixing Example 1 or the conventional activated carbon material, polytetrafluoroethylene (PTFE), and acetylene black at a mass ratio of 90: 5: 5. The electrode mixture prepared and molded into a predetermined shape was used.
Then, the current collector 1 a, the current collector 1 b, the electrode 2 a, the electrode 2 b, and the separator 3 were assembled by a conventional method in the storage container 5, and the electrolytic solution 4 was filled to produce the electric double layer capacitor 10.

[Evaluation of cycle characteristics]
About the electric double layer capacitor 10, the discharge capacity at the time of repeating charge / discharge of 100 cycles in 25 degreeC, the constant current of 1 mA, and the voltage range of 0-2.5V was measured.

[Evaluation of rate characteristics]
For the electric double layer capacitor 10, the ratio of the discharge capacity at the first cycle when the current is changed to the discharge capacity at the first cycle in a constant current at 25 ° C. and a voltage range of 0 to 2.5 V is expressed as “ It was calculated | required as an initial discharge capacity maintenance factor.

FIG. 4 is a graph showing the results of measuring the discharge capacity of the electric double layer capacitor 10 when 100 cycles of charge and discharge were repeated.
From FIG. 4, the electric double layer capacitor using the spherical activated carbon material obtained in Example 1 has a higher discharge capacity than the conventional electric double layer capacitor using the activated carbon material, and even after 100 cycles. It can be confirmed that the initial discharge capacity is substantially maintained.

FIG. 5 is a graph showing the results of obtaining the initial discharge capacity retention rate when the current is changed for the electric double layer capacitor 10.
As can be seen from FIG. 5, the spherical activated carbon material obtained in Example 1 was used for any of the electric double layer capacitors, although the initial discharge capacity retention rate decreased with increasing current (increasing applied current). It can be confirmed that the electric double layer capacitor has a higher initial discharge capacity retention rate than an electric double layer capacitor using a conventional activated carbon material.

<Use for lithium ion secondary batteries>
Characteristics when the spherical activated carbon material obtained in Example 1 and the conventional activated carbon material (powder carbon material AC: average particle size 5.0 μm) are used as the active material of the electrode in the lithium ion secondary battery, respectively. Evaluated.
FIG. 6 is a cross-sectional view of the coin-type lithium ion secondary battery used in this example.
In the lithium ion secondary battery 100 shown in FIG. 6, an electrode 23 adjacent to the current collector 21 and an electrode 24 adjacent to the current collector 22 are connected to each other through the separator 30 in the storage container 50. 21 and 22 are arranged facing the storage container 50 side. The storage container 50 is filled with the electrolytic solution 40.
Suspension mesh was used for the current collector 21 and the current collector 21.
As the separator 30, glass wool punched into a predetermined shape was used.
As the electrolytic solution 40, an electrolytic solution in which LiPF ₆ as a Li electrolyte was dissolved in a mixed solvent of ethylene carbonate and dimethyl carbonate so as to have a 1 molar concentration was used.
The electrode 23 is prepared by mixing the active carbon material of Example 1 or a conventional activated carbon material, PTFE, and acetylene black at a mass ratio of 90: 5: 5 to prepare an electrode mixture. What was molded into was used. As the electrode 24, lithium metal punched into a predetermined shape was used.
Then, the current collector 21, the current collector 22, the electrode 23, the electrode 24, and the separator 30 were assembled in a storage container 50 by a conventional method, and the electrolyte solution 40 was filled therein, whereby the lithium ion secondary battery 100 was produced.

[Evaluation of cycle characteristics]
About the lithium ion secondary battery 100, the discharge capacity at the time of repeating charge / discharge of 20 cycles was measured in the voltage range of 25 degreeC, 1 mA constant current, and 0.01-3.0V.

[Evaluation of rate characteristics]
For the lithium ion secondary battery 100, the discharge capacity of the first cycle when the current is changed with respect to the discharge capacity of the first cycle in the voltage range of 25 ° C., 1 mA, 0.01 to 3.0 V. The ratio was determined as “discharge capacity maintenance rate”.

FIG. 7 is a graph showing the results of measuring the discharge capacity when 20 cycles of charge / discharge were repeated for the lithium ion secondary battery 100.
Generally, in a lithium ion secondary battery, when charging and discharging are repeated, the number of cycles increases and the discharge capacity decreases.
From FIG. 7, in the case of a lithium ion secondary battery using a conventional activated carbon material, it can be confirmed that the discharge capacity rapidly decreases after two cycles. On the other hand, in the lithium ion secondary battery using the spherical activated carbon material obtained in Example 1, the discharge capacity gradually decreased over about 8 cycles, and the degree of decrease in the discharge capacity with respect to the number of cycles. Can be confirmed to be small.
In addition, the lithium ion secondary battery using the spherical activated carbon material obtained in Example 1 has a higher discharge capacity than the lithium ion secondary battery using the conventional activated carbon material, and after 20 cycles. However, it can be confirmed that a high discharge capacity is maintained.

FIG. 8 is a graph showing the results of obtaining the initial discharge capacity retention rate when the current is changed for the lithium ion secondary battery 100.
From FIG. 8, all lithium ion secondary batteries used the spherical activated carbon material obtained in Example 1, although the discharge capacity retention rate decreased with increasing current (increasing applied current). It can be confirmed that the lithium ion secondary battery has a higher discharge capacity maintenance rate than a lithium ion secondary battery using a conventional activated carbon material.
Lithium ion secondary batteries are said to be vulnerable to large currents. However, in the case of a spherical activated carbon material obtained by applying the present invention, the particle size is small, and Li ion diffusion and entry into the micropores is easy ( Since the diffusion path is short), the discharge capacity retention rate is high even when a large current is applied. On the other hand, in the case of the conventional activated carbon material, since the particle size is large, it takes time for the diffusion of Li ions inside the micropore, and there are many activated carbon particles that are not used, that is, not used. It is thought that.

The carbon material and the activated carbon material produced by the production method of the present invention are suitable as an active material for a lithium ion secondary battery negative electrode, an active material for an electric double layer capacitor electrode, and an active material for a lithium ion capacitor positive electrode.
By using such a carbon material and activated carbon material as an active material for a negative electrode of a lithium ion secondary battery, it is possible to increase the output of the lithium ion secondary battery.
By using such a carbon material and activated carbon material as an active material for an electric double layer capacitor electrode and an active material for a lithium ion capacitor positive electrode, capacity and output can be improved.
The carbon material and activated carbon material produced by the production method of the present invention can also be used as an additive mixed with various resin materials and as an adsorbent in the pharmaceutical field.

  DESCRIPTION OF SYMBOLS 1a Current collector, 1b Current collector, 2a electrode, 2b electrode, 3 Separator, 4 electrolyte, 5 Storage container, 10 Electric double layer capacitor, 21 Current collector, 22 Current collector, 23 Electrode, 24 Electrode, 30 Separator, 40 electrolytic solution, 50 storage container, 61 spherical phenol resin particles, 63 spherical phenol resin particles, 70 spherical activated carbon particles, 100 lithium ion secondary battery

Claims (7)

A step (1) of obtaining a spherical phenol resin dispersion in which a spherical phenol resin is dispersed by subjecting a phenol containing polyhydric phenols and an aldehyde to a condensation reaction in an aqueous medium in the presence of a condensation reaction catalyst; ,
Adding an organic coagulant to the spherical phenol resin dispersion to obtain a coagulum (2);
A step (3) of separating and recovering the condensed product;
A step (4) of drying the separated and recovered coagulated product to obtain a dried product;
A step (5) of mixing the dried product and a binder to obtain a mixture;
Granulating the mixture possess a step (6) to obtain a granulated product,
The phenol containing the polyhydric phenol includes one or more polyhydric phenols selected from dihydric phenols and trihydric phenols, and monohydric phenols,
The spherical phenol resin granulated product for carbonization / activation is characterized by performing the condensation reaction in the step (1) under conditions of a temperature of 105 to 200 ° C. and a pressure of 0.13 to 1.5 MPa . Production method. The method for producing a spherical phenol resin granulated product according to claim 1, wherein the condensation reaction catalyst is a basic catalyst. 3. The spherical phenol resin granulated product according to claim 1, wherein an average particle size of the spherical phenol resin dispersed in the spherical phenol resin dispersion is 0.05 to 10 μm. Manufacturing method. A method for producing a carbon material, wherein the spherical phenol resin granulated product produced by the method for producing a spherical phenol resin granulated product according to any one of claims 1 to 3 is carbonized. The method for producing a carbon material according to claim 4 , wherein crushing is performed after the carbonization. An activated carbon material, characterized by activating the spherical phenol resin granulated product produced by the method for producing the spherical phenol resin granulated product according to any one of claims 1 to 3 and then activating it. Production method. The method for producing an activated carbon material according to claim 6 , wherein crushing is performed after the activation.