JP2010013570A - Cured phenol resin particle, method for producing the same, and method for producing activated carbon particle by using the resin particle - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide: cured phenol resin particles having a large surface area; a method for advantageously producing the same; and a method for advantageously producing useful activated carbon particles by using the cured phenol resin particles. <P>SOLUTION: When the cured phenol resin particles are produced by reacting phenols and aldehydes in the presence of an alkylbenzene sulfonic acid and a protective colloid to obtain heat-curable phenol resin particles and then, curing the heat-curable phenol resin particles, the aldehydes are used in a ratio of ≥1.1 mol to 1 mol of the phenols, Arabian gum derived from trees of the Acacia senegal species is used as the protective colloid, and the use amount of the Arabian gum is adjusted to be ≥0.001 and <0.1 wt.% based on the use amount of the phenols. Thereby, cured phenol resin particles in each of which many roundish bump-like small projections are integrally formed on the particle surface can be obtained. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a cured phenol resin particle, a method for producing the same, and a method for producing activated carbon particles using the same, and in particular, a cured phenol resin particle in which a large number of knob-shaped small protrusions are integrally formed on the particle surface. The present invention relates to a method for producing it advantageously, and further to a method for producing activated carbon particles having a large number of surface protrusions using such cured phenol resin particles.

  Conventionally, particles or powders composed of cured phenol resin particles have been widely used as fillers (additives), as raw materials for carbon materials such as activated carbon, etc. Have been proposed.

  For example, in JP-A-11-60664 (Patent Document 1) and JP-A-2001-114852 (Patent Document 2), a predetermined alkylamine compound as a condensation reaction catalyst and an emulsifying dispersant are used in an aqueous medium. A method for producing a spherical phenol resin characterized by a condensation reaction of phenols and aldehydes in the presence of a polymeric surfactant having a glycosidic bond has been clarified, and Japanese Patent Publication No. 62-30211. In the publication (Patent Document 3), a method for producing a powdered phenol / formaldehyde resin using hydrochloric acid as a condensation reaction catalyst is proposed.

  However, since the cured phenol resin particles and powder produced according to such a method contain a relatively large amount of nitrogen, chlorine ions, etc., the cured phenol resin particles and powder produced by such a method On the other hand, when heat treatment is performed separately, nitrogen oxides and chlorides are generated from nitrogen contained in the particles and powder, and these nitrogen oxides corrode equipment and are environmentally friendly. There were problems such as adverse effects.

  On the other hand, the applicant of the present application previously described in JP-A-3-7714 (Patent Document 4), phenols and aldehydes in the presence of an alkylbenzenesulfonic acid having an alkyl group having 10 or more carbon atoms and a protective colloid. And a second step of curing the resin particles by continuing or separating from the first step to form thermosetting resin particles. A method for producing cured phenolic resin particles was proposed. According to this method, since an acid catalyst (alkylbenzene sulfonic acid) with low corrosivity is used, as a reaction vessel of phenols and aldehydes, glass lining or made of Hastelloy is used. The existing stainless steel equipment can be used as it is without requiring an expensive corrosion-resistant reaction tank, and the cured phenol resin particles can be produced safely and with high yield under mild reaction conditions. It becomes possible.

  By the way, in the cured phenol resin particles obtained according to such various conventionally proposed techniques, the surface of each particle has a substantially smooth spherical shape. Therefore, there is a problem that it is difficult to obtain particles with a large surface area. Therefore, when used as a filler, the filling effect may not be fully exhibited. In addition, problems such as the need to adopt stronger processing conditions in the carbide forming process are inherent.

Japanese Patent Laid-Open No. 11-60664 JP 2001-114852 A Japanese Examined Patent Publication No. 62-30211 JP-A-3-7714

  Here, the present invention has been made in the background of such circumstances, and the problem to be solved is to provide a cured phenol resin particle having a large particle surface area and a method for advantageously producing the same. It is another object of the present invention to provide a method for advantageously producing useful activated carbon particles by using such a cured phenol resin particle having a large surface area.

  Therefore, the present inventors have made extensive studies based on the technique proposed in Patent Document 4 in order to solve such problems, and as a result, the amount of aldehydes used for phenols is as follows. In addition to defining a specific molar ratio or more, in addition to using a specific gum arabic as a protective colloid, by adjusting the amount of use to a very small ratio, a large number of rounded knob-shaped small protrusions It has been found that it is possible to advantageously obtain surface-roughened cured phenolic resin particles that are integrally formed on the surface of the particles and have an effectively increased surface area.

  Therefore, the present invention has been completed on the basis of such knowledge, and is suitably implemented in various modes as listed below. However, each mode described below is also optional. It is possible to adopt in the combination. It should be noted that aspects or technical features of the present invention are not limited to those described below, and can be recognized based on the description of the entire specification or the inventive idea disclosed therein. Should be understood.

(1) In the presence of alkylbenzene sulfonic acid and protective colloid, phenols and aldehydes are reacted to form thermosetting phenol resin particles, and then the phenol resin particles are cured to obtain cured phenol resin particles. In the production, the aldehydes are used in a ratio of 1.1 mol or more with respect to 1 mol of the phenols, and gum arabic derived from an Acacia / Senegal tree is used as the protective colloid, and further used. By adjusting the amount to be 0.001% by mass or more and less than 0.1% by mass with respect to the phenols, a large number of round-shaped small protrusions are integrally formed on the particle surface. A method for producing cured phenol resin particles, comprising: obtaining cured phenol resin particles.

(2) The method for producing cured phenol resin particles according to the aspect (1), wherein phenol is used as the phenol and formaldehyde is used as the aldehyde.

(3) The cured gum resin particles according to the aspect (1) or (2), wherein the gum arabic is used in a proportion of 0.01 to 0.08% by mass with respect to the phenols. Production method.

(4) The above aspects (1) to (1), wherein the cured phenol resin particles are produced by heating thermosetting phenol resin particles generated by reacting the phenols with the aldehydes. (3) The manufacturing method of the hardening phenol resin particle as described in any one of.

(5) Cured phenolic resin particles obtained by curing thermosetting phenolic resin particles obtained by reacting phenols with aldehydes, and having an average particle diameter of 100 μm to 1500 μm and a round nodule A cured phenolic resin particle having a large number of small protrusions integrally on the particle surface, and at least one small protrusion per 1 μm ^{2 of} the particle surface.

(6) The cured phenol resin particles according to the aspect (5), wherein the small protrusions have a diameter of 0.1 μm to 1.2 μm.

(7) After carbonizing the cured phenol resin particles obtained by the production method according to any one of the above aspects (1) to (4) at a temperature of 650 ° C. to 1000 ° C., 700 A method for producing activated carbon particles, wherein steam activation is performed at a temperature of from 1000C to 1000C.

  Therefore, according to the method for producing cured phenol resin particles according to the present invention as described above, the reaction between phenols and aldehydes is allowed to proceed using alkylbenzene sulfonic acid as a catalyst in the presence of a protective colloid, The resulting phenol resin can be effectively made into particles, and at this time, aldehydes are used in a molar ratio of 1.1 or more with respect to phenols, and as a protective colloid, Acacia By using gum arabic derived from Senegal tree, the amount used is adjusted to be 0.001% by weight or more and less than 0.1% by weight of the amount of phenols used. It was possible to effectively obtain surface-roughened cured phenolic resin particles in which a large number of small protrusions were integrally formed on the particle surface. There, and by such uneven surfaces, than is advantageously obtained achieving effective increase in the surface area of the cured phenolic resin particles.

  Further, in such a cured phenol resin particle according to the present invention, when it is used as a filler due to the presence of a large number of rounded knob-like small protrusions integrally formed on the surface thereof In addition to the contact effect with the matrix due to its large surface area, the anchor effect by the knob-like small projections can be advantageously exerted, and thus the effect of filling the cured phenol resin particles is It can be advantageously increased.

  Furthermore, when producing activated carbon particles according to the present invention using such surface roughened cured phenol resin particles, the presence of a large number of knob-like small protrusions contributes to pores that contribute to the adsorption action as activated carbon, particularly large The formation of pores is facilitated. Therefore, there is an advantage that the water vapor activation process can be easily performed, and also in the obtained activated carbon particles, spherical or ellipsoidal small protrusions are formed on the surface. Since many exist, the function of such activated carbon particles as activated carbon can be further enhanced.

  By the way, in the manufacturing method of the cured phenol resin particles according to the present invention, both phenols and aldehydes which are reaction raw materials that give the target phenol resin are conventionally used in the manufacture of phenol resin particles. Of these, for example, those described in the above-mentioned Patent Documents 1 to 4 are appropriately selected and used. In particular, in the present invention, the phenol is an unsubstituted form of phenol. Formaldehyde is preferably used as the aldehyde. In general, formaldehyde supply substances such as formalin, paraformaldehyde, trioxane, tetraoxane, and acetal can be suitably used for this formaldehyde from the viewpoint of reactivity, raw material price, and the like.

  And in this invention, it is necessary to use such aldehydes so that it may become a ratio of 1.1 mol or more with respect to 1 mol of phenols. In addition, when the molar ratio (F / P) of the aldehydes (F) and the phenols (P) is lower than 1.1, the target knob-like small protrusions are formed on the surface of the formed phenol resin particles. This is because it becomes difficult to form the film, resulting in a smooth surface. In addition, the upper limit of the molar ratio (F / P) is appropriately determined from the viewpoint of the manufacturing environment, economy, and the like, but is generally about 2 or less.

  In the present invention, as the alkylbenzene sulfonic acid serving as a reaction catalyst for phenols and aldehydes, various conventionally known alkyl benzene sulfonic acids can be used. Preferably, the number of carbon atoms is 10 or more. An alkylbenzenesulfonic acid having an alkyl group will be advantageously used. Examples of the alkylbenzenesulfonic acid having an alkyl group having 10 or more carbon atoms include decylbenzenesulfonic acid, dodecylbenzenesulfonic acid, tetradecylbenzenesulfonic acid, hexadecylbenzenesulfonic acid, octadecylbenzenesulfonic acid, and mixtures thereof. Among these, dodecylbenzenesulfonic acid is particularly advantageously used from the viewpoints of economy, availability, catalytic function, and the like.

  The amount of the alkylbenzene sulfonic acid used is appropriately determined according to the blending conditions and reaction conditions of the reaction raw materials, but generally, the amount of phenols used is 0.5. It is used in such an amount as to give a ratio of ˜2.0% by mass. Thus, in the present invention, the amount of alkylbenzene sulfonic acid used as a reaction catalyst is relatively small compared to the amount used when a conventional alkylamine compound or the like is used as a catalyst. The obtained phenol resin particles also have a relatively low content of impurities. However, since the phenol resin formation reaction proceeds in the presence of alkylbenzene sulfonic acid, the obtained phenol resin particles contain a small amount of impurities such as sulfur compounds.

  And in the present invention, as a protective colloid used to obtain a phenol resin produced by the reaction of phenols and aldehydes in the form of spherical particles, among the known gum arabic, so-called Senegal type The selected gum arabic was selected and the specific amount was used, so that a large number of rounded knob-shaped protrusions having the desired surface morphology were formed on the particle surface. The cured phenol resin particles formed integrally can be advantageously obtained.

  In other words, gum arabic is also known as gum arabic and gum arabic, and is well known as a dried secretion of the leguminous acacia tree. Among them, dried secretions collected from the trunks and branches of Acacia senegal trees, in other words, gum arabic from Acacia Senegal trees, are used. In addition, this Senegal type gum arabic is widely used in foods as a thickener, stabilizer and the like, and is also used in sugar coating, emulsifying flavor, powder flavor, etc. It will be appropriately selected from various commercial products for those uses.

  In addition, the Senegal type gum arabic used in the present invention is adjusted to be used in a proportion of 0.001% by mass or more and less than 0.1% by mass of the amount of phenol used. Become. If the amount of this specific gum arabic used is too small, problems such as formation of resin particles and formation of the target knob-shaped small protrusions on the particle surface become difficult. In addition, if the amount used is too large, the resin particles to be produced become too small, and the significance of surface irregularity due to the provision of small protrusions on the particle surface decreases, This causes problems such as difficulty in forming small protrusions. In addition, as a preferable usage-amount of this Senegal type gum arabic, about 0.01-0.08 mass% of the usage-amount of phenols is employ | adopted advantageously.

  By the way, in the method for producing cured phenolic resin particles according to the present invention, first, phenols and aldehydes are present in a state where the specific protective colloid composed of the above-mentioned alkylbenzenesulfonic acid and Senegal type gum arabic is present. Are advantageously carried out according to the following procedure.

  First, in a normal reaction vessel equipped with a reflux condenser, a thermometer, and a stirrer, phenols and aldehydes as reaction raw materials, alkylbenzene sulfonic acid, and Senegal type gum arabic, and if necessary, diluting water (distilled) Water) and various modifiers (for example, urea, melamine, guanamine, aniline, tall oil, etc.) are added.

  Here, the timing of addition (addition) of Senegal type gum arabic as a protective colloid to the reaction system is not particularly limited as long as the condensate (reaction product) is cured. In general, it is preferable to add at or before resinification (emulsification), and particularly from the viewpoint of simplification of operations, it is desirable to add from the start of the reaction. In the present invention, in order to perform granulation smoothly and prevent agglomeration of the generated spherical uncured phenol resin particles, the amount of water in the reaction system is 80 mass with respect to phenols. It is also advantageous in terms of waste liquid treatment, production efficiency, etc., to adjust to a ratio of about 100 to 180% by mass so that the ratio is at least%. It is to be noted that the time for adjusting the amount of water is appropriate at the start of the reaction or when a protective colloid is added.

  Next, while stirring the charged materials such as phenols in the reaction tank, the inside of the reaction tank is generally heated at a temperature rising rate of about 0.5 to 2.0 ° C./min, preferably 70 ° C. or more, preferably Reacts phenols and aldehydes at a temperature of 90 ° C. or higher (reaction temperature) for a predetermined time to produce fusible uncured phenol resin particles (step 1). Subsequently, the reaction is continued for a predetermined time at the same temperature as or slightly lower than the reaction temperature, thereby forming infusible cured phenol resin particles (step 2). The time required for these series of reactions is usually about 0.5 to 6 hours.

  Thereafter, the inside of the reaction vessel is cooled, and further, if necessary, the alkylbenzene sulfonic acid is neutralized, and then the produced cured phenol resin particles are separated by solid-liquid separation means such as filtration or a centrifugal separator. Next, the separated cured phenol resin particles are washed as necessary, and various conventionally known drying methods such as air drying and heat drying (for example, heating, hot air circulation, vibration, fluidized tank, etc.), etc. The target spherical cured phenol resin particles can be obtained by drying by a technique.

  In addition, the fusible uncured phenol resin particles produced according to the above step 1 are further reacted to a state where they can be handled, then separated according to the same method as described above, and further washed as necessary. It is also possible to obtain infusible cured phenol resin particles by thermosetting using the above-described heat drying method.

  In the cured phenol resin particles thus obtained, the surface of the particles is rounded as clearly shown in the scanning electron microscope (SEM) photograph of the surface of the resin particles obtained in the examples described later. A large number of knob-shaped small protrusions, that is, so-called warped small protrusions, are formed integrally, and the presence of the large number of knob-shaped small protrusions effectively increases the surface area of the resin particles. It has been increased. In short, a large number of knob-shaped small protrusions present on the surface of such cured phenol resin particles have a shape in which at least a part of the outer edge has a curve on the surface (for example, SEM photograph) on which the resin particles are projected. It is doing. Here, the shape having a curve on at least a part of the outer edge means a shape in which all the outer edges are curved, and a shape in which the outer edge is a straight line and a curve connected from one end of the straight line to the other end. Examples of the shape whose outer edges are all curved include a circle, an ellipse or a flat ellipse, and a shape having a constriction at a part of the outer edge of the ellipse. The shape of the outer edge consisting of a straight line and a curve connecting from one end of the straight line to the other end includes, for example, a shape in which a part of the outer edge of the circle forms a straight line, a shape in which a part of the outer edge of the ellipse forms a straight line, etc. Can be mentioned. The protrusions having such shapes may be present independently or mixed on the particle surface, and there is no problem.

  In addition, the cured phenol resin particle in which many of such round-shaped small protrusions are integrally formed on the particle surface is prepared to have an average particle diameter of 100 μm to 1500 μm. . When the average particle size is smaller than 100 μm, various problems are caused in the application, and it is difficult to sufficiently exert the effect of forming small protrusions, and the average particle diameter exceeds 1500 μm. In the case of such an average particle size, since the surface area per mass of the resin particles becomes small, when used as a filler, activated carbon, etc., the effect cannot be fully exhibited, or the activated carbon particles In the production of particles, causes problems such as insufficient activation to the inside of the particles. In particular, in the present invention, the resin particles are advantageously formed as resin particles having a particle size of about 120 μm to 1200 μm.

Further, in such cured phenolic resin particles, rounded or curved small protrusions are formed on the particle surface at a ratio of at least one per 1 μm ^{2 of} the particle surface. As a result, it is possible to effectively contribute to an increase in the surface area of the particles and to exhibit an excellent effect when applied to the application. In addition, the upper limit of the number of such small protrusions is appropriately selected according to the use of the cured phenol resin particles, but is generally about 20 or less per 1 μm ² on the particle surface, preferably 15 or less, more preferably 10 or less.

Here, the number of small protrusions present per 1 μm ^{2 on} the particle surface can be calculated by the following method. That is, SEM photographs at a predetermined magnification are taken at a plurality of locations on the surface of the cured phenol resin particles, and the number of small protrusions projected on each SEM photograph is measured. Next, the number of small protrusions per 1 μm ² in each SEM photograph is calculated by dividing the measured number of small protrusions by the area of the SEM photograph obtained from the magnification at the time of photographing. Then, the number of those calculated 1 [mu] m ² per small projection, and a number of SEM photographs, is the average value of the number of small protrusions per 1 [mu] m ² is obtained. In addition, when a small protrusion existing in the field of view of the SEM photograph is missing at the edge of the field of view, the chipped small protrusion is measured as one if it is more than half the normal size, Anything less than that will be excluded from the measurement. In addition, since the density of small protrusions is obtained as an average value of the number of small protrusions per 1 μm ² at a plurality of locations on the surface of the cured phenol resin particle, the number of protrusions per 1 μm ² is not an integer, but a decimal point. You may have it.

  In addition, the shape of such a small protrusion has a substantially spherical or ellipsoidal shape, and has a protruding shape raised on the particle surface. Such a small protrusion is generally 0.1 μm to 1 μm. The diameter of the projections is preferably about 0.05 μm to 1 μm, more preferably about 0.05 μm to 0.5 μm. Here, the diameter of the small protrusion is a length that crosses the center from the two points of the outer edge of the small edge having a curved shape on at least a part of the outer edge on the projected surface of the cured phenol resin particle. For example, in the case of a circular small protrusion, the diameter becomes the “small protrusion diameter”.

  In the case of surface-roughened hardened phenolic resin particles in which a large number of round-shaped small protrusions are integrally formed on the particle surface as described above, for example, the resin material can be reduced in weight and flame resistance. For the purpose of chemical conversion, etc., it is blended as a filler in thermosetting resins, thermoplastic resins, rubbers and elastomers, etc., and is also suitably used as a friction modifier, raw material for carbon and ion exchange resins, etc. However, particularly when such cured phenol resin particles according to the present invention are used as a filler, in addition to the effect of increasing the surface area, the presence of such a large number of knob-like small projections results in an anchor effect. It will be exhibited effectively, and features such as a reinforcing effect can be exhibited.

  Further, in the present invention, spherical activated carbon particles are advantageously produced using the above-described surface roughened cured phenol resin particles.

  That is, by using the cured phenol resin particles in which many of the rounded ridge-like small protrusions are integrally formed on the particle surface, they are advantageously used at a temperature of 650 ° C. to 1000 ° C. according to a conventional method. Is carbonized under a reducing atmosphere, and then activated with water vapor at a temperature of 700 ° C. to 1000 ° C. according to a conventional method, so that a spherical or elliptical nodule corresponding to the surface of the cured phenol resin particles is obtained. Activated carbon particles in which small protrusions are integrally formed on the particle surface are advantageously obtained.

  In particular, in the production of such activated carbon particles, pores are effectively formed by integrally forming a large number of small protrusions on the surface of the cured phenol resin particles used as a raw material. Thus, it exhibits the feature that the activation operation for obtaining the activated carbon particles having the intended adsorption characteristics is facilitated.

  Some examples of the present invention will be shown below to clarify the present invention more specifically. However, the present invention is not limited by the description of such examples. Needless to say. In addition to the following examples, the present invention includes various changes and modifications based on the knowledge of those skilled in the art without departing from the spirit of the present invention, in addition to the above specific description. It should be understood that improvements and the like can be added.

In this example, for the surface state of the cured phenol resin particles and the spherical activated carbon obtained therefrom (the presence or absence of protrusions and their form), each particle surface was photographed with a scanning electron microscope (SEM), Each was evaluated based on the photograph. The number of protrusions was measured using three SEM photographs taken at three locations on the surface of the cured phenol resin particles, and the number of protrusions projected on each of the three SEM photographs was measured. By dividing by the area obtained from the magnification of the photograph, the number of protrusions projected on each SEM photograph per 1 μm ² was calculated, and the number of protrusions per 1 μm ² calculated from the three SEM photographs was further calculated. After the addition, the added number is divided by 3 to obtain the average value of the number of protrusions per 1 μm ^{2 on the} surface of the cured phenol resin particles. In addition, when the protrusion existing in the field of view of the SEM photograph is missing at the edge of the field of view, the number of protrusions that are recognized to be half or more of the normal size is measured as one, Protrusions considered to be less than that were excluded from measurement. Moreover, number of protrusions per 1 [mu] m ² of Table 1 is shown as a value obtained by rounding off a decimal.

  Moreover, about the average particle diameter of hardening phenol resin particle | grains, it measured as follows. That is, using a particle size distribution measuring device (manufactured by Nikkiso Co., Ltd .: Microtrac particle size distribution measuring device 9320HRA <X-100>), the particle size (particle size) distribution of each cured phenol resin particle was determined by a light scattering method. . Then, from the particle size distribution, when a cumulative curve was obtained with the volume of the entire particle being 100%, the particle size at which the curve was 50% was obtained as the average particle size (average particle size). That is, the cumulative average diameter (center diameter: Median diameter) is the average particle diameter.

Example 1
In a reaction vessel equipped with a reflux condenser, a thermometer and a stirrer, phenol: 500 parts by mass, 92% by mass of paraformaldehyde: 191 parts by mass (F / P = 1.1, where F: number of moles of formalin) , P: mole number of phenol), water: 750 parts by mass, dodecylbenzenesulfonic acid: 5 parts by mass and Senegal type gum arabic (Ara gum A, manufactured by Ina Food Industry Co., Ltd.): 0.2 parts by mass After charging, while stirring and mixing the contents, the temperature is raised (heated) at a rate of about 1 ° C./min until the temperature in the reaction vessel reaches the reflux temperature, and the reaction is continued while maintaining the reflux temperature. Made progress. After 45 minutes from the formation of the phenol resin particles, the temperature in the reaction vessel is slightly lowered and kept for another 4 hours in order to prevent the generated particles from being combined. The resin particles were cured.

And after neutralizing the inside of the reaction vessel with sodium hydroxide and then cooling the inside of the reaction vessel to room temperature, the contents are taken out and filtered and washed to obtain the desired spherical cured phenol resin particles. It was. An SEM photograph of the obtained cured phenol resin particles is shown in FIG. 1. As is clear from such a photograph, the surface of the obtained cured phenol resin particles has a rounded or lobed small shape. It was recognized that many of the protrusions were integrally formed. Moreover, when the average particle diameter of the cured phenol resin particles was determined from the SEM photograph, it was 401 μm. Furthermore, the number of protrusions was 2 / μm ² .

  Subsequently, 300 parts by mass of the obtained cured phenol resin particles were charged into a rotary kiln, heated to 900 ° C., and baked for 1 hour. Further, after cooling to 800 ° C., a steam activation treatment is carried out for 5 hours while adding water, and then cooled to room temperature, so that a round nodular shape similar to that of the raw material resin particles is obtained. It was possible to obtain spherical activated carbon (particles) in which a large number of small protrusions were integrally formed on the particle surface. A SEM photograph of the surface of the obtained spherical activated carbon is shown in FIG.

-Example 2-
Except that the amount of paraformaldehyde at 92% by mass was changed to 208 parts by mass (F / P = 1.2), a large number of small protrusions were integrally formed on the particle surface in the same manner as in Example 1. The surface uneven | corrugated hardening phenol resin particle | grains obtained were obtained. An SEM photograph of the particle surface is shown in FIG. Further, when the average particle diameter of the cured phenol resin particles was determined from the SEM photograph, it was 357 μm. Furthermore, the number of protrusions was 2 / μm ² .

  Further, by using the obtained surface roughened hard phenol resin particles, carbonization and water vapor activation are carried out in the same manner as in Example 1, so that a large number of spherical round-shaped knob-like small protrusions are integrated. A spherical activated carbon having a shape formed in the above was obtained. A surface SEM photograph of the obtained spherical activated carbon is shown in FIG.

-Example 3-
Cured phenol resin particles and spherical activated carbon were produced in the same manner as in Example 1 except that 92% by mass of paraformaldehyde was changed to 260 parts by mass (F / P = 1.5). In addition, the SEM photograph of each surface of this obtained hardening phenol resin particle and spherical activated carbon is shown in FIG.5 and FIG.6. Moreover, when the average particle diameter of the cured phenol resin particles was determined from the SEM photograph, it was 380 μm. Furthermore, the number of protrusions was 3 / μm ² .

Example 4
In a reaction vessel equipped with a thermometer, a stirring device and a stirring cooler, phenol: 500 parts by mass, 92% by mass of paraformaldehyde: 208 parts by mass (F / P = 1.2, F: number of moles of formalin, P : Mol of phenol), water: 750 parts by mass, dodecylbenzenesulfonic acid: 5 parts by mass, and Senegal-type gum arabic (Arabic Coal JP, Senegal) manufactured by Sanei Pharmaceutical Trading Co., Ltd .: 0.2 parts by mass Thereafter, the contents were heated and reacted while stirring and mixing. Then, after the reaction, the inside of the reaction vessel was cooled to room temperature, and after the contents were filtered, washing was performed to obtain spherical cured phenol resin particles. It was confirmed by the SEM photograph shown in FIG. 7 that the obtained cured phenol resin particles were obtained by integrally forming a large number of rounded, bump-like small protrusions on the particle surface. Moreover, when the average particle diameter of the cured phenol resin particles was determined from the SEM photograph, it was 461 μm. Furthermore, the number of protrusions was 2 / μm ² .

  Next, 300 parts by mass of the obtained spherical cured phenol resin particles were charged in a rotary kiln, heated to 900 ° C., and baked for 1 hour. Then, after continuously cooling to 800 ° C., water activation is performed for 5 hours while water is added, and then cooling to room temperature makes it possible to integrate a large number of spherical or elliptical knob-like projections. A spherical activated carbon formed in the above was obtained. The particle shape was confirmed by the SEM photograph shown in FIG.

-Example 5
Commercially available Senegal type gum arabic: Except that the amount of gum arabic A used is 0.4 parts by mass, many of the small lumps are integrated on the particle surface in the same manner as in Example 2. The formed surface uneven | corrugated cured phenol resin particle was obtained. An SEM photograph of the particle surface is shown in FIG. Moreover, when the average particle diameter of the cured phenol resin particle was calculated | required from the SEM photograph, it was 127 micrometers. Furthermore, the number of protrusions was 2 / μm ² .

  In addition, by using the obtained hard-surface roughened hard resin resin particles, carbonization and water vapor activation are performed in the same manner as in Example 2, so that a large number of spherical round-shaped small protrusions are integrated. A spherical activated carbon having a shape formed in the above was obtained.

-Example 6
Senegal type of gum arabic: Commercial gum arabic gum A, except that the amount of gum arabic A used is 0.05 parts by mass, in the same manner as in Example 2, many of the small lumps are integrated on the particle surface. The formed surface uneven | corrugated hardening phenol resin particle | grains were obtained. An SEM photograph of the particle surface is shown in FIG. Moreover, when the average particle diameter of the cured phenol resin particles was determined from the SEM photograph, it was 1107 μm. Furthermore, the number of protrusions was 2 / μm ² .

  In addition, by using the obtained hard-surface roughened hard resin resin particles, carbonization and water vapor activation are performed in the same manner as in Example 2, so that a large number of spherical round-shaped small protrusions are integrated. A spherical activated carbon having a shape formed in the above was obtained.

-Comparative Example 1-
Spherical cured phenol resin particles were obtained in the same manner as in Example 1 except that the amount of 92% by mass of paraformaldehyde was changed to 173 parts by mass (F / P = 1.0). And about this obtained spherical hardening phenol resin particle | grains, when the SEM photograph was taken and the form of the particle | grain surface was investigated, as shown in FIG. 11, a smooth surface was exhibited and the presence of the bump-like small processus | protrusion was confirmed. I couldn't admit anything. Moreover, it was 486 micrometers when the average particle diameter of the cured phenol resin particle was calculated | required from the SEM photograph.

  Moreover, when activated carbon was produced by performing carbonization and steam activation in the same manner as in Example 1 using such spherical cured phenol resin particles, the activated carbon exhibited a smooth spherical shape. Admitted. An SEM photograph of the obtained activated carbon surface is shown in FIG.

-Comparative Example 2-
As gum arabic, Acacia seyal species derived from trees, so-called sial type gum arabic J (seal species; manufactured by Ina Food Industry Co., Ltd.): Except for using 0.2 parts by mass When the production of cured phenol resin particles was attempted in the same manner as in Example 4, the intended cured phenol resin particles could not be obtained.

  From this, it is clear that granulation is difficult and the desired cured phenolic resin particles cannot be obtained when using the other gum arabic gum, the type of gum arabic. It became.

-Comparative Example 3-
In a reaction vessel equipped with a thermometer, a stirrer and a reflux condenser, phenol: 500 parts by mass, 92% by mass of paraformaldehyde: 208 parts by mass (F / P = 1.2, F: number of moles of formalin, P : Number of moles of phenol), water: 750 parts by mass, dodecylbenzenesulfonic acid: 5 parts by mass, and Sear type gum arabic (Ara gum J, manufactured by Ina Food Industry Co., Ltd.): 7.5 parts by mass After that, the contents were heated and reacted with stirring and mixing. And after the reaction, the inside of the reaction vessel was cooled to room temperature, the contents were taken out, then filtered and washed to obtain spherical cured phenol resin particles. Thereafter, the obtained cured phenol resin particles were examined by SEM photographs for the morphology of the particle surface. As shown in FIG. 13, the surface was smooth, and the presence of the bump-like small protrusions was I was not able to admit. Moreover, when the average particle diameter of the cured phenol resin particles was determined from the SEM photograph, it was 249 μm.

  Moreover, after charging 300 parts by mass of the obtained spherical cured phenol resin particles into a rotary kiln, heating to 900 ° C. and performing carbonization by firing for 1 hour, followed by cooling to 800 ° C. Further, after that, water activation was performed for 5 hours while water was added, and then cooled to room temperature to obtain spherical activated carbon. In addition, when the particle | grain surface of this obtained spherical activated carbon was investigated by the SEM photograph, it was recognized that it is a spherical activated carbon which has a smooth surface with almost no surface unevenness.

  Table 1 below summarizes the results of evaluation of the charged amounts in the above Examples 1 to 6 and Comparative Examples 1 to 3, and the average particle diameter, surface morphology, and number of protrusions of the obtained cured phenol resin particles.

2 is a SEM photograph showing the surface morphology of the cured phenol resin particles obtained in Example 1. 3 is a SEM photograph showing the surface morphology of the spherical activated carbon obtained in Example 1. 2 is a SEM photograph showing the surface morphology of cured phenol resin particles obtained in Example 2. 4 is a SEM photograph showing the surface morphology of the spherical activated carbon obtained in Example 2. 4 is a SEM photograph showing the surface morphology of the cured phenol resin particles obtained in Example 3. 4 is a SEM photograph showing the surface morphology of the spherical activated carbon obtained in Example 3. 3 is a SEM photograph showing the surface morphology of cured phenol resin particles obtained in Example 4. 4 is a SEM photograph showing the surface morphology of the spherical activated carbon obtained in Example 4. 4 is a SEM photograph showing the surface morphology of the cured phenol resin particles obtained in Example 5. It is a SEM photograph which shows the surface form of the cured phenol resin particle obtained in Example 6. 4 is a SEM photograph showing the surface morphology of the cured phenol resin particles obtained in Comparative Example 1. 4 is a SEM photograph showing the surface morphology of the spherical activated carbon obtained in Comparative Example 1. 4 is a SEM photograph showing the surface morphology of the cured phenol resin particles obtained in Comparative Example 3.

Claims (7)

In the production of cured phenol resin particles by reacting phenols and aldehydes in the presence of alkylbenzene sulfonic acid and protective colloid to form thermosetting phenol resin particles and then curing the phenol resin particles. ,
The aldehydes are used in a proportion of 1.1 mol or more per 1 mol of the phenols, and the gum used is gum arabic derived from an Acacia / Senegal tree as the protective colloid. Hardened phenol in which a large number of rounded knob-shaped small protrusions are integrally formed on the particle surface by adjusting the amount to be 0.001% by mass or more and less than 0.1% by mass with respect to phenols. A method for producing cured phenol resin particles, comprising obtaining resin particles.   The method for producing cured phenol resin particles according to claim 1, wherein phenol is used as the phenol and formaldehyde is used as the aldehyde.   The said gum arabic is used in the ratio of 0.01-0.08 mass% with respect to the said phenols, The manufacturing method of the cured phenol resin particle of Claim 1 or Claim 2 characterized by the above-mentioned.   4. The cured phenol resin particles are produced by heating thermosetting phenol resin particles generated by reacting the phenols with the aldehydes. The manufacturing method of the cured phenol resin particle of Claim 1. Cured phenol resin particles obtained by curing thermosetting phenol resin particles obtained by reacting phenols and aldehydes,
It has an average particle diameter of 100 μm to 1500 μm, and has a large number of rounded knob-like small protrusions integrally on the particle surface, and such small protrusions are present in a ratio of 1 or more per 1 μm ^{2 of} the particle surface. Cured phenolic resin particles characterized by being caulked.   The cured phenol resin particles according to claim 5, wherein the small protrusions have a diameter of 0.1 μm to 1.2 μm. The cured phenol resin particles obtained by the production method according to any one of claims 1 to 4 are carbonized at a temperature of 650 ° C to 1000 ° C, and then a temperature of 700 ° C to 1000 ° C. A process for producing activated carbon particles characterized by steam activation with

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