WO2018181778A1 - Method for producing activated carbon - Google Patents

Abstract

Provided is a method for efficiently producing activated carbon having an increased proportion of extremely small-sized micropores 1 nm or less in diameter even among micropores 2 nm or less in diameter. This method for producing activated carbon includes an activation step that activates an activated carbon precursor containing a metal component by carbon dioxide gas as an introduction gas and obtains activated carbon having a ratio (pore volume B/total pore volume A) of the pore volume B 1.0 nm or less in diameter to the total pore volume A of 0.5 or higher, and the metal element that constitutes the metal component is selected from the group consisting of group 2 elements, group 3 elements, group 4 elements, group 5 elements, group 6 elements, group 7 elements, group 9 elements, and rare earth elements.

Description

Method for producing activated carbon

The present invention relates to a method for producing activated carbon, and more particularly to a method for producing activated carbon for efficiently producing activated carbon having a high proportion of micropores.

Conventionally, gas activation methods and chemical activation methods are known as activation methods for producing activated carbon. Among these, as the gas activation method, a steam activation method, a carbon dioxide activation method, and an oxygen activation method are known.

From an industrial point of view, a steam activation method having a high activation reaction rate and advantageous in terms of productivity is generally used as a gas activation method. In the steam activation method, the activation reaction is advanced by an endothermic reaction between water vapor and carbon. For example, a method of obtaining activated carbon in an activation time of 120 minutes by activating phenol novolac fibers with water vapor at 950 ° C. is known (see Patent Document 1).
Furthermore, in the steam activation, at least one metal component of Mg, Mn, Fe, Y, Pt and Gd is included in the pitch as the activated carbon precursor, so that the obtained activated carbon has a mesopore mode of 30 to 45 mm. A method of opening mesopores having a diameter is known (see Patent Document 2).

On the other hand, the carbon dioxide activation method is known to have a very low activation reaction rate. For example, a method of obtaining activated carbon in an activation time of 24 hours is known by activating a coconut shell carbonized product with carbon dioxide at 1050 ° C. (see Patent Document 3). Therefore, the carbon dioxide activation method was not suitable for industrial production.

Japanese Patent No. 5781164 JP 2004-182511 A JP 2007-221108 A

The inventors industrially produce activated carbon with an increased proportion of micropores having a diameter of 1 nm or less, which is suitable for, for example, adsorption of dichloromethane in the gas phase among micropores having a diameter of 2 nm or less. Focused on that. Here, when it is going to manufacture the activated carbon which raised the ratio of the micropore of the extremely small size 1 nm or less in diameter, the method of making activation temperature low normally is considered. However, if the activation temperature is lowered, the activation reaction takes time, the production cannot be performed efficiently, and it is not suitable for industrial production. That is, conventionally, there has been a problem that it is difficult to industrially manufacture activated carbon having an increased proportion of micro pores having a diameter of 1 nm or less. Specifically, for example, Patent Document 1 describes activated carbon in which the ratio of micropores having a diameter of 2 nm or less in Examples 1 to 18 is 0.44 to 0.67, whereas the minimum is 1 nm or less in diameter. No investigation has been made on activated carbon having an increased proportion of size micropores and a method for efficiently producing the activated carbon. In Patent Document 2, a method for controlling the distribution of mesopores (diameter 2 to 50 nm), which is much larger than the pore size noted by the present inventors, to a desired range, specifically, the type of a specific metal component Is described to control the mesopore mode diameter of the resulting activated carbon. However, no investigation has been made on activated carbon with a high proportion of micro pores having a diameter of 1 nm or less, which has been focused on by the present inventors, and a method for efficiently producing the activated carbon. And in patent document 2, from the viewpoint of controlling the distribution of mesopores to a desired range, examples shown as being practically possible are only examples of the steam activation method. Moreover, in the method of activating the coconut shell carbonized product disclosed in Patent Document 3 at 1050 ° C. with carbon dioxide, there is a problem that it takes too much activation time to be industrially produced. Therefore, Patent Documents 1 to 3 do not disclose or suggest any industrial production of activated carbon with an increased proportion of micro pores having a diameter of 1 nm or less.

Therefore, the main object of the present invention is to provide a method for efficiently producing activated carbon having an increased proportion of micropores having a diameter of 1 nm or less among micropores having a diameter of 2 nm or less.

As a result of intensive studies, the inventors of the present invention dared to use activated carbon precursors that have been used to control mesopores, which are pores having a size much larger than the size of the pores the inventors have focused on. Attention was paid to the technical elements containing metal components and the carbon dioxide activation method known to have a very low activation reaction rate. As a result of further intensive studies, it was surprising that activated carbon with an increased proportion of micro pores having a diameter of 1 nm or less was selected by adding a specific metal to the activated carbon precursor in the carbon dioxide activation method. It was found that it can be obtained with a short activation time.
The present invention has been completed by further studies based on these findings.

That is, this invention provides the invention of the aspect hung up below.
Item 1. The activated carbon precursor containing a metal component is activated with carbon dioxide gas as an introduction gas, and the ratio of the pore volume B with a diameter of 1.0 nm or less to the total pore volume A (pore volume B / total pore volume A) is 0. Including an activation step of obtaining activated carbon that is 5 or more, and the metal elements constituting the metal component are Group 2 elements, Group 3 elements, Group 4 elements, Group 5 elements, Group 7 elements, and rare earth elements A method for producing activated carbon, selected from the group consisting of:
Item 2. Item 2. The method for producing activated carbon according to Item 1, wherein the metal element is selected from the group consisting of Y, Mg, Mn, La, V, Zr, Ti, and Ce.
Item 3. Item 3. The method for producing activated carbon according to Item 1 or 2, wherein the metal element is selected from the group consisting of Y, Mg, Ce, Ti and V.
Item 4. The activated carbon precursor containing a metal component is activated with carbon dioxide gas as an introduction gas, and the ratio of the pore volume B with a diameter of 1.0 nm or less to the total pore volume A (pore volume B / total pore volume A) is 0. The manufacturing method of activated carbon including the activation process which obtains the activated carbon which is 5 or more, and the metal element which comprises the said metal component is selected from the group which consists of a 6th group element and a 9th group element.
Item 5. Item 5. The method for producing activated carbon according to Item 4, wherein the metal element is selected from the group consisting of Mo and Co.
Item 6. Item 6. The method for producing activated carbon according to any one of Items 1 to 5, wherein the activated carbon has a specific surface area of 600 m ² / g or more.
Item 7. Item 7. The method for producing activated carbon according to any one of Items 1 to 6, wherein the composition of the introduced gas is not changed in the activation step.
Item 8. Item 8. The method for producing activated carbon according to any one of Items 1 to 7, wherein the flow rate of the introduced gas is 1.5 L / min or more in terms of 1 atm at 0 ° C per 1 g of the activated carbon precursor.
Item 9. Item 9. The method for producing activated carbon according to any one of Items 1 to 8, wherein the activation temperature in the activation step is 800 to 1000 ° C.
Item 10. Item 10. The method for producing activated carbon according to any one of Items 1 to 9, wherein a content of the metal component is 0.05 to 1.0% by mass in the activated carbon precursor.
Item 11. Item 11. The method for producing activated carbon according to any one of Items 1 to 10, wherein the activated carbon precursor is an infusible pitch.
Item 12. Any of the items 1 to 11, wherein in the activated carbon, a ratio of a pore volume C having a diameter of 2.0 nm or less to a total pore volume A ({pore volume C / pore volume A} × 100) is 85% or more. The method for producing activated carbon according to claim 1.
Item 13. Item 13. The method for producing activated carbon according to any one of Items 1 to 12, wherein in the activated carbon, a pore volume B having a diameter of 1.0 nm or less is 0.25 cc / g or more.

According to the method for producing activated carbon of the present invention, there is provided a method for efficiently producing activated carbon with an increased proportion of micro pores having a diameter of 1 nm or less. Therefore, the time required for activation up to a predetermined activation level can be greatly shortened, and this makes it possible to industrialize activated carbon with high adsorption performance.

4 is a graph showing, in a linear approximation, an increasing tendency of specific surface area with respect to activation time in the production methods of Examples 1 to 8 and Comparative Examples 1 to 3. 5 is a graph showing, by linear approximation, an increasing tendency of specific surface area with respect to activation time in the production methods of Examples 9 to 15 and Comparative Examples 1 to 3. 6 is a graph showing, in a linear approximation, an increasing tendency of specific surface area with respect to activation time in the production methods of Examples 16 to 20 and Comparative Examples 1 to 3. 6 is a graph showing, in a linear approximation, an increasing tendency of specific surface area with respect to activation time in the production methods of Examples 21 to 27 and Comparative Examples 1 to 3. 6 is a graph showing, by linear approximation, an increasing tendency of specific surface area with respect to activation time in the production methods of Comparative Examples 1 to 10.

Hereinafter, the production method of the activated carbon of the present invention will be described in detail.

[1. Production target (activated carbon)]
[1-1. Activated carbon surface structure]
Hereinafter, the pore volume refers to the pore volume calculated by the QSDFT method (quenched solid density functional method). The QSDFT method is an analysis method capable of calculating pore size distributions from about 0.5 nm to about 40 nm for geometrically and chemically irregular microporous and mesoporous carbon pore size analysis. . In the QSDFT method, the influence of the roughness and nonuniformity of the pore surface is clearly taken into account, so that the accuracy of the pore diameter distribution analysis is greatly improved. In the present invention, measurement of nitrogen adsorption isotherm and pore size distribution analysis by QSDFT method are performed using “AUTOSORB-1-MP” manufactured by Quantachrome. By applying N2 at 77K on carbon [slit pore, QSDFT equilibrium model] as a calibration model to the nitrogen desorption isotherm measured at a temperature of 77 K, the pore size distribution is calculated to obtain a fine pore size range. The pore volume can be calculated.

The activated carbon produced by the production method of the present invention has a ratio of pore volume B (cc / g) having a diameter of 1.0 nm or less to total pore volume A (cc / g), that is, (pore volume B / total pores). The volume A) ratio is 0.5 or more. Usually, pores having a diameter of 2.0 nm or less are referred to as micropores. However, in the present invention, the volume ratio of the extremely small pores having a diameter of 1.0 nm or less among the micropores is increased. Adsorption performance can be obtained satisfactorily. From the viewpoint of obtaining better adsorption performance per unit specific surface area, the ratio (pore volume B / total pore volume A) is preferably 0.53 or more, more preferably 0.60 or more, and even more preferably 0.7. As described above, it may be particularly preferably 0.8 or more. In the present invention, the adsorption performance can be evaluated by, for example, the adsorption performance of dichloromethane. Further, the upper limit value of (pore volume B / total pore volume A) ratio is not particularly limited, and examples thereof include 1.00 or less, and 0.95 or less.

The total pore volume A (cc / g) may be, for example, 0.45 cc / g or more, preferably 0.50 cc / g or more, from the viewpoint of securing a sufficient pore volume for adsorption.
Further, the total pore volume A (cc / g) is, for example, 1.50 cc / g or less, preferably 0 from the viewpoint of favorably obtaining micropores having a diameter of 2 nm or less, preferably micropores having a minimum size of 1 nm or less. It may be 8 cc / g or less.

The specific surface area is, for example, 600 m ² / g or more, preferably 1000 m ² / g or more, more preferably 1300 m ² / g or more, further preferably 1400 m ² / g or more, particularly preferably 1600 m from the viewpoint of obtaining good adsorption performance. It may be ² / g or more.
Moreover, although the upper limit of a specific surface area is not specifically limited, For example, 3000 m < ² > / g or less is mentioned, 2500 m < ² > / g or less is mentioned, 2000 m < ² > / g or less is mentioned.
In the present invention, the specific surface area is a value measured by a BET method (one-point method) using nitrogen as an adsorbed substance.

The pore volume B (cc / g) having a diameter of 1.0 nm or less is, for example, 0.25 cc / g or more, preferably 0.35 cc / g or more from the viewpoint of obtaining good adsorption performance per unit specific surface area. Good.
Further, the upper limit value of the pore volume B having a diameter of 1.0 nm or less is not particularly limited, and for example, 0.60 cc / g or less, preferably 0.50 cc / g or less.

In the activated carbon produced by the production method of the present invention, the pore volume (cc / g) having a diameter of 1.5 nm or less is, for example, 0.45 cc / g or more from the viewpoint of obtaining good adsorption performance per unit specific surface area. Preferably it may be 0.5 cc / g or more.
Moreover, the upper limit value of the pore volume (cc / g) having a diameter of 1.5 nm or less is not particularly limited, and examples thereof include 0.7 cc / g or less.

In the activated carbon produced by the production method of the present invention, the pore volume C (cc / g) having a diameter of 2.0 nm or less is, for example, 0.35 cc / g or more from the viewpoint of obtaining good adsorption performance per unit specific surface area. , Preferably 0.45 cc / g or more.
Further, the upper limit value of the pore volume C (cc / g) having a diameter of 2.0 nm or less is not particularly limited, and examples thereof include 0.8 cc / g or less.

The ratio of the pore volume C having a diameter of 2.0 nm or less to the total pore volume A ({pore volume C / total pore volume A} × 100, that is, the micropore volume ratio (%)) per unit specific surface area From the viewpoint of obtaining a satisfactory adsorption performance, it may be, for example, 80% or more, preferably 85% or more, more preferably 90% or more. In addition, when intended for use in water purifiers, etc., there are micropores with a diameter of 1.0 nm or less that contribute effectively to adsorption and moderate mesopores that assist the diffusion of the adsorbate in the pores. In some cases, it is preferable to have a pore structure. From this viewpoint, the micropore volume ratio (%) is preferably 80 to 95%, more preferably 90 to 95%. Further, the micropore volume (%) may be more than 95% or 96% or more.

In the activated carbon produced by the production method of the present invention, the ratio of the pore volume having a diameter of more than 2.0 nm and not more than 50 nm to the total pore volume A, that is, the mesopore volume ratio (%) is not particularly limited. Assuming applications such as, the pore structure has micropores with a diameter of 1.0 nm or less that contribute effectively to adsorption and moderate mesopores that assist the diffusion of the adsorbate in the pores. In this respect, the mesopore volume ratio is preferably 5 to 20%, more preferably 5 to 10%. Further, the mesopore volume ratio may be less than 5% or 4% or less. The total ratio (%) of the micropore volume and the mesopore volume to the total pore volume A is 98% to 100% (in the case of 100%, the macropore volume ratio (%) is 0%) It can be.

[1-2. Metal content in activated carbon]
Since the metal component is used in the production method of the present invention as described later, the metal component remains in the obtained activated carbon. The ratio of the metal component contained in the activated carbon to the total mass of the activated carbon (in terms of metal element) may be, for example, 0.15 to 0.60 mass%, preferably 0.15 to 0.45 mass%. More preferably, it may be 0.20 to 0.40% by mass. The above ratio in the activated carbon is a ratio in terms of a metal element measured by an ICP emission spectroscopic analyzer (model 715-ES manufactured by Varian).

[1-3. Activated carbon form]
Although the form of the activated carbon manufactured by the manufacturing method of this invention is not specifically limited, For example, granular activated carbon, powdered activated carbon, fibrous activated carbon, etc. are mentioned. From the viewpoint of workability when used in filter processing or the like, or when used in a water purifier or the like, it is more preferable to use fibrous activated carbon that is fibrous. In the present invention, the adsorption rate can be evaluated by, for example, a trihalomethane water adsorption test. The average fiber diameter of the fibrous activated carbon is preferably 30 μm or less, more preferably about 5 to 20 μm. In addition, the average fiber diameter in this invention is the value measured with the image processing fiber diameter measuring apparatus (based on JISK1477). Examples of the particle sizes of the granular activated carbon and the powdered activated carbon include an integrated volume percentage D ₅₀ measured by a laser diffraction / scattering method of 0.01 to 5 mm.

[1-4. Activated carbon adsorption performance]
The activated carbon produced by the production method of the present invention can be used either in the gas phase or in the liquid phase, but is particularly preferably used for adsorbing dichloromethane in the gas phase.

Examples of the dichloromethane adsorption performance (equilibrium adsorption amount (% by mass)) that can be provided in the activated carbon produced by the production method of the present invention include 60% by mass or more, preferably 65% by mass or more, and more preferably 75% by mass. % Or more, and particularly preferably 80% by mass or more. The dichloromethane adsorption performance is measured as follows. That is, the activated carbon sample is dried with a dryer at 110 ° C. for 12 hours, cooled with a desiccator, and 0.5 g is quickly measured and filled into a U-shaped tube. Next, the adsorption operation is performed by blowing dry air at a flow rate of 500 ml / min into dichloromethane (special grade reagent, containing 0.5% of methanol in the stabilizer) in a constant temperature bath at 28 ° C. and introducing it into the U-shaped tube. . The equilibrium point is calculated when the mass increase of the activated carbon stops, and the equilibrium adsorption amount is calculated by the following equation.
Equilibrium adsorption amount (% by mass) = mass increase / active carbon mass x 100

The dichloromethane adsorption performance per unit specific surface area that can be provided by the activated carbon produced by the production method of the present invention includes 0.045% by mass / g / m ² or more, and 0.046% by mass / g / m. ² or more are preferred, and specifically, 0.046 to 0.055 mass% · g / m ² is mentioned. The dichloromethane equilibrium adsorption amount per unit specific surface area of the activated carbon is calculated by dividing the dichloromethane adsorption performance determined as described above by the specific surface area (m ² / g) of the activated carbon.

[2. Activated carbon precursor]
In the production method of the present invention, a specific metal component is contained in the activated carbon precursor that is a raw material of the activated carbon.

[2-1. Raw material of activated carbon precursor]
In the carbon dioxide gas activation, pores are generated by the reaction (C _x + CO ₂ → 2CO + C _x-1 ) between carbon in the activated carbon precursor and carbon dioxide gas. Further, the reaction between carbon and carbon dioxide gas is promoted by a catalytic action by a metal component described later. The reaction between carbon and carbon dioxide and the promoting effect thereof are common regardless of the raw material species and form of the activated carbon precursor. Therefore, the raw material species and form of the activated carbon precursor are not particularly limited.

Examples of the raw material species of the activated carbon precursor include infusible or carbonized organic materials, curable resins such as phenol resins, and the like, for example, polyacrylonitrile, pitch, polyvinyl alcohol, cellulose, etc. Is mentioned. Also sawdust, wood chips, wood, peat, charcoal, coconut husk, coal, oil, carbonaceous materials (petroleum coke, coal coke, petroleum pitch, coal pitch, coal tar pitch, and composites thereof), synthesis Examples thereof include resins (phenol resins, polyacrylonitrile (PAN), polyimides, furan resins, etc.), cellulosic fibers (paper, cotton fibers, etc.), and composites thereof (paper-phenol resin laminates, etc.), fullerenes, and the like. Among these, in terms of the theoretical carbonization yield at the time of carbonization, pitch is preferable, and coal pitch is more preferable. Examples of the form of the activated carbon precursor include granular activated carbon, powdered activated carbon, fibrous activated carbon and the like.

The softening point (° C.) of the activated carbon precursor is not particularly limited, but is preferably 275 ° C. to 288 ° C., more preferably 277 ° C. to 283 ° C., from the viewpoint of handleability during infusibilization. In the present invention, the softening point (° C.) is measured by the Mettler method (measured according to ASTM-D3461).

[2-2. Metal component]
The metal component promotes the reaction between carbon and carbon dioxide in the carbon dioxide activation by catalytic action. The metal element constituting the metal component is a group consisting of a Group 2 element, a Group 3 element, a Group 4 element, a Group 5 element, a Group 6 element, a Group 7 element and a Group 9 element, and a rare earth element 1 type or multiple types are selected from.

The metal element constituting the metal component is selected from one or more kinds selected from the group consisting of Group 2 elements, Group 3 elements, Group 4 elements, Group 5 elements, Group 7 elements, and rare earth elements Good. Examples of the Group 2 element include Be, Mg, Ca, Sr, Ba, and Ra. Examples of the Group 3 element include Sc and Y. Examples of Group 4 elements include Ti, Zr, and Hf. Examples of Group 5 elements include V, Nb, and Ta. Examples of the Group 7 element include Mn, Tc, and Re. Examples of rare earth elements include La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. Among these, Mg is preferable as the Group 2 element, Y is preferable as the Group 3 element, Zr and Ti are preferable as the Group 4 element, from the viewpoint of obtaining a large carbon dioxide activation promoting effect. V is preferable as the group element, Mn is preferable as the Group 7 element, and La and Ce are preferable as the rare earth element. Furthermore, when it is assumed to be used in a water purifier or the like, there are micropores having a diameter of 1.0 nm or less that contribute effectively to adsorption and fine mesopores that assist the diffusion of the adsorbate in the pores. A pore structure is preferable, and Y, Mg, Ce, and Ti are preferable as the metal element from this viewpoint. Moreover, when assuming a gas adsorption application, it is preferable to increase the specific surface area by keeping the ratio of pores having a diameter of 1.0 nm or less high, and from this viewpoint, V is preferable as the metal element.
On the other hand, from the viewpoint of controlling the carbon dioxide activation promoting effect, the above-mentioned Mg, Y, among the Group 2 element, Group 3 element, Group 4 element, Group 5 element, Group 7 element, and rare earth element are included. Elements other than Zr, V, Mn, La and Ce can also be selected.

Among the metal elements described above, Mg, Y, La, Zr, Ce and Ti can be used from the viewpoint of accompanying the generation of mesopores (pores having a diameter of more than 2.0 nm). Among the above metal elements, Mg and V can be used from the viewpoint of suppressing the formation of mesopores. In addition, when water vapor | steam is contained in introduction gas, V can be used from a viewpoint which suppresses the production | generation of a mesopore although it is the conditions which water vapor | steam inherently tends to form a mesopore among the above-mentioned metal elements. . In this way, different activated carbon pore structures can be obtained depending on the metal species. Therefore, a metal element can be appropriately selected according to the pore structure suitable for the use of the activated carbon to be produced.

As the metal element constituting the metal component, one or more kinds may be selected from the group consisting of Group 6 elements and Group 9 elements. Examples of Group 6 elements include Cr, Mo, and W. Examples of Group 9 elements include Co, Rh, and Ir. Among these, Mo is preferable as the Group 6 element and Co is preferable as the Group 9 element from the viewpoint of obtaining a large carbon dioxide activation promoting effect. Furthermore, when it is assumed to be used in a water purifier or the like, there are micropores having a diameter of 1.0 nm or less that contribute effectively to adsorption and fine mesopores that assist the diffusion of the adsorbate in the pores. A pore structure is preferable, and Co is preferable as the metal element from that viewpoint. On the other hand, from the viewpoint of controlling the carbon dioxide activation promoting effect, elements other than the above-described Mo and Co can be selected from Group 6 elements and Group 9 elements.

Among the above-described metal elements, Mo and Co can be used from the viewpoint of accompanying the generation of mesopores (pores having a diameter of more than 2.0 nm). Of the metal elements described above, Mo can be used from the viewpoint of suppressing the formation of mesopores. In addition, when water vapor | steam is contained in introduction gas, Mo is used from a viewpoint which suppresses the production | generation of a mesopore among the above-mentioned metal elements, although water vapor | steam is a condition which is easy to form a mesopore intrinsically. it can. In this way, different activated carbon pore structures can be obtained depending on the metal species. Therefore, a metal element can be appropriately selected according to the pore structure suitable for the use of the activated carbon to be produced.

In the production method of the present invention, the method for causing the activated carbon precursor to contain a metal component is not particularly limited. For example, a metal component may be added to the activated carbon precursor or kneaded.

The form of the metal component may be a single metal or a metal compound. Examples of the metal compound include inorganic metal compounds such as metal oxides, metal hydroxides, metal halides, and metal sulfates, salts of organic acids and metals such as acetic acid and benzoic acid, and organic metal compounds. Examples of the organometallic compound include metal complexes such as metal acetylacetonate and aromatic metal compounds (for example, metallocene). Metal complexes are preferred in that they are well melted or dispersed in the activated carbon precursor.

The content of the metal component in the activated carbon precursor (in terms of metal element) may be, for example, 0.01 to 1.0% by mass, preferably 0.05 to 0.5% by mass. Further, the content of the metal component in the activated carbon precursor is more preferably 0.05 to 0.4% by mass, further preferably 0.1 to 0%, for example, when the metal element constituting the metal component is Mg. When the metal element is Mn, it may be more preferably 0.1 to 0.4% by mass, and still more preferably 0.15 to 0.3% by mass; When Y is Y, it may be more preferably 0.05 to 0.4% by mass, and still more preferably 0.05 to 0.3% by mass; when the metal element is La, more preferably 0 0.1 to 0.4% by mass, more preferably 0.15 to 0.3% by mass; when the metal element is V, more preferably 0.05 to 0.4% by mass, still more preferably May be from 0.05 to 0.3% by weight; the metal element is Zr In this case, it may be more preferably 0.05 to 0.4% by mass, further preferably 0.1 to 0.3% by mass; when the metal element is Ce, more preferably 0.05 to 0%. 4 mass%, more preferably 0.1 to 0.3 mass%; when the metal element is Ti, more preferably 0.1 to 0.4 mass%, still more preferably 0.15 It may be up to 0.3% by weight. When the metal element constituting the metal component is Mo, it may be more preferably 0.1 to 0.4% by mass, further preferably 0.15 to 0.3% by mass; the metal element is Co In this case, it may be more preferably 0.1 to 0.4% by mass, and still more preferably 0.15 to 0.3% by mass.

The content of the metal component in the activated carbon precursor is a ratio in terms of a metal element measured by an ICP emission spectroscopic analyzer (model 715-ES manufactured by Varian).

[2-3. Introduced gas]
Carbon dioxide gas (carbon dioxide) is used as the introduction gas (gas introduced into the activation furnace), and nitrogen, carbon monoxide, a rare gas, or the like can be contained within a range that does not impair the effects of the present application.

In the present invention, from the viewpoint of efficiently producing activated carbon, it is preferable to perform the activation step in one step without changing the composition of the introduced gas during the activation step.

The composition of the introduced gas is a value measured according to JIS K 0301 5.1 Orsat analysis method.

From the viewpoint of obtaining good activation efficiency, the flow rate of the introduced gas may be 1.5 L / min or more per 1 g of the activated carbon precursor in terms of 1 atm at 0 ° C., and the activation is efficiently performed while avoiding excessive introduction. From the viewpoint, it may be 5.0 L / min or less. This flow rate may be, for example, an amount per about 0.044 m ³ as the activation furnace volume.

[2-4. Activation temperature and activation time]
The atmospheric temperature (activation temperature) in the activation furnace in the activation step may be, for example, 800 to 1000 ° C., preferably 900 to 1000 ° C.

Further, the activation time may be adjusted so as to have a predetermined pore distribution according to the main component of the activated carbon precursor, the added metal species, the content of the metal component, the carbon dioxide concentration in the introduced gas, and the like. For example, the activation time may be 10 to 80 minutes, preferably 10 to 70 minutes. Alternatively, for example, when the metal element constituting the metal component is Mg, the activation time may be more preferably 15 to 50 minutes, and even more preferably 25 to 45 minutes; when the metal element is Mn, More preferably 15 to 60 minutes, even more preferably 20 to 50 minutes; when the metal element is Y, more preferably 15 to 70 minutes, even more preferably 20 to 65 minutes; When the element is La, it may be more preferably 15 to 40 minutes, even more preferably 20 to 35 minutes; when the metal element is V, more preferably 10 to 60 minutes, still more preferably 15 to 35 minutes. May be 50 minutes; more preferably 15 to 60 minutes, even more preferably 20 to 50 minutes when the metal element is Zr; more preferred when the metal element is Ce Ku is 15 to 55 minutes, more preferably may be 20 to 50 minutes; when it is a metal element Ti is more preferably 15 to 60 minutes, more preferably may be 20 to 50 minutes. Alternatively, for example, when the metal element constituting the metal component is Mo, the activation time may be more preferably 15 to 60 minutes, still more preferably 20 to 50 minutes; when the metal element is Co, More preferably, it may be 15 to 60 minutes, and further preferably 20 to 50 minutes.

[2-5. Specific surface area development speed]
According to the production method of the present invention, activated carbon precursor containing a metal component is activated with carbon dioxide gas as an introduction gas, and the ratio of pore volume B having a diameter of 1.0 nm or less to total pore volume A (pore volume B / Including an activation step of obtaining activated carbon having a total pore volume A) of 0.5 or more, and the metal elements constituting the metal component are Group 2 elements, Group 3 elements, Group 4 elements, Group 5 elements Therefore, there is provided a method for efficiently producing activated carbon having an increased proportion of micropores having a minimum size of 1.0 nm or less in diameter, which is selected from the group consisting of Group 7 elements and rare earth elements. In the present invention, the preferred specific surface area development rate is, for example, preferably 25 m ² / g / min or more, more preferably 30 m ² / g / min or more, until the specific surface area reaches 800 m ² / g. 40 m ² / g / min or more is preferable, and 50 m ² / g / min or more is particularly preferable. Further, preferably at least 25m ² / g / min developmental rate to reach a specific surface area of 1100 m ² / g, more preferably at least 30m ² / g / min, more 40m ² / g / min is preferable, 50 m ² / Particularly preferred is g / min or more.

As development rate of the preferred specific surface area of the case where the metal element is Y, the rate of development to reach the specific surface area of 871m ² / g, rate of development until reaching the specific surface area of 1237m ² / g, and / or a specific surface area The development rate until reaching 1603 m ² / g is 25 m ² / g / min or more, the development rate until reaching the specific surface area 917 m ² / g, the development rate until reaching the specific surface area 1168 m ² / g , and / or specific rate of development until reaching the surface area of 1338m ² / g are mentioned it is 30 m ² / g / min or more. As the preferred specific surface area growth rate when the metal element is Mg, the development rate until reaching the specific surface area of 981 m ² / g and / or the development rate until reaching the specific surface area of 1461 m ² / g is 30 m ² / g. g / min or more. As development rate of the preferred specific surface area of the case where the metal element is Mn, the rate of development to reach the development rate and / or a specific surface area of 1214m ² / g to reach the specific surface area of 953m ² / g is 28 m ² / g / min or more. The preferred specific surface area growth rate when the metal element is La includes a development rate until reaching a specific surface area of 675 m ² / g, a development rate until reaching a specific surface area of 758 m ² / g, and / or a specific surface area. The development rate until reaching 916 m ² / g is 28 m ² / g / min or more. As development rate of the preferred specific surface area of the case where the metal element is V, the specific surface area 863M ² / development to reach the g rate and / or a specific surface area of 1426m ² / g rate of development until reaching the are 50 m ² / g / min or more. As development rate of the preferred specific surface area of the case where the metal element is Zr, the specific surface area of 790m ² / development to reach the g rate and / or a specific surface area of 1052m ² / g rate of development until reaching the are 25 m ² / g / min or more. As development rate of the preferred specific surface area of the case where the metal element is Ce, the rate of development to reach the specific surface area of 821m ² / g, rate of development until reaching the specific surface area of 1078m ² / g, and / or a specific surface area rate of development to reach 1249m ² / g can be cited more 25m ² / g / min. As development rate of the preferred specific surface area of the case where the metal element is Ti, the rate of development to reach the development rate and / or a specific surface area of 1170 m ² / g to reach the specific surface area of 781m ² / g is 28 m ² / g / min or more.

As development rate of the preferred specific surface area of the case where the metal element is Y, the rate of development to reach the specific surface area of 871m ² / g, rate of development until reaching the specific surface area of 1237m ² / g, and specific surface area 1603M ² The value of the slope (that is, the development rate of specific surface area per minute) when linearly approximating each of the development rates until reaching / g by the least square method is 25 m ² / g / min or more. is, rate of development until reaching the specific surface area of 917m ² / g, the minimum respective development velocity until it reaches the rate of development, and a specific surface area of 1338m ² / g to reach the specific surface area of 1168m ² / g ² squares It is mentioned that the value of the slope when linear approximation is performed is 25 m ² / g / min or more. As development rate of the preferred specific surface area of the case where the metal element is Mg, the minimum respective development velocity to reach the development rate and a specific surface area of 1461m ² / g to reach the specific surface area of 981m ² / g ² squares The value of the slope when linear approximation is performed is 30 m ² / g / min or more. The preferred specific surface area growth rate when the metal element is Mn is the least square method for each of the growth rate until reaching the specific surface area of 953 m ² / g and the growth rate until reaching the specific surface area of 1214 m ² / g. The value of the slope when linear approximation is performed is 15 m ² / g / min or more. The preferable development rate of the specific surface area when the metal element is La includes the development rate until reaching the specific surface area of 675 m ² / g, the development rate until reaching the specific surface area of 758 m ² / g, and the specific surface area of 916 m ^2. The value of the slope when linearly approximating each of the development rates until reaching / g by the least square method is 20 m ² / g / min or more. As development rate of the preferred specific surface area of the case where the metal element is V, the minimum respective development velocity to reach the development rate and a specific surface area of 1426m ² / g to reach the specific surface area of 863m ² / g ² squares The value of the slope when linear approximation is performed is 50 m ² / g / min or more. The preferred specific surface area growth rate when the metal element is Zr is the least square method for each of the growth rate until reaching the specific surface area of 790 m ² / g and the growth rate until reaching the specific surface area of 1052 m ² / g. The value of the slope when linear approximation is performed is 15 m ² / g / min or more. As development rate of the preferred specific surface area of the case where the metal element is Ce, the rate of development to reach the specific surface area of 821m ² / g, rate of development until reaching the specific surface area of 1078m ² / g, and specific surface area 1249M ² The value of the slope when linearly approximating each of the development rates until reaching / g by the least square method is 18 m ² / g / min or more. The preferred specific surface area growth rate when the metal element is Ti is the least square method for the growth rate until reaching the specific surface area of 781 m ² / g and the growth rate until reaching the specific surface area of 1170 m ² / g. The value of the slope when linear approximation is performed is 20 m ² / g / min or more.

According to the production method of the present invention, activated carbon precursor containing a metal component is activated with carbon dioxide gas as an introduction gas, and the ratio of pore volume B having a diameter of 1.0 nm or less to total pore volume A (pore volume B / Including an activation step of obtaining activated carbon having a total pore volume A) of 0.5 or more, and the metal element constituting the metal component is selected from the group consisting of Group 6 elements and Group 9 elements; Provided is a method for efficiently producing activated carbon having an increased proportion of micropores having an extremely small size of 1.0 nm or less. In the present invention, the preferred specific surface area development rate is, for example, preferably 25 m ² / g / min or more, more preferably 30 m ² / g / min or more, until the specific surface area reaches 800 m ² / g. 40 m ² / g / min or more is preferable, and 50 m ² / g / min or more is particularly preferable. Further, preferably at least 25m ² / g / min developmental rate to reach a specific surface area of 1100 m ² / g, more preferably at least 30m ² / g / min, more 40m ² / g / min is preferable, 50 m ² / Particularly preferred is g / min or more.

The preferred specific surface area growth rate when the metal element is Mo includes a development rate until reaching a specific surface area of 784 m ² / g, a development rate until reaching a specific surface area of 1171 m ² / g, and / or a specific surface area. The development rate until reaching 1684 m ² / g is 25 m ² / g / min or more. As development rate of the preferred specific surface area of the case where the metal element is Co, the specific surface area 844M ² / development to reach the g rate and / or a specific surface area of 1447m ² / g rate of development until reaching the are 30 m ² / g / min or more.

When the metal element is Mo, the preferable development rate of the specific surface area is a development rate until reaching the specific surface area of 784 m ² / g, a development rate until reaching the specific surface area of 1171 m ² / g, and a specific surface area of 1684 m ^2. It is mentioned that the slope value (that is, the development rate of the specific surface area per minute) is 20 m ² / g / min or more when linearly approximating each of the development speeds until reaching / g by the least square method. It is done. As development rate of the preferred specific surface area of the case where the metal element is Co, the minimum respective development velocity to reach the development rate and a specific surface area of 1447m ² / g to reach the specific surface area of 844m ² / g ² squares The value of the slope when linear approximation is performed is 35 m ² / g / min or more.

[2-6. Other processes]
The manufacturing method of the present invention may include other steps in addition to the activation step described above. Examples of other processes include processes known in the method for producing activated carbon, such as a molding process (including a spinning process in the case of fibrous activated carbon) that molds an organic material into a predetermined shape before the activation process. It includes the infusibilization step. Moreover, when the obtained activated carbon is a water purifier use, the washing | cleaning process of wash | cleaning the metal component adhering to the surface of the obtained activated carbon can be included after an activation process.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the examples.

Each Example and Comparative Example were evaluated by the following methods.
(1) Metal content (mass%) of infusible pitch fiber (activated carbon precursor)
The pitch fiber was incinerated, the ash was dissolved in acid, and the ratio in terms of metal element measured by an ICP emission spectrophotometer (Varian model 715-ES) was defined as the metal content.

(2) Composition of introduced gas The composition of the introduced gas was measured according to JIS K 0301 5.1 Orsat analysis method.

(3) Metal content in activated carbon The fibrous elemental activated carbon was dissolved in an acid, and the ratio in terms of metal element measured by an ICP emission spectroscopic analyzer (model 715-ES manufactured by Varian) was defined as the metal content.

(4) Specific surface area (m ² / g) and pore volume (cc / g)
The specific surface area was calculated from the measurement point of relative pressure 0.1 by the BET method.
The pore physical properties were measured from a nitrogen adsorption isotherm at 77K using “AUTOSORB-1-MP” manufactured by Quantachrome. For the total pore volume and the pore volume in each pore diameter range described in the following tables, N ₂ at 77K on carbon [slit pore, QSDFT equilibrium model] is applied as a calibration model to the measured nitrogen desorption isotherm. Thus, the pore size distribution was calculated and analyzed. Specifically, the pore volume at each pore diameter described in the following tables is a reading of a pore diameter distribution chart obtained from a nitrogen adsorption / desorption isotherm. More specifically, the pore volume B having a pore diameter of 1.0 nm or less is a readout value of Cumulative Pore Volume (cc / g) when the horizontal axis Pore Width of the pore diameter distribution chart is 1.0 nm. Similarly, a pore volume having a pore diameter of 1.5 nm or less and a pore (that is, micropore) volume C having a pore diameter of 2.0 nm or less were obtained.
The pore volume ratio (B / A) with a pore diameter of 1.0 nm or less was calculated by dividing the pore volume B with a pore diameter of 1.0 nm or less by the total pore volume A obtained by QSDFT analysis. The micropore volume ratio ({C / A} × 100) was expressed as a percentage by dividing the pore volume C having a pore diameter of 2.0 nm or less by the total pore volume A given by the QSDFT analysis. The mesopore volume ratio (%) was calculated by subtracting the micropore volume ratio (%) from 100%.

(5) A pore growth rate of 1.0 nm or less and a pore development rate of 1.0 nm or less were calculated by dividing a pore volume B of 1.0 nm or less by an activation time. The development rate of the specific surface area was calculated by dividing the BET specific surface area by the activation time.

(6) Fiber diameter of fibrous activated carbon (μm)
It measured with the image processing fiber diameter measuring apparatus (based on JISK1477).

Example 1
As an organic material, a mixture obtained by adding 0.5 parts by mass of trisacetylacetonatoyttrium (CAS number: 15554-47-9) as a metal component to 100 parts by mass of a granular coal pitch having a softening point of 280 ° C. and mixing them, Pitch fibers were obtained by feeding to a melt extruder, melt mixing at a melting temperature of 320 ° C., and spinning at a discharge rate of 16 g / min. The obtained pitch fiber was heated from normal temperature to 354 ° C. in air at a rate of 1 to 30 ° C./min for 54 minutes to effect infusibilization to obtain an activated carbon precursor as an infusible pitch fiber. In the activated carbon precursor, the yttrium content was 0.10% by mass.

10 g of the obtained activated carbon precursor was charged into an activation furnace (volume 0.044 m ³ ), and the introduced gas having a CO ₂ concentration of 100% by volume and a temperature of about 20 ° C. was flowed at a flow rate of about 15 L / min (converted to 0 ° C. and 1 atm). It was introduced into the activation furnace. Activation was performed by heat treatment for 32 minutes at an ambient temperature of 950 ° C. in the activation furnace, and activated carbon of Example 1 was obtained. During the activation process, the composition of the introduced gas was not changed. The obtained activated carbon has a specific surface area of 871 m ² / g, a total pore volume A of 0.336 cc / g, a micropore volume ratio ({C / A} × 100) of 100%, and a pore diameter of 1.0 nm or less. The pore volume B was 0.305 cc / g, and the pore volume ratio (B / A) with a pore diameter of 1.0 nm or less was 0.907.

(Example 2)
Activated carbon of Example 2 was obtained in the same manner as in Example 1 except that the activation time was 44 minutes. The obtained activated carbon has a specific surface area of 1237 m ² / g, a total pore volume A of 0.491 cc / g, a micropore volume ratio ({C / A} × 100) of 99%, and a pore diameter of 1.0 nm or less. The pore volume B was 0.383 cc / g, and the pore volume ratio (B / A) with a pore diameter of 1.0 nm or less was 0.779.

(Example 3)
Activated carbon of Example 3 was obtained in the same manner as Example 1 except that the activation time was 58 minutes. The obtained activated carbon has a specific surface area of 1603 m ² / g, a total pore volume A of 0.654 cc / g, a micropore volume ratio ({C / A} × 100) of 97%, and a pore diameter of 1.0 nm or less. The pore volume B was 0.434 cc / g, and the pore volume ratio (B / A) with a pore diameter of 1.0 nm or less was 0.663.

Example 4
Example 1 except that the addition amount of the metal component (trisacetylacetonatoyttrium) was 1.0 part by mass (the metal content in the activated carbon precursor was 0.16% by mass) and the activation time was 25 minutes. The activated carbon of Example 4 was obtained. The obtained activated carbon has a specific surface area of 917 m ² / g, a total pore volume A of 0.381 cc / g, a micropore volume ratio ({C / A} × 100) of 95%, and a pore diameter of 1.0 nm or less. The pore volume B was 0.278 cc / g, and the pore volume ratio (B / A) with a pore diameter of 1.0 nm or less was 0.730.

(Example 5)
Activated carbon of Example 5 was obtained in the same manner as Example 4 except that the activation time was 32 minutes. The obtained activated carbon has a specific surface area of 1168 m ² / g, a total pore volume A of 0.502 cc / g, a micropore volume ratio ({C / A} × 100) of 92%, and a pore diameter of 1.0 nm or less. The pore volume B was 0.302 cc / g, and the pore volume ratio (B / A) with a pore diameter of 1.0 nm or less was 0.602.

(Example 6)
Activated carbon of Example 6 was obtained in the same manner as in Example 4 except that the activation time was 40 minutes. The obtained activated carbon has a specific surface area of 1338 m ² / g, a total pore volume A of 0.592 cc / g, a micropore volume ratio ({C / A} × 100) of 90%, and a pore diameter of 1.0 nm or less. The pore volume B was 0.352 cc / g, and the pore volume ratio (B / A) with a pore diameter of 1.0 nm or less was 0.595.

(Example 7)
As an organic material, a mixture of 2.3 parts by mass of acetylacetone magnesium (II) (CAS number: 14024-56-7) with 100 parts by mass of a granular coal pitch having a softening point of 280 ° C. is supplied to a melt extruder. Then, melt mixing was performed at a melting temperature of 320 ° C., and spinning was performed at a discharge rate of 16 g / min to obtain pitch fibers. The obtained pitch fiber was heated from normal temperature to 354 ° C. in air at a rate of 1 to 30 ° C./min for 54 minutes to effect infusibilization to obtain an activated carbon precursor as an infusible pitch fiber. In the activated carbon precursor, the magnesium content was 0.18% by mass.

10 g of the obtained activated carbon precursor was charged into an activation furnace (volume 0.044 m ³ ), and the introduced gas having a CO ₂ concentration of 100% by volume and a temperature of about 20 ° C. was flowed at a flow rate of about 15 L / min (converted to 0 ° C. and 1 atm). It was introduced into the activation furnace. Activation was performed by heat treatment for 25 minutes at an ambient temperature of 950 ° C. in the activation furnace, and activated carbon of Example 7 was obtained. During the activation process, the composition of the introduced gas was not changed. The obtained activated carbon has a specific surface area of 981 m ² / g, a total pore volume A of 0.395 cc / g, a micropore volume ratio ({C / A} × 100) of 95%, and a pore diameter of 1.0 nm or less. The pore volume B was 0.331 cc / g, and the pore volume ratio (B / A) with a pore diameter of 1.0 nm or less was 0.838.

(Example 8)
Activated carbon of Example 8 was obtained in the same manner as in Example 7 except that the activation time was 40 minutes. The obtained activated carbon has a specific surface area of 1461 m ² / g, a total pore volume A of 0.635 cc / g, a micropore volume ratio ({C / A} × 100) of 87%, and a pore diameter of 1.0 nm or less. The pore volume B was 0.417 cc / g, and the pore volume ratio (B / A) with a pore diameter of 1.0 nm or less was 0.656.

Example 9
As an organic material, a mixture of 1.7 parts by mass of manganese benzoate (CAS number: 636-13-5) to 100 parts by mass of a granular coal pitch having a softening point of 280 ° C. is supplied to a melt extruder, Pitch fibers were obtained by melt mixing at a melting temperature of 320 ° C. and spinning at a discharge rate of 16 g / min. The obtained pitch fiber was heated from normal temperature to 354 ° C. in air at a rate of 1 to 30 ° C./min for 54 minutes to effect infusibilization to obtain an activated carbon precursor as an infusible pitch fiber. In the activated carbon precursor, the manganese content was 0.20% by mass.

10 g of the obtained activated carbon precursor was charged into an activation furnace (volume 0.044 m ³ ), and the introduced gas having a CO ₂ concentration of 100% by volume and a temperature of about 20 ° C. was flowed at a flow rate of about 15 L / min (converted to 0 ° C. and 1 atm). It was introduced into the activation furnace. Activation was performed by heat treatment for 25 minutes at an ambient temperature of 950 ° C. in the activation furnace, and activated carbon of Example 9 was obtained. During the activation process, the composition of the introduced gas was not changed. The obtained activated carbon has a specific surface area of 953 m ² / g, a total pore volume A of 0.367 cc / g, a micropore volume ratio ({C / A} × 100) of 100%, and a pore diameter of 1.0 nm or less. The pore volume B was 0.345 cc / g, and the pore volume ratio (B / A) with a pore diameter of 1.0 nm or less was 0.941.

(Example 10)
Activated carbon of Example 10 was obtained in the same manner as Example 9 except that the activation time was 40 minutes. The obtained activated carbon has a specific surface area of 1214 m ² / g, a total pore volume A of 0.484 cc / g, a micropore volume ratio ({C / A} × 100) of 98%, and a pore diameter of 1.0 nm or less. The pore volume B was 0.348 cc / g, and the pore volume ratio (B / A) with a pore diameter of 1.0 nm or less was 0.720.

(Example 11)
As an organic material, a mixture of 1.3 parts by mass of acetylacetonatlantan (CAS number: 64424-12-0) to 100 parts by mass of a granular coal pitch having a softening point of 280 ° C. is supplied to a melt extruder. Pitch fibers were obtained by melt mixing at a melting temperature of 320 ° C. and spinning at a discharge rate of 16 g / min. The obtained pitch fiber was heated from normal temperature to 354 ° C. in air at a rate of 1 to 30 ° C./min for 54 minutes to effect infusibilization to obtain an activated carbon precursor as an infusible pitch fiber. In the activated carbon precursor, the content of lanthanum was 0.21% by mass.

10 g of the obtained activated carbon precursor was charged into an activation furnace (volume 0.044 m ³ ), and the introduced gas having a CO ₂ concentration of 100% by volume and a temperature of about 20 ° C. was flowed at a flow rate of about 15 L / min (converted to 0 ° C. and 1 atm). It was introduced into the activation furnace. Activation was performed by heat treatment at 950 ° C. in an activation furnace for 20 minutes to obtain activated carbon of Example 11. During the activation process, the composition of the introduced gas was not changed. The obtained activated carbon has a specific surface area of 675 m ² / g, a total pore volume A of 0.267 cc / g, a micropore volume ratio ({C / A} × 100) of 99%, and a pore diameter of 1.0 nm or less. The pore volume B was 0.234 cc / g, and the pore volume ratio (B / A) with a pore diameter of 1.0 nm or less was 0.875.

(Example 12)
Activated carbon of Example 12 was obtained in the same manner as Example 11 except that the activation time was 25 minutes. The obtained activated carbon has a specific surface area of 758 m ² / g, a total pore volume A of 0.304 cc / g, a micropore volume ratio ({C / A} × 100) of 97%, and a pore diameter of 1.0 nm or less. The pore volume B was 0.256 cc / g, and the pore volume ratio (B / A) with a pore diameter of 1.0 nm or less was 0.841.

(Example 13)
Activated carbon of Example 13 was obtained in the same manner as Example 11 except that the activation time was 30 minutes. The obtained activated carbon has a specific surface area of 916 m ² / g, a total pore volume A of 0.368 cc / g, a micropore volume ratio ({C / A} × 100) of 96%, and a pore diameter of 1.0 nm or less. The pore volume B was 0.283 cc / g, and the pore volume ratio (B / A) with a pore diameter of 1.0 nm or less was 0.770.

(Example 14)
As an organic material, 1.3 parts by mass of bis (2,4-pentanedionato) vanadium (IV) oxide (CAS number: 3153-26-2) per 100 parts by mass of a granular coal pitch having a softening point of 280 ° C. The mixture was supplied to a melt extruder, melted and mixed at a melting temperature of 320 ° C., and spun at a discharge rate of 16 g / min to obtain pitch fibers. The obtained pitch fiber was heated from normal temperature to 354 ° C. in air at a rate of 1 to 30 ° C./min for 54 minutes to effect infusibilization to obtain an activated carbon precursor as an infusible pitch fiber. In the activated carbon precursor, the vanadium content was 0.18% by mass.

10 g of the obtained activated carbon precursor was charged into an activation furnace (volume 0.044 m ³ ), and the introduced gas having a CO ₂ concentration of 100% by volume and a temperature of about 20 ° C. was flowed at a flow rate of about 15 L / min (converted to 0 ° C. and 1 atm). It was introduced into the activation furnace. Activation was performed by heat treatment at 950 ° C. in an activation furnace for 15 minutes to obtain activated carbon of Example 14. During the activation process, the composition of the introduced gas was not changed. The obtained activated carbon has a specific surface area of 863 m ² / g, a total pore volume A of 0.332 cc / g, a micropore volume ratio ({C / A} × 100) of 100%, and a pore diameter of 1.0 nm or less. The pore volume B was 0.305 cc / g, and the pore volume ratio (B / A) with a pore diameter of 1.0 nm or less was 0.918.

(Example 15)
Activated carbon of Example 15 was obtained in the same manner as Example 14 except that the activation time was 25 minutes. The obtained activated carbon has a specific surface area of 1426 m ² / g, a total pore volume A of 0.569 cc / g, a micropore volume ratio ({C / A} × 100) of 97%, and a pore diameter of 1.0 nm or less. The pore volume B was 0.437 cc / g, and the pore volume ratio (B / A) with a pore diameter of 1.0 nm or less was 0.767.

(Example 16)
As an organic material, a mixture of 0.8 parts by mass of acetylacetonatozirconium (CAS number: 17501-44-9) to 100 parts by mass of granular coal pitch having a softening point of 280 ° C. is supplied to a melt extruder. Pitch fibers were obtained by melt mixing at a melting temperature of 320 ° C. and spinning at a discharge rate of 16 g / min. The obtained pitch fiber was heated from normal temperature to 354 ° C. in air at a rate of 1 to 30 ° C./min for 54 minutes to effect infusibilization to obtain an activated carbon precursor as an infusible pitch fiber. In the activated carbon precursor, the zirconium content was 0.19% by mass.

10 g of the obtained activated carbon precursor was charged into an activation furnace (volume 0.044 m ³ ), and the introduced gas having a CO ₂ concentration of 100% by volume and a temperature of about 20 ° C. was flowed at a flow rate of about 15 L / min (converted to 0 ° C. and 1 atm). It was introduced into the activation furnace. Activation was performed by heat treatment for 25 minutes at an ambient temperature of 950 ° C. in the activation furnace to obtain activated carbon of Example 16. During the activation process, the composition of the introduced gas was not changed. The obtained activated carbon has a specific surface area of 790 m ² / g, a total pore volume A of 0.317 cc / g, a micropore volume ratio ({C / A} × 100) of 97%, and a pore diameter of 1.0 nm or less. The pore volume B was 0.259 cc / g, and the pore volume ratio (B / A) with a pore diameter of 1.0 nm or less was 0.817.

(Example 17)
Activated carbon of Example 17 was obtained in the same manner as Example 16 except that the activation time was 40 minutes. The obtained activated carbon has a specific surface area of 1052 m ² / g, a total pore volume A of 0.445 cc / g, a micropore volume ratio ({C / A} × 100) of 91%, and a pore diameter of 1.0 nm or less. The pore volume B was 0.315 cc / g, and the pore volume ratio (B / A) with a pore diameter of 1.0 nm or less was 0.707.

(Example 18)
As an organic material, a mixture of 0.8 parts by mass of acetylacetonatocerium (CAS number: 15653-01-7) to 100 parts by mass of a granular pitch having a softening point of 280 ° C. is supplied to a melt extruder, Pitch fibers were obtained by melt mixing at a melting temperature of 320 ° C. and spinning at a discharge rate of 16 g / min. The obtained pitch fiber was heated from normal temperature to 354 ° C. in air at a rate of 1 to 30 ° C./min for 54 minutes to effect infusibilization to obtain an activated carbon precursor as an infusible pitch fiber. In the activated carbon precursor, the cerium content was 0.14% by mass.

10 g of the obtained activated carbon precursor was charged into an activation furnace (volume 0.044 m ³ ), and the introduced gas having a CO ₂ concentration of 100% by volume and a temperature of about 20 ° C. was flowed at a flow rate of about 15 L / min (converted to 0 ° C. and 1 atm). It was introduced into the activation furnace. Activation was performed by heat treatment for 25 minutes at an ambient temperature of 950 ° C. in the activation furnace, and activated carbon of Example 18 was obtained. During the activation process, the composition of the introduced gas was not changed. The obtained activated carbon has a specific surface area of 821 m ² / g, a total pore volume A of 0.341 cc / g, a micropore volume ratio ({C / A} × 100) of 92%, and a pore diameter of 1.0 nm or less. The pore volume B was 0.276 cc / g, and the pore volume ratio (B / A) with a pore diameter of 1.0 nm or less was 0.808.

(Example 19)
Activated carbon of Example 19 was obtained in the same manner as Example 18 except that the activation time was 35 minutes. The obtained activated carbon has a specific surface area of 1078 m ² / g, a total pore volume A of 0.464 cc / g, a micropore volume ratio ({C / A} × 100) of 89%, and a pore diameter of 1.0 nm or less. The pore volume B was 0.337 cc / g, and the pore volume ratio (B / A) with a pore diameter of 1.0 nm or less was 0.726.

(Example 20)
Activated carbon of Example 20 was obtained in the same manner as in Example 18 except that the activation time was 45 minutes. The obtained activated carbon has a specific surface area of 1249 m ² / g, a total pore volume A of 0.550 cc / g, a micropore volume ratio ({C / A} × 100) of 88%, and a pore diameter of 1.0 nm or less. The pore volume B was 0.352 cc / g, and the pore volume ratio (B / A) with a pore diameter of 1.0 nm or less was 0.641.

(Example 21)
As an organic material, 0.8 part by mass of (2,4-pentanedionato) molybdenum (VI) dioxide (CAS number: 17524-05-9) was mixed with 100 parts by mass of a granular pitch having a softening point of 280 ° C. The product was supplied to a melt extruder, melted and mixed at a melting temperature of 320 ° C., and spun at a discharge rate of 16 g / min to obtain pitch fibers. The obtained pitch fiber was heated from normal temperature to 354 ° C. in air at a rate of 1 to 30 ° C./min for 54 minutes to effect infusibilization to obtain an activated carbon precursor as an infusible pitch fiber. In the activated carbon precursor, the molybdenum content was 0.23% by mass.

10 g of the obtained activated carbon precursor was charged into an activation furnace (volume 0.044 m ³ ), and the introduced gas having a CO ₂ concentration of 100% by volume and a temperature of about 20 ° C. was flowed at a flow rate of about 15 L / min (converted to 0 ° C. and 1 atm). It was introduced into the activation furnace. Activation was performed by heat treatment for 25 minutes at an ambient temperature of 950 ° C. in the activation furnace, and activated carbon of Example 21 was obtained. During the activation process, the composition of the introduced gas was not changed. The obtained activated carbon has a specific surface area of 784 m ² / g, a total pore volume A of 0.313 cc / g, a micropore volume ratio ({C / A} × 100) of 98%, and a pore diameter of 1.0 nm or less. The pore volume B was 0.269 cc / g, and the pore volume ratio (B / A) with a pore diameter of 1.0 nm or less was 0.861.

(Example 22)
Activated carbon of Example 22 was obtained in the same manner as Example 21 except that the activation time was 40 minutes. The obtained activated carbon has a specific surface area of 1171 m ² / g, a total pore volume A of 0.479 cc / g, a micropore volume ratio ({C / A} × 100) of 95%, and a pore diameter of 1.0 nm or less. The pore volume B was 0.365 cc / g, and the pore volume ratio (B / A) with a pore diameter of 1.0 nm or less was 0.761.

(Example 23)
Activated carbon of Example 23 was obtained in the same manner as Example 21 except that the activation time was 60 minutes. The obtained activated carbon had a specific surface area of 1684 m ² / g, a total pore volume A of 0.714 cc / g, a micropore volume ratio ({C / A} × 100) of 92%, and a pore diameter of 1.0 nm or less. The pore volume B was 0.427 cc / g, and the pore volume ratio (B / A) with a pore diameter of 1.0 nm or less was 0.598.

(Example 24)
As an organic material, a mixture of 1.5 parts by mass of acetylacetonatocobalt (CAS number: 21679-46-9) to 100 parts by mass of a granular pitch having a softening point of 280 ° C. is supplied to a melt extruder, Pitch fibers were obtained by melt mixing at a melting temperature of 320 ° C. and spinning at a discharge rate of 16 g / min. The obtained pitch fiber was heated from normal temperature to 354 ° C. in air at a rate of 1 to 30 ° C./min for 54 minutes to effect infusibilization to obtain an activated carbon precursor as an infusible pitch fiber. In the activated carbon precursor, the cobalt content was 0.21% by mass.

10 g of the obtained activated carbon precursor was charged into an activation furnace (volume 0.044 m ³ ), and the introduced gas having a CO ₂ concentration of 100% by volume and a temperature of about 20 ° C. was flowed at a flow rate of about 15 L / min (converted to 0 ° C. and 1 atm). It was introduced into the activation furnace. Activation was performed by heat treatment for 25 minutes at an ambient temperature of 950 ° C. in the activation furnace, and activated carbon of Example 25 was obtained. During the activation process, the composition of the introduced gas was not changed. The obtained activated carbon has a specific surface area of 844 m ² / g, a total pore volume A of 0.357 cc / g, a micropore volume ratio ({C / A} × 100) of 89%, and a pore diameter of 1.0 nm or less. The pore volume B was 0.315 cc / g, and the pore volume ratio (B / A) with a pore diameter of 1.0 nm or less was 0.882.

(Example 25)
Activated carbon of Example 25 was obtained in the same manner as Example 24 except that the activation time was 40 minutes. The obtained activated carbon has a specific surface area of 1447 m ² / g, a total pore volume A of 0.616 cc / g, a micropore volume ratio ({C / A} × 100) of 89%, and a pore diameter of 1.0 nm or less. The pore volume B was 0.431 cc / g, and the pore volume ratio (B / A) with a pore diameter of 1.0 nm or less was 0.700.

(Example 26)
As an organic material, 1.4 parts by mass of bis (2,4-pentanedionato) titanium (IV) oxide (CAS number: 14024-64-7) is mixed with 100 parts by mass of a granular pitch having a softening point of 280 ° C. The product was supplied to a melt extruder, melted and mixed at a melting temperature of 320 ° C., and spun at a discharge rate of 16 g / min to obtain pitch fibers. The obtained pitch fiber was heated from normal temperature to 354 ° C. in air at a rate of 1 to 30 ° C./min for 54 minutes to effect infusibilization to obtain an activated carbon precursor as an infusible pitch fiber. In the activated carbon precursor, the titanium content was 0.25% by mass.

10 g of the obtained activated carbon precursor was charged into an activation furnace (volume 0.044 m ³ ), and the introduced gas having a CO ₂ concentration of 100% by volume and a temperature of about 20 ° C. was flowed at a flow rate of about 15 L / min (converted to 0 ° C. and 1 atm). It was introduced into the activation furnace. Activation was performed by heat treatment for 25 minutes at an ambient temperature of 950 ° C. in the activation furnace, and activated carbon of Example 26 was obtained. During the activation process, the composition of the introduced gas was not changed. The obtained activated carbon has a specific surface area of 781 m ² / g, a total pore volume A of 0.335 cc / g, a micropore volume ratio ({C / A} × 100) of 89%, and a pore diameter of 1.0 nm or less. The pore volume B was 0.240 cc / g, and the pore volume ratio (B / A) with a pore diameter of 1.0 nm or less was 0.717.

(Example 27)
Activated carbon of Example 27 was obtained in the same manner as in Example 26 except that the activation time was 40 minutes. The obtained activated carbon has a specific surface area of 1170 m ² / g, a total pore volume A of 0.557 cc / g, a micropore volume ratio ({C / A} × 100) of 80%, and a pore diameter of 1.0 nm or less. The pore volume B was 0.320 cc / g, and the pore volume ratio (B / A) with a pore diameter of 1.0 nm or less was 0.575.

(Comparative Example 1)
As an organic material, granular coal pitch having a softening point of 280 ° C. was supplied to a melt extruder, melted and mixed at a melting temperature of 320 ° C., and spun at a discharge rate of 20 g / min to obtain pitch fibers. The obtained pitch fiber was heated from normal temperature to 354 ° C. in air at a rate of 1 to 30 ° C./min for 54 minutes to effect infusibilization to obtain an activated carbon precursor as an infusible pitch fiber. Since the metal component is not added, the metal content of the activated carbon precursor is 0% by mass.

10 g of the obtained activated carbon precursor was charged into an activation furnace (volume 0.044 m ³ ), and the introduced gas having a CO ₂ concentration of 100% by volume and a temperature of about 20 ° C. was flowed at a flow rate of about 15 L / min (converted to 0 ° C. and 1 atm). It was introduced into the activation furnace. Activation was performed by heat treatment for 60 minutes at an ambient temperature of 950 ° C. in the activation furnace, and activated carbon of Comparative Example 1 was obtained. During the activation process, the composition of the introduced gas was not changed. The obtained activated carbon has a specific surface area of 814 m ² / g, a total pore volume A of 0.315 cc / g, a micropore volume ratio ({C / A} × 100) of 100%, and a pore diameter of 1.0 nm or less. The pore volume B was 0.311 cc / g, and the pore volume ratio (B / A) with a pore diameter of 1.0 nm or less was 0.988.

(Comparative Example 2)
Activated carbon of Comparative Example 2 was obtained in the same manner as Comparative Example 1 except that the activation time was 90 minutes. The obtained activated carbon has a specific surface area of 1304 m ² / g, a total pore volume A of 0.497 cc / g, a micropore volume ratio ({C / A} × 100) of 100%, and a pore diameter of 1.0 nm or less. The pore volume B was 0.428 cc / g, and the pore volume ratio (B / A) with a pore diameter of 1.0 nm or less was 0.862.

(Comparative Example 3)
Activated carbon of Comparative Example 3 was obtained in the same manner as Comparative Example 1 except that the activation time was 125 minutes. The obtained activated carbon has a specific surface area of 1741 m ² / g, a total pore volume A of 0.692 cc / g, a micropore volume ratio ({C / A} × 100) of 100%, and a pore diameter of 1.0 nm or less. The pore volume B was 0.462 cc / g, and the pore volume ratio (B / A) with a pore diameter of 1.0 nm or less was 0.667.

(Comparative Example 4)
As an organic material, a mixture obtained by adding 1.3 parts by mass of zinc caprylate (CAS number: 557-09-5) as a metal component to 100 parts by mass of a granular coal pitch having a softening point of 280 ° C. is melt-extruded. Pitch fiber was obtained by feeding to a machine, melt mixing at a melting temperature of 320 ° C., and spinning at a discharge rate of 16 g / min. The obtained pitch fiber was heated from normal temperature to 354 ° C. in air at a rate of 1 to 30 ° C./min for 54 minutes to effect infusibilization to obtain an activated carbon precursor as an infusible pitch fiber. In the activated carbon precursor, the zinc content was 0.19% by mass.

10 g of the obtained activated carbon precursor was charged into an activation furnace (volume 0.044 m ³ ), and the introduced gas having a CO ₂ concentration of 100% by volume and a temperature of about 20 ° C. was flowed at a flow rate of about 15 L / min (converted to 0 ° C. and 1 atm). It was introduced into the activation furnace. Activation was performed by heat treatment for 60 minutes at an ambient temperature of 950 ° C. in the activation furnace, and activated carbon of Comparative Example 4 was obtained. During the activation process, the composition of the introduced gas was not changed. The obtained activated carbon has a specific surface area of 1021 m ² / g, a total pore volume A of 0.387 cc / g, a micropore volume ratio ({C / A} × 100) of 100%, and a pore diameter of 1.0 nm or less. The pore volume B was 0.383 cc / g, and the pore volume ratio (B / A) with a pore diameter of 1.0 nm or less was 0.991.

(Comparative Example 5)
Activated carbon of Comparative Example 5 was obtained in the same manner as Comparative Example 4 except that the activation time was 100 minutes. The obtained activated carbon has a specific surface area of 1484 m ² / g, a total pore volume A of 0.577 cc / g, a micropore volume ratio ({C / A} × 100) of 100%, and a pore diameter of 1.0 nm or less. The pore volume B was 0.467 cc / g, and the pore volume ratio (B / A) with a pore diameter of 1.0 nm or less was 0.809.

(Comparative Example 6)
As an organic material, a mixture of 1.0 part by mass of acetylacetonato copper (CAS number: 13395-16-9) as a metal component and mixed with 100 parts by mass of a granular coal pitch having a softening point of 280 ° C. is melted. Pitch fibers were obtained by feeding to an extruder, melting and mixing at a melting temperature of 320 ° C., and spinning at a discharge rate of 16 g / min. The obtained pitch fiber was heated from normal temperature to 354 ° C. in air at a rate of 1 to 30 ° C./min for 54 minutes to effect infusibilization to obtain an activated carbon precursor as an infusible pitch fiber. In the activated carbon precursor, the copper content was 0.18% by mass.

10 g of the obtained activated carbon precursor was charged into an activation furnace (volume 0.044 m ³ ), and the introduced gas having a CO ₂ concentration of 100% by volume and a temperature of about 20 ° C. was flowed at a flow rate of about 15 L / min (converted to 0 ° C. and 1 atm). It was introduced into the activation furnace. Activation was performed by heat treatment for 60 minutes at an ambient temperature of 950 ° C. in the activation furnace, and activated carbon of Comparative Example 6 was obtained. During the activation process, the composition of the introduced gas was not changed. The obtained activated carbon has a specific surface area of 1125 m ² / g, a total pore volume A of 0.427 cc / g, a micropore volume ratio ({C / A} × 100) of 100%, and a pore diameter of 1.0 nm or less. The pore volume B was 0.416 cc / g, and the pore volume ratio (B / A) with a pore diameter of 1.0 nm or less was 0.974.

(Comparative Example 7)
Activated carbon of Comparative Example 7 was obtained in the same manner as Comparative Example 6 except that the activation time was 130 minutes. The obtained activated carbon has a specific surface area of 1690 m ² / g, a total pore volume A of 0.681 cc / g, a micropore volume ratio ({C / A} × 100) of 100%, and a pore diameter of 1.0 nm or less. The pore volume B was 0.415 cc / g, and the pore volume ratio (B / A) with a pore diameter of 1.0 nm or less was 0.610.

(Comparative Example 8)
As an organic material, 0.7 parts by mass of silver sebacate added as a metal component to 100 parts by mass of granular coal pitch having a softening point of 280 ° C. and mixed, are supplied to a melt extruder and melted at 320 ° C. Pitch fibers were obtained by melt mixing and spinning at a discharge rate of 16 g / min. The obtained pitch fiber was heated from normal temperature to 354 ° C. in air at a rate of 1 to 30 ° C./min for 54 minutes to effect infusibilization to obtain an activated carbon precursor as an infusible pitch fiber. In the activated carbon precursor, the silver content was 0.27% by mass.

10 g of the obtained activated carbon precursor was charged into an activation furnace (volume 0.044 m ³ ), and the introduced gas having a CO ₂ concentration of 100% by volume and a temperature of about 20 ° C. was flowed at a flow rate of about 15 L / min (converted to 0 ° C. and 1 atm). It was introduced into the activation furnace. Activation was performed by heat treatment at 950 ° C. atmosphere temperature in the activation furnace for 25 minutes to obtain activated carbon of Comparative Example 8. During the activation process, the composition of the introduced gas was not changed. The obtained activated carbon has a specific surface area of 389 m ² / g, a total pore volume A of 0.156 cc / g, a micropore volume ratio ({C / A} × 100) of 100%, and a pore diameter of 1.0 nm or less. The pore volume B was 0.156 cc / g, and the pore volume ratio (B / A) with a pore diameter of 1.0 nm or less was 0.999.

(Comparative Example 9)
Activated carbon of Comparative Example 9 was obtained in the same manner as Comparative Example 8 except that the activation time was 100 minutes. The obtained activated carbon has a specific surface area of 1280 m ² / g, a total pore volume A of 0.495 cc / g, a micropore volume ratio ({C / A} × 100) of 100%, and a pore diameter of 1.0 nm or less. The pore volume B was 0.397 cc / g, and the pore volume ratio (B / A) with a pore diameter of 1.0 nm or less was 0.802.

(Comparative Example 10)
Activated carbon of Comparative Example 10 was obtained in the same manner as Comparative Example 8 except that the activation time was 130 minutes. The obtained activated carbon has a specific surface area of 1730 m ² / g, a total pore volume A of 0.700 cc / g, a micropore volume ratio ({C / A} × 100) of 100%, and a pore diameter of 1.0 nm or less. The pore volume B was 0.420 cc / g, and the pore volume ratio (B / A) with a pore diameter of 1.0 nm or less was 0.600.

(Comparative Example 11)
As an organic material, a material obtained by adding 1.3 parts by weight of trisacetylacetonatoyttrium (CAS number: 15554-47-9) as a metal component to 100 parts by weight of a granular coal pitch having a softening point of 280 ° C. and mixing them, Pitch fibers were obtained by feeding to a melt extruder, melt mixing at a melting temperature of 320 ° C., and spinning at a discharge rate of 16 g / min. The obtained pitch fiber was heated from normal temperature to 354 ° C. in air at a rate of 1 to 30 ° C./min for 54 minutes to effect infusibilization to obtain an activated carbon precursor as an infusible pitch fiber. In the activated carbon precursor, the yttrium content was 0.25% by mass.

10 g of the obtained activated carbon precursor was charged into an activation furnace (volume 0.044 m ³ ), and an introduction gas having a H ₂ O concentration of 100% by volume was introduced into the activation furnace at a flow rate of about 1.0 kg / hr. Activation was performed by heat treatment at an ambient temperature of 900 ° C. in the activation furnace for 20 minutes to obtain activated carbon of Comparative Example 11. During the activation process, the composition of the introduced gas was not changed. The obtained activated carbon has a specific surface area of 1078 m ² / g, a total pore volume A of 0.572 cc / g, a micropore volume ratio ({C / A} × 100) of 72%, and a pore diameter of 1.0 nm or less. The pore volume B was 0.241 cc / g, and the pore volume ratio (B / A) with a pore diameter of 1.0 nm or less was 0.421.

Tables 1 to 5 show production conditions and physical property values of the activated carbon obtained by the production methods of Examples 1 to 27 and Comparative Examples 1 to 11. Further, graphs showing the increase tendency of the specific surface area with respect to the activation time in the production methods of Examples 1 to 27 and Comparative Examples 1 to 10 are shown in FIG. 1 to FIG.

As shown in Tables 1 to 3, in the production methods of Examples 1 to 27, a specific metal component was included in the activated carbon precursor and activated by carbon dioxide gas, thereby increasing the diameter of the total pore volume A from 1. An activated carbon having a pore volume B ratio of 0 nm or less (pore volume B / total pore volume A) of 0.5 or more could be obtained. Further, as shown in FIGS. 1 to 4, in the manufacturing methods of Examples 1 to 27, the development rate of the specific surface area is larger than that of Comparative Examples 1 to 10 (see FIG. 5), and the introduced gas is made of carbon dioxide. It was shown that activated carbon can be produced efficiently while carbon dioxide is activated with 100% carbon. That is, the activation time required for activating up to a predetermined specific surface area was greatly shortened. In particular, Examples 14 and 15 using a metal component containing vanadium have a remarkably large development rate of specific surface area.

On the other hand, as shown in Tables 4 and 5 and FIG. 5, in Comparative Examples 1 to 10, the development rate of the specific surface area is small, and activated carbon cannot be produced efficiently. Further, as shown in Comparative Examples 4 to 10, even when the metal component is included in the activated carbon precursor and activated by carbon dioxide gas, if the metal component does not contain the specific metal element in the present invention, The development rate of specific surface area cannot be increased. Further, as shown in Table 5, Comparative Example 11 contained a specific metal component in the activated carbon precursor, but was activated by the water vapor activation method, so that the diameter with respect to the total pore volume A was 1.0 nm. The following ratio of pore volume B (pore volume B / total pore volume A) was less than 0.5.

Claims (13)

1. The activated carbon precursor containing a metal component is activated with carbon dioxide gas as an introduction gas, and the ratio of the pore volume B with a diameter of 1.0 nm or less to the total pore volume A (pore volume B / total pore volume A) is 0. Including an activation step to obtain activated carbon that is 5 or more,
   The method for producing activated carbon, wherein the metal element constituting the metal component is selected from the group consisting of Group 2 elements, Group 3 elements, Group 4 elements, Group 5 elements, Group 7 elements, and rare earth elements .
2. The method for producing activated carbon according to claim 1, wherein the metal element is selected from the group consisting of Y, Mg, Mn, La, V, Zr, Ti, and Ce.
3. The method for producing activated carbon according to claim 1 or 2, wherein the metal element is selected from the group consisting of Y, Mg, Ce, Ti and V.
4. The activated carbon precursor containing a metal component is activated with carbon dioxide gas as an introduction gas, and the ratio of the pore volume B with a diameter of 1.0 nm or less to the total pore volume A (pore volume B / total pore volume A) is 0. Including an activation step to obtain activated carbon that is 5 or more,
   The method for producing activated carbon, wherein the metal element constituting the metal component is selected from the group consisting of Group 6 elements and Group 9 elements.
5. The method for producing activated carbon according to claim 4, wherein the metal element is selected from the group consisting of Mo and Co.
6. The manufacturing method of the activated carbon of any one of Claim 1 to 5 whose specific surface area of the said activated carbon is 600 m < ² > / g or more.
7. The method for producing activated carbon according to any one of claims 1 to 6, wherein the composition of the introduced gas is not changed in the activation step.
8. The method for producing activated carbon according to any one of claims 1 to 7, wherein a flow rate of the introduced gas is 1.5 L / min or more in terms of 1 atm at 0 ° C per 1 g of the activated carbon precursor.
9. The method for producing activated carbon according to any one of claims 1 to 8, wherein an activation temperature in the activation step is 800 to 1000 ° C.
10. The method for producing activated carbon according to any one of claims 1 to 9, wherein a content of the metal component is 0.05 to 1.0 mass% in the activated carbon precursor.
11. The method for producing activated carbon according to any one of claims 1 to 10, wherein the activated carbon precursor is an infusible pitch.
12. In the activated carbon, the ratio of the pore volume C having a diameter of 2.0 nm or less to the total pore volume A ({pore volume C / pore volume A} × 100) is 85% or more. The manufacturing method of activated carbon of any one of Claims 1.
13. The method for producing activated carbon according to any one of claims 1 to 12, wherein in the activated carbon, a pore volume B having a diameter of 1.0 nm or less is 0.25 cc / g or more.

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