JP2017179616A - Manufacturing method of active charcoal containing at least one of metal element and metal compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an active charcoal having effectively reduced mechanical strength by containing at least one of a metal element and a metal compound.SOLUTION: There is provided a manufacturing method of active charcoal containing at least one of a metal element and a metal compound having a process 1 for mixing at least one of the metal element and the metal compound and a granular pitch having softening point of 250°C to 300°C at a solid state to obtain a mixture and a process 2 for melting the mixture obtained in the process 1, then solidifying the same to obtain a solidified body.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing activated carbon containing at least one of a simple metal and a metal compound.

  Conventionally, activated carbon containing a simple metal or a metal compound is known. As a method for producing activated carbon containing a single metal or a metal compound, for example, a low softening point pitch and a hydrocarbon solution of an organometallic compound were mixed, and then the mixture was distilled under reduced pressure to remove hydrocarbons. Oxygen-containing gas is blown into the distillation pitch to obtain a metal-containing pitch for producing activated carbon fiber, and after spinning the metal-containing pitch for producing activated carbon fiber, the obtained pitch fiber is infusibilized, carbonized, and activated. A method for producing activated carbon fibers characterized by processing is known (for example, see Patent Document 1).

  According to the production method of Patent Document 1, activated carbon fibers can be produced with a high activation yield, and the obtained activated carbon fibers have a large pore radius and a pore volume in a specific specific surface area range. It is said to have a very unique property of being extremely large. In Patent Document 1, specifically, a solution in which an organometallic compound is dissolved in quinoline is dropped onto coal tar heated to 80 ° C. to obtain a low softening point pitch with a softening point of 90.9 ° C., The low softening point pitch is reacted for 180 minutes while blowing air at a reaction temperature of 330 ° C. and normal pressure to obtain an yttrium-containing spinning pitch (softening point of 264.1 ° C.), and spinning using the spinning pitch. Has been disclosed.

JP-A-8-259957

  However, the activated carbon containing a metal simple substance or a metal compound obtained by a conventional manufacturing method such as Patent Document 1 is inferior in mechanical strength as compared with a normal activated carbon not containing a metal simple substance or a metal compound. There is a problem. Moreover, there exists a tendency for the mechanical strength of activated carbon to be inferior, so that content of a metal simple substance or a metal compound becomes large. Accordingly, the present invention provides a method for producing activated carbon containing at least one of a metal simple substance and a metal compound, which can solve the above problems and suppress a decrease in mechanical strength due to containing the metal simple substance or the metal compound. The main issue is provision.

  In the method disclosed in Patent Document 1, in order to uniformly contain a single metal or a metal compound in the obtained activated carbon, the organometallic compound is previously dispersed in a hydrocarbon solution such as quinoline and is easy to mix. Mixed with low melting pitch. Then, the operation of making the high melting point pitch by proceeding the reaction of the low melting point pitch at a high temperature so as to enable forming such as spinning is carried out. Before the operation, the low melting point pitch previously mixed with the above metal simple substance or metal compound. Is distilled under reduced pressure to remove hydrocarbon components such as quinoline. In addition, when the low melting point pitch is changed to the high melting point pitch at a high temperature as described above, it is considered that organic components derived from the metal compound are volatilized. Therefore, it is considered that volatilization of organic components derived from hydrocarbon components such as quinoline and metal compounds is unlikely to occur during molding such as spinning, and in the subsequent infusibilization and consolidating steps.

  From these prior arts, the present inventors have found that when a metal compound or the like is mixed in a solid phase without being dispersed in a hydrocarbon solution such as quinoline, the metal compound is not uniformly dispersed in the pitch and is uneven. As a result, it was considered that the physical properties of the obtained activated carbon may be adversely affected in terms of mechanical strength and the like. In addition, if the metal compound is mixed with the high melting point pitch as it is without going through the process of changing from the low melting point pitch to the high melting point pitch at high temperature, the organic component derived from the metal compound when forming processing such as spinning is performed. And the like volatilized during the molding process, and the physical properties of the resulting activated carbon were adversely affected in terms of mechanical strength.

  However, as a result of intensive studies by the present inventors in order to solve the above-described problems, unexpectedly, the metal compound is not dispersed in a hydrocarbon solution such as quinoline but mixed with a high melting point pitch in the solid phase. The inventors have found that the activated carbon obtained is excellent in mechanical strength when subjected to spinning forming processing as it is. 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. A method for producing activated carbon containing at least one of a simple metal and a metal compound,
Step 1 for obtaining a mixture by mixing at least one of a simple metal and a metal compound and a granular pitch having a softening point of 250 ° C. to 300 ° C. in a solid phase, and the mixture obtained in Step 1 above, Step 2 after solidifying to obtain a solidified body
A method for producing activated carbon containing at least one of a simple metal and a metal compound.
Item 2. The step 2 is a spinning step, and the mixture is melted and then solidified to obtain a fibrous solidified body,
Item 2. The method for producing activated carbon according to Item 1, wherein the activated carbon is activated carbon fiber.
Item 3. Step 3 for insolubilizing the solidified solidified body obtained in Step 2 and Step 4 for activating the solidified body infusible at Step 3
Item 3. The method for producing activated carbon according to Item 1 or 2, further comprising:

  According to the production method of the present invention, at least one of a simple metal and a metal compound and a granular pitch having a softening point of 250 ° C. to 300 ° C. are mixed in a solid phase to obtain a mixture, and the above step The mixture obtained in 1 is melted and then solidified to obtain a solidified body. Therefore, the activated carbon obtained has a decrease in mechanical strength due to containing at least one of a single metal and a metal compound. Is effectively suppressed.

  The present invention is a method for producing activated carbon containing at least one of a simple metal and a metal compound. In the production method of the present invention, at least one of a simple metal and a metal compound and a granular pitch (hereinafter, may be referred to as a high melting point pitch) having a softening point of 250 ° C. to 300 ° C. in a solid state. It is characterized by comprising Step 1 for obtaining a mixture by mixing, and Step 2 for obtaining a solidified body by solidifying the mixture obtained in Step 1 after melting. Hereinafter, the production method of the present invention will be described in detail.

  In the present invention, Step 1 is a mixing step in which at least one of a single metal and a metal compound and a granular pitch having a softening point of 250 ° C. to 300 ° C. are mixed in a solid phase to obtain a mixture.

  As described above, the present inventors, when the metal compound is mixed in a solid phase state without being dispersed in a hydrocarbon solution such as quinoline, the metal compound is not uniformly dispersed in the pitch, resulting in unevenness, Due to this, it was considered that the physical properties of the obtained activated carbon might be adversely affected in terms of mechanical strength. In addition, if the metal compound is mixed into the high melting point pitch as it is without passing through the process of changing from the low melting point pitch to the high melting point pitch at high temperature, the organic component derived from the metal compound is used for forming processing such as spinning. And the like volatilizes during molding and the like, and from the viewpoint of mechanical strength, the physical properties of the obtained activated carbon are considered to be adversely affected.

  However, contrary to the expectation of the present inventors, when the metal simple substance or metal compound is mixed with the high melting point pitch in the solid phase without being dispersed in the hydrocarbon solution, and the molding process is performed as it is, the obtained activated carbon is a machine It was found that the mechanical strength is excellent. Although this mechanism is not necessarily clear, it can be estimated as follows. That is, in the prior art disclosed in Patent Document 1, for example, an organometallic compound is mixed in advance with a low melting point pitch that is easy to mix in a state of being dispersed in a hydrocarbon solution such as quinoline. Then, the obtained low melting point pitch is distilled under reduced pressure to remove hydrocarbon components, and the reaction of the low melting point pitch is advanced at a high temperature so that the forming process such as spinning can be performed. Is going. Therefore, it is true that the conventional technology has good dispersibility of the metal compound, and volatilization of organic components and the like derived from the hydrocarbon solution, the metal compound, and the like is unlikely to occur. Therefore, it is considered that the dispersibility of the metal compound and the above volatilization hardly cause an adverse effect on the physical properties (such as mechanical strength) of the activated carbon. However, on the other hand, hydrocarbon solutions such as quinoline are not completely volatilized and are considered to remain slightly in the low melting point pitch. Further, when the low melting point pitch containing the metal compound is reacted at a high temperature to obtain a high melting point pitch, the metal compound causes a catalytic action, and the low melting point pitch component is less than the state containing no metal compound. It is considered that gasification is promoted and some adverse effect is exerted on the structure of the resulting high melting point pitch. And the hydrocarbon solution slightly remaining in the low melting point pitch and the low melting point pitch are reacted at a high temperature in a state containing the metal compound, and the high adverse effect due to the high melting point pitch is large, activated carbon such as mechanical strength It is considered that the physical properties of the material have deteriorated.

  On the other hand, according to the production method of the present invention, in the mixing step of Step 1, at least one of a single metal and a metal compound and a granular pitch having a softening point of 250 ° C. to 300 ° C. in a solid state. Mixing to obtain a mixture (that is, mixing a metal compound or the like and a high melting point pitch in a solid phase), so that a hydrocarbon solution such as quinoline remaining in the low melting point pitch of the prior art and the metal compound were included. Even if the influence of the dispersibility of the metal compound and the volatilization of organic components derived from the metal compound is subtracted, the mechanical strength of the activated carbon is not affected. It is considered that the deterioration of physical properties is effectively suppressed.

  It does not specifically limit as a metal element which comprises at least one of the metal simple substance and metal compound which are used at the process 1. Examples of metal elements include alkali metals, alkaline earth metals, transition metals, rare earth metals (including lanthanoids), aluminum, gallium, indium, tin, lead, thallium and bismuth, depending on the application of activated carbon. It is done. Each of the simple metal and the metal compound may be used alone or in combination of two or more.

  For example, from the viewpoint of imparting adsorption performance to an activated gas such as NOx and SOx to activated carbon, the metal element is preferably an alkali metal or an alkaline earth metal. Further, for example, from the viewpoint of forming a large number of pores having a relatively large pore size belonging to mesopores in activated carbon by the catalytic ability of at least one of a single metal and a metal compound, the metal element may be an alkali such as magnesium or calcium. Group IIIA elements such as earth metals, aluminum, typical metals such as zinc, phosphorus, germanium, tin, selenium, rare earth metals such as scandium, yttrium and lanthanum series elements (ytterbium, lanthanum, cerium, etc.), or actinium, thorium And actinium series elements. For example, from the viewpoint of imparting antibacterial properties to activated carbon, examples of the metal element include silver, copper, tin, and lead.

  In addition, as the metal compound, an inorganic metal compound such as a metal oxide, a metal hydroxide, a metal halide, and a metal sulfate, the salt of an organic acid such as acetic acid and a metal, the metal element being a constituent metal element, And organometallic compounds. Examples of the organometallic compound include metal acetylacetonate and metallocene.

Moreover, in the manufacturing method of this invention, the particle size of a metal simple substance and a metal compound will not be specifically limited if it can respectively adhere to a granular pitch. As the particle diameter, for example, the cumulative volume percentage D ₅₀ measured by a laser diffraction / scattering method is preferably 10 to ₅₀ μm. In the present invention, the cumulative volume percentage D ₅₀ is the particle size distribution of a single metal and a metal compound measured using a laser diffraction / scattering particle size distribution measuring device (trade name LA-920 manufactured by Horiba, Ltd.). The particle size at which the integrated value is 50%.

  In the production method of the present invention, a granular pitch having a softening point of 250 ° C to 300 ° C is used. In the present invention, the softening point is measured by the Mettler method (measurement is performed according to ASTM-D3461). The softening point is more preferably 270 ° C to 290 ° C, particularly preferably 275 ° C to 285 ° C.

  In step 1, the granular pitch mixed with at least one of the metal simple substance and the metal compound is preferably substantially free of the metal simple substance and the metal compound. In addition, that a metal simple substance and a metal compound do not contain substantially means that the content rate of a metal simple substance and a metal compound is less than the density | concentration which affects the mechanical strength of activated carbon.

  In the production method of the present invention, a known pitch used for activated carbon production can be used as the granular pitch. Therefore, for example, a pitch derived from any material such as petroleum-based, coal-based, and naphthalene polymer can be used. For example, the pitch etc. which are obtained by using a coal tar etc. as a raw material and carrying out a vacuum distillation and oxygen-containing gas blowing process according to a well-known method can be used. In the present invention, the optical property of the pitch may be either isotropic or anisotropic. Further, as the particle size distribution of the granular pitch, the proportion of the particle size of 1 mm or less is preferably 40% by mass or less, the proportion of the particle size of 1 mm or less is 40% by mass or less, and the maximum particle size is More preferably, it is 11.2 mm or less, the ratio of the particle diameter of 1 mm or less is 40 mass% or less, the maximum particle diameter is 11.2 mm or less, and the mode diameter is in the range of 4.75 mm to 6.7 mm. It is particularly preferred that Here, in the present invention, the particle size distribution is measured according to JIS K 0069: 1992, and the sieve has an opening of 1.0 mm, 2.0 mm, 4.75 mm, 6.7 mm, 9 It is a value measured using 0.5 mm and 11.2 mm.

  The solid phase state in step 1 is a state where substantially no liquid phase exists, that is, at least one of a simple metal and a metal compound and a granular pitch having a softening point of 250 to 300 ° C. are both dissolved and melted. It means not in a state and does not mean that there is no liquid such as water. When a liquid such as water is present, the ratio of the mass of the liquid such as water with respect to the total mass of the metal simple substance and the metal compound and the granular pitch is preferably 1.0% by mass or less, more preferably 0. 0.5 mass% or less is mentioned. In Step 1, “mixture in a solid phase to obtain a mixture” means that at least one of a metal simple substance and a metal compound is actively mixed with a granular pitch having a softening point of 250 to 300 ° C. It shows that. Therefore, for example, when activated carbon (activated carbon X) in which at least one of a metal simple substance and a metal compound is kneaded and activated carbon not containing the metal simple substance and the metal compound (activated carbon Y) is mixed and melted and solidified, In this case, at least one of the metal simple substance and the metal compound exposed on the surface of the activated carbon X may come into contact with the activated carbon Y, but this is not included in the “mixing in a solid phase state to obtain a mixture” in the present invention. .

  In Step 1, the atmosphere mixed in the solid phase is not particularly limited, and examples thereof include an air atmosphere and an inert gas atmosphere such as nitrogen. Moreover, it does not specifically limit as temperature of the said atmosphere, For example, 5 to 40 degreeC, Preferably 10 to 30 degreeC is mentioned.

  The method for mixing in the solid phase is not particularly limited, and may be a known mixing method. For example, the method of mixing using a stirrer etc. are mentioned.

  In the production method of the present invention, the mixing ratio of the metal simple substance and the metal compound and the granular pitch having a softening point of 250 to 300 ° C. is not particularly limited, and is appropriately determined depending on the function imparted to the obtained activated carbon. Can be set. For example, from the viewpoint of imparting antibacterial properties to activated carbon, a metal compound (preferably silver, copper, tin, lead, etc.) is used as a constituent metal element with respect to 100 parts by mass of the granular pitch having a softening point of 250 to 300 ° C. It is preferable to mix 0.01 to 5.0 parts by mass, and more preferably 0.05 to 3.0 parts by mass. In addition, for example, from the viewpoint of imparting excellent removal performance of organic chlorine compounds (free residual chlorine, trihalomethane, etc.) contained in tap water to the activated carbon obtained, a granular pitch 100 having a softening point of 250 to 300 ° C. The metal compound (preferably alkaline earth metals such as magnesium and calcium, Group IIIA elements such as aluminum, other typical metals such as zinc, phosphorus, germanium, tin and selenium, scandium, yttrium and It is preferable to mix 0.05 to 5.0 parts by mass of a rare earth metal such as a lanthanum series element (ytterbium, lanthanum, cerium, etc.) or a metal compound having an actinium series element such as actinium or thorium as a constituent metal element, More preferably, 0.1 to 3.0 parts by mass are mixed.

  In the present invention, Step 2 is a step in which the mixture obtained in Step 1 is melted and then solidified to obtain a solidified body.

  In step 2, the mixture obtained in step 1 may be melted by heating to a temperature equal to or higher than the softening point of the granular pitch. For example, the melting may be performed at a temperature of 30 ° C. or higher and 80 ° C. or lower of the softening point (° C.) of the granular pitch. At the time of melting, for example, the melt may be stirred, and it is preferable to use a melt extruder that melts while stirring.

  Next, as a method of solidifying after melting in Step 2, any known method may be used. For example, the melt obtained by melting is naturally cooled in the air or actively using a cooling means. Cooling may be accelerated. In step 2, the obtained solidified body can be formed into a desired shape in accordance with the use form of activated carbon, and for example, it can be formed into a spherical shape by molding.

  In the production method of the present invention, step 2 can be a spinning step. In this case, the solidified body obtained can be made into a fibrous form (activated carbon fiber). That is, when the mixture obtained in Step 1 is melted and solidified, the resulting solidified body can be formed into a fiber by spinning the mixture into a fiber. The form of the fiber can be a long fiber or a short fiber. A known method can be adopted as the spinning method.

  Further, in the present invention, the mixture obtained in the above-mentioned step 1 is used as a master batch, and the mixture and a granular pitch that has substantially no soft metal and a metal compound and has a softening point of 250 to 300, It can also be melt-mixed and solidified to obtain a solidified product.

  In this invention, you may further provide the process 3 which activates the process 3 which insolubilizes the solidified body obtained at the above-mentioned process 2, and the mixture infusible at the said process 3.

  The infusibilization in the step 3 is a heat treatment applied so that the shape of the organic material used as a raw material of the activated carbon can be maintained even after the activated carbon is formed in the carbonization treatment such as the activation treatment of the activated carbon. For example, the process which makes an organic material thermosetting by oxidative dehydrocyclization or condensation is mentioned. As a method for infusibilization, a known method can be employed. For example, in an air atmosphere, the temperature is raised from a temperature 80 ° C. or more lower than the softening point (° C.) of the granular pitch to a temperature 70 ° C. or higher higher than the softening point. The method of letting it be mentioned.

  Further, the summarization in step 4 refers to the development of a pore structure and the addition of pores to the pitch infusible in step 3. Examples of the activation method include a chemical activation method and a gas activation method. From the viewpoint of further improving the mechanical strength of the obtained activated carbon, the gas activation method is particularly preferable as the activation method. Examples of the gas activation method include a method of activation by heat treatment using an activation gas at an ambient temperature of 600 ° C. to 1200 ° C., preferably 800 ° C. to 1000 ° C. The composition of the activation gas may be a known one, for example, water vapor, carbon dioxide, oxygen, a mixture of at least two of these, a gas obtained by diluting at least one of these with an inert gas (nitrogen gas, etc.) Etc.

  The activated carbon obtained by the production method of the present invention contains at least one of a simple metal and a metal compound. The metal element constituting the metal simple substance or metal compound contained in the obtained activated carbon is the metal element constituting the metal simple substance or metal compound mixed in the above-described solid phase state. Further, the metal simple substance or metal compound contained in the obtained activated carbon is the same as described above.

  As a ratio (total) of the mass of the metal simple substance and the metal compound contained in the activated carbon in the total mass of the activated carbon obtained by the production method of the present invention, for example, 0.01 to 5.0 mass% can be mentioned, 0.05-3.0 mass% is mentioned preferably. For example, from the viewpoint of imparting antibacterial properties to activated carbon, the ratio (total) of simple metals and metal compounds (preferably metal compounds having silver, copper, tin, lead, etc. as constituent metal elements) contained in activated carbon As, for example, 0.01-5.0 mass% is mentioned, 0.05-3.0 mass% is mentioned preferably. In addition, for example, a large number of pores with relatively large pore sizes belonging to mesopores are formed in activated carbon, and the resulting activated carbon has excellent removal of organic chlorine compounds (free residual chlorine, trihalomethane, etc.) contained in tap water. From the viewpoint of imparting performance, simple metals and metal compounds (preferably alkaline earth metals such as magnesium and calcium, Group IIIA elements such as aluminum, other typical metals such as zinc, phosphorus, germanium, tin and selenium, scandium The ratio (total) of rare earth metals such as yttrium and lanthanum series elements (ytterbium, lanthanum, cerium, etc., or metal compounds containing actinium series elements such as actinium and thorium) as constituent metal elements is, for example, 0. 05-5.0 mass% is mentioned, 0.1-3.0 mass% is preferable And the like Ku. The said ratio is a value measured by ICP emission-spectral-analysis apparatus (Varian model 715-ES).

In the production method of the present invention, the specific surface area of the resulting activated carbon is not particularly limited, for example, 500~3500m ² / g, preferably include 700~2700m ² / g. In the present invention, the specific surface area is measured using QUANTCHROME trade name AUTOSORB-6 as a measuring instrument, and JISK1477.7.1. Based on the above, it is measured as a BET method one-point method. In the production method of the present invention, the total pore volume of the obtained activated carbon is not particularly limited, but is, for example, 0.3 to 1.5 ml / g, preferably 0.3 to 1.2 ml / g. It is done. In the present invention, the total pore volume is an adsorption capacity at a relative pressure of 0.995 based on a nitrogen adsorption isotherm obtained using “AUTOSORB-6” (manufactured by QUANTCHROME) based on JIS K 1477.7.2. Calculate

  Moreover, in the manufacturing method of this invention, although it does not specifically limit as a fiber diameter when making the activated carbon obtained into a fiber form, For example, 10-20 micrometers is mentioned, Preferably 12-18 micrometers is mentioned.

  Moreover, in the manufacturing method of this invention, when making the activated carbon obtained into a fiber form, as mechanical strength of activated carbon fiber, 0.10 GPa or more is preferable, 0.10-0.40 GPa is more preferable, 0.12 -0.36 GPa is particularly preferred. In the present invention, the mechanical strength of the activated carbon fiber is compliant with the method a of JIS K 1477: 2007 7.3.1, and an Anritsu Co., Ltd. product (trade name: Laser outer diameter measuring device M550A) is used as a measuring device. The fiber diameter is measured, and the tensile strength is measured using a tensile tester (trade name: SIMADZU EZ-EX) manufactured by Shimadzu Corporation as a measuring instrument according to JIS K 1477: 2007 7.3.2. A mechanical strength is calculated from the fiber diameter and the tensile strength.

  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.

1. Measurement Methods Evaluations in Examples and Comparative Examples were performed by the following methods.
(1) Granular pitch softening point (° C)
It was measured by the Mettler method (according to ASTM-D3461).

(2) Granular pitch and particle size distribution of metal compound It was measured by the method described above.

(3) Metal content (wt%)
Measurement was performed by the method described above.

(4) Total pore volume (cc / g) and specific surface area (m ² / g) of the obtained activated carbon
Measurement was performed by the method described above.

(5) Fiber strength (GPa)
It was measured and calculated by the method described above.

(6) Ratio of mass of water with respect to total mass of simple metal and metal compound and granular pitch (mass%)
Measured according to JIS K 0068.6.5 moisture vaporization method (quantitative titration method).

2. Raw materials used (1) Granular pitch:
(I) Granular pitch A: Coal as a raw material, granular pitch A (the ratio of the particle size of 1 mm or less of 5 mm) with a softening point of 280.0 ° C. Mass%, maximum particle size 9.5 mm, mode diameter 4 to 6.7 mm).
(Ii) Granular pitch B: A solution in which trisacetylacetonatoyttrium is dissolved in quinoline is dropped onto coal tar heated to 80 ° C., and the reaction is performed for 180 minutes while blowing air at a reaction temperature of 330 ° C. and normal pressure. And granular pitch B with a metal content of 2.1% by weight (softening point 281 ° C., proportion of particle size of 1 mm or less 10% by mass, maximum particle size 9.5 mm, mode diameter 4.0 to 6.7 mm) Got.
(Iii) Granular pitch C: A solution in which acetylacetonatomagnesium is dissolved in quinoline is dropped onto coal tar heated to 80 ° C., and reaction is performed for 180 minutes while blowing air at a reaction temperature of 330 ° C. and normal pressure. The granular pitch C having a metal content of 0.14% by weight (softening point 281 ° C., ratio of particle size of 1 mm or less 10% by mass, maximum particle size 9.5 mm, mode diameter 4.0 to 6.7 mm) Obtained.
(Iv) Granular pitch D: A solution in which acetylacetonatomanganese is dissolved in quinoline is dropped onto coal tar heated to 80 ° C., and the reaction is performed for 180 minutes while blowing air at a reaction temperature of 330 ° C. and normal pressure. The granular pitch D having a metal content of 0.27% by weight (softening point 281 ° C., proportion of particle size of 1 mm or less, 10% by mass, maximum particle size 9.5 mm, mode diameter 4.0 to 6.7 mm) Obtained.

(2) Metal compound mixed with granular pitch:
(I) Trisacetylacetonatoyttrium: The one having an integrated volume percentage D ₅₀ measured by a laser diffraction / scattering method of 20 μm was used.
(Ii) Magnesium acetylacetone: A cumulative volume percentage D ₅₀ measured by a laser diffraction / scattering method was 20 μm.
(Iii) Acetylacetone manganese: The one having an integrated volume percentage D ₅₀ measured by a laser diffraction / scattering method of 20 μm was used.
(Iv) Trisacetylacetonatocerium: An accumulative volume percentage D ₅₀ measured by a laser diffraction / scattering method was 20 μm.

[Example 1]
The above-mentioned 4 parts by weight of trisacetylacetonatotrium was mixed with 100 parts by weight of the granular pitch A to obtain a mixture of the metal compound and the granular pitch. In addition, the ratio of the mass of liquids, such as water with respect to the total mass of the granular pitch whose metal compound and softening point are 250-300 degreeC, was 0.0 mass%.

  The obtained mixture and the granular pitch A were respectively supplied to a melt extruder at a mass ratio of 1: 2 using a feeder, melt mixed at a melting temperature of 320 ° C., and spun to obtain pitch fibers. The metal content in the pitch fiber was 0.25% by mass.

  The obtained pitch fiber was infusible. Specifically, the resulting pitch fiber was infusibilized by raising the temperature from normal temperature in air to 354 ° C. at a rate of 1 to 24 ° C./min for 54 minutes.

  The infusibilized pitch fiber was exposed to saturated water vapor at 860 ° C. for 46 minutes for activation treatment to obtain activated carbon fiber. Table 1 shows the physical properties of the obtained activated carbon fibers.

[Example 2]
The above-described trisacetylacetonatotrium 1.3 parts by weight was mixed with 100 parts by weight of the granular pitch A to obtain a mixture of the metal compound and the granular pitch. In addition, the ratio of the mass of liquids, such as water with respect to the total mass of the granular pitch whose metal compound and softening point are 250-300 degreeC, was 0.0 mass%.

  The obtained mixture was supplied to a melt extruder, melt mixed at a melting temperature of 320 ° C., and spun to obtain pitch fibers. The metal content in the pitch fiber was 0.25% by mass.

  The obtained pitch fiber was infusible. Specifically, the resulting pitch fiber was infusibilized by raising the temperature from normal temperature in air to 354 ° C. at a rate of 1 to 24 ° C./min for 54 minutes.

  The infusibilized pitch fiber was exposed to saturated water vapor at 875 ° C. for 45 minutes for activation treatment to obtain activated carbon fiber. Table 1 shows the physical properties of the obtained activated carbon fibers.

[Example 3]
The above-mentioned 5.0 parts by weight of acetylacetone magnesium was mixed with 100 parts by weight of the granular pitch A to obtain a mixture of the metal compound and the granular pitch. In addition, the ratio of the mass of liquids, such as water with respect to the total mass of the granular pitch whose metal compound and softening point are 250-300 degreeC, was 0.0 mass%.

  The obtained mixture was supplied to a melt extruder, melt mixed at a melting temperature of 320 ° C., and spun to obtain pitch fibers. The metal content in the pitch fiber was 0.33% by mass.

  The obtained pitch fiber was infusible. Specifically, the resulting pitch fiber was infusibilized by raising the temperature from normal temperature in air to 354 ° C. at a rate of 1 to 24 ° C./min for 54 minutes.

  The infusibilized pitch fiber was exposed to saturated water vapor at 850 ° C. for 45 minutes for activation treatment to obtain activated carbon fiber. Table 1 shows the physical properties of the obtained activated carbon fibers.

[Example 4]
5.0 parts by weight of the aforementioned acetylacetone manganese was mixed with 100 parts by weight of the granular pitch A to obtain a mixture of the metal compound and the granular pitch. In addition, the ratio of the mass of liquids, such as water with respect to the total mass of the granular pitch whose metal compound and softening point are 250-300 degreeC, was 0.0 mass%.

  The obtained mixture was supplied to a melt extruder, melt mixed at a melting temperature of 320 ° C., and spun to obtain pitch fibers. The metal content in the pitch fiber was 0.39% by mass.

  The obtained pitch fiber was infusible. Specifically, the resulting pitch fiber was infusibilized by raising the temperature from normal temperature in air to 354 ° C. at a rate of 1 to 24 ° C./min for 54 minutes.

  The infusibilized pitch fiber was exposed to saturated water vapor at 850 ° C. for 45 minutes for activation treatment to obtain activated carbon fiber. Table 1 shows the physical properties of the obtained activated carbon fibers.

[Example 5]
The above-mentioned 1.3 parts by weight of trisacetylacetonatocerium was mixed with 100 parts by weight of the granular pitch A to obtain a mixture of the metal compound and the granular pitch. In addition, the ratio of the mass of liquids, such as water with respect to the total mass of the granular pitch whose metal compound and softening point are 250-300 degreeC, was 0.0 mass%.

  The obtained mixture was supplied to a melt extruder, melt mixed at a melting temperature of 320 ° C., and spun to obtain pitch fibers. The metal content in the pitch fiber was 0.23% by mass.

  The obtained pitch fiber was infusible. Specifically, the resulting pitch fiber was infusibilized by raising the temperature from normal temperature in air to 354 ° C. at a rate of 1 to 24 ° C./min for 54 minutes.

  The infusibilized pitch fiber was exposed to saturated water vapor at 900 ° C. for 18 minutes for activation treatment to obtain activated carbon fiber. Table 1 shows the physical properties of the obtained activated carbon fibers.

[Comparative Example 1]
The granular pitch A and the granular pitch B described above are prepared as the granular pitch, and the granular pitch A and the granular pitch B are respectively supplied to the melt extruder at a mass ratio of 7: 1 using a feeder, and the melting temperature is 320 ° C. The pitch fiber was obtained by melt-mixing and spinning. The metal content in the pitch fiber was 0.28% by mass.

  The obtained pitch fiber was infusible. Specifically, the resulting pitch fiber was infusibilized by raising the temperature from normal temperature in air to 354 ° C. at a rate of 1 to 24 ° C./min for 54 minutes.

  The infusibilized pitch fiber was exposed to saturated water vapor at 860 ° C. for 40 minutes for activation treatment to obtain activated carbon fiber. Table 1 shows the physical properties of the obtained activated carbon fibers.

[Comparative Example 2]
The aforementioned granular pitch C was prepared as a granular pitch, and the granular pitch C was supplied to a melt extruder, melted at a melting temperature of 320 ° C., and spun to obtain pitch fibers. The metal content in the pitch fiber was 0.14% by mass.

  The obtained pitch fiber was infusible. Specifically, the resulting pitch fiber was infusibilized by raising the temperature from normal temperature in air to 354 ° C. at a rate of 1 to 24 ° C./min for 54 minutes.

  The infusibilized pitch fiber was exposed to saturated water vapor at 850 ° C. for 45 minutes for activation treatment to obtain activated carbon fiber. Table 1 shows the physical properties of the obtained activated carbon fibers.

[Comparative Example 3]
The aforementioned granular pitch D was prepared as a granular pitch, and the granular pitch D was supplied to a melt extruder, melted at a melting temperature of 320 ° C., and spun to obtain pitch fibers. The metal content in the pitch fiber was 0.27% by mass.

  The obtained pitch fiber was infusible. Specifically, the resulting pitch fiber was infusibilized by raising the temperature from normal temperature in air to 354 ° C. at a rate of 1 to 24 ° C./min for 54 minutes.

  The infusibilized pitch fiber was exposed to saturated water vapor at 850 ° C. for 45 minutes for activation treatment to obtain activated carbon fiber. Table 1 shows the physical properties of the obtained activated carbon fibers.

  When Examples 1 and 2 using trisacetylacetonatoyttrium as a metal compound are compared with Comparative Example 1, Examples 1 and 2 are methods for producing activated carbon containing a simple metal, After melting at least one of the metal compound and granular pitch having a softening point of 250 ° C. to 300 ° C. in a solid phase to obtain a mixture, and the mixture obtained in step 1, Since the activated carbon was produced by the production method comprising the step 2 of solidifying to obtain a solidified body, the obtained activated carbon fiber has the same metal content, total pore volume and specific surface area as compared with the comparative example 1. However, a decrease in mechanical strength due to the inclusion of the metal compound was suppressed. On the other hand, in Comparative Example 1, at least one of a simple metal and a metal compound and a granular pitch having a softening point of 250 ° C. to 300 ° C. were mixed in a solid phase to obtain a mixture. Since coal tar was mixed and reacted in the liquid phase to form granular pitch B, the mechanical strength was greatly reduced as compared with Examples 1 and 2.

  When Example 3 and Comparative Example 2 using acetylacetone magnesium as a metal compound are compared, Example 3 is a method for producing activated carbon containing a metal simple substance, and at least one of the metal simple substance and the metal compound is softened. Step 1 for obtaining a mixture by mixing granular pitches having a point of 250 ° C. to 300 ° C. in a solid phase state, and a step for obtaining a solidified body by melting and solidifying the mixture obtained in Step 1 Since the activated carbon was produced by the production method comprising 2, the obtained activated carbon fiber had a slightly larger total pore volume and specific surface area and a metal content of about 2.8 times compared to Comparative Example 2. Although it was large, a decrease in mechanical strength due to containing a metal compound was suppressed. On the other hand, in Comparative Example 2, at least one of a simple metal and a metal compound and a granular pitch having a softening point of 250 ° C. to 300 ° C. were mixed in a solid phase to obtain a mixture, Coal tar was mixed in the liquid phase and reacted to form granular pitch C. Therefore, the total pore volume and specific surface area were slightly smaller than in Example 3, and the metal content was much smaller. Nevertheless, the mechanical strength was greatly reduced.

  Comparing Example 4 and Comparative Example 3 using acetylacetonatomanganese as a metal compound, Example 4 is a method for producing activated carbon containing a metal simple substance, and includes at least one of the metal simple substance and the metal compound. Step 1 for obtaining a mixture by mixing granular pitches having a softening point of 250 ° C. to 300 ° C. in a solid phase, and the mixture obtained in Step 1 are melted and then solidified to obtain a solidified body. Since the activated carbon was produced by the production method comprising the obtaining step 2, the obtained activated carbon fiber had the same specific surface area, a slightly larger total pore volume, and a metal content of about 1.7 as compared with Comparative Example 3. Although it was twice as large, a decrease in mechanical strength due to containing a metal compound was suppressed. On the other hand, in Comparative Example 3, at least one of a simple metal and a metal compound and a granular pitch having a softening point of 250 ° C. to 300 ° C. were mixed in a solid state to obtain a mixture, Coal tar was mixed and reacted in the liquid phase to obtain a granular pitch D. Therefore, the specific surface area was the same as in Example 4, the total pore volume was slightly smaller, and the metal content was smaller. Nevertheless, the mechanical strength was greatly reduced.

Claims (3)

A method for producing activated carbon containing at least one of a simple metal and a metal compound,
Step 1 for obtaining a mixture by mixing at least one of a simple metal and a metal compound and a granular pitch having a softening point of 250 ° C. to 300 ° C. in a solid phase, and the mixture obtained in Step 1 above, Step 2 after solidifying to obtain a solidified body
A method for producing activated carbon containing at least one of a simple metal and a metal compound. The step 2 is a spinning step, and the mixture is melted and then solidified to obtain a fibrous solidified body,
The method for producing activated carbon according to claim 1, wherein the activated carbon is activated carbon fiber. Step 3 for insolubilizing the solidified solidified body obtained in Step 2 and Step 4 for activating the solidified body infusible at Step 3
The method for producing activated carbon according to claim 1, further comprising: