JPH0640771A - Production of metal dispersed carbon material - Google Patents

Abstract

PURPOSE:To provide a method by which the selection of a metal used is diversified, a process for obtaining a metal dispersed carbon material contg. uniformly dispersed fine metal particles is facilitated and the carbon matrix is made variously porous or microporous. CONSTITUTION:A carbonaceous material having 0.55-4.1 atomic ratio of carbon to hydrogen and >=40 deg.C softening point is chemically treated so that the oxygen content of the carbonaceous material is increased by >=20.0wt.% when measured by element analysis, a metallic salt is brought into contact with the chemically treated carbonaceous material and they are fired at 500-2,000 deg.C in an inert atmosphere.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metal-carbon composite material, and more particularly to a method for manufacturing a metal-dispersed carbon material which is inexpensive, can be easily manufactured, and has excellent metal dispersibility. In the present specification, the metal species dispersed in the carbon material also include metal-containing compounds such as metal sulfides and metal nitrides.

[0002]

2. Description of the Related Art Metal-carbon composite materials, in addition to the characteristics of carbon materials such as light weight, heat resistance, chemical resistance, slidability, electrical conductivity and thermal conductivity,
Various functions such as catalyst, magnetic material, conductive material, antibacterial material, deodorant material, etc. as an excellent material that has the characteristics of metal such as conductivity, magnetism, catalytic activity, antibacterial property and deodorant property. It is expected to be used as a flexible material. Among such metal-carbon composite materials, particularly, a material in which metal fine particles are highly dispersed in a carbon matrix is regarded as a material having a uniform composite structure as a whole, and a magnetic material, a conductive material, etc. When it has pores, it is suitable as a deodorizing / deodorizing material.

As a technique for producing a material in which a metal is highly dispersed in a carbon matrix, for example, there is a method of carbonizing an organometallic complex polymer. This is disclosed in JP-A-1-234309.
JP-A-1-252514 and JP-A-2-631
As disclosed in No. 3 or the like, a polymer obtained by polymerizing a polymerizable organometallic coordination compound is heat-treated in an inert atmosphere to obtain a metal-carbon composite material. Further, as a method that pays attention to the adsorption property of the carbon material, there is a method for producing metal-containing activated carbon. This is one in which a mixture of pitch and an organometallic compound is infusibilized and then activated to obtain metal-containing activated carbon (Japanese Patent Laid-Open No. 3-265510).
issue).

Each of these conventional metal-carbon composite materials uses a complex compound having a complicated structure as a raw material, and further uses as a raw material a polymer obtained by performing a polymerization reaction including complicated steps. Moreover, in the subsequent firing step, the rate of temperature rise must be low in order to promote the slow carbonization of the polymer. Therefore, preparation requires a lot of time and cost, and the obtained product is inevitably expensive. Furthermore, since the kinds of metals to be dispersed are limited to those that can coordinate to the complex compound that is the raw material,
The type of carbon material to be obtained is limited. From the above, it is considered that this method is difficult to industrialize.

Another method is to carbonize a halide of a Group IV element of the periodic table into an organic compound (JP-A-2-133372), or to mix an organic compound with a metal oxide having an average diameter of 1 μm or less. Method for post-carbonization
No. 6308) is disclosed, but also in these methods, the kinds of metals are limited, toxic gas is generated during carbonization, and the dispersed state of the metal is not necessarily in the form of fine particles. There are problems such as.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned points, and it is possible to diversify the selection of metal types and to disperse metal species of fine particles uniformly in a material. It is an object of the present invention to provide a method in which the process for obtaining carbon is facilitated and further, the carbon matrix is diversified such as porous and fine pores.

Previously, the present inventors have conducted a chemical treatment on a carbonaceous material to introduce a functional group of a certain kind, whereby a new property such as pulverization property, solubilization property, foaming property and binder property has been obtained. It has been found that a function can be imparted (JP-A-63-139080, JP-A-63-13).
9011, JP-A-64-9808, Japanese Patent Application No. 2-20
7770, Japanese Patent Application No. 3-72458). As a result of further intensive studies, the present inventors have utilized the fact that this chemically treated product has an ion-exchange property with a metal ion to bring the metal salt into contact with the treated product by bringing a metal salt into contact with the treated product. The present invention has been completed based on the finding that the metal ions are dispersed and are present in the carbon in a uniformly dispersed state as a metal species even after the baking treatment.

That is, in the method for producing metal-dispersed carbon according to the present invention, the atomic ratio of carbon to hydrogen (C / H) is 0.5.
By chemically treating a carbonaceous material having a softening point of 40 ° C. or higher in the range of 5 to 4.1, the increase in oxygen content in the elemental analysis value of the carbonaceous material is 20.0% by weight. It is characterized in that it is prepared as described above, then, a metal salt is brought into contact with this chemically treated carbonaceous material, and then baked in a temperature range of 500 to 2000 ° C. in an inert atmosphere. .

The present invention will be described in more detail below. (1) Carbonaceous Material The carbonaceous material that is a raw material of the metal-dispersed carbon material according to the present invention is coal, petroleum-based or (and) coal-based pitch and / or heavy oil that is a heavy bituminous product, Alternatively, carbonaceous mesophase and / or raw coke produced by heat treatment of these pitches and / or heavy oils may be used.

The coal used as a raw material for these carbonaceous substances is coal such as lignite, brown coal, anthracite, and pitch and / or heavy oil is coal tar pitch,
Coal liquefied coal pitch, petroleum distillation residue oil, naphtha tar pitch by-produced during thermal decomposition of naphtha, petroleum pitch such as FCC decant oil by-produced by fluid catalytic cracking (FCC method) such as naphtha, and (Or) heavy oil, PV
Examples thereof include pitches obtained by thermal decomposition of synthetic polymers such as C, but the kind is not particularly limited as long as carbonization treatment gives graphitizable carbon. However, as the carbonaceous material in the present invention, the atomic ratio (C / H) of carbon and hydrogen is in the range of 0.55 to 4.1, and the softening point is 40 ° C.
Use the above. If the atomic ratio is less than 0.55 or exceeds 4.1, it is difficult to obtain the desired good metal-dispersed carbon material, which is not preferable.

It is important that the softening point is 40 ° C. or higher. In the method of the present invention, a method for chemically treating a carbonaceous substance is carried out by a heterogeneous reaction, but by treating this heterogeneous reaction as a liquid-solid system or a gas-solid system reaction, a chemical treatment operation is performed. Is preferable because it can be efficiently performed. Therefore, the softening point of carbonaceous material is 40
When the temperature is lower than 0 ° C, it becomes difficult to perform an efficient chemical treatment operation, which is not preferable.

When a pitch having a softening point of less than 40 ° C. is used, it is necessary to previously adjust the softening point to 40 ° C. or higher by performing an air blowing process. Of course, the air blowing treatment may be performed in advance even on a pitch having a softening point of 40 ° C. or higher, and such an embodiment is also included in the scope of the present invention.

Further, in the present invention, carbonaceous mesophase and raw coke obtained by heat-treating pitches can also be used as a raw material as long as the above conditions are satisfied. (2) Chemically treated product This chemically treated product is an aromatic substitution reaction or side reaction of a functional group such as a carboxyl group, a hydroxyl group or a sulfonic acid group, which is necessary for exhibiting ion exchangeability with a metal in the next step. It is carried out in order to introduce into the carbonaceous substance by chain oxidation reaction, but it is possible to control the increase of oxygen content in the elemental analysis value of the chemically treated carbonaceous substance to be 20.0% by weight or more. It is essential.

The rate of increase of the oxygen content is particularly important for making the ion exchange amount of the obtained metal ion exchanger and the dispersity of the metal excellent. That is, when the amount of increase in the oxygen content is less than 20.0% by weight, it is difficult to obtain metal-dispersed carbon exhibiting a good dispersion state, which is not preferable.

As a method of performing the above-mentioned chemical treatment,
This can be done by treating the carbonaceous material with nitric acid or a mixed acid of sulfuric acid and nitric acid or / and an oxidizing agent such as aqueous hydrogen peroxide, an aqueous dichromate solution, an aqueous permanganate solution. In this case, the sulfuric acid and nitric acid are both highly concentrated, that is, the sulfuric acid having a concentration of 95% or more and the nitric acid having a concentration of 60% or more are preferably used. Also,
As the mixed acid of sulfuric acid and nitric acid, various mixed ratios are used. Further, the solution used as the oxidant is preferably a solution having a high concentration of 30% or more. (3) Metal salt The metal salt used in the present invention should be interpreted in a broad sense, and includes neutralized products of metals and acids such as nitrates, sulfates, acetates, chlorides, double salts and complexes. A salt of a higher-order compound, a chelate compound, a metal carbonyl compound, or the like, which is itself melted and ionized, or ionized when dissolved in a solvent is used.

The solvent is not particularly limited as long as it dissolves the metal salt and produces a metal ion. Examples thereof include water, acidic or basic aqueous solutions, alcohols, ketones, ethers, amines, carboxylic acids, and polar organic solvents such as heterocyclic compounds. Among them, water is conveniently used. (4) Contact with metal salt solution In the chemically treated product prepared in (2) above, there are functional groups (carbonyl group, carboxyl group, hydroxyl group, sulfonic acid group, etc.) introduced by the reaction. Since these functional groups have high ionizability in an ionic solvent, they are easily ion-exchanged with metal ions, and the metal ions are incorporated into the chemically treated product. Moreover, since the functional group is uniformly introduced into the chemically treated product, the metal ions are uniformly incorporated into the chemically treated product. Moreover, since this reaction occurs rapidly at room temperature, it is sufficient to bring the chemically treated product into contact with the metal salt solution. The excess metal salt solution is separated by filtration or the like as necessary, but the mixture may be dried as it is.

As mentioned above, the chemically treated product has a binder property. Therefore, the mixed slurry after being brought into contact with the metal salt is mixed as it is or after being mixed as a filler, and then molded into a block body using a conventional molding and molding machine to obtain a block-shaped metal dispersion. A carbon material can be manufactured. At this time, the mixing of the filler may be performed after removing the solvent. Further, by using a spray drying method as a method for removing the solvent, it is also possible to granulate or shape into a spherical shape.

By the way, the chemically treated product obtained by preparing the carbonaceous substance by the method (2) may be soluble in a basic aqueous solution or a polar organic solvent due to the action of the hydrophilic functional group. Known (Japanese Patent Application No. 2-207770)
No. 3-72458). Therefore, when a basic water-soluble or polar organic solvent is used as the solvent for dissolving the metal salt, the chemically treated product is also dissolved in the solvent, and therefore the ion exchange product with the metal ion is once in a uniform solution state or It becomes a suspended state in which a part is dissolved. The component in the soluble state at this time is recovered by being precipitated by adjusting the pH and evaporating the solvent. In this case, the metal is in a more uniformly dispersed state in the chemically treated product as compared with the case where it does not go through the dissolved state, so this method is preferably used when increasing the degree of dispersion. A spherical metal-dispersed carbon material can be produced by using the spray-drying method for this solution mixture. (5) Firing treatment The material prepared in (4) above is fired in an inert atmosphere in the range of 500 ° C to 2000 ° C. Although the firing temperature depends on the kind of the metal to be dispersed, it is usually preferable to set the temperature to the melting point of the metal or lower. However, adjusting the firing conditions (temperature, time) to a temperature equal to or higher than the melting point causes coalescence of highly dispersed metal particles with each other, so that the metal particle size is adjusted to a larger one.

The rate of temperature increase is not usually limited, but in particular, in order to obtain a porous metal-dispersed carbon material, a chemical treatment containing a nitro group as a functional group is performed, and the rate of temperature increase is 60 ° C./hr. This can be obtained by firing as described above.

Further, in the contact with the metal salt solution of the above (4), the contact is adjusted so that the functional group in the chemical treatment product prepared in the above (2) is left, so that expansion and foaming at the time of firing. The reaction can be carried out to form a cellularly developed porous structure. Then, the metal-dispersed carbon material having the cellular porous structure has a graphitized structure developed by firing, whereby a metal-dispersed carbon material having an elastic function of compression-recovery characteristics can be obtained.
As described above, in the present invention, a porous structure is formed by controlling the contact step of the metal salt so that the functional groups in the chemically treated carbonaceous material remain in the nuclear carbonaceous material. Moreover, it is possible to obtain a carbon material in which a metal is dispersed in a porous structure.

By the way, the metal species dispersed in this calcination process generate carbides, oxides, sulfides, nitrides, etc., depending on the kind of metal and the elemental composition contained at the same time. In particular, carbide is likely to be formed by the reaction between the metal and the matrix carbon, and the carbide layer formed at the metal-carbon interface improves the chemical stability of the metal.

It is known that most metals have a catalytic action for promoting the development of carbon crystals ("Introduction to Revised Carbon Materials", Japan Carbon Society, p.34, A. Oya,
S. Otani, Carbon, 19, 391 (198
1) etc.). According to the method of the present invention, when these metals are used, the graphite structure is likely to be developed at a relatively low firing temperature, and therefore, when the graphitization of carbonaceous material is attempted to proceed, It can be lowered.

Further, as a solvent for the metal salt solution, KO
When an aqueous solution of an alkali metal hydroxide such as H or NaOH is used, the metal-dispersed carbon material having fine pores can be obtained by performing a rinsing treatment and a water rinsing treatment due to the action of these activating aids. Further, as another method for forming fine pores, a gas activation method or a chemical activation method, which is well known as a method for producing activated carbon from an ordinary carbon material, can be directly applied to the calcined product. (6) Metal Content The metal content in the metal-dispersed carbon is preferably 1 to 30% by weight. If it is less than 1% by weight, the effect of metal addition is small, and if it exceeds 30% by weight, it is difficult to obtain a uniform dispersed state. The method for adjusting the metal content is as follows.

That is, in the chemical treatment of the carbonaceous substance, the amount of functional groups in the treated product can be adjusted by adjusting the treatment conditions such as temperature, time and acid concentration. Therefore,
As a result, the amount of ion exchange with the metal ions changes, and the amount of metal can be adjusted. In addition, since the absolute amount of the metal ion is changed by changing the concentration of the metal salt solution that is brought into contact with the chemically treated product, the amount of metal can be adjusted.
Furthermore, it is also possible to wash the calcined product with a metal-soluble solution, such as a mineral acid. By the way, not only the metal existing on the carbon surface but also the metal particles dispersed in the matrix are eluted by this treatment, so that the treated product can be made porous.

On the other hand, the metal content can be adjusted by adjusting the amount of carbon, and it is possible to make the atmosphere into an oxidizing atmosphere during the firing treatment or to subject the fired product to an oxidation treatment. Also, by this method, porosity,
Further, the surface of the metal for activation is exposed.

The surface state, metal identification, dispersity and content of the metal-dispersed carbon material obtained as described above were confirmed by the following methods. That is, the surface state was observed with a scanning electron microscope (SEM), and the macroscopic identification and dispersion state of metal were analyzed with an electron beam microanalyzer (EPMA). Further, X-ray diffraction analysis was performed on the crystallinity of the metal at that time. Further, the microscopic distribution and dispersion state of metal and the state of carbon were observed by a transmission electron microscope (TEM). The metal dispersion amount was measured by the flame method according to JIS-KO102 after ashing the sample in air at 800 ° C.

[0027]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to the description of these examples.

Example 1 A petroleum-based raw coke obtained by the delayed coker method was pulverized to 0.35 mm or less. This elemental composition is carbon 9
The content was 5.1% by weight, 3.1% by weight hydrogen, and 0.6% by weight nitrogen. 96% of this 5 g in a 300 ml Erlenmeyer flask
After adding 100 ml of a mixed acid of sulfuric acid and 70% nitric acid in a volume ratio of 1: 1 in 100 ml with stirring, add 80
It was kept in an oil bath heated to ° C for 4 hours. Then, after filtering with a glass filter (No. 4) and thoroughly washing with water,
Dried. The yield was 140% by weight. The elemental composition is as follows: carbon 52.3% by weight, hydrogen 1.7% by weight, nitrogen 6.
It was 6% by weight and oxygen was 39.4% by weight. 5 g of cobalt nitrate hexahydrate was added to 10 g of the obtained chemically treated product in 50 m of water.
The solution dissolved in 1 was added and stirred. After drying at 100 ° C. overnight, put in a graphite crucible, and under a nitrogen gas flow, 25
The temperature was raised at .degree. C./hr and the temperature was kept at 1000.degree. C. for 1 hour for firing. The yield was 30.6% by weight based on the chemically treated product. The fired product was further treated in 10% hot hydrochloric acid, washed thoroughly with water and dried. The weight loss due to this acid washing was 5.0% by weight.

With respect to the sample (No. 1 in Table 1) thus obtained, the dispersion state of cobalt was observed by EPMA and TEM, and the results are shown in FIGS. From these results, cobalt is about 10 nm in the carbon matrix.
It can be seen that they become fine particles and are uniformly dispersed.
The X-ray diffraction result is shown in FIG. Although the peak was weak, cobalt metal was confirmed. Table 1 also shows the results obtained by changing the type of metal and the type of salt by the same method. About this, the measurement result of EPMA, SEM, etc. is shown in FIGS. Further, with respect to Nos. 2, 6, 10 and 12 in Table 1, quantitative analysis of metals was performed. The results are also shown in Table 1.

[0030]

[Table 1] Example 2 10 kg of FCC decant oil from which low-boiling components having a boiling point of about 430 ° C. or less were previously removed by vacuum distillation was placed in a 20 L container, heated to 430 ° C. with stirring in a nitrogen gas stream, and held for 12 hours. The heating was stopped and the mixture was allowed to cool.
When the internal temperature reached 250 ° C., the contents were taken out to obtain 4.0 kg of pitch. This pitch was treated with a bucket centrifuge at 50 rpm and 280 ° C. for 60 minutes to separate the optically anisotropic component. The yield of the obtained pitch was 3.6 kg, which was optically isotropic. This is further heated to 425 ° C and held for 1 hour,
The temperature was lowered to 400 ° C. and kept for 10 hours. The yield of the obtained product was 1.7 kg, and the entire surface was optically anisotropic (carbonaceous mesophase). 78% by weight of toluene insoluble matter,
The quinoline insoluble content was 40% by weight, the softening point was 260 ° C., and the elemental analysis values were carbon 95.3% by weight and hydrogen 4.3% by weight.

This carbonaceous mesophase was pulverized to 0.25 mm or less, and 5 g was put in a 300 ml Erlenmeyer flask at 96%.
Sulfuric acid was added to 100 ml and the mixture was kept in an oil bath heated at 100 ° C. for 1 hour. Then glass filter (N
o. It was filtered in 4), washed thoroughly with water, and then dried. The yield was 130% by weight, and the elemental composition was as follows: carbon 65.4% by weight, hydrogen 3.0% by weight, oxygen 25.5% by weight, sulfur 6.
It was 1% by weight. The obtained chemically treated product was used in the same manner as in Example 1 using cobalt nitrate hexahydrate.
The yield of 1000 ° C calcined product is 5 with respect to the chemically treated product.
At 7.3% by weight, the weight loss after treatment with 10% hot hydrochloric acid was 12.5% by weight. EPMA and SEM images of this sample are shown in FIG.

Example 3 5 g of the same carbonaceous mesophase used in Example 2 was added to 3 g.
Add 100% 31% hydrogen peroxide to a 00 ml Erlenmeyer flask.
The solution was added to the solution in a ml, and the mixture was kept in an oil bath heated at 100 ° C. for 3 hours. Then, it was filtered with a glass filter (No. 4), washed with water, and then dried. The yield is 90% and the elemental composition is as follows: carbon 75.8% by weight, hydrogen 3.0% by weight, oxygen 2
It was 0.5% by weight. The obtained chemically treated product was used in the same manner as in Example 1 using cobalt nitrate hexahydrate. The yield of the 1000 ° C. calcined product was 59.1% by weight based on the chemically treated product, and the weight loss after the treatment with 10% hot hydrochloric acid was 10.8% by weight. For this sample, E
The results of PMA observation are shown in FIG. Example 4 No. 1 in Table 1 shown in Example 1 14 samples (10 g of chemically treated petroleum-based raw coke, 5 g of ferric chloride hexahydrate in an aqueous solution, and then evaporated to dryness) 1
Put 1.7g into a 500ml cylindrical glass container, 3
It was put into a salt bath heated to 00 ° C. and kept for 30 minutes. Furthermore, in an argon stream, it was heated to 2000 ° C. at a temperature rising rate of 400 ° C./hr and kept for 30 minutes for graphitization. The yield was 17.1 wt% based on the raw material (chemically treated product + ferric chloride). Next, the compression elasticity was determined as follows. The graphitized sample was 0.3 mm or less, and 0.2 g of the sample was placed in a cylindrical container having an inner diameter of 10 mm, and a load of 1 kg / cm ² was applied from above. The height of the sample at this time was used as a reference (h0). Then, a load of 500 or 5000 kg / cm ² was applied and the height was measured (h
1). Then, the load was removed and the height at that time was set to h2. From these values, the packing density, compression rate and recovery rate were calculated by the following equations. Packing density (g / cm ³ ) = Sample weight (g) ÷ 0.5 ² πho (1) Compressibility (%) = ((ho −h1) ÷ h0) × 100 (2) Recovery rate (%) = ((H2-h1) / (h0-h1)) * 100 (3) The results are shown in Table 2. Furthermore, when the crystallinity parameter was determined for a sharp peak in the spectrum by the X-ray diffraction method (Gakushin method), d002 = 0.
It was 3354 nm and Lc> 100 nm. Table 2 Packing density Load Compressibility Recovery rate (g / cm ³ ) (kg / cm ² ) (%) (%) 0.25 500 85 85 89 5000 92 85

[Brief description of drawings]

FIG. 1 is a schematic diagram of Example 1, No. The EPMA (electron beam microanalyzer) figure of the cobalt dispersion carbon material obtained by 1.

FIG. 2 shows Example 1, No. SEM (scanning electron microscope) showing the image analysis result of the cobalt-dispersed carbon material obtained in 1.
Photo.

FIG. 3 is an image analysis photograph of the SEM photograph of FIG.

FIG. 4 shows Example 1, No. 1 is a TEM (transmission electron microscope) image of the cobalt-dispersed carbon material obtained in 1.

FIG. 5 is an enlarged photograph of FIG.

FIG. 6 is a diffraction graph showing an X-ray diffraction result.

FIG. 7: Example 1, No. EPMA of 2 (cobalt)
Fig.

FIG. 8: Example 1, No. EPMA of 3 (cobalt)
Fig.

9 is a schematic diagram of Example 1, No. EPMA of 4 (cobalt)
Fig.

10 is a schematic diagram of Example 1, No. EPMA of 5 (nickel)
Fig.

FIG. 11: Example 1, No. 5 (nickel) SEM
image.

12 is a schematic diagram of Example 1, No. EPMA of 6 (nickel)
Fig.

13 is a schematic diagram of Example 1, No. EPMA of 7 (nickel)
Fig.

14 is a schematic diagram of Example 1, No. 8 (nickel) EPMA
Fig.

15 is a schematic diagram of Example 1, No. 8 (nickel) SEM
image.

16 is a schematic diagram of Example 1, No. EPMA figure of 9 (copper).

FIG. 17: Example 1, No. 9 (copper) SEM image.

FIG. 18 is an image analysis photograph of the SEM photograph of FIG.

19 is a schematic diagram of Example 1, No. The diffraction graph which shows the X-ray-diffraction result of 9 (copper).

FIG. 20 shows Example 1, No. EPMA figure of 10 (copper).

21 shows Example 1, No. EPMA diagram of 11 (copper).

22 is a schematic diagram of Example 1, No. SEM image of 12 (iron).

23 is a schematic diagram of Example 1, No. TEM image of 12 (iron).

FIG. 24 is an enlarged photograph of FIG. 23.

25 is a schematic diagram of Example 1, No. EPMA diagram of 13 (iron).

26 is a schematic diagram of Example 1, No. EPMA diagram of 14 (iron).

FIG. 27 is an EPMA diagram of Example 2.

28 is an SEM image of Example 2. FIG.

FIG. 29 is an EPMA diagram of Example 3.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] June 24, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Brief description of the drawing

[Correction method] Change

[Correction content]

[Brief description of drawings]

FIG. 1 is a schematic diagram of Example 1, No. The EPMA (electron beam microanalyzer) figure of the cobalt dispersion carbon material obtained by 1.

FIG. 2 shows Example 1, No. 1 is an SEM (scanning electron microscope) photograph showing the structure of a ceramic material showing the image analysis result of the cobalt-dispersed carbon material obtained in 1.

FIG. 3 is a photograph showing the structure of a ceramic material in the image analysis of the SEM photograph of FIG.

FIG. 4 shows Example 1, No. TEM of the cobalt-dispersed carbon material obtained in 1 (a photograph showing the structure of the ceramic material of a transmission electron microscope).

5 is a photograph showing the structure of the enlarged ceramic material of FIG.

FIG. 6 is a diffraction graph showing an X-ray diffraction result.

FIG. 7: Example 1, No. EPMA of 2 (cobalt)
Fig.

FIG. 8: Magazine example 1, No. EPMA of 3 (cobalt)
Fig.

9 is a schematic diagram of Example 1, No. EPMA of 4 (cobalt)
Fig.

10 is a schematic diagram of Example 1, No. EPMA of 5 (nickel)
Fig.

FIG. 11: Example 1, No. The photograph which shows the structure of the ceramic material of 5 (nickel) SEM.

12 is a schematic diagram of Example 1, No. EPMA of 6 (nickel)
Fig.

13 is a schematic diagram of Example 1, No. EPMA of 7 (nickel)
Fig.

14 is a schematic diagram of Example 1, No. 8 (nickel) EPMA
Fig.

15 is a schematic diagram of Example 1, No. The photograph which shows the structure of the ceramic material of 8 (nickel) SEM.

16 is a schematic diagram of Example 1, No. EPMA figure of 9 (copper).

FIG. 17: Example 1, No. The photograph which shows the structure of the ceramic material of 9 (copper) SEM.

FIG. 18 is a photograph showing the structure of the ceramic material in the image analysis of the SEM of FIG.

19 is a schematic diagram of Example 1, No. The diffraction graph which shows the X-ray-diffraction result of 9 (copper).

FIG. 20 shows Example 1, No. EPMA figure of 10 (copper).

21 shows Example 1, No. EPMA diagram of 11 (copper).

22 is a schematic diagram of Example 1, No. The photograph which shows the structure of the ceramic material of 12 (iron) SEM.

23 is a schematic diagram of Example 1, No. The photograph which shows the structure of the ceramic material of 12 (iron) TEM.

FIG. 24 is a photograph showing the structure of the enlarged ceramic material of FIG. 23.

25 is a schematic diagram of Example 1, No. EPMA diagram of 13 (iron).

26 is a schematic diagram of Example 1, No. EPMA diagram of 14 (iron).

FIG. 27 is an EPMA diagram of Example 2.

28 is a photograph showing the structure of the ceramic material of the SEM of Example 2. FIG.

FIG. 29 is an EPMA diagram of Example 3.

Claims (6)

[Claims] 1. The atomic ratio of carbon to hydrogen (C / H) is 0.5.
By chemically treating a carbonaceous material having a softening point of 40 ° C. or higher in the range of 5 to 4.1, the increase in oxygen content in the elemental analysis value of the carbonaceous material is 20.0% by weight. A metal dispersion characterized by being prepared as described above and then contacting the chemically treated carbonaceous substance with a metal salt, followed by firing in a temperature range of 500 to 2000 ° C. in an inert atmosphere. Carbon material manufacturing method. 2. The method of claim 1, wherein the carbonaceous material comprises carbonaceous mesophase, coal, coke, petroleum-based and / or coal-based pitch and / or heavy oil. 3. The method according to claim 1, comprising the step of adjusting the softening point of the carbonaceous material to 40 ° C. or higher by an air blowing treatment. 4. The chemical treatment is carried out by treating the carbonaceous substance with nitric acid, sulfuric acid or a mixed acid of nitric acid and sulfuric acid and / or an oxidizing agent such as hydrogen peroxide solution, dichromate aqueous solution, permanganate aqueous solution. The method of claim 1, comprising: 5. A metal salt, such as a nitrate, a sulfate, an acetate, a neutralized product of a metal and an acid such as a chloride, a double salt, a salt of a higher compound such as a complex, a chelate compound, a solvent such as a metal carbonyl compound. The method according to claim 1, which is soluble in water. 6. A porous structure is formed and a porous structure is formed by controlling the contact process of the metal salt so that the functional group in the chemically treated carbonaceous material remains in the carbonaceous material. The method according to claim 1, wherein the metal is dispersed in the structure.