JP2016183084A - Carbon material and method for producing the same, and electrode for fuel cell - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a carbon material that allows a carbon material having high electrochemical properties to be produced continuously in quantity, and a carbon material obtained by the production method, and an electrode for fuel cell prepared with the carbon material.SOLUTION: A method for producing carbon material has a reaction step in which, in a combustion gas at 600°C-1900°C obtained by the combustion of a mixed gas comprising fuel and oxygen, a raw material comprising carbon atoms, nitrogen atoms, and transition metal atoms is subjected to thermal decomposition reaction or combustion reaction, a carbon material comprising the nitrogen atoms and the transition metal atoms is obtained.SELECTED DRAWING: None

Description

  The present invention relates to a carbon material, a method for producing the same, and an electrode for a fuel cell.

  The polymer electrolyte fuel cell has advantages such as high power generation efficiency, high output density, rapid start / stop, small size and light weight. Portable power source, mobile power source, small stationary device Application to generators is expected. In a polymer electrolyte fuel cell, platinum or a platinum alloy is generally used as a catalyst in order to promote the oxygen reduction reaction occurring at the positive electrode. However, since the amount of platinum resources is extremely small and expensive, it is put to practical use. It has become a big barrier. Therefore, as an electrode catalyst for a fuel cell that does not require a noble metal such as platinum, a carbon catalyst that expresses oxygen reduction activity by containing nitrogen (see, for example, Patent Document 3) and a transition metal are contained. Carbon catalysts that have expressed oxygen reduction activity have attracted attention (see, for example, Patent Documents 1 and 2).

JP2011-256093A JP 2014-201443 A JP 2014-118494 A

  In the method for producing a carbon material exhibiting high oxygen reduction activity, treatment under an inert gas atmosphere or treatment under a gas atmosphere with a small amount of oxygen that hardly burns the carbon catalyst even when oxygen remains is performed. Needed. Therefore, Patent Documents 1 and 2 disclose a method for producing a small amount of a carbon material in a batch method. However, it is difficult to industrially produce a large amount of carbon catalyst with such conventional techniques.

  Patent Document 3 describes that carbon black is produced by reacting acetylene gas and pyridine gas in an oxygen-containing atmosphere, and the carbon black is used as a fuel cell catalyst. Carbon black contains no transition metal and has a problem of low catalyst performance.

  The present invention has been made in view of the above problems, and is obtained by a method for producing a carbon material capable of continuously producing a large amount of a carbon material having high electrochemical characteristics, and the production method. It is an object of the present invention to provide a carbon material and a fuel cell electrode using the carbon material.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by having a predetermined reaction step, and have completed the present invention.

That is, the present invention is as follows.
[1]
By subjecting a raw material containing carbon atoms, nitrogen atoms, and transition metal atoms to a pyrolysis reaction or a combustion reaction in a combustion gas of 600 ° C. to 1900 ° C. in which a mixed gas containing fuel and oxygen is burned. The manufacturing method of a carbon material which has the reaction process of obtaining the carbon material containing the said nitrogen atom and the said transition metal atom.
[2]
In the said carbon material, the atomic ratio N / C of the said nitrogen atom with respect to the said carbon atom is a manufacturing method of the carbon material of the preceding clause [1] which is 0.001 or more.
[3]
The method for producing a carbon material according to [1] or [2], wherein the transition metal atom includes at least one selected from the group consisting of Fe, Co, and Ni.
[4]
The method for producing a carbon material according to any one of [1] to [3], wherein the transition metal atom is in a state of forming a complex in the raw material.
[5]
The method for producing a carbon material according to any one of [1] to [4], wherein an atomic ratio M / C of the transition metal atom to the carbon atom is 0.0001 or more in the carbon material. .
[6]
The raw materials are primary to tertiary amines, amides, imines, imides, nitriles, azides, aziridines, azos, diazos, isocyanates, isocyanides, enamines, oximes, carbamates. The method for producing a carbon material according to any one of [1] to [5] above, comprising at least one selected from the group consisting of nitros, nitros, hydrazines, and lactams.
[7]
Before or during the reaction step,
Any one of the preceding items [1] to [6], including a temperature adjustment step of adjusting the temperature of the combustion gas to 600 ° C. to 1900 ° C. by mixing the combustion gas and a non-combustible gas or liquid. The manufacturing method of the carbon material as described in 2.
[8]
The nonflammable gas is water vapor;
The method for producing a carbon material according to [7], wherein the liquid is water.
[9]
The method for producing a carbon material according to any one of [1] to [8], wherein the raw material contains acetylene.
[10]
The method for producing a carbon material according to any one of [1] to [9], wherein the raw material includes a compound containing the nitrogen atom and a solvent for dissolving the compound.
[11]
The method for producing a carbon material according to [10], wherein the solvent contains a nitrogen atom.
[12]
The method for producing a carbon material according to any one of [1] to [11], wherein the raw material is a slurry containing an insoluble component and a solvent.
[13]
A carbon material obtained by the method for producing a carbon material according to any one of [1] to [12].
[14]
The carbon material according to [13], wherein the DBP absorption amount is 50 mL / 100 g or more.
[15]
A fuel cell electrode comprising the carbon material according to [13] or [14].

  According to the present invention, a carbon material production method capable of continuously producing a large amount of a carbon material having high electrochemical characteristics, a carbon material obtained by the production method, and the carbon material The used fuel cell electrode can be provided.

It is the schematic which shows the aspect of the apparatus A which can be used for the reaction process of this embodiment. It is the schematic which shows the aspect of the apparatus B which can be used for the reaction process of this embodiment. It is the schematic which shows the aspect of the apparatus C which can be used for the reaction process of this embodiment.

Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail with reference to the drawings as necessary. However, the present invention is not limited to this. Various modifications are possible without departing from the scope of the invention.

[Method for producing carbon material]
The method for producing a carbon material according to the present embodiment includes a raw material containing carbon atoms, nitrogen atoms, and transition metal atoms in a combustion gas of 600 ° C. to 1900 ° C. obtained by burning a mixed gas containing fuel and oxygen. Is subjected to a thermal decomposition reaction or a combustion reaction to obtain a carbon material containing the nitrogen atom and the transition metal atom.

  By having the said process, it becomes possible to manufacture a carbon material which has high oxygen reduction activity continuously in large quantities. Moreover, since the carbon material obtained by this contains a nitrogen atom and a transition metal atom, it can show high oxygen reduction activity in an electrode reaction.

[Raw material preparation process]
The method for producing a carbon material of the present embodiment may have a raw material preparation step of adjusting a raw material containing a carbon atom, a nitrogen atom, and a transition metal atom before the reaction step.

〔material〕
The raw material includes a carbon atom, a nitrogen atom, and a transition metal atom. More specifically, the raw materials include a compound containing a carbon atom, a compound containing a nitrogen atom, and a compound containing a transition metal atom; a mixture containing a carbon atom and a nitrogen atom, and a compound containing a transition metal atom. A mixture of a compound containing a carbon atom and a transition metal atom, and a compound containing a nitrogen atom; a mixture of a compound containing a carbon atom and a compound containing a nitrogen atom and a transition metal atom; a carbon atom, a nitrogen atom, and a transition metal atom. Including compounds. Moreover, the raw material may contain a solvent as needed.

  In the present specification, the “carbon-containing compound” is a compound that contains a carbon element in its molecule and does not contain a nitrogen atom and a transition metal element, and specifically refers to a compound containing a carbon atom. And

  The “nitrogen-containing compound” is a compound that contains a nitrogen element in the molecule and does not contain a transition metal element. Specifically, a compound containing a nitrogen atom, and a compound containing a carbon atom and a nitrogen atom The compound containing is generically named.

  Furthermore, the “transition metal-containing compound” means a compound containing a transition metal atom, a compound containing a carbon atom and a transition metal atom, a compound containing a nitrogen atom and a transition metal atom, and a carbon atom, a nitrogen atom, and a transition metal atom. The compound containing is generically named.

  The raw material adjustment method is not particularly limited, and examples thereof include a method of mixing each component (carbon-containing compound, nitrogen-containing compound, transition metal-containing compound, solvent, and the like). Each component may be added simultaneously or sequentially in any order. The mixing method is not particularly limited, and examples thereof include a method of shaking the mixed solution, a method of stirring the mixed solution, and a method of applying ultrasonic waves to the mixed solution.

  Although it does not restrict | limit especially as a property of a raw material, The slurry containing a uniform liquid, an insoluble component, and a solvent, or powder is mentioned. Among these, a uniform liquid is preferable. Moreover, when it is inevitable to use an insoluble component, it is preferably a slurry. In comparison with the case where a raw material with low solubility is dissolved in a solvent and sprayed, the raw material is in a slurry state, and thus production efficiency tends to be further improved. The insoluble component contained in the slurry is not particularly limited, and examples thereof include a nitrogen-containing compound, a mixture (for example, a complex) of a nitrogen-containing compound and a transition metal-containing compound, or a transition metal-containing compound.

  In particular, when the nitrogen-containing compound is solid, the raw material is used as a solution in which the nitrogen-containing compound is dissolved in a solvent, or as a slurry in which the nitrogen-containing compound is pulverized and mixed with a liquid. be able to. Further, when the nitrogen-containing compound is liquid and the transition metal-containing compound is dissolved and it is difficult to form a complex with the nitrogen-containing compound, a solvent may be used. The mixing method in these cases is not particularly limited, and the same method as described above can be used.

  When the raw material is a slurry, the average particle size of insoluble components contained in the slurry is preferably 10 μm or less, more preferably 5 μm or less, further preferably 1 μm or less, and most preferably 0.1 μm or less. It is. When the average particle diameter of the insoluble component contained in the slurry is within the above range, the reaction efficiency in the reaction process tends to be further improved.

  When the raw material is a slurry, the content of insoluble components contained in the slurry is preferably 1 to 50% by mass, more preferably 5 to 40% by mass, based on the total amount of the slurry (raw material). Yes, more preferably 10 to 30% by mass. When the content of the insoluble component contained in the slurry is within the above range, the production efficiency tends to be further improved. Further, when the slurry concentration is within the above range, an increase in viscosity, formation of aggregates, and the like can be suppressed. Therefore, clogging of the spray nozzle can be suppressed, and thus production efficiency tends to be further improved.

  Moreover, it is preferable that mixing temperature is more than melting | fusing point of a nitrogen-containing compound. The mixing temperature is preferably not higher than the boiling point of the solvent in which the nitrogen-containing compound is dissolved or not higher than the decomposition temperature of the nitrogen-containing compound. When the mixing temperature is within the above range, production efficiency tends to be further improved.

  Furthermore, the mixing time is preferably 1 minute to 200 hours, more preferably 10 minutes to 100 hours, and even more preferably 30 minutes to 50 hours. When the mixing time is within the above range, production efficiency tends to be further improved.

  In the raw material, the transition metal atom is preferably in a state of forming a complex. In this case, the ligand of the transition metal atom is not particularly limited, and examples thereof include a carbon-containing compound and a nitrogen-containing compound, and among these, a nitrogen-containing compound is preferable. When the transition metal atom forms a complex, the transition metal tends to be more uniformly distributed in the carbon material.

[Carbon-containing compounds]
Although it does not specifically limit as a carbon containing compound, For example, acetylene, ethylene, and a butadiene are mentioned. Among these, acetylene is preferable. By including such a carbon-containing compound, the DBP absorption amount of the obtained carbon material tends to be further improved.

[Nitrogen-containing compounds]
In the raw material, the nitrogen-containing compound may form a complex with the transition metal-containing compound. The complex thus obtained is preferably soluble in the solvent. Thereby, there exists a tendency for a transition metal to distribute more uniformly in a carbon material.

  The content of nitrogen element in the nitrogen-containing compound is preferably 1.0% by mass to 80% by mass, more preferably 10% by mass to 70% by mass, and still more preferably based on the total amount of the nitrogen-containing compound. Is 20% by mass to 60% by mass, and more preferably 40% by mass to 55% by mass. When the content of the nitrogen element in the nitrogen-containing compound is in the above range, the oxygen reduction activity of the obtained carbon material tends to be further improved.

  The nitrogen-containing compound is not particularly limited, and examples thereof include primary to tertiary amines, amides, imines, imides, nitriles, azides, aziridines, azos, diazos, isocyanates, isocyanides. , Enamines, oximes, carbamates, nitros, nitrosos, hydrazines, and at least one selected from the group consisting of lactams.

  From another viewpoint, the nitrogen-containing compound is not particularly limited. For example, a nitrogen-containing compound having no ring structure, a nitrogen-containing compound having no heterocyclic structure, a nitrogen-containing compound having a heterocyclic monocyclic structure, Examples thereof include nitrogen-containing compounds having a condensed heterocyclic structure, and other compounds.

  The nitrogen-containing compound having no ring structure is not particularly limited. For example, acrylonitrile, ethylenediamine, tetracyanoethylene, diaminomaleonitrile, maleonitrile, adiponitrile, cyanoacetylene, hydrazine, hydrazide, acetonitrile, N, N-dimethylformamide, Urea is mentioned.

  The nitrogen-containing compound having no heterocyclic structure is not particularly limited, and examples thereof include aniline, tetracyanobenzene, phthalonitrile, N-methyl-2-pyrrolidone, and salen.

  The nitrogen-containing compound having a heterocyclic monocyclic structure is not particularly limited, but examples thereof include 5-membered ring compounds such as pyrroles and derivatives thereof, diazoles and derivatives thereof such as pyrazole and imidazole, triazoles and derivatives thereof; and Pyridines and derivatives thereof, diazines such as pyridazine, pyrimidine and pyrazine and derivatives thereof, triazines and triazine derivatives such as melamine and cyanuric acid, six-membered ring compounds such as piperazine, morpholine and cyanuric acid; or chitin And polymers such as chitosan.

  The nitrogen-containing compound having a condensed heterocyclic structure is not particularly limited, and examples thereof include quinolines, indoles, phenanthrolines, and purines. More specifically, phenanthroline, benzimidazole, quinoxaline, azulmic acid, polyamideimide resin, polybenzimidazole, polyimide, DNA, and RNA can be mentioned.

  Other compounds are not particularly limited, for example, melamine resin, polyaniline, polypyrrole, polyvinylpyrrole, polyvinylpyridine, polyacrylonitrile, polyacrylonitrile-polymethacrylic acid copolymer, polyamide, polyamino acid, silk, hair, polyurethane, Polyamideamine, polycarbodiimide, polybismaleimide and polyaminobismaleimide are mentioned.

  In addition, a nitrogen containing compound may be used individually by 1 type, or may use 2 or more types together.

  When the mixture of nitrogen-containing compound and transition metal-containing compound or the complex formed is uniform and has a low viscosity, it can be sprayed or heated and supplied as steam to the high-temperature combustion gas. Moreover, when the mixture or complex of a nitrogen-containing compound and a transition metal is solid or has a high boiling point, it is preferable to use a solvent described later.

〔solvent〕
The raw material may contain a solvent, if necessary. In particular, the raw material preferably contains a nitrogen-containing compound and a solvent for dissolving the nitrogen-containing compound. Thereby, there exists a tendency for production efficiency to improve more.

  Solvents that can be used are not particularly limited. For example, water, alcohols (methanol, ethanol, propanol, butanol, etc.), ketones (acetone), ethers (diethyl ether, tetrahydrofuran, etc.), organic acids (formic acid, acetic acid, etc.) ), Chlorinated hydrocarbons (dichloromethane, chloroform, dichloroethylene, trichloroethylene, carbon tetrachloride, etc.), glycols (ethylene glycol, propylene glycol, etc.), nitriles (acetonitrile, propionitrile, benzonitrile, etc.), amides (N, N-dimethylformamide, dimethylacetamide, etc.), lactams (N-methyl-2-pyrrolidone, etc.), dimethyl sulfoxide, aliphatic hydrocarbons (n-pentane, n-hexane, cyclohexane, n-heptane, n - ), Aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.), ammonia, primary amines (methylamine, ethylamine, propylamine, isopropylamine, butylamine, amylamine, hexylamine, heptylamine, octylamine) , Nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, cetylamine, cyclopropylamine, cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine, aniline, catecholamine, phenethylamine, amantadine , Toluidine, benzylamine, naphthylamine, allylamine, etc., secondary amine (dimethylamine, diethylamine, dipropyl) Amine, dibutylamine, etc.), tertiary amine (trimethylamine, triethylamine, tripropylamine, tributylamine, dicyclohexylmethylamine, tetramethylammonium hydroxide, N-methylpyrrolidine, 1,5-diazabicyclo [4.3.0] Nonene-5 (DBN), 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), N, N-diisopropylethylamine, triethanolamine, etc.), quaternary amine (tetraethylammonium hydroxide, tetra Methylammonium chloride, tetramethylammonium bromide, tetraethylammonium chloride, tetraethylammonium bromide, etc.), cyclic amine (pyridine, 4-dimethylaminopyridine, pyrimidine, piperidine, morpholine, Piperazine, quinuclidine, 1,4-diazabicyclo [2.2.2] octane, etc.), polyvalent amine (trimethylenediamine, ethylenediamine, diethylethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,7-diamino Heptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, phenylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethyleneexamine, tetramethylethylenediamine, diethylenetriamine, 1,2 , 3-triaminopropane, triaminobenzene, triaminophenol, melamine, spermidine, 1,8-bis (dimethylamino) naphthalene, spermine, etc.).A solvent may be used individually by 1 type, or may use 2 or more types together.

  Among these, the solvent preferably contains at least one selected from the group consisting of methanol, ethanol, acetone, tetrahydrofuran, acetonitrile, N, N-dimethylformamide, and water. By using such a solvent, the solubility of the nitrogen-containing compound is further improved, and the spraying to the high-temperature combustion gas in the reaction process tends to be further improved. Specifically, by using a solvent with high raw material solubility, the viscosity can be lowered even with the same raw material supply amount, thus reducing clogging during spraying and droplet miniaturization during spraying. As a result, production efficiency and catalyst performance due to atomization of carbon materials tend to be further improved.

  Moreover, as a solvent, the solvent containing a nitrogen atom is also preferable. Although it does not specifically limit as a solvent containing a nitrogen atom, For example, nitriles, amides, lactams, dimethyl sulfoxide, ammonia, a primary amine, a secondary amine, a tertiary amine, a quaternary amine, cyclic Examples include amines and polyvalent amines. By using such a solvent, the atomic ratio (N / C) of the carbon material can be adjusted. Specifically, the use of such a solvent tends to improve the atomic ratio (N / C) of the carbon material as compared with the case of using a solvent that does not contain a nitrogen atom.

  The boiling point of the solvent is preferably 300 ° C. or lower, more preferably 200 ° C. or lower, and further preferably 150 ° C. or lower. When the boiling point of the solvent is within the above range, the solubility of the nitrogen-containing compound and the spraying to the high-temperature combustion gas in the reaction process tend to be further improved. Specifically, by using a solvent with high raw material solubility, the viscosity can be lowered even with the same raw material supply amount, thus reducing clogging during spraying and droplet miniaturization during spraying. As a result, production efficiency and catalyst performance due to atomization of carbon materials tend to be further improved.

[Transition metal-containing compound]
The transition metal-containing compound is not particularly limited, and examples thereof include transition metal complexes, inorganic acid salts, organic acid salts, and other transition metal-containing compounds. More specifically, transition metal nitrites, nitrates, sulfates, sulfites, acetates, ammonium salts, hydrochlorides, odorates and other inorganic acid salts; oxalates, carbonates and other organic acid salts; Other transition metal-containing compounds such as hydroxides, oxides, and alkoxides can be mentioned.

  Although it does not specifically limit as a transition metal element contained in a transition metal containing compound, For example, Ti (titanium), V (vanadium), Cr (chromium), Mn (manganese), Fe (iron), Co (cobalt), Ni (nickel), Cu (copper), Y (yttrium), Zr (zirconium), Nb (niobium), Mo (molybdenum), Tc (technetium), Ru (ruthenium), Rh (rhodium), Pd (palladium), Examples include at least one selected from the group consisting of Ag (silver), Ta (tantalum), W (tungsten), Re (rhenium), Ir (iridium), Pt (platinum), Au (gold), and lanthanoid elements. Among these, at least one selected from the group consisting of Fe, Co, Ni, Pd, Pt, Au, La and Ce is preferable, and at least one selected from the group consisting of Fe, Co, Ni and Pt is more preferable. Further, at least one selected from the group consisting of Co and Ni is more preferable, and Fe is most preferable. By using such a transition metal, the oxygen reduction activity of the obtained carbon material tends to be further improved.

  These transition metals may be used alone or in combination of two or more. When two or more transition metals are used in combination, one of the transition metals is preferably selected from the group consisting of Fe, Co, and Ni. When two or more transition metals are used in combination, Ti, V, Cr, Mn, Cu, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Ta, W, Re, Ir, Pt, The content of Au and lanthanoid elements is preferably 1.0 or less, more preferably 0.50 or less, and even more preferably 0.10 or less with respect to 1 part by mass of Fe, Co and Ni in total. is there. By using such a transition metal in combination, the oxygen reduction activity of the obtained carbon material tends to be further improved.

  When the transition metal is iron, the transition metal-containing compound is not particularly limited, and examples thereof include iron complexes, iron inorganic acid salts, iron organic acid salts, and other iron compounds. More specifically, iron (II) chloride, iron (III) chloride, ferric citrate, ferric phosphide, ferric tartrate, ferrous fumarate, ammonium hexacyanoferrate (II), shu Ammonium iron (III) trihydrate, iron (III) ammonium sulfate, iron (III) ammonium sulfate, iron ethylenediaminetetraacetate, ammonium iron citrate, ferric nitrate, iron (II) acetate, iron fumarate (II ), Iron (II) gluconate, iron oxalate, iron hydroxide (III), iron (III) acetylacetonate, iron (II) methoxide, iron (III) ethoxide, iron (III) isopropoxide, bis ( Cyclopentadienyl) iron, bis (methylcyclopentadienyl) iron, bis (ethylcyclopentadienyl) iron, bis (isopropylcyclopentadienyl) iron and Scan (tetramethylcyclopentadienyl) iron can be exemplified. Among these, from the viewpoint of obtaining a carbon material having better oxygen reduction activity in the electrode reaction, iron complexes and iron inorganic acid salts are preferable, and iron chloride (II) and iron nitrate are more preferable. Such transition metal-containing compounds are used singly or in combination of two or more.

  When the transition metal is cobalt, the transition metal-containing compound is not particularly limited, and examples thereof include cobalt complexes, cobalt inorganic acid salts, cobalt organic acid salts, and other cobalt compounds. More specifically, cobalt (II) chloride, cobalt bromide, cobalt carbonate (II), cobalt formate (II), hexafluoroacetylacetonato cobalt (II), cobalt oxide (II), cobalt cobalt acetate (II) , Cobalt (II) lactate, cobalt nitrate, cobalt oxalate (II), cobalt (II) 2,4-pentandionate, cobalt sulfate, cobalt amidosulfate, cobalt hydroxide, hexaamminecobalt bromide (II), chloride Hexaamminecobalt (II), cobalt (II) acetate tetrahydrate, cobalt (II) acetylacetonate, cobalt ammonium sulfate, cobalt (II) trifluoroacetylacetonate, bis (cyclopentadienyl) cobalt, bis (isopropyl) Cyclopentadienyl) cobalt, bis (pen Methylcyclopentadienyl) cobalt, bis (tetramethylcyclopentadienyl) cobalt, cobalt borate, cobalt hydroxyacetate, cobalt naphthenate, bis (ethylcyclopentadienyl) cobalt, cobalt (II) ammonium sulfate, bis ( Examples include 1,5-cyclooctadiene) cobalt and bis (tetramethylcyclopentadienyl) cobalt. Among these, from the viewpoint of obtaining a carbon material having better oxygen reduction activity in the electrode reaction, a cobalt complex and an inorganic acid salt of cobalt are preferable, and cobalt (II) chloride and cobalt nitrate are more preferable. Such transition metal-containing compounds are used singly or in combination of two or more.

  When the transition metal is nickel, the transition metal-containing compound is not particularly limited, and examples thereof include nickel complexes, nickel inorganic acid salts, nickel organic acid salts, and other nickel compounds. More specifically, nickel chloride (II), nickel bromide, nickel carbonate (II), nickel formate (II), hexafluoroacetylacetonato nickel (II), nickel oxide (II), nickel hydroxyacetate (II) , Nickel lactate (II), nickel naphthenate (II), nickel nitrate, nickel oxalate (II), 2,4-pentanedioic acid nickel (II), nickel sulfate, amido nickel sulfate, nickel hydroxide, hexabromide Ammine nickel (II), hexaammine nickel chloride (II), nickel acetate (II) tetrahydrate, nickel (II) acetylacetonate, nickel ammonium sulfate, nickel (II) trifluoroacetylacetonate, bis (cyclopentadidi) Enyl) nickel, bis (isopropylcyclopentadi) Nyl) nickel, bis (pentamethylcyclopentadienyl) nickel, bis (tetramethylcyclopentadienyl) nickel, nickel borate, nickel hydroxyacetate, nickel naphthenate, bis (ethylcyclopentadienyl) nickel, nickel sulfate (II) Ammonium, bis (1,5-cyclooctadiene) nickel and bis (tetramethylcyclopentadienyl) nickel can be exemplified. Among these, from the viewpoint of obtaining a carbon material with better oxygen reduction activity in the electrode reaction, a nickel complex and an inorganic acid salt of nickel are preferable, and nickel (II) chloride and nickel nitrate are more preferable. Such transition metal-containing compounds are used singly or in combination of two or more.

  When the transition metal is platinum, the transition metal-containing compound is not particularly limited, and examples thereof include a platinum complex, a platinum compound having a halogen atom, and other platinum compounds. More specifically, platinum (II) acetylacetonate, ammonium hexabromoplatinate (IV), ammonium hexachloroplatinate (IV), ammonium tetrachloroplatinate (II), bis (acetylacetonate) platinum (II), Bis (ethylenediamine) platinum (II) chloride, chloroplatinic acid hexahydrate, chloroplatinic acid hexahydrate, dichlorodiammineplatinum (II), tetrachlorodiammineplatinum (IV), 1,1-cyclobutanedicarboxylatodiammine Platinum (II), diamminedichloroplatinum (II), diammineplatinum (II) nitrite, dichlorobis (benzonitrile) platinum (II), hexachloroplatinic acid (IV) dihydrogen, hexabromoplatinic acid (IV) dihydrogen, hexahydro Oxoplatinic acid (IV), diphenyl (1,5-cyclothio Tadiene) platinum (II), hexahydroxoplatinum (IV) acid, platinum (II) bromide, platinum (II) chloride, platinum (II) hexafluoroacetylacetonate, tetraammineplatinum chloride (II), tetraammineplatinum hydrogen carbonate (II) ), Tetraammineplatinum (II) hydroxide, tetraamineplatinum nitrate (II), tetraamineplatinum (II) tetrachloroplatinum (II) acid and hexahydroxoplatinum nitrate aqueous solution. Such transition metal-containing compounds are used singly or in combination of two or more.

[Reaction process]
In the reaction step, a raw material containing carbon atoms, nitrogen atoms, and transition metal atoms in a combustion gas of 600 ° C. to 1900 ° C. obtained by burning a mixed gas containing fuel and oxygen is subjected to thermal decomposition reaction or combustion. In this step, a carbon material containing the nitrogen atom and the transition metal atom is obtained by the reaction.

  The method of reacting the raw material in the combustion gas is not particularly limited, and examples thereof include a method of spraying the raw material on a high-temperature combustion gas.

[Combustion gas]
The combustion gas in the reaction step is a high-temperature gas of 600 ° C. to 1900 ° C. obtained by burning a mixed gas containing fuel and oxygen. This combustion gas may contain fuel, oxygen, and other gases.

  Although it does not specifically limit as a fuel, For example, coal-type liquefied fuels, such as petroleum liquid fuels, such as natural gas, coal gas, petroleum gas, carbon monoxide, and heavy oil, and creosote oil are mentioned. Moreover, it does not specifically limit as other gas, For example, an inert gas and a nonflammable gas are mentioned.

  The temperature of the combustion gas is 600 to 1900 ° C, preferably 700 to 1700 ° C, more preferably 800 to 1500 ° C, and further preferably 900 to 1200 ° C.

  The combustion gas combustion method is not particularly limited, and examples thereof include a method of igniting a mixed gas containing fuel and oxygen with a burner or the like.

  Although it does not specifically limit as an apparatus which can be used in a reaction process, For example, the combustion zone which generates a high temperature combustion gas of 600-1900 degreeC, the mixing zone which sprays a raw material with respect to combustion gas, and thermal decomposition of a raw material Examples include an apparatus including a reaction zone for reaction or combustion reaction and a cooling zone for cooling the product. Hereinafter, the apparatus which can be used for the reaction process of this embodiment is demonstrated in detail using FIGS.

  In FIG. 1, the aspect of the apparatus A which can be used for the reaction process of this embodiment is shown. The apparatus A includes a combustion unit 1 that generates combustion gas, a mixing reaction unit 2 that performs a reaction by mixing the combustion gas generated in the combustion unit 1 and a raw material, and a carbon material obtained by the mixing reaction unit 2. A cooling unit 3 for cooling.

  The combustion unit 1 includes a fuel burner 4 for combusting the gas in the combustion unit 1, an air inlet 5 for introducing combustion oxygen (for example, air) into the combustion unit 1, and fuel to the combustion unit 1. A fuel supply nozzle (not shown) for introduction. The fuel burner 4 and the air inlet 5 can be arranged to face different directions. Moreover, the combustion part 1 has a shape in which the downstream outlet (connection port to the mixing reaction part 2) is gradually reduced in diameter. Although the dimension of the trunk | drum of the combustion part 1 is not specifically limited, A maximum internal diameter of 0.4 m and length 2m can be used. In the combustion section 1, the combustion oxygen and the fuel are mixed and burned by the fuel burner 4, thereby generating high-temperature combustion gas. At this time, the temperature of the fuel gas can be adjusted by mixing incombustible gas or liquid.

  The mixing reaction unit 2 has a raw material supply nozzle 6 for introducing the raw material into the mixing reaction unit 2. Moreover, the mixing reaction part 2 has a shape in which the downstream outlet (connection port to the cooling part 3) gradually increases in diameter. Although the dimension of the trunk | drum of the mixing reaction part 2 is not specifically limited, A diameter (furnace internal diameter) 0.15m and length 1m can be used. When the raw material is liquid or slurry, the raw material can be introduced into the mixing reaction unit 2 by spraying the raw material from the raw material supply nozzle 6 onto the mixing reaction unit 2. At this time, since the high-temperature combustion gas passes through the center of the mixing reaction section 2, it is preferable to spray the raw material from a direction perpendicular thereto. In the mixing reaction part 2, a thermal decomposition reaction or a combustion reaction of the raw material is performed.

  The cooling unit 3 includes a cooling water supply nozzle 7 for introducing cooling water (or other refrigerant) into the cooling unit 3. Although the dimension of the trunk | drum of the cooling part 3 is not specifically limited, A diameter (furnace internal diameter) 0.4m and length 2.5m can be used. The inside of the cooling unit 3 is preferably made of heat-resistant bricks. Further, the connection part of the mixing reaction part 2 and the cooling part 3 having different diameters can be smoothly connected in a conical shape with an inclination of 45 degrees. In the cooling unit 3, the carbon material obtained in the mixing reaction unit 2 is cooled by a refrigerant. The cooled carbon material containing the transition metal can be separated and recovered by separating it from gas with a collection bag filter.

  In FIG. 2, the aspect of the apparatus B which can be used for the reaction process of this embodiment is shown. The apparatus B includes a combustion unit 8 that generates combustion gas, a mixing unit 9 that mixes the combustion gas generated in the combustion unit 8 and the raw material, and a reaction that reacts the combustion gas mixed in the mixing unit 9 and the raw material. And a cooling unit 11 for cooling the carbon material obtained in the reaction unit 10.

  The combustion unit 8 includes a fuel burner 12 for burning the gas in the combustion unit 8, an air inlet 13 for introducing combustion oxygen (for example, air) into the combustion unit 8, and fuel to the combustion unit 8. A fuel supply nozzle (not shown) for introduction. The fuel burner 12 and the air inlet 13 can be arranged so as to face the coaxial direction. Moreover, the combustion part 8 has a shape in which the downstream outlet (connection port to the mixing part 9) is gradually reduced in diameter. Although the dimension of the trunk | drum of the combustion part 8 is not specifically limited, The maximum internal diameter can be 0.6 m and length can be 1.3 m. In the combustion section 8, the combustion oxygen and fuel are mixed and burned by the fuel burner 12, thereby generating high-temperature combustion gas. At this time, the temperature of the fuel gas can be adjusted by mixing incombustible gas or liquid.

  The mixing unit 9 has a raw material supply nozzle 14 for introducing the raw material into the mixing unit 9. Although the dimension of the trunk | drum of the mixing part 9 is not specifically limited, Diameter 0.2m and length 0.2m can be used. When the raw material is liquid or slurry, the raw material can be introduced into the mixing unit 9 by spraying the raw material from the raw material supply nozzle 14 onto the mixing unit 9. At this time, since the high-temperature combustion gas passes through the center of the mixing section 9, it is preferable to spray the raw material from a direction perpendicular thereto.

  In the reaction unit 10, a raw material thermal decomposition reaction or a combustion reaction is performed. Although the dimension of the trunk | drum of the reaction part 10 is not specifically limited, A diameter can be 0.15 m and length can be 0.4 m.

  The cooling unit 11 includes a cooling water supply nozzle 15 for introducing cooling water (or other refrigerant) into the cooling unit 11. Although the dimension of the trunk | drum of the cooling part 11 is not specifically limited, The maximum diameter can be 1 m and length can be 2.5 m. The inside of the cooling unit 11 is preferably made of heat-resistant bricks. Further, the connecting portion between the reaction portion 10 and the cooling portion 11 having different diameter dimensions can be smoothly connected in a conical shape with an inclination of 45 degrees. In this cooling part 11, the carbon material obtained in the reaction part 10 is cooled by a refrigerant.

  In FIG. 3, the aspect of the apparatus C which can be used for the reaction process of this embodiment is shown. The apparatus C includes a combustion unit 16 that generates combustion gas, a temperature adjustment unit 17 that adjusts the temperature of the combustion gas, a mixing reaction unit 18 that mixes and reacts the combustion gas generated in the combustion unit 16 and a raw material. And a cooling unit 19 for cooling the carbon material obtained in the mixed reaction unit 18.

  The combustion unit 16 includes a fuel burner 20 for combusting the gas in the combustion unit 16, an air introduction port 21 for introducing combustion oxygen (for example, air) into the combustion unit 16, and fuel to the combustion unit 16. A fuel supply nozzle (not shown) for introduction. Moreover, the combustion part 16 has a shape in which the downstream outlet (connection port to the mixing reaction part 18) is gradually reduced in diameter. The size of the conductor of the burning part 16 can be a maximum inner diameter of 0.6 m and a length of 2 m. In the combustion section, the combustion oxygen and the fuel are mixed and burned by the fuel burner 4 to generate high-temperature combustion gas.

  The temperature adjustment unit 17 includes a coolant supply nozzle 22 for introducing the coolant into the temperature adjustment unit 17. Although the dimension of the trunk | drum of the temperature control part 17 is not specifically limited, A diameter can be 0.6 m and length can be 1 m. Although it does not specifically limit as a coolant, For example, nitrogen, argon, carbon dioxide, helium, inert gas, such as a carbon dioxide, water vapor | steam, water etc. are mentioned. Among these, water vapor or water is preferable from the viewpoint of the cooling effect. In this temperature control part 17, the temperature of combustion gas is adjusted to 600-1900 degreeC.

  The mixing reaction unit 18 has a material supply nozzle 23 for introducing the material into the mixing reaction unit 18. Moreover, the mixing reaction part 18 has a shape in which the downstream outlet (connection port to the cooling part 19) gradually increases in diameter. Although the dimension of the trunk | drum of the mixing reaction part 18 is not specifically limited, A diameter can be 0.15 m and length can be 1 m. When the raw material is liquid or slurry, the raw material can be introduced into the mixing reaction unit 18 by spraying the raw material from the raw material supply nozzle 23 onto the mixing reaction unit 18. At this time, since the high-temperature combustion gas passes through the center of the mixing reaction section 18, it is preferable to spray the raw material from a direction perpendicular thereto. In the mixing reaction unit 18, a thermal decomposition reaction or a combustion reaction of the raw material is performed.

  The cooling unit 19 includes a cooling water supply nozzle 24 for introducing cooling water (or other refrigerant) into the cooling unit 19. Although the dimension of the trunk | drum of the cooling part 19 is not specifically limited, Diameter 0.6m and length 2.5m can be used. The inside of the cooling unit 19 is preferably made of heat-resistant bricks. Further, the connecting portion of the mixing reaction portion 18 and the cooling portion 19 having different diameters can be smoothly connected in a conical shape with an inclination of 45 degrees. In the cooling unit 19, the carbon material obtained in the mixing reaction unit 18 is cooled by a refrigerant.

[Temperature adjustment process]
In the method for producing a carbon material of the present embodiment, before or during the reaction step, the combustion gas is mixed with an inert gas, a non-flammable gas, or a liquid, and the temperature of the combustion gas is set to 600 ° C. to 1900. You may have the temperature adjustment process adjusted to (degreeC).

  Examples of the inert gas include those described above. Moreover, it is although it does not specifically limit as a nonflammable gas, For example, water vapor | steam is mentioned. Moreover, it does not specifically limit as a liquid, For example, water is mentioned.

[Cooling process]
The manufacturing method of the carbon material of this embodiment may further have a cooling process which cools the carbon material obtained by the reaction process. Although it does not specifically limit as a cooling method, For example, the method of spraying water with respect to a carbon material etc. are mentioned. Further, in the cooling step, the carbon material can be activated with water, carbon dioxide, oxygen, and the like, thereby tending to obtain necessary catalyst performance.

[Heat treatment process]
The manufacturing method of the carbon material of this embodiment may have the heat processing process which heat-processes the carbon material obtained by the reaction process. Thereby, a carbon material with higher performance can be obtained. Note that the heat treatment step can be omitted when the carbon material is sufficiently activated by water, carbon dioxide, oxygen, or the like in the cooling step and the necessary catalytic performance is obtained. When carbonization of the carbon material is insufficient in the reaction step, it is preferable to perform heat treatment in the heat treatment step.

  The heat treatment method may be any process in which the carbon material is heated in the gas phase, and the temperature (maximum temperature) and temperature pattern of the heat treatment and the atmosphere around the carbon material composite during the heat treatment are changed for each heat treatment. Can do.

  The number of heat treatments is preferably 1 to 10 times, more preferably 1 to 5 times, and further preferably 1 to 3 times, from the viewpoint of the properties of the obtained carbon material and the process.

  Although it does not specifically limit as an apparatus used for heat processing, For example, a box furnace, a rotary furnace, a tunnel furnace, a tubular furnace, a fluidized-fired furnace is mentioned. The temperature of the heat treatment is preferably increased every time the heat treatment step proceeds, from the viewpoint of proceeding carbonization while maintaining a high content ratio of the nitrogen element in the carbon material composite.

  As the gas in the ambient atmosphere of the carbon material at the time of the heat treatment, an inert gas and an activation gas can be appropriately selected, and one kind or two or more kinds can be used. Although it does not specifically limit as an inert gas, For example, nitrogen gas and a noble gas (For example, argon gas, helium gas, and neon gas) are mentioned. Further, the activation gas is not particularly limited, but for example, air, hydrogen gas, water vapor, carbon monoxide gas, carbon dioxide gas, methane gas, oxygen gas, nitrogen monoxide gas, ammonia gas and the above inert gas. The diluted one is mentioned. The activation gas is preferably pure ammonia gas or ammonia-containing gas obtained by diluting pure ammonia with an inert gas from the viewpoint of high nitrogen content of water vapor or the resulting carbon material.

  Further, the pressure of the gas phase during the heat treatment may be any of normal pressure, pressurization, and reduced pressure (for example, 10 kPa or less, preferably in a vacuum). The gas around the carbon material may be stationary or in circulation, but is preferably in circulation from the viewpoint of the yield of the carbon material. Under an inert gas atmosphere, although the specific surface area of the obtained carbon material is relatively small, the gasification reaction of the carbon material hardly occurs and carbonization proceeds at a high yield. On the other hand, when the carbon material composite is preferably heat-treated once in an inert gas atmosphere and carbonized to some extent, and then heat-treated in an ammonia-containing gas atmosphere, the specific surface area is maintained while maintaining a high nitrogen content. It becomes easy to obtain a large carbon material. Therefore, it is preferable to first perform the heat treatment of the carbon material composite in an inert gas atmosphere and then perform the heat treatment in an ammonia-containing gas atmosphere.

  In the inert gas, the heat treatment temperature is preferably 400 ° C to 1500 ° C, more preferably 500 ° C to 1200 ° C, and further preferably 600 ° C to 1000 ° C. In the activation gas, the heat treatment temperature is preferably 400 ° C to 1500 ° C, more preferably 600 ° C to 1400 ° C, further preferably 700 ° C to 1200 ° C, and most preferably 800 ° C to 1000 ° C. It is. When the heat treatment temperature is 400 ° C. or higher, the yield of the finally obtained carbon material tends to be further improved. Moreover, when the heat treatment temperature is 1500 ° C. or lower, the nitrogen content in the raw material carbon material tends to be maintained higher. The temperature of the heat treatment is preferably increased every time the heat treatment step proceeds from the viewpoint of proceeding carbonization while keeping the content ratio of the nitrogen element in the carbon material high.

  The heat treatment time is preferably 5.0 minutes to 50 hours, more preferably 15 minutes to 20 hours, and further preferably 30 minutes to 10 hours. When the heat treatment time is within the above range, the oxygen reduction activity is further improved or the productivity of the carbon material is improved.

  The pressure during the heat treatment is preferably 0.010 to 5.0 MPa, more preferably 0.050 to 1.0 MPa, still more preferably 0.080 to 0.30 MPa, and particularly preferably 0. 0.090 to 0.15 MPa. When the pressure is 5.0 MPa or less, the carbon material tends to be more effectively suppressed from being composed of sp3 orbitals and having a low conductivity diamond structure. Moreover, it exists in the tendency for the maintenance of the airtightness of an installation to become easy because a pressure is 0.010 Mpa or more.

[Acid treatment process]
The carbon material manufacturing method of the present embodiment may include an acid treatment step of removing a part of the transition metal from the carbon material using an acid before or after the heat treatment step. In particular, when transition metal particles are generated by heat treatment, it is preferable to remove the transition metal particles from the viewpoint of suppressing increase in crystallinity in the heat treatment step. The ease with which transition metal particles can be produced varies depending on the type, concentration, dispersibility, or heat treatment temperature of the transition metal. The acid that can be used is not particularly limited, and examples thereof include hydrochloric acid, nitric acid, and sulfuric acid.

[Carbon material]
The carbon material according to the present embodiment is manufactured by the above manufacturing method. The atomic ratio (N / C) of the nitrogen atom (N) to the carbon atom (C) of the carbon material is preferably 0.001 or more, more preferably 0.005 to 0.3, and still more preferably 0. 0.01 to 0.2, and even more preferably 0.02 to 0.15. When the atomic ratio (N / C) is within the above range, the oxygen reduction activity tends to be further improved. In addition, atomic ratio (N / C) can be adjusted by adjusting the usage-amount of a carbon containing compound, a nitrogen containing compound, and a transition metal containing compound.

  In the present embodiment, the atomic ratio (M / C) of the transition metal atom (M) to the carbon atom (C) is preferably 0.0001 or more, more preferably 0.0001 to 0.05. More preferably, it is 0.001-0.04, More preferably, it is 0.005-0.03. When the atomic ratio (M / C) is within the above range, the oxygen reduction activity tends to be further improved and the hydrogen peroxide yield tends to be reduced. In addition, atomic ratio (M / C) can be adjusted by adjusting the usage-amount of a carbon containing compound, a nitrogen containing compound, a transition metal containing compound, and the processing conditions of a raw material.

  The carbon material which concerns on this embodiment expresses oxygen reduction activity by including a nitrogen atom and a transition metal atom. On the other hand, when the atomic ratio (N / C) and the atomic ratio (M / C) have the above upper limit, the oxygen reduction activity tends to be suppressed.

  The atomic ratio (N / C) and the atomic ratio (M / C) can be obtained by an electron beam microanalyzer. An “electron beam microanalyzer” is an apparatus that separates characteristic X-rays generated when an electron beam is irradiated onto a sample with a wavelength dispersive X-ray spectrometer, and identifies and quantifies elements contained in the sample. . As a specific method for measuring the atomic ratio, the methods described in Examples can be used.

The specific surface area of the carbon material determined by the BET method is preferably 400 m ² / g or more, more preferably 500 m ² / g or more, and further preferably 600 m ² / g or more. The upper limit of the BET specific surface area is not particularly limited, but is preferably 3000 m ² / g or less. When the BET specific surface area is within the above range, the oxygen reduction activity becomes higher. The specific surface area of the carbon material can be measured according to JIS Z8830 “Method for measuring specific surface area of powder (solid) by gas adsorption”.

  The DBP absorption amount of the carbon material is preferably 50 mL / 100 g or more, more preferably 100 mL / 100 g or more, further preferably 150 mL / 100 g or more, and most preferably 200 mL / 100 g or more. When the DBP absorption amount of the carbon material is within the above range, the catalyst performance tends to be further improved. The DBP absorption can be measured according to the method defined in JISK6217-4.

(Average particle size)
The average particle diameter of the carbon material is preferably 1 nm to 100 μm, more preferably 5 nm to 10 μm, and still more preferably 10 nm to 1 μm. When a carbon material is used as an electrode, it is preferable to appropriately adjust the average particle diameter (volume-based median diameter: 50% D) in order to efficiently exhibit the performance as an electrode. When the average particle diameter of the carbon material is 100 μm or less, the specific activity of the electrode tends to be further improved. In addition, when the average particle diameter of the carbon material is 1 nm or more, the particles tend to aggregate closely and inhibit the substance transport from being inhibited. The substance transport is inhibited when, for example, it is difficult to supply oxygen molecules to the active site when used as a positive electrode catalyst of a polymer electrolyte fuel cell. The average particle diameter can be measured by a known method such as a laser diffraction / scattering method, a dynamic light scattering method, an image imaging method, or a gravity sedimentation method.

  Further, the carbon material preferably has a peak in a range where the diffraction angle (2θ) is 23.5 to 26.5 ° in an X-ray diffraction diagram obtained using CuKα rays as an X-ray source. The diffraction angle (2θ) is more preferably in the range of 24.0 to 26.5 °, and further preferably in the range of 24.5 to 26.4 °. The full width at half maximum of the peak is more preferably 0.0010 ° or more, further preferably 0.010 ° or more, and particularly preferably 0.040 ° or more. When the half width of the peak is 0.0010 ° or more, the oxygen reduction activity tends to be further improved. The half width of the peak is preferably 15 ° or less, more preferably 14 ° or less, and further preferably 12 ° or less. When the half width of the peak is 15 ° or less, the oxygen reduction activity tends to be further improved.

  The content of the transition metal in the final carbon material obtained through the above production method is preferably 0.0010% by mass to 20% by mass with respect to 100% by mass of the carbon material, and is 0.010% by mass. It is more preferably 10% by mass or less, further preferably 0.050% by mass or more and 5.0% by mass or less, and most preferably 0.10% by mass or more and 3.0% by mass or less. When the content of the transition metal is within the above range, the oxygen reduction activity tends to be further improved.

[Use]
The carbon material of the present embodiment can be used as a material for various electrodes such as a fuel cell electrode typified by a solid polymer type and a metal-air battery electrode.

  A method for producing an electrode using the carbon material of the present embodiment, that is, an electrode including the carbon material is not particularly limited, and the electrode can be produced by a general method similar to a conventional carbon material. For example, the electrode can be produced by mixing a carbon material and a proton conductive material in a solvent to form a paste, applying the paste directly to the proton conductive membrane, and then drying the applied layer.

  Any proton-conducting material can be used as long as it can transmit protons. Nafion (trade name, manufactured by DuPont), Flemion (trade name, manufactured by Asahi Glass), Aciplex (trade name, Asahi Kasei) And fluorine-containing ion exchange resins having a sulfonic acid group. As the proton conductive membrane, a membrane made of the same material as the proton conductive substance can be used. As a method for producing an electrode, not only a method of directly applying a paste to a proton conductive membrane, but also an electrode is produced by applying a paste on a sheet such as a tetrafluoroethylene sheet, and then the electrode is applied to the proton conductive membrane. A transfer method can also be adopted.

  Hereinafter, although an example etc. are given and the present invention is explained still in detail, these are illustrations and the present invention is not limited to these. Accordingly, those skilled in the art can implement the present invention by making various modifications to the examples described below.

  First, the measurement method performed in this example will be described.

(Electron microanalyzer measurement)
The carbon materials obtained in the examples and comparative examples were pressed and compacted with a manual tablet molding machine, and the electron beam microanalyzer (manufactured by JEOL Ltd., “JXA-8200” was used) was measured as a 3 mmφ pellet. The acceleration voltage was set to 15 kV, the irradiation current was set to 20 nA, the probe diameter was set to 50 μm, C, N, O, and Fe were measured and corrected by the “ZAF Metal” program attached to the apparatus. As a result, atomic ratios N / C and M / C of C, N and Fe (hereinafter also referred to as “M”) were obtained.

(Electrochemical measurement)
A carbon material and a proton conductive material were mixed in a solvent to form a paste, which was directly applied to the proton conductive membrane, and then the applied layer was dried to produce an electrode. As the proton conductive substance, 5 wt% Nafion (product name, manufactured by DuPont) was used. As the proton conductive membrane, Nafion (product name, manufactured by DuPont) was used.

A measurement method of linear sweep voltammetry by the rotating electrode method using the electrode produced as described above (using a rotating ring disk electrode device “RRDE-1” manufactured by Nissan Gakko) is shown below. The rotating electrode has a disk made of glassy carbon and a ring made of platinum. An oxygen reduction catalyst is applied to the disk as shown in the examples and comparative examples. The rotating electrode was the working electrode, the reversible hydrogen electrode (RHE) was the reference electrode, and the carbon electrode was the counter electrode. 0.5M sulfuric acid was used as the electrolyte, and oxygen was bubbled through the electrolyte for 30 minutes, and then the electrochemical measurement was performed by sweeping the disk potential from 1.1 V to 0 V at 5 mV / s at a rotational speed of 1500 rpm. The ring potential was 1.2V. The oxygen reduction start potential E ₀ was determined as a potential that gives a current of −10 μA / cm ² .

The current (iD) flowing through the disk is due to the oxygen reduction reaction on the oxygen reduction catalyst, and is the sum of the 4-electron reduction reaction from oxygen to water and the 2-electron reduction reaction from oxygen to hydrogen peroxide. . On the other hand, the current (iR) flowing through the ring is generated when a part of the hydrogen peroxide generated in the disk is captured by the ring and oxidized to oxygen. Here, the hydrogen peroxide generation rate was determined by the following formula. Table 2 shows the hydrogen peroxide generation rate of 0.6V.
Hydrogen peroxide generation rate = 200 × (| iR | / N) / (| iD | + | iR | / N)
iD: current flowing through the disk N: capture rate (N = 0.372 in this apparatus)
iR: current flowing in the ring

(DBP absorption)
The DBP absorption was measured according to the method specified in JISK6217-4. As an apparatus, an absorption measuring device S-500 (product name, manufactured by Asahi Soken Co., Ltd.) was used.

(BET surface area)
The BET surface area was measured according to the method specified in JISK6217-2. As a device, “Belsorb mini-II” manufactured by Nippon Bell was used.

  The devices A, B, and C used in the examples and comparative examples are shown in FIGS.

[Example 1]
0.4 kg of diaminomaleonitrile, 0.91 g of iron (II) chloride anhydride, and 9.6 kg of methanol as a solvent were prepared and mixed to prepare a raw material A. Apparatus A was used to burn methane 20 m ³ / hr and air 263 m ³ / hr with a fuel burner in the combustion section to generate high-temperature gas. After the raw material A produced above was sprayed and reacted at 10 kg / hr from the direction perpendicular to the combustion gas flow from the head of the combustion section to the most upstream part of the mixing section of 2 m, from the cooling section of 3 m from the furnace head Water was sprayed to cool the product. The temperature of the reaction part was 1000 ° C. The cooled carbon material was separated and recovered by separating it from gas with a bag filter.

  1 g of the recovered carbon material was placed on a quartz boat and accommodated in a quartz tube furnace having an inner diameter of 36 mm. The inside of the furnace was heated from room temperature to 975 ° C. over 60 minutes under an atmospheric pressure, 1 NL / min ammonia gas flow, and kept at 975 ° C. for 1 hour to obtain 0.2 g of a carbon material after the heat treatment step. The results of each measurement are shown in Table 2.

[Example 2]
A raw material B was prepared by preparing 0.4 kg of diaminomaleonitrile, 0.88 g of cobalt (II) chloride anhydride, and 9.6 kg of methanol as a solvent and mixing them. Using the apparatus A, methane 22 m ³ / hr and air 287 m ³ / hr were burned with a fuel burner in the combustion section to generate high-temperature gas. After the raw material B prepared above was sprayed and reacted at a rate of 10 kg / hr from the direction perpendicular to the combustion gas flow to the most upstream part of the mixing part 2 m from the furnace head of the combustion part, from the cooling part 3 m from the furnace head Water was sprayed to cool the product. The temperature of the reaction part was 1000 ° C. The cooled carbon material was separated and recovered by separating it from gas with a bag filter.

  1 g of the collected carbon material was heat-treated in the same manner as in Example 1 to obtain 0.2 g of the carbon material after the heat treatment step. The results of each measurement are shown in Table 2.

[Example 3]
0.4 kg of diaminomaleonitrile, 0.89 g of nickel (II) chloride and 9.6 kg of methanol as a solvent were prepared and mixed to prepare a raw material C. Using the apparatus A, methane 13m ³ / hr at a fuel burner in the combustion section, caused a high-temperature gas by combustion of air 167m ³ / hr. After the raw material C prepared above was sprayed and reacted at a rate of 10 kg / hr from the direction perpendicular to the combustion gas flow from the head of the combustion section to the uppermost stream of the mixing section of 2 m, from the cooling section of 3 m from the head of the furnace. Water was sprayed to cool the product. The temperature of the reaction part was 1000 ° C. The cooled carbon material was separated and recovered by separating it from gas with a bag filter.

  1 g of the collected carbon material was heat-treated in the same manner as in Example 1 to obtain 0.2 g of the carbon material after the heat treatment step. The results of each measurement are shown in Table 2.

[Example 4]
6 kg of diaminomaleonitrile, 13.6 g of iron (II) chloride anhydride, and 144 kg of methanol as a solvent were prepared and mixed to prepare a raw material A2. The raw material A2 was dried by a spray dryer (MDL-015MGC-S) to produce 3 kg of particles (raw material A3) having an average particle diameter of 3 μm. 2 kg of raw material A3 and 8 kg of water were mixed to produce slurry raw material A4. Using the apparatus A, methane 15 m ³ / hr at a fuel burner in the combustion section, caused a high-temperature gas by combustion of air 206m ³ / hr. After the raw material A4 prepared above was sprayed and reacted at a rate of 10 kg / hr from the direction perpendicular to the combustion gas flow from the head of the combustion section to the most upstream part of the mixing section of 2 m, from the cooling section of 3 m from the furnace head Water was sprayed to cool the product. The temperature of the reaction part was 1000 ° C. The cooled carbon material was separated and recovered by separating it from gas with a bag filter.

  1 g of the collected carbon material was heat-treated in the same manner as in Example 1 to obtain 0.2 g of the carbon material after the heat treatment step. The results of each measurement are shown in Table 2.

[Example 5]
1.9 kg of pyridine and 4.3 g of iron (II) chloride anhydride were mixed and stirred at 250 rpm for 1 hour to prepare a raw material D. Using the apparatus A, methane 11m ³ / hr at a fuel burner in the combustion section, caused a high-temperature gas by combustion of air 146m ³ / hr. After the raw material D prepared above was sprayed and reacted at a rate of 3.8 kg / hr from the direction perpendicular to the combustion gas flow from the head of the combustion section to the most upstream part of the mixing section of 2 m, it was cooled by 3 m from the furnace head. Water was sprayed from the part to cool the product. The temperature of the reaction part was 1000 ° C. The cooled carbon material was separated and recovered by separating it from gas with a bag filter.

  1 g of the collected carbon material was heat-treated in the same manner as in Example 1 to obtain 0.2 g of the carbon material after the heat treatment step. The results of each measurement are shown in Table 2.

[Example 6]
Polyacrylonitrile 0.3 kg, iron (II) chloride anhydride 3.5 g, N, N-dimethylformamide 3 kg were mixed, heated to 80 ° C. and stirred at 250 rpm for 1 hour to prepare a raw material E. Using the apparatus A, methane 9m ³ / hr at a fuel burner in the combustion section, caused a high-temperature gas by combustion of air 125m ³ / hr. The raw material E prepared above is sprayed at a rate of 3.6 kg / hr from the direction perpendicular to the combustion gas flow from the furnace head of the combustion part to the most upstream part of the mixing part, and then cooled by 3 m from the furnace head. Water was sprayed from the part to cool the product. The temperature of the reaction part was 1000 ° C. The cooled carbon material was separated and recovered by separating it from gas with a bag filter.

  1 g of the collected carbon material was heat-treated in the same manner as in Example 1 to obtain 0.2 g of the carbon material after the heat treatment step. The results of each measurement are shown in Table 2.

[Example 7]
The raw material F was produced by mixing 2.1 kg of aniline and 4.8 g of iron (II) chloride anhydride and stirring at 250 rpm for 1 hour. Using the apparatus A, methane 13m ³ / hr at a fuel burner in the combustion section, caused a high-temperature gas by combustion of air 167m ³ / hr. The raw material F prepared above is sprayed at a rate of 4.2 kg / hr from the direction perpendicular to the combustion gas flow to the most upstream part of the mixing part 2 m from the furnace head of the combustion part, and then cooled by 3 m from the furnace head. Water was sprayed from the part to cool the product. The temperature of the reaction part was 1000 ° C. The cooled carbon material was separated and recovered by separating it from gas with a bag filter.

  1 g of the collected carbon material was heat-treated in the same manner as in Example 1 to obtain 0.2 g of the carbon material after the heat treatment step. The results of each measurement are shown in Table 2.

[Example 8]
1.4 kg of acetonitrile and 3.2 g of iron (II) chloride anhydride were mixed and stirred at 250 rpm for 1 hour to prepare a raw material G. Using the apparatus A, methane 12 m ³ / hr and air 160 m ³ / hr were burned with a fuel burner in the combustion section to generate high-temperature gas. After the raw material G prepared above was sprayed and reacted at a rate of 2.8 kg / hr from the direction perpendicular to the combustion gas flow from the furnace head of the combustion section to the most upstream part of the mixing section 2 m, cooling was performed 3 m from the furnace head. Water was sprayed from the part to cool the product. The temperature of the reaction part was 1000 ° C. The cooled carbon material was separated and recovered by separating it from gas with a bag filter.

  1 g of the collected carbon material was heat-treated in the same manner as in Example 1 to obtain 0.2 g of the carbon material after the heat treatment step. The results of each measurement are shown in Table 2.

[Example 9]
Acrylonitrile (3.5 kg) and iron (II) chloride anhydride (7.9 g) were mixed and stirred at 250 rpm for 1 hour to prepare a raw material H. Using the apparatus A, methane 14m ³ / hr at a fuel burner in the combustion section, caused a high-temperature gas by combustion of air 183m ³ / hr. After the raw material H prepared above is sprayed and reacted at a rate of 3.5 kg / hr from the direction perpendicular to the combustion gas flow from the head of the combustion section to the most upstream part of the mixing section of 2 m, cooling is performed 3 m from the furnace head. Water was sprayed from the part to cool the product. The temperature of the reaction part was 1000 ° C. The cooled carbon material was separated and recovered by separating it from gas with a bag filter.

  1 g of the collected carbon material was heat-treated in the same manner as in Example 1 to obtain 0.2 g of the carbon material after the heat treatment step. The results of each measurement are shown in Table 2.

[Example 10]
0.6 kg of melamine, 1.4 g of iron (II) chloride anhydride, and 5.4 kg of N, N-dimethylformamide were mixed, heated to 80 ° C., and stirred at 250 rpm for 1 hour to prepare a raw material I. Using the apparatus A, methane 13m ³ / hr at a fuel burner in the combustion section, caused a high-temperature gas by combustion of air 170m ³ / hr. After the raw material I prepared above was sprayed and reacted at 6.0 kg / hr from the direction perpendicular to the combustion gas flow to the most upstream part of the mixing part 2 m from the furnace head of the combustion part, it was cooled 3 m from the furnace head. Water was sprayed from the part to cool the product. The temperature of the reaction part was 1000 ° C. The cooled carbon material was separated and recovered by separating it from gas with a bag filter.

  1 g of the collected carbon material was heat-treated in the same manner as in Example 1 to obtain 0.2 g of the carbon material after the heat treatment step. The results of each measurement are shown in Table 2.

[Example 11]
5 kg of N-methylpyrrolidone and 11.3 g of iron (II) chloride anhydride were mixed and stirred at 250 rpm for 1 hour to prepare a raw material J. Using the apparatus A, methane 11 m ³ / hr and air 151 m ³ / hr were combusted with a fuel burner in the combustion section to generate high-temperature gas. After the raw material J prepared above was sprayed and reacted at a rate of 5 kg / hr from the direction perpendicular to the combustion gas flow from the head of the combustion section to the uppermost mixing section of 2 m, from the cooling section of 3 m from the furnace head. Water was sprayed to cool the product. The temperature of the reaction part was 1000 ° C. The cooled carbon material was separated and recovered by separating it from gas with a bag filter.

  1 g of the collected carbon material was heat-treated in the same manner as in Example 1 to obtain 0.2 g of the carbon material after the heat treatment step. The results of each measurement are shown in Table 2.

[Example 12]
Using the apparatus B, natural gas 9m ³ / hr and air 133m ³ / hr having the composition shown in Table 1 below were burned with a fuel burner in the combustion section to generate high-temperature gas. After the raw material D prepared in Example 5 was sprayed and reacted at a rate of 3.8 kg / hr from the direction perpendicular to the combustion gas flow to the most upstream part of the mixing unit 2 m from the furnace head of the combustion unit, 3 m from the furnace head The product was cooled by spraying water from the cooling part. The temperature of the reaction part was 1100 degreeC. The cooled carbon material was separated and recovered by separating it from gas with a bag filter.

  1 g of the collected carbon material was heat-treated in the same manner as in Example 1 to obtain 0.2 g of the carbon material after the heat treatment step. The results of each measurement are shown in Table 2.

[Example 13]
By using the apparatus B, methane 12 m ³ / hr and air 180 m ³ / hr were combusted with a fuel burner in the combustion section to generate high-temperature gas. The slurry raw material A4 prepared in Example 4 was sprayed at a rate of 10 kg / hr from the direction perpendicular to the combustion gas flow from the furnace head of the combustion part to the most upstream part of the mixing part 2 m, and then reacted 3 m from the furnace head. Water was sprayed from the cooling section to cool the product. The temperature of the reaction part was 1000 ° C. The cooled carbon material was separated and recovered by separating it from gas with a bag filter.

  1 g of the collected carbon material was heat-treated in the same manner as in Example 1 to obtain 0.2 g of the carbon material after the heat treatment step. The results of each measurement are shown in Table 2.

[Example 14]
2.5 kg of pyridine and 5.7 g of iron (II) chloride anhydride were mixed and stirred at 250 rpm for 1 hour to prepare a raw material K. Using the apparatus B, natural gas 6m ³ / hr and air 86m ³ / hr having the composition shown in Table 1 were burned with a fuel burner in the combustion section to generate high-temperature gas. After the raw material K prepared above was sprayed and reacted at a rate of 2.5 kg / hr from the direction perpendicular to the combustion gas flow to the most upstream part of the mixing part 2 m from the furnace head of the combustion part, it was cooled 3 m from the furnace head. Water was sprayed from the part to cool the product. The temperature of the reaction part was 600 degreeC. The cooled carbon material was separated and recovered by separating it from gas with a bag filter.

  1 g of the collected carbon material was heat-treated in the same manner as in Example 1 to obtain 0.2 g of the carbon material after the heat treatment step. The results of each measurement are shown in Table 2.

[Example 15]
A raw material L was prepared by mixing 4.9 kg of pyridine and 11.1 g of iron (II) chloride anhydride and stirring at 250 rpm for 1 hour. Using the apparatus B, natural gas of 15 m ³ / hr and air of 224 m ³ / hr having the composition shown in Table 1 were burned with a fuel burner in the combustion section to generate high-temperature gas. After the raw material L prepared above is sprayed and reacted at 4.9 kg / hr from the direction perpendicular to the combustion gas flow from the head of the combustion section to the most upstream part of the mixing section of 2 m, cooling is performed 3 m from the furnace head. Water was sprayed from the part to cool the product. The temperature of the reaction part was 1200 degreeC. The cooled carbon material was separated and recovered by separating it from gas with a bag filter.

  1 g of the collected carbon material was heat-treated in the same manner as in Example 1 to obtain 0.2 g of the carbon material after the heat treatment step. The results of each measurement are shown in Table 3.

[Example 16]
Using the apparatus B, natural gas 6m ³ / hr and air 86m ³ / hr having the composition shown in Table 1 were burned with a fuel burner in the combustion section to generate high-temperature gas. After the raw material E produced in Example 6 was sprayed and reacted at 5.7 kg / hr from the direction perpendicular to the combustion gas flow to the most upstream part of the mixing unit 2 m from the furnace head of the combustion unit, 3 m from the furnace head The product was cooled by spraying water from the cooling part. The temperature of the reaction part was 900 degreeC. The cooled carbon material was separated and recovered by separating it from gas with a bag filter.

  1 g of the collected carbon material was heat-treated in the same manner as in Example 1 to obtain 0.2 g of the carbon material after the heat treatment step. The results of each measurement are shown in Table 3.

[Example 17]
Using the apparatus A, 10 kg / hr C heavy oil and 150 m ³ / hr air were burned with a fuel burner in the combustion section to generate high-temperature gas. After the raw material D prepared in Example 5 was sprayed and reacted at a rate of 3.8 kg / hr from the direction perpendicular to the combustion gas flow to the most upstream part of the mixing unit 2 m from the furnace head of the combustion unit, 3 m from the furnace head The product was cooled by spraying water from the cooling part. The temperature of the reaction part was 1000 ° C. The cooled carbon material was separated and recovered by separating it from gas with a bag filter.

  1 g of the collected carbon material was heat-treated in the same manner as in Example 1 to obtain 0.2 g of the carbon material after the heat treatment step. The results of each measurement are shown in Table 3.

[Example 18]
Using the apparatus A, 13 kg / hr C heavy oil and 189 m ³ / hr air were burned with a fuel burner in the combustion section to generate high-temperature gas. After the raw material E produced in Example 6 was sprayed and reacted at 5.7 kg / hr from the direction perpendicular to the combustion gas flow to the most upstream part of the mixing unit 2 m from the furnace head of the combustion unit, 3 m from the furnace head The product was cooled by spraying water from the cooling part. The temperature of the reaction part was 1100 degreeC. The cooled carbon material was separated and recovered by separating it from gas with a bag filter.

  1 g of the collected carbon material was heat-treated in the same manner as in Example 1 to obtain 0.2 g of the carbon material after the heat treatment step. The results of each measurement are shown in Table 3.

[Example 19]
Using the apparatus A, 13 kg / hr C heavy oil and 183 m ³ / hr air were burned with a fuel burner in the combustion section to generate high-temperature gas. The slurry raw material A4 prepared in Example 4 was sprayed at a rate of 10 kg / hr from the direction perpendicular to the combustion gas flow from the furnace head of the combustion part to the most upstream part of the mixing part 2 m, and then reacted 3 m from the furnace head. Water was sprayed from the cooling section to cool the product. The temperature of the reaction part was 1000 ° C. The cooled carbon material was separated and recovered by separating it from gas with a bag filter.

  1 g of the collected carbon material was heat-treated in the same manner as in Example 1 to obtain 0.2 g of the carbon material after the heat treatment step. The results of each measurement are shown in Table 3.

[Example 20]
Using apparatus A, 11 kg / hr C heavy oil and 161 m ³ / hr air were burned with a fuel burner in the combustion section to generate high-temperature gas. After the raw material A produced in Example 1 was sprayed at a rate of 10 kg / hr from the direction perpendicular to the combustion gas flow to the most upstream part of the mixing part 2 m from the furnace head of the combustion part, it was cooled by 3 m from the furnace head. Water was sprayed from the part to cool the product. The temperature of the reaction part was 1000 ° C. The cooled carbon material was separated and recovered by separating it from gas with a bag filter.

  1 g of the collected carbon material was heat-treated in the same manner as in Example 1 to obtain 0.2 g of the carbon material after the heat treatment step. The results of each measurement are shown in Table 3.

[Example 21]
Using the device C, the methane 4m ³ / hr at a fuel burner in the combustion section, caused a high-temperature gas by combustion of air 60 m ³ / hr. Nitrogen was mixed at 4 m ³ / hr from the furnace head of the combustion section to a temperature adjustment section of 2 m, and the raw material D produced in Example 5 from the direction perpendicular to the combustion gas flow at the most upstream mixing section of 1 m downstream Was sprayed at 3.8 kg / hr for reaction, and then water was sprayed from the cooling section of 3 m from the top of the furnace to cool the product. The temperature of the reaction part was 900 degreeC. The cooled carbon material was separated and recovered by separating it from gas with a bag filter.

  1 g of the collected carbon material was heat-treated in the same manner as in Example 1 to obtain 0.2 g of the carbon material after the heat treatment step. The results of each measurement are shown in Table 3.

[Example 22]
Using the device C, the methane 5 m ³ / hr at a fuel burner in the combustion section, caused a high-temperature gas by combustion of air 50 m ³ / hr. The raw material prepared in Example 5 from the direction perpendicular to the combustion gas flow into the uppermost stream part of the mixing part of 1 m downstream from the furnace head of the combustion part at a temperature adjustment part of 2 m mixed with water at 2.5 kg / hr. After D was sprayed and reacted at 3.8 kg / hr, water was sprayed from a cooling part of 3 m from the top of the furnace to cool the product. The temperature of the reaction part was 900 degreeC. The cooled carbon material was separated and recovered by separating it from gas with a bag filter.

  1 g of the collected carbon material was heat-treated in the same manner as in Example 1 to obtain 0.2 g of the carbon material after the heat treatment step. Table 3 shows the results.

[Example 23]
Using the device C, the methane 5 m ³ / hr at a fuel burner in the combustion section, caused a high-temperature gas by combustion of air 51m ³ / hr. The raw material prepared in Example 5 from the direction perpendicular to the combustion gas flow in the mixing part uppermost part of the 1m wake mixing part at a temperature adjustment part of 2m from the furnace head of the combustion part mixed at 2.6kg / hr. After D was sprayed and reacted at 3.8 kg / hr, water was sprayed from a cooling section of 3.5 m from the top of the furnace to cool the product. The temperature of the reaction part was 900 degreeC. The cooled carbon material was separated and recovered by separating it from gas with a bag filter.

  The recovered carbon material was not heat-treated. The results of each measurement are shown in Table 3.

[Example 24]
Using the device C, the methane 5 m ³ / hr at a fuel burner in the combustion section, caused a high-temperature gas by combustion of air 56m ³ / hr. Carbon dioxide is mixed at 2.8 m ³ / hr from the furnace head of the combustion section to the temperature adjustment section of 2 m, and further produced in Example 5 from the direction perpendicular to the combustion gas flow at the most upstream mixing section of 1 m downstream. After the raw material D was sprayed and reacted at 3.8 kg / hr, water was sprayed from a 3 m cooling section from the top of the furnace to cool the product. The temperature of the reaction part was 900 degreeC. The cooled carbon material was separated and recovered by separating it from gas with a bag filter.

  1 g of the collected carbon material was heat-treated in the same manner as in Example 1 to obtain 0.2 g of the carbon material after the heat treatment step. The results of each measurement are shown in Table 3.

[Example 25]
Using the apparatus A, methane 10 m ³ / hr at a fuel burner in the combustion section, caused a high-temperature gas by combustion of air 105m ³ / hr. The raw material D produced in Example 5 was sprayed at 3.8 kg / hr from the direction perpendicular to the combustion gas flow to the most upstream part of the mixing unit 2 m from the furnace head of the combustion unit, and 1.5 kg / hr of acetylene was mixed. After the reaction, water was sprayed from a cooling part 3 m from the top of the furnace to cool the product. The temperature of the reaction part was 1000 ° C. The cooled carbon material was separated and recovered by separating it from gas with a bag filter.

  1 g of the collected carbon material was heat-treated in the same manner as in Example 1 to obtain 0.2 g of the carbon material after the heat treatment step. The results of each measurement are shown in Table 3.

[Example 26]
Using the apparatus A, methane 4 m ³ / hr and air 48 m ³ / hr were burned with a fuel burner in the combustion section to generate high-temperature gas. After the raw material D produced in Example 5 was sprayed and reacted at 1.2 kg / hr from the direction perpendicular to the combustion gas flow from the furnace head of the combustion section to the most upstream part of the mixing section 2 m, 3 m from the furnace head. The product was cooled by spraying water from the cooling part. The temperature of the reaction part was 800 ° C. The cooled carbon material was separated and recovered by separating it from gas with a bag filter.

  1 g of the collected carbon material was heat-treated in the same manner as in Example 1 to obtain 0.2 g of the carbon material after the heat treatment step. The results of each measurement are shown in Table 3.

[Example 27]
1.9 kg of pyridine and 1.2 g of iron (II) chloride anhydride were mixed and stirred at 250 rpm for 1 hour to prepare a raw material J. Using the apparatus A, methane 59m ³ / hr at a fuel burner in the combustion section, caused a high-temperature gas by combustion of air 785m ³ / hr. The raw material D prepared in Example 5 was sprayed and reacted at 6.8 kg / hr from the direction perpendicular to the combustion gas flow to the most upstream part of the mixing part 2 m from the furnace head of the combustion part, and then 3 m from the furnace head. The product was cooled by spraying water from the cooling part. The temperature of the reaction part was 1500 degreeC. The cooled carbon material was separated and recovered by separating it from gas with a bag filter.

  The recovered carbon material was not heat-treated. The results of each measurement are shown in Table 3.

[Comparative Example 1]
Methane 10 m ³ / hr and air 140 m ³ / hr were burned with a fuel burner in the combustion section to generate high-temperature gas. After pyridine is sprayed at a rate of 3.8 kg / hr from the direction perpendicular to the combustion gas flow from the furnace head of the combustion section to the most upstream part of the mixing section of 2 m, water is sprayed from the cooling section of 3 m from the furnace head. The product was cooled. The temperature of the reaction part was 1000 ° C. The cooled carbon material was separated and recovered by separating it from gas with a bag filter.

  1 g of the collected carbon material was heat-treated in the same manner as in Example 1 to obtain 0.2 g of the carbon material. The results of each measurement are shown in Table 3.

  According to the above examples, it was found that a carbon material having high electrochemical characteristics can be continuously produced in large quantities.

  The method for producing a carbon material of the present invention has industrial applicability as a method for producing a carbon material that can be used as an electrode for a fuel cell.

DESCRIPTION OF SYMBOLS 1 ... Combustion part 2 ... Mixing reaction part 3 ... Cooling part 4 ... Fuel burner 5 ... Air inlet 6 ... Raw material supply nozzle 7 ... Cooling water supply nozzle 8 ... Combustion part 9 ... Mixing part 10 ... Reaction part 11 ... Cooling part 12 ... fuel burner 13 ... Air inlet 14 ... raw material supply nozzle 15 ... cooling water supply nozzle 16 ... combustion part 17 ... temperature control part 18 ... mixing reaction part 19 ... cooling part 20 ... fuel burner 21 ... Air inlet 22 ... coolant Supply nozzle 23 ... Raw material supply nozzle 24 ... Cooling water supply nozzle

Claims (15)

  By subjecting a raw material containing carbon atoms, nitrogen atoms, and transition metal atoms to a pyrolysis reaction or a combustion reaction in a combustion gas of 600 ° C. to 1900 ° C. in which a mixed gas containing fuel and oxygen is burned. The manufacturing method of a carbon material which has the reaction process of obtaining the carbon material containing the said nitrogen atom and the said transition metal atom.   The method for producing a carbon material according to claim 1, wherein in the carbon material, an atomic ratio N / C of the nitrogen atom to the carbon atom is 0.001 or more.   The method for producing a carbon material according to claim 1 or 2, wherein the transition metal atom includes at least one selected from the group consisting of Fe, Co, and Ni.   The manufacturing method of the carbon material as described in any one of Claims 1-3 which is the state in which the said transition metal atom formed the complex in the said raw material.   The manufacturing method of the carbon material as described in any one of Claims 1-4 whose atomic ratio M / C of the said transition metal atom with respect to the said carbon atom is 0.0001 or more in the said carbon material.   The raw materials are primary to tertiary amines, amides, imines, imides, nitriles, azides, aziridines, azos, diazos, isocyanates, isocyanides, enamines, oximes, carbamates. The manufacturing method of the carbon material as described in any one of Claims 1-5 containing at least 1 type selected from the group which consists of nitro, nitros, nitroso, hydrazine, and lactams. Before or during the reaction step,
The said combustion gas and a nonflammable gas or a liquid are mixed, The temperature adjustment process of adjusting the temperature of the said combustion gas to 600 to 1900 degreeC is included. A method for producing a carbon material. The nonflammable gas is water vapor;
The method for producing a carbon material according to claim 7, wherein the liquid is water.   The manufacturing method of the carbon material as described in any one of Claims 1-8 in which the said raw material contains acetylene.   The method for producing a carbon material according to claim 1, wherein the raw material includes a compound containing the nitrogen atom and a solvent for dissolving the compound.   The method for producing a carbon material according to claim 10, wherein the solvent contains a nitrogen atom.   The manufacturing method of the carbon material as described in any one of Claims 1-11 whose said raw material is a slurry form containing an insoluble component and a solvent.   The carbon material obtained by the manufacturing method of the carbon material as described in any one of Claims 1-12.   The carbon material according to claim 13, wherein the DBP absorption amount is 50 mL / 100 g or more.   The electrode for fuel cells containing the carbon material of Claim 13 or 14.

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