JPH09316457A - Production of both high-softening point pitch having mesopore and carbonaceous material supporting metal - Google Patents

Abstract

PROBLEM TO BE SOLVED: To simply produce the subject pitch useful as a material for a metal- supporting carbonaceous material without requiring a pretreatment for a raw material such as heat treatment from an inexpensive raw material by shaping a specific starting raw material into a specified form, then bringing the shaped raw material into contact with a specific organic solvent and extracting a specified amount of a light component in the shaped material. SOLUTION: A starting raw material which is (A1 ) a heavy oil having 0.8-1.2 atomic ratio H/C without containing an insoluble substance in a BTX solvent or (A2 ) a low- softening point pitch obtained by distilling off a light component from the component A1 is shaped into a particulate, a powdery or a fibrous form having <=100μm diameter to provide a shaped material, which is then brought into contact with (B) an organic solvent capable of making >=10wt.% shaped material remain as an insoluble material to extract a light component in an amount of 20-90wt.% based on the shaped material. Thereby, a high-softening point pitch having >=150 deg.C softening point measured by a temperature gradient method, <=5wt.% heating loss up to 300 deg.C and mesopores having >=100mm<3> /g pore volume calculated from an adsorption isotherm for nitrogen at the liquid nitrogen temperature according to a Dollimore-Heal method is obtained.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a high softening point pitch having mesopores, and a method for producing a carbonaceous material supporting a metal obtained by using the high softening point pitch.

[0002]

2. Description of the Related Art Carbonaceous materials supporting metals have been conventionally used as various reaction catalysts, but recently, for example, deodorization by supporting a odor decomposition function by supporting metals such as silver and manganese on activated carbon. Agents, adsorption and separation materials for macromolecules such as sugars, vitamins, dyes and humic substances contained in tap water, obtained by carbonizing or activating organic substances containing metal complexes, and by decomposing iron-containing organic substances The obtained iron-containing carbon magnetic material and the like have been developed, and it is considered that the utilization of the iron-containing carbon magnetic material will be expanded in the future by utilizing the new function.

As a method for supporting a metal on carbon, a method of impregnating activated carbon with an aqueous solution of a metal salt is generally known. In this method, the crystal structure and pore structure of carbon depend on the type of activated carbon used. Therefore, it was difficult to intentionally control the crystal structure or the pore structure for the purpose of imparting functionality.

Therefore, some methods have been proposed in which the metal is supported or heat-treated in the presence of the metal to uniformly disperse the metal and control the pore structure.

For example, a method of carbonizing a mixture of an ultrafine particle size metal oxide and an organic substance such as a phenol resin by heating and carbonization (Japanese Patent Application Laid-Open No. 2-6308), and having a coordination ability in a main chain and / or a side chain. A method of coordinating a metal with a polymer compound having an atomic group, and heat-treating the obtained organometallic polymer compound (JP-A-2-6309, JP-A-2-6310,
JP-A-2-6311, JP-A-2-6312, JP-A-2-6313), a pitch and an organometallic compound are mixed,
A method (in Japanese Patent Laid-Open No. 3-265510) of activating or carbonizing the infusible material has been proposed.

However, in these methods, since the metal compound used is ultrafine particles, it is difficult to coagulate and precipitate during the operation to uniformly disperse in an organic substance, or an organic metal complex soluble in an organic solvent or pitch is used. However, since it is a special complex, it is expensive, and the resulting carbonaceous material is inevitably expensive.

As a method of using a raw material obtained from heavy oil, mesophase pitch is oxidized with an oxidizing agent such as nitric acid, and the resulting aromatic condensation compound having a hydrophilic group and a metal salt solution are mixed with an alkaline aqueous solution. After that, a method of decomposing this alkaline aqueous solution (JP-A-5-59414),
The carbonaceous bituminous material is treated with an oxidizing agent to introduce a functional group,
A method of dissolving this in a specific organic solvent, adding an organometallic complex soluble in the solvent, gelling the solution as it is, and firing the resulting carbonaceous gelled product (Japanese Patent Laid-Open No. 5-32066).
No. 2), a method of treating a carbonaceous material such as raw coke with an oxidizing agent to introduce a functional group, contacting this with a metal salt, and then calcining in an inert atmosphere (JP-A-6-40771) and the like. Is proposed. In these methods, it is necessary to first oxidize the raw material with an oxidizing agent such as nitric acid for the purpose of introducing a functional group, but in order to introduce a sufficient amount of the functional group, a large amount of tens of times or more of the raw material is required. It is necessary to use
A large amount of equipment and cost are required for washing with water and treatment of waste liquid after the treatment. Further, when a high softening point pitch such as mesophase pitch is used as a raw material, the production itself of this mesophase pitch requires complicated steps such as heat treatment at high temperature and polymerization using a catalyst. It lacks stability and is costly.

On the other hand, as a method in which an organic compound originally having a functional group is used as a starting material, an α, β-unsaturated monomer having a specific functional group is emulsion polymerized to obtain polymer particles, which are present on the surface. A method in which a metal is bound in the form of a metal complex using a functional group as a ligand and then the metal is fired (JP-A-5-9).
No. 8302) has been proposed, but in this method, only the functional groups on the surface of the polymer particles can be utilized, and the metal loading occurs only on the surface.

[0009]

In view of the above situation, the first object of the present invention is to use an inexpensive starting material,
It is to provide a method for producing a high softening point pitch having a mesopore that allows a required metal to uniformly enter inside a particle without requiring pretreatment of a complicated raw material such as heat treatment or catalytic polymerization, and The purpose of is to use a high softening point pitch with this mesopore, without using a complicated oxidizing agent such as nitric acid, to uniformly disperse and support a metal on a carbonaceous material industrially, It is to provide a method for manufacturing efficiently.

The carbonaceous material referred to in the present invention means a high softening point pitch after metal supporting treatment, which is made from a high softening point pitch having mesopores, an infusible material obtained by making it infusible, and this infusible material. It includes any of a carbide, a graphitized product, and a molded product thereof obtained by performing a baking treatment in an inert atmosphere or an oxidizing gas atmosphere.

[0011]

Means for Solving the Problems The present inventors first used a heavy oil having a specific property as a starting material, first shaped it into particles, powder or fibers, and then shaped this shaped body. A high softening point pitch is obtained by extracting and removing a light component from an organic solvent, and is further infusibilized by heating it in an atmosphere containing oxygen to take in oxygen, and then carbonizing under a specific condition, It has been found that a carbon material having uniform and fine pores can be obtained easily and drastically (Japanese Patent Application No. 7-329935).

The inventors of the present invention use the high softening point pitch obtained in the process of the present invention as a starting material, that is, a heavy oil having a specific property, and first shape this into particles, powder or fibrous material, and then shape it. The high softening point pitch obtained by a method of extracting and removing a light component from this shaped body with an organic solvent is higher than the high softening point pitch produced by a conventional heat treatment method, etc., and its properties, as well as infusibilization and firing. , The behavior at the time of carbonization is greatly different, that is, a unique pitch different from the conventional high softening point pitch, and as a result of further research, it was obtained by extracting the light component under specific conditions. The high softening point pitch has a mesopore of 20 to 500 Å in it, and a surfactant can be easily adsorbed to this mesopore. In, the cation exchange reaction occurs in an aqueous solution containing a metal ion, therefore, it is possible to obtain a high softening point pitch carrying various metals, further infusibilize the high softening point pitch carrying this metal, The inventors have found that when carbonized or graphitized, carbonaceous materials supporting various metals can be obtained as they are, and completed the present invention.

That is, the gist of the first invention is a heavy oil having an H / C atomic ratio in the range of 0.8 to 1.2 and containing substantially no BTX solvent-insoluble matter, or the heavy oil. Starting material is a low softening point pitch obtained by distilling light components from
This is shaped into particles, powder or fibrous particles having a diameter of 100 μm or less to obtain a shaped body, and at least 10% by weight of the shaped body is brought into contact with an organic solvent capable of remaining as an insoluble component,
20 to 90% by weight of the light component of the shaped body is extracted, and the softening point of the temperature gradient method is 150 ° C. or higher, and 30
High softening point pitch having a mesopore with a weight loss up to 0 ° C of 5% by weight or less and a pore volume of 100 mm ³ / g or more calculated by the Dollimore-Heal method from the adsorption isotherm of nitrogen at liquid nitrogen temperature. The production method of the present invention, the gist of the second invention is to contact the high softening point pitch with an anionic surfactant to obtain a high softening point pitch having an anionic surfactant adsorbed. In a method for producing a metal-supported high softening point pitch, which comprises contacting a high softening point pitch adsorbing a surface-active agent with an aqueous metal salt solution to replace the cations of the surfactant with the metal ion. Then, the gist of the third invention is the production of a carbon-containing infusible material carrying a metal, characterized in that the high softening point pitch carrying the metal is infusibilized by heating in an atmosphere containing oxygen. In the method of the fourth invention The effect is to heat-treat this infusible material in an inert atmosphere at a temperature range of 500 to 3,000 ° C., or in an atmosphere containing at least one oxidizing gas selected from steam and carbon dioxide, , 50
The present invention resides in a method for producing a carbonaceous material supporting a metal, which comprises performing a heat treatment in a temperature range of 0 ° C., and the gist of the fifth invention is to fill the carbonaceous infusible material supporting the above metal with a filler. And, using a high softening point pitch as described in the gist of the first invention or a high softening point pitch carrying a metal as described in the gist of the second invention as a binder, forming a molded body, and making it infusible , A method for producing a carbonaceous material molded body carrying a metal, which is characterized by carrying out a carbonization or graphitization treatment.

The BTX solvent in the present invention means an aromatic solvent such as benzene, toluene, xylene and ethylbenzene.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. (Starting material) In the starting material of the present invention, the H / C atomic ratio needs to be in the range of 0.8 to 1.2. H
When the / C atomic ratio is less than 0.8, that is, when the aromaticity is high and the aliphatic side chains are extremely small, the solubility in organic solvents is low and extraction of light components is insufficient, resulting in high pitch. It becomes difficult to soften or form mesopores having a sufficiently large pore volume. In addition, since the pitch of which the aromaticity is extremely high has a slow oxidation reaction rate during the infusibilization treatment, it takes a long time to infusibilize the treatment, and it becomes difficult to uniformly infusibilize the inside.

On the contrary, if the H / C atomic ratio is larger than 1.2, that is, if the aromaticity is low and the aliphaticity is very high, the recovery rate during extraction of the light component with the organic solvent is remarkably low. It is inefficient, and if the recovery rate is low, the shape initially shaped may collapse and the original shape may not be retained. Further, a compound having a remarkably high aliphaticity is not preferable because desorption due to decomposition increases more than oxygen uptake during infusibilization.

Further, the starting material contains substantially no component insoluble in the BTX solvent, that is, the value of the insoluble component measured by a general insoluble component measuring method as defined by JIS is 1% by weight. % Or less is required. this is,
The presence of a component insoluble in the BTX solvent not only hinders the formation of the starting material into particles, powders or fibers of the micron order, but these BTX solvent-insoluble components also have a molecular weight generated by thermal polymerization or the like. Since the high softening point pitch containing it has a large molecular weight distribution, the subsequent infusibilization and the reaction in the firing process become non-uniform.

As the raw materials satisfying the conditions of the invention, heavy oil (naphtha cracked by-product oil) and gas oil (light oil fraction), which are by-produced when naphtha is decomposed to produce olefins, are used. Heavy oil (pyrolysis tar) that is by-produced when cracked to produce olefins, heavy oil (decant oil or F) that is by-produced during fluid catalytic cracking (FCC) of petroleum
There are petroleum-based cracked heavy oils such as CC slurry oil). Of these, naphtha-decomposed by-product oil is originally composed of naphtha, so that it has a very small content of hetero elements such as sulfur, nitrogen and oxygen, and is suitable from the viewpoint of exhaust gas treatment during carbonization.

Further, in the case of a coal-based heavy oil such as coal tar, the aromaticity is usually considerably high (H / C is small), and a large amount of BTX solvent insoluble matter is contained, so that it is not preferable to use it as it is. However, separation of BTX solvent insoluble matter,
It can be used as the starting material of the present invention if it is subjected to a reforming operation so as to meet the conditions of the present invention by treatment such as removal or hydrocracking. However, considering the cost involved in such reforming operation, it is difficult to say that it is a preferable raw material as compared with the above-mentioned heavy petroleum oil.

Such a heavy oil can be used as it is as a starting material of the present invention, and a low softening point pitch having a softening point of 150 ° C. or lower obtained by removing light components by a distillation operation. Can also be used. What is the temperature gradient method softening point here? Place the sample pitch powder on an aluminum plate with a temperature gradient, brush it off, and find the position where the sample begins to melt and adheres to the aluminum plate surface. It is a method of using the surface temperature of the plate as the softening point (measuring instrument: manufactured by Asia Rikaki Co., Ltd., AMK-B2CEFH-3), and although it varies depending on the type and property of the pitch, the temperature gradient method softening point is approximately , R & specified in JIS
The value is 15 to 20 ° C. lower than that of B (ring & ball method), and the value is 25 to 50 ° C. lower than the METTLER method softening point specified in ASTM.

(Shaping of Starting Material) In the method of the present invention, first, the starting material is shaped into particles, powder or fibers having a diameter of 100 μm or less.

The reason why the diameter is 100 μm or less is that extraction can be carried out rapidly and uniformly in the subsequent extraction process of the light component. If the diameter is larger than, for example, the mm order, the extraction of the outer surface occurs quickly, but the extraction to the inside takes time, so if the extraction time is insufficient, the extraction state becomes non-uniform. Another reason is that when a surfactant is adsorbed on a high softening point pitch from which a light component is extracted, and when it is replaced with a metal ion, if the diameter of the shaped object is large, adsorption and replacement do not occur evenly inside. This is because it takes a long time for adsorption, adsorption and replacement. If the diameter is large, even in the infusibilizing treatment with a high softening point pitch, the infusibilized state becomes non-uniform because oxygen diffusion to the inside is delayed.

As the shaping method, various methods such as crushing, spinning or emulsification can be adopted. In the case of pulverization, since the starting material of the present invention has a low temperature gradient method softening point of 150 ° C. or less, the particles generated may be fused with each other due to the heat generated during pulverization. It is preferable to mill while mixing with gas.

When the softening point of the starting material by the temperature gradient method is sufficiently higher than room temperature, for example, 45 ° C. or higher, spinning can be used. The starting material used in the present invention is BT
Since it does not substantially contain the X-solvent-insoluble matter, melt spinning can be easily carried out by heating it so that its viscosity becomes several hundred to several thousand poises. The spinning method is a long fiber manufacturing method in which a filament is extruded from a nozzle and pulled to make it fine, a centrifugal spinning method in which the pitch extruded from the nozzle is made fine by centrifugal force, and a high-speed gas is flowed immediately below the nozzle. A method such as a melt blow method or a vortex method in which the fibers are finely divided by force can be adopted. The spinning temperature may be higher by about 50 to 70 ° C. than the temperature gradient method softening point of the raw material used, and therefore the temperature gradient method softening point of the low softening point pitch used in the present invention of 45 to 150 ° C. Spinning temperature is 95-220 ℃
Is preferred. Since this temperature range is sufficiently lower than the temperature range in which general organic substances are decomposed and deteriorated in an inert gas, spinning that causes a problem in the spinning process of pitch-based carbon fibers produced from ordinary high softening point pitch Disassembly on board,
Stable spinning can be performed without the phenomenon of alteration and coking.

When the softening point by the temperature gradient method is relatively low, the pitch fibers discharged from the nozzle holes may be fused with each other if they are not sufficiently cooled, but in such a case, Pitch fibers that have come out from the nozzle holes and are finely divided,
It is possible to prevent fusion of fibers by dropping directly into the organic solvent used in the subsequent extraction step of the light component.

Further, the softening point of the temperature gradient method of the starting material is 4
When the temperature is lower than 5 ° C. or is liquid at room temperature, such means as pulverization and spinning cannot be adopted as a shaping method, and emulsification is performed. The application of the emulsification method is not limited to those having the specific properties described above, as will be apparent from the description below, and can be applied to a wide variety of raw materials. Regarding the emulsification method, the present inventors have previously described Japanese Patent Application No. 6-331.
No. 132 disclosed. That is, "the raw material heavy oil is in a liquid state having a viscosity of 1,000 poise or less, but when the raw material heavy oil is not in the state,
State of the raw material heavy oils by means of heating, means of diluting or dissolving with an organic solvent that is incompatible with water and dissolves 90% by weight or more of the raw material heavy oils, or a combination of these means Was prepared in this state and stirred with water in the presence of a surfactant by a stirring method in which a shearing force was applied, and the raw material heavy oil was dispersed in water as fine spherical particles having a diameter of 100 μm or less. It can be shaped by the method of "forming an emulsion".

The characteristic of this method is that heavy oils and pitches are once made into an emulsion state in water, and a shaping method utilizing that heavy oils in an emulsion state become spherical due to their surface tension Is. Further, this prior application also discloses a method for extracting the heavy oils and pitches already in an emulsion state to obtain a high softening point, and therefore, the operation of increasing the softening point by solvent extraction in the next step of the present invention. Is included. For the emulsification, a newly developed film emulsification method can be adopted in addition to the above-mentioned "stirring with shearing force". In this method, glass or ceramics having uniform micron-order pores is used as an emulsion film medium, and water containing a surfactant as a dispersion medium is put into one of the emulsion film media and is circulated or stirred to form an emulsion film medium. This is a method in which heavy oils, pitches, or pitches that are dispersoids are dissolved and diluted in an organic solvent from the opposite side of the medium, and a diluted solution is extruded into water by a pressure difference. When extruded, the dispersoids pass through the uniform pores of the emulsion membrane media and are dispersed in water as particles proportional to the size of the pores, thus obtaining emulsion particles with a very sharp particle size distribution. be able to.

As described above, a particle, powder or fibrous shaped product having a diameter of 100 μm or less can be easily obtained. The shape of the shaped body is too small, for example, a state in which a large amount of fine particles less than 0.1 μ is contained is not preferable in view of the subsequent infusibilization and handling during firing, but the above method The diameter of the shaped body obtained in step 1 is usually 0.1 μm or more.

(Extraction of Light Ingredient) Next, by extracting the light ingredient from the shaped material of the starting material with an organic solvent, it has the properties necessary for the infusibilization to proceed smoothly in the subsequent infusibilization step. , A high softening point pitch with mesopores of sufficiently large pore volume for the adsorption of surfactants is obtained.

Usually, the oxidation starting temperature of pitch produced from petroleum-based cracked heavy oil in an air atmosphere is 140 to 1.
Since the temperature is about 60 ° C., if the softening point of the pitch is lower than this temperature, melting and fusion of the pitch occur and it becomes difficult to make it infusible. Therefore, the softening point of the pitch before infusibilization should be higher than this, at least 150 ° C or higher, preferably 180 ° C.
C. or higher, more preferably 200.degree. C. or higher is required.
Also, if the heating loss of the pitch up to 300 ° C. exceeds 5% by weight, the same melting in the infusible step,
At the same time that the problem of fusion occurs, a large amount of organic matter may volatilize from the pitch, which is not preferable from the viewpoint of safety. Therefore, the heating loss of the pitch before infusibilization to 300 ° C. is required to be 5% by weight or less, preferably 3% by weight or less.

For such a purpose, the light component is extracted from the shaped material of the starting material, but it is necessary that the organic solvent used is capable of leaving at least 10% by weight of the starting material as an insoluble component. If a solvent having a higher solubility is used, the recovery rate of the obtained high softening point pitch decreases, not only the efficiency deteriorates, but also the shape formed with care may collapse, which is not preferable.

Examples of the organic solvent satisfying the above conditions include paraffinic hydrocarbons, ketones and alcohols. Paraffin hydrocarbons include, for example, n-
Pentane, cyclopentane, n-hexane, isohexane, cyclohexane, n-heptane, isooctane, etc.
Examples of ketones include acetone, methyl ethyl ketone (MEK), diethyl ketone, methyl isopropyl ketone, and methyl isobutyl ketone (MIBK), and examples of alcohols include methanol, ethanol, n-.
Propanol, isopropanol (IPA), n-butanol, sec-butanol (SBA), n-pentanol, n-hexanol, cyclohexanol and the like can be mentioned, and these are used alone or in admixture to adjust to an appropriate solubility. Used as a mixed solvent. Furthermore, it is also possible to mix and use these organic solvents with the BTX solvent within the above-mentioned solubility range. According to this method, the dissolving power of the extraction solvent is enhanced, so that the amount of solvent used can be reduced.

When the starting material is shaped by the emulsification method, if a paraffinic hydrocarbon solvent that is incompatible with water is used alone, scum-like substances are formed and separation becomes difficult. In this case, it is preferable to use alcohols and ketones which form a uniform layer with water in the organic solvent.

The method of extracting the light component is not particularly limited, and a generally known method may be adopted.
In the case of the present invention, since the raw material is already shaped to have a diameter of 100 μm or less, for example, the shaped raw material is stirred with an organic solvent, and this is filtered and centrifuged to recover the insoluble matter promptly. To be extracted. The extraction operation is not limited to once, and the extraction and separation operations may be repeated. Further, when a solvent having a high boiling point is used, it takes time to remove the solvent and dry the pitch, so after sufficiently removing the solvent used by a method such as filtration, the solubility is lower than that solvent, and the boiling point is Washing with a low solvent to remove the solvent having a high boiling point and then drying is also a preferable method. During the washing, the light component is further extracted according to the solubility of the low boiling point solvent used.

The amount of solvent to be used may be selected in the range of several times to several tens of times that of the raw material. However, if the amount of solvent used is small, the extracted amount may be limited and the softening point may not be sufficiently high. In addition, when the shaped particles have a small diameter, the fluidity after mixing may be deteriorated and the extraction operation may be hindered. Therefore, a solvent having a weight of about 3 to 30 times is usually used. Is desirable. The temperature at the time of extraction is sufficiently around room temperature, but it is also possible to heat it to increase the solubility. The extraction time is not particularly limited, but several hours or less is usually sufficient.

According to the method of the present invention, by performing the above-mentioned light component extraction operation, it is possible to increase the softening point of the raw shaped material and to form mesopores having a pore diameter of 20 to 500 Å.

The pore volume calculated by the DH method from the adsorption isotherm of nitrogen at the liquid nitrogen temperature, which is useful for forming the mesopores, particularly for supporting the metal, has a pore volume of 100 mm ^3.
The formation condition of mesopores of not less than / g is 20 to 90% by weight, preferably 35 to 90% by weight of the shaped product by the above extraction operation.
It suffices to extract a light component of weight%. However, in the case of the present invention, if the number of extraction is increased, the pore volume does not increase linearly, and if the same solvent is used in the same amount,
There is an extraction frequency that maximizes the pore volume, and the solvent species used does not mean that the higher the solubility, the larger the pore volume. There exists a local maximum. Since the generation state of this mesopore and the size of the pore volume affect the subsequent adsorption amount of the surfactant, and thus the metal substitution amount, the type of solvent, the amount of solvent, and the extraction for efficiently producing the desired mesopore. It is preferable to confirm beforehand the combination of conditions such as the number of times, the washing method, and the drying method by a small-scale test.

As described above, the temperature gradient method softening point is 1
50 ° C or higher, preferably 180 ° C or higher, more preferably 200 ° C or higher, and the weight loss upon heating up to 300 ° C is 5% by weight.
A high softening point pitch having mesopores having a pore volume of 100 mm ³ / g or more, which is preferably 3% by weight or less and has a pore volume calculated by the DH method from the adsorption isotherm of nitrogen at a liquid nitrogen temperature, is easily obtained. be able to.

Regarding the high softening point pitch obtained by this extraction operation, the direct reading surface area measuring device MONOSOR
B (MS-8 type, manufactured by QUANTACHROME) using ASTM method (Draft Proposal 7-18-76, Revision 2)
4-6-81) BET 1-point method specific surface area value (SA (BET), m ² / g) and adsorption isotherm measuring device BE
The adsorption isotherm at the liquid nitrogen temperature was measured using LSORP-28SA type (manufactured by Nippon Bell Co., Ltd.), and the pore volume value calculated by the DH method from this data (DH method, mm ³ /
experimentally, the pore volume (DH method, mm ³ / g) = specific surface area (SA (BET),
A correlation of m ² /g)×(2.0 to 2.3) is recognized. Therefore, the simple method BET
By measuring the 1-point method specific surface area, the approximate value of the pore volume of the obtained high softening point pitch can be known. In addition, the value of the BET one-point method specific surface area satisfying the pore volume of 100 mm ³ / g or more by the above formula or DH method is 44 m ² / g or more,
It means that 50 m ² / g or more is sufficient.

(Loading of Metal) In order to load a metal on a high softening point pitch having mesopores, first, the high softening point pitch is brought into contact with an anionic surfactant, and the high softening point is adsorbed with the anionic surfactant. A point pitch is obtained, and then the highly softened point pitch having the anionic surfactant adsorbed thereon is brought into contact with an aqueous metal salt solution to replace the cation of the surfactant with the metal ion.

Examples of the anionic surfactant include, for example,
Fatty acid salt, alkyl sulfate ester salt, alkyl benzene sulfonate, alkyl naphthalene sulfonate, dialkyl sulfosuccinate ester salt, alkyl phosphate ester salt, alkyl ether sulfate salt, naphthalene sulfonate formalin condensate and alkyl ether phosphate ester salt, etc. Can be given.

As the surfactant, besides the above-mentioned anionic surfactant, there are a cationic surfactant, a nonionic surfactant, a water-soluble polymer and the like. Since the substitution of the metal ion does not occur or is small even if it occurs, when the metal ion (cation) is to be substituted for the purpose of the present invention, the anionic surfactant is adsorbed. Need to be kept.

The method of adsorbing the anionic surfactant on the high softening point pitch can be carried out by adding the high softening point pitch to water in which the anionic surfactant is dissolved and allowing the water to sufficiently adjust by stirring or the like. Can be judged by observing whether or not the total amount of the high softening point pitch is settled when it is allowed to stand. This is because the apparent specific gravity calculated from the true density (about 1.15 g / cm ³ ) of the high softening point pitch with mesopores and the pore volume is 1.0 or less, usually about 0.7. This is because the apparent specific gravity after completely adsorbing the ionic surfactant is 1 or more.

The time required for adsorption depends on the concentration of the anionic surfactant, the method of stirring, etc., but is several hours or less, usually 1 hour or less, and the temperature at this time is high softening point. The pitch is not particularly limited as long as it is equal to or lower than the softening point of the pitch.

The amount of the anionic surfactant is determined by the pore volume of the high softening point pitch used, but in the present invention, it is at most about 30% by weight based on the high softening point pitch,
It is preferable to use a little more than the amount of the high softening point pitch adsorbed. At this time, the surplus surfactant remains in the filtrate obtained by separating the high softening point pitch after adsorption of the surfactant by a method such as filtration, but if the filtrate is circulated and used, the remaining surfactant is regenerated. Since it can be adsorbed to the high softening point pitch, it is not wasted. Further, the concentration of the anionic surfactant aqueous solution has almost no effect on the amount adsorbed on the high softening point pitch, but if the amount of water is too large, the treatment amount increases, and conversely, if the amount of water is small, mixing is performed. Since problems in operation such as improper operation occur, the concentration is usually about 0.1 to 10% by weight, preferably about 0.5 to 5% by weight.

After adsorbing the anionic surfactant,
If necessary, the high softening point pitch is separated from the aqueous solution by a method such as filtration, centrifugation or decantation, and dried.

Next, the high softening point pitch having the anionic surfactant adsorbed thereon is brought into contact with an aqueous solution of a metal salt to replace the cation of the surfactant with the metal ion.

Any metal salt may be used as long as it dissolves in water to generate a metal ion. For example, nitrates, sulfates, chlorides and acetates can be preferably used. The metal species at this time is not particularly limited, and depending on the application of the carbonaceous material, for example, metals such as calcium, barium, cobalt, manganese, iron, nickel, copper and silver can be appropriately selected. Metals are used as the metal salts mentioned above.

The method of contacting the high softening point pitch adsorbing the anionic surfactant with the metal salt is as follows. After adsorbing the surfactant on the high softening point pitch in an aqueous solution, the metal salt is directly added to this mixed solution. Either by adding, or by adding a preliminarily prepared metal salt aqueous solution, separating the high softening point pitch having a surfactant adsorbed by a method such as filtration, and putting it in the preliminarily prepared metal salt aqueous solution. Good.
At this time, the concentration of the metal salt aqueous solution is preferably in the range of 0.01 to 1% by weight as the concentration of metal ions, and it is not necessary to make it more concentrated than necessary. The time required for metal replacement is several hours at the longest, and one hour or less is usually sufficient. After replacing the metal, the solid-liquid is separated by a method such as normal filtration, centrifugation, decantation, etc., washed with water containing no metal ions, and then dried at a temperature lower than the softening point of the high softening point pitch. Is good.

The amount of metal substituted by this operation varies depending on the amount of anionic surfactant adsorbed on the high softening point pitch, the valence and atomic weight of the metal, but is approximately 5 with respect to the high softening point pitch. It is not more than 3% by weight, usually not more than 3% by weight. However, the dispersion of this metal is fine and uniform, so even if the amount of metal is small, it has a significantly large effect on the subsequent infusibilization, carbonization, and graphitization.
In addition, the obtained carbonaceous material will be provided with remarkable properties.

The metal-supported high softening point pitch obtained as described above becomes a new type of carbonaceous material if it is subjected to treatments such as infusibilization, carbonization and graphitization described later.
Since this high softening point pitch itself has moldability and self-sinterability, it can be used as a binder for producing a molded body composed of homogeneous carbon, as will be described later. It can also be used for the compounding with the binder of the carbon material, other carbon materials, ceramics and the like.

(Infusibilization) Next, the metal-supported high softening point pitch is heated to infusibilize in an atmosphere containing oxygen. In this infusibilization treatment, it is preferable to infusibilize the carbonization and graphitization afterwards so that melting and fusion do not occur.

The high softening point pitch obtained by the method of the present invention does not contain BTX solvent insoluble matter as it is, but when this is gradually heated in an atmosphere containing oxygen, for example, in air, 140 to 160 ° C. The increase in weight due to oxidation began to be observed at a certain temperature, and BT
X solvent insoluble matter and quinoline insoluble matter are produced.
At this time, even if the BTX solvent insoluble content is 100% by weight, but the quinoline insoluble content is not yet 100% by weight, the pitch is melted and fused in the subsequent heating process, resulting in a change in shape. Cause problems such as According to the knowledge of the present inventors, the fact that melting or fusion does not occur in the subsequent firing step substantially coincides with the point that the quinoline insoluble content in the infusible material reaches 100% by weight, that is, melting This point corresponds to the minimum condition necessary for infusibilization in order to cause neither fusion nor fusion, and this point also has the highest yield after carbonization (hereinafter, this condition is referred to as optimum infusibilization condition). Therefore, the infusibilization here needs to be processed under the condition of the optimum infusibilization condition or more (hereinafter, this state is referred to as excessive infusibilization).

This infusibilization method is not particularly limited as long as it can be heated in an atmosphere containing oxygen to take in oxygen, but the treatment conditions differ depending on the oxygen concentration in the atmosphere. For example, in the case of an air atmosphere. , Heating rate 0.1
-10 ° C / min, holding temperature 200-400 ° C, holding time 0.1-10 hours are adopted.

In the case of infusibilizing the high softening point pitch carrying a metal, an oxidation promoting effect is clearly recognized, unlike the case where no metal is carried, and depending on the kind of metal, it rapidly burns when heated above a certain temperature. Therefore, care must be taken because there may be a case where almost no infusibilized product remains.

Further, under the above-mentioned optimum infusibilization conditions, the oxygen concentration in the infusibilized product is not yet saturated, and if this is heated under the optimum infusibilization conditions or higher, the recovery rate after infusibilization gradually decreases. However, the oxygen concentration in the infusible substance gradually increases, and becomes saturated at a certain condition or more and becomes a substantially constant value. As will be described later, when the purpose is to effectively form fine pores with a carbonaceous material, such an infusibilized one is preferable.

The infusible substance obtained as described above is unique as a carbonaceous material on which a metal is uniformly supported as described above, and in the state of this infusible substance is compounded with another material. It can be used for such purposes.

Further, by using this infusible material as a filler and using the high softening point pitch obtained in the process of the present invention or the metal having the high softening point pitch supported by the above-mentioned method as a binder, It is possible to obtain a carbonaceous material molded body carrying. At this time, when a high softening point pitch carrying a metal is used as a binder, a molded carbonaceous material is obtained in which both the filler portion and the binder portion are made of homogeneous carbon.

The production of this molded article can be carried out by a method substantially similar to the method for producing a molded article when the present inventors did not carry a metal, which was previously disclosed in Japanese Patent Application No. 8-18327. it can. That is, a metal-supported infusible material is used as a filler, and a high softening point pitch, or a metal-supporting high softening point pitch is used as a binder, and the amount of the binder with respect to the total mixed weight of the filler and the binder is 20 to 70 weight. %, Mixed and kneaded so as to be crushed, and crushed if necessary, and then molded to obtain a molded body having a shortest distance from the central portion to the outer surface of 5 mm or less. A molded body can be obtained by a method in which both the filler portion and the binder portion are infusibilized by the fusion treatment. Furthermore, when carbonization or graphitization of this molded body is necessary, a firing treatment is carried out in the same manner as described below.

(Calcination of Infusible Material) In order to obtain a carbide or a graphitized material, the above infusible material is baked in an inert atmosphere or an oxidizing gas atmosphere. Here, carbonization is 2,000
This means heat treatment at 0 ° C or lower, usually 1,500 ° C or lower, and treatment at 2,000 ° C or higher is called graphitization.

When carbonization is carried out in an inert atmosphere of nitrogen, argon, helium or the like, the temperature is 500 to 2,0.
00 ° C., preferably 500 to 1,500 ° C., time 10 minutes to several hours, and when carried out in an atmosphere containing an oxidizing gas selected from at least one of carbon dioxide and steam, the temperature is 500 to 1, 500 ° C., preferably 600 to 1,000
Heat treatment is performed at 0 ° C. for 10 minutes to several hours. Carburizing in an oxidizing gas atmosphere is for the purpose of activating the carbide to form fine pores having a larger specific surface area, and as the oxidizing gas to be used, other known ones are known. Although there are some, it is preferable to use carbon dioxide or steam from the viewpoints of easy handling, exhaust gas treatment and the like.

In the case where the carbonization treatment is carried out in the temperature range of 600 to 800 ° C. and in the infusibilized state in which oxygen is sufficiently taken in by the infusibilization, 500 to 1,100 ° C. (in the case of an oxidizing gas atmosphere) When it is performed in the temperature range of 600 to 1,000 ° C., most of them form uniform fine pores in the carbide. Therefore, when it is necessary to form fine pores depending on the intended use of the object, carbonization may be performed under the above conditions.

Further, in this carbonization treatment, the activation reaction rate, the amount of generated pores, the pore size, the pore distribution, the specific surface area, etc. are significantly different depending on the supported metal species, and the effect of the metal on the activation reaction behavior is obviously affected. Is recognized. For example, in the case of an infusible material that does not carry a metal, 800 ° C in a carbon dioxide atmosphere
The oxidation reaction rate is slow in the treatment of 1, and a very long treatment time of several hours is required to obtain a large specific surface area, but in the case of calcium-supported one, the oxidation reaction rate is too fast under the same conditions and almost no carbon Since the oxidation progresses to such an extent that no material remains, a more mild carbonaceous material containing a large amount of mesopores of 20 to 500 Å can be obtained under the conditions of 700 ° C. and 40 minutes.

As described above, in the method of the present invention, in the carbonization treatment, the carbonaceous material having various kinds of pores or no pores can be prepared by manipulating the metal to be supported, the infusibilizing condition, the carbonizing condition and the like. Is obtained. Therefore, it can be said that the method of the present invention provides the porosity control method which is required for the carbonaceous material to exhibit a novel function.

When graphitization treatment is carried out after carbonization,
The carbide is fired in the range of 2,000 to 3,000 ° C. under an inert atmosphere of nitrogen, argon, helium or the like.

In this graphitization treatment, the crystal structure of the obtained carbonaceous material is largely changed by the catalytic action of the supported metal. The crystal structure change of the carbonaceous material can be known by, for example, X-ray diffraction, but in the case of the one obtained by making the high softening point pitch in which no metal is supported infusible, and further carbonizing and graphitizing in an inert atmosphere. , The pattern of (002) diffraction line by X-ray diffraction is
A very complex diffraction pattern around 6 ° and a small peak of the ideal graphite structure around 26.5 ° form a complex figure. From this, most of the crystals have low crystallinity and some graphite structure develops slightly. It can be seen that the structure is On the other hand, for example, in the case of manganese-supported, infusibilized, carbonized, and graphitized, the diffraction line around 26 ° was significantly increased, and it was confirmed that the structure was obviously changed to have high crystallinity.

The method of intentionally changing the crystal structure of the thus obtained graphitized product is also an important technique as a method of expressing a novel function, and therefore the method of the present invention is a method for controlling the crystal structure. It can be said to give one way.

By carrying out the method of the present invention as described above, a high softening point pitch having mesopores and a carbonaceous material having a metal supported thereon can be easily and efficiently produced.

[0069]

EXAMPLES The method of the present invention will be described in more detail below with reference to examples and comparative examples, but the scope of the present invention is not limited by these examples. Note that the embodiment,
Unless otherwise specified,% in Comparative Examples means% by weight.

(Example 1) Heavy oil by-produced when naphtha is decomposed to produce olefins (naphtha-decomposed by-product oil)
Was distilled under reduced pressure to obtain a low softening point pitch having a temperature gradient method softening point of 71 ° C. The yield of this product with respect to naphtha cracked by-product oil was 73%. The properties of this pitch were 30% xylene-insoluble matter, 0% quinoline-insoluble matter, and were measured with a thermobalance.
Loss on heating to 0 ° C was 17.9%, elemental analysis value was C92.
9%, H7.0%, S0.02%, H / C atomic ratio 0.9
It was 0.

This pitch was put into a melt spinning machine equipped with a nozzle having a diameter (D) of 0.25 mm and a length (L) of 0.75 mm (L / D ratio of 3), and the spinning temperature was 135 ° C. and the discharge pressure was 5 kg / cm.
^It was discharged at ² · G and taken up by an air sucker installed at the lower part of the nozzle to obtain a low softening point pitch fiber with a diameter of 20μ.

Next, 2 g of this low softening point pitch fiber is shown in Table 1.
The mixture was put in 50 ml of various organic solvents shown in 1 and stirred with a magnetic stirrer for 1 hour. Then, the solution was filtered through a G-4 glass filter to recover the solvent-insoluble matter, which was again put into 50 ml of fresh solvent and stirred for 1 hour. After filtering this with the same filter, it was washed with methanol three times (however, when n-propanol was used, the washing with methanol was not performed), and it was placed in a vacuum dryer and kept at 30 ° C.
For 5 hours. When the obtained product was observed with a scanning electron microscope (SEM), the fiber diameter was almost the same as that before extraction, but it was a fibrous powder cut into lengths of several tens of μm.

Yield of this fibrous powder with respect to low softening point pitch, temperature gradient method softening point, direct reading surface area measuring device MO
NOSORB (MS-8 type, QUANTACHROME
Manufactured by the company, using the ASTM method (Draft Proposal 7-18-76,
Specific surface area (BET 1-point method specific surface area, determined from nitrogen adsorption amount at liquid nitrogen temperature according to Revision 2 4-6-81)
SA (BET) is shown in Table 1.

The properties of the high softening point pitch obtained by using n-pentanol as the extraction solvent were as follows: xylene insoluble content 0%, quinoline insoluble content 0%, heating loss up to 300 ° C. 2.1%, elemental analysis value was C92. 0.8%, H7.1%, S0.03%,
The H / C atomic ratio was 0.91. Moreover, about this thing, the result of having measured the adsorption isotherm in liquid nitrogen temperature using the adsorption isotherm measuring device BELSORP-28SA type (made by Nippon Bell Co., Ltd.) is shown in FIG.
The pore distribution curve and the pore volume integral curve analyzed by the Heal method (DH method) are shown in FIGS. 2 and 3, respectively. In FIG. 1, the horizontal axis represents the relative pressure at the time of measurement (P / Ps, P: adsorption equilibrium pressure of nitrogen at the measurement temperature, Ps: saturated vapor pressure of nitrogen at the measurement temperature), and the vertical axis represents the adsorption capacity of nitrogen at the liquid nitrogen temperature. (Ml / g), Fig. 2 shows the pore radius (nm unit, pore diameter (Å unit) is 20 times this value) on the horizontal axis, and the differential value of the pore volume on the vertical axis. In Fig. 3, the horizontal axis shows the pore radius (nm unit),
The vertical axis is the integrated value of pore volume (mm ³ / g).

From FIG. 2, the high softening point pitch fiber obtained by using n-pentanol has a pore radius of 2 to 20 nm (pore diameter 40 to 400Å) and a central pore radius of about 6 to 7 nm (central pore). The existence of mesopores with a diameter of 120 to 140Å),
Further, it can be seen from FIG. 3 that the pore volume is 504 mm ³ / g.

Further, the values of the pore volumes measured in the same manner for the cases using other solvents are also shown in Table 1.

From the same table, when the light component of about 20% or more is extracted and removed by the method of the present invention with the organic solvent,
It can be seen that a high softening point pitch having a mesopore having a pore volume of 100 mm ³ / g or more and a softening point of 150 ° C. or more can be obtained.

It should be noted that, between the specific surface area of the obtained high softening point pitch and the pore volume, it is approximately experimentally that the pore volume (DH method, mm ³ / g) = specific surface area (SA (BET),
It can be seen that the correlation of m ² /g)×(2.0 to 2.3) is recognized (hereinafter, the above formula is referred to as “empirical formula”).

[0079]

[Table 1]

(Example 2) The same naphtha cracked by-product oil as in Example 1 was distilled to obtain a low softening point pitch with a temperature gradient method softening point of 49 ° C. Xylene 3 is added to 70 parts by weight of this low softening point pitch.
0 parts by weight was mixed and dissolved to prepare a solution having a low softening point pitch.

Next, using a water containing 2% of a nonionic surfactant (polyoxyethylene nonylphenyl ether, Emulgen 985 manufactured by Kao Corporation) as a dispersion medium, a membrane emulsification tester (manufactured by Ise Chemical Co., Ltd.). Using a microporous glass with a pore size of 4μ as a dispersion medium, the solution with a low softening point pitch is extruded into the dispersion medium through this dispersion medium to give a low softening point pitch solution in water at 11% by volume.
A dispersed so-called O / W emulsion was obtained.

Next, this emulsion was mixed with 10 times the volume of S.
The mixture was gradually added dropwise to BA with stirring to extract the soluble component in the low softening point pitch and the xylene used for dissolution. The mixture was centrifuged to collect the solid content, washed with methanol, and dried under reduced pressure at 60 ° C. The yield of this product with respect to the low softening point pitch was 53%.

Further, this solid content was put in 20 times by weight of n-pentanol, stirred, filtered, washed with methanol and dried to obtain a high softening point pitch of 48% with respect to a low softening point pitch. Spherical particles were obtained.

The high softening point pitch obtained by shaping by this emulsification method and extracting the light component has an average particle diameter of 16 μ, and its properties are a temperature gradient method softening point of 243 ° C.,
Xylene insoluble content 0%, quinoline insoluble content 0%, heating loss up to 300 ° C 1.7%, elemental analysis value is C92.7%, H
7.1%, S0.02%, H / C atomic ratio 0.92, BE
The specific surface area measured by the T1 point method was 187 m ² / g. Also,
From the value of the specific surface area, the pore volume obtained by the empirical formula is 374 to 430 mm ³ / g.

Example 3 100 g of the same naphtha-decomposed by-product oil as in Example 1 was heated to 80 ° C. and 5,000 rp.
A non-ionic surfactant (Emulgen 985, manufactured by Kao Corporation) was stirred with a homogenizer rotating at m (KINEMATICA, POLYTORON) 10
g was added. After sufficiently stirring and mixing, 300 ml of ion-exchanged water was gradually added to this to obtain a yellow emulsion in which naphtha-decomposed byproduct oil was dispersed as fine particles.

Next, this emulsion and SBA / ME
K = 80/20 (volume ratio) and a mixed solvent are mixed by continuously dropping the mixture in a mixing tank equipped with a stirrer so that the weight ratio becomes 1:10 by different pumps, The light components and water in the raw material were extracted. The solid content was recovered by centrifuging the mixture, and the solid content thus obtained was recovered by 10 times.
After extracting with a double weight of SBA / MEK mixed solvent and centrifuging, the obtained solid content is washed with methanol three times, and the temperature is 60 ° C.
And dried under reduced pressure.

By the above operation, a spherical high softening point pitch was obtained with a yield of 25% based on the raw material naphtha cracked by-product oil, and the properties thereof were as follows: temperature gradient method softening point 242 ° C., average particle size about The specific surface area according to the BET1 method was 3 m, and the specific surface area was 152 m ² / g. The pore volume calculated from this specific surface area by an empirical formula is 304 to 350 mm ³ / g.

Example 4 2 g of high softening point pitch obtained by using n-pentanol as an extraction solvent in Example 1 and commercially available anionic surfactants shown in Table 2 were used.
Was added to a solution dissolved in 50 ml of ion-exchanged water so that the mixture was sufficiently stirred for 1 hour or more. After that, the whole amount is G-4
Suction filtration with a glass filter, and the resulting pitch is 60
It was dried under reduced pressure at 5 ° C for 5 hours.

The weight of the pitch after drying was measured, the recovery rate for the pitch before the treatment was determined, and the results are shown in Table 2.

From the table, it can be seen that the high softening point pitch after the adsorption treatment of the surfactant showed a weight increase of 13 to 23% depending on the kind of the surfactant used. It can be seen that a high softening point pitch with the agent adsorbed is obtained.

[0091]

[Table 2]

Example 5 A solution prepared in the same manner as in Example 4 using sodium dodecylbenzenesulfonate (hard type) as an anionic surfactant was added with n-pentanol in Example 1. 2 g of the high softening point pitch obtained as an extraction solvent was added and sufficiently stirred for 1 hour or more to adsorb the surfactant on the high softening point pitch. Next, in this mixed solution,
The aqueous solutions of various metal salts shown in Table 3 were added so that the metal salt concentration was twice the molar amount of the surfactant present in the system, and the mixture was stirred for 1 hour. Then, the whole amount was filtered with a G-4 glass filter and dried under reduced pressure at 60 ° C. for 5 hours to recover a high softening point pitch.

With respect to the obtained product, the recovery rate for the high softening point pitch before adsorption of the surfactant, the metal content and the sulfur content by an X-ray fluorescence analyzer were measured,
The results are shown in Table 3.

From the table, according to the method of the present invention, by replacing the cation of the surfactant adsorbed on the high softening point pitch having mesopores with a metal ion, the metal having a high softening point can be easily supported. It can be seen that the pitch can be obtained.

[0095]

[Table 3]

Comparative Example 1 Acetic acid was prepared in the same manner as in Example 5 except that polyoxyethylene nonylphenyl ether (Emulgen 985, manufactured by Kao Corporation), which is a nonionic surfactant, was used as the surfactant. Metal loading with calcium monohydrate was performed.

With respect to the obtained product, the recovery rate with respect to the high softening point pitch before adsorption of the surfactant and the result of measuring the metal content by the fluorescent X-ray analyzer are respectively as follows.
It is 116% and 0.06%. Therefore, when this nonionic surfactant is used, the surfactant is adsorbed, but the substitution of metal ion hardly occurs, and the amount of metal supported is anion. It can be seen that the amount is much smaller than when the system surfactant is used.

Example 6 A predetermined amount of cobalt acetate was dissolved in 25 to 400 ml of ion-exchanged water to prepare an aqueous solution having a cobalt ion concentration of 0.006 to 0.224%. To this aqueous solution, 2 g of a high softening point pitch having sodium dodecylbenzenesulfonate (hard type) adsorbed therein obtained in the same manner as in Example 4 was added and stirred for 30 minutes. afterwards,
The whole amount was filtered with a G-4 glass filter, sufficiently sucked until no liquid came out, and dried under reduced pressure at 60 ° C.

The cobalt content of the obtained product was measured by fluorescent X-ray analysis, and the results are shown in Table 4.

From the table, it is possible to obtain a metal-supported high softening point pitch also by a method of adding a high softening point pitch in which an anionic surfactant is adsorbed to an aqueous solution of a metal salt.
And, the amount of metal supported at this time is influenced by the amount of metal ions present in the system rather than the concentration of the metal salt aqueous solution, and in the case of the present embodiment, the amount of metal ions with respect to the high softening point pitch is 1.2%. It can be seen that the amount of metal carried is almost constant if the above is satisfied.

[0101]

[Table 4]

Example 7 A metal obtained by using ferrous sulfate heptahydrate, cobalt acetate, manganese acetate tetrahydrate and calcium acetate monohydrate in the same manner as in Example 5 was loaded. The high softening point pitch was set to 0.
Heat at a predetermined temperature of 245 to 365 ° C at 5 ° C / min,
It was made infusible by holding at this temperature for 1 hour. Then, the infusible material was heated in a nitrogen atmosphere at a temperature rising rate of 10 ° C / mi.
Carbonization was carried out by heating to 1,000 ° C. with n and holding at this temperature for 1 hour.

For each of the obtained carbonaceous materials,
The infusibilization with respect to the metal-supported high softening point pitch, the yield after the carbonization treatment, the specific surface area of the carbide by the BET 1-point method, and the metal content of the carbide by the fluorescent X-ray analysis were measured, and the results are shown in Table 5.

From the table, there is a temperature range in which the supported metal causes a rapid combustion state during infusibilization and the yield is remarkably reduced, and the specific surface area of the carbide is different depending on the supported metal. It can be seen that the loading of the carbon has a significant effect on the behavior during infusibilization and carbonization.

Also, the adsorption isotherms measured in the same manner as in Example 1 for cobalt and manganese-supported infusibilized materials at 345 ° C. and carbonized at 1,000 ° C. are shown in FIGS. 4 and 5, respectively. Shown in. From these figures, the relative pressure (P / Ps) when measuring cobalt bearing
Although most of the adsorption occurs at a small value, the adsorption of manganese shows a gentle adsorption over a wide range, and it can be seen that the state of pore formation obviously differs depending on the loaded metal species.

Further, the state of dispersion of metallic cobalt was observed by observing the backscattered electron image of a scanning electron microscope (SEM) with respect to the material which carried cobalt and was made infusible at 345 ° C and carbonized at 1,000 ° C. FIG. 6 shows the result of observing the cut surface of the fibrous sample in the direction perpendicular to the fiber axis. From the figure,
It can be seen that the metallic cobalt is sufficiently diffused into the inside of the fiber and is not attached only to the outer peripheral portion of the fiber.

[0107]

[Table 5]

(Example 8) The high softening point pitch supporting cobalt, manganese, nickel and copper and the high softening point pitch not supporting metal obtained by the same method as in Example 5 were heated in air. The mixture is heated to 340 ° C. at a rate of 0.5 ° C./min and kept at this temperature for 1 hour to make it infusible. Carbonization was carried out by heating to 0 ° C and holding at this temperature for 1 hour.

For each of the obtained carbonaceous materials,
The yield for high softening point pitch and the specific surface area by the BET 1-point method were measured, and the results are shown in Table 6.

From the table, when carbonized in an oxidizing atmosphere, a carbonaceous material having fine pores having a larger specific surface area than in an inert atmosphere can be obtained, and the activation reaction rate varies depending on the supported metal species. Therefore, it is understood that the values of yield and specific surface area are also different.

[0111]

[Table 6]

Example 9 Cobalt- and manganese-supported high softening point pitches and metal-free high softening point pitches obtained in the same manner as in Example 5 were subjected to air
It is made infusible by heating to 340 ° C. at a temperature rising rate of 0.5 ° C./min and holding at this temperature for 1 hour, and then this infusible substance is heated to 1,000 ° C. and 2,000 ° C. in a nitrogen atmosphere.
And a temperature of 2,700 ° C. for 1 hour.

The X-ray diffraction (002) diffraction line profiles of the obtained carbonaceous material (carbide or graphitized product) are shown in FIGS. 7, 8 and 9.

From these figures, it can be seen that the one that does not support metal (FIG. 7) is (002) even after the high temperature treatment of 2,700 ° C.
The diffraction line is a complex figure of a very broad diffraction line near a diffraction angle of 26 ° and a small diffraction line around 26.5 ° (corresponding to a graphite crystal), that is, the crystallinity is low as a whole. Although it is carbon, it has cobalt and manganese supported (FIGS. 8 and 9), but at 2,000 ° C.
Also, it can be seen that the graphitized product fired at 2,700 ° C. has a remarkably large diffraction line in the vicinity of 26 ° and has a structure with a clearly high degree of crystallinity.

(Example 10) Calcium-supported infusible substance obtained by the same method as in Example 7 (infusible temperature 345)
C.) 2.5 g of a high softening point pitch supporting calcium obtained in the same manner as in Example 5 was mixed, and 3 ml of xylene was added to this to sufficiently knead while dissolving the high softening point pitch. After that, xylene was removed by vacuum drying at 60 ° C. to obtain a molding raw material. After the total amount was crushed to 35 mesh or less in a mortar, 0.2 g of this molding raw material was put into a mold having a diameter of 13 mm and pressure-molded at a pressing pressure of 500 Kg / cm ² · G.
The obtained molded product has a thickness of 1.35 mm and a bulk density of 1.10 g /
It was cm ^3.

Next, this molded body was made infusible by raising the temperature to 100 ° C. in 1 hour in air, then to 255 ° C. in 5 hours and 10 minutes, and holding at 255 ° C. for 1 hour. The obtained infusibilized molded product had a yield of 91% and a bulk density of 1.27 g / cm ³ with respect to the infusibilized product.

Further, the infusible substance was carbonized by heating it to 1,000 ° C. at a temperature rising rate of 10 ° C./min in a nitrogen atmosphere and holding at this temperature for 1 hour. The obtained calcium carbide-supported molded body had a yield of 56% based on the infusibilized product and a bulk density of 0.776 g / cm ³ , and had sufficient strength so as not to be crushed by fingertips.

[0118]

According to the method of the present invention, a novel high softening point pitch having mesopores can be easily produced from a heavy oil or an inexpensive starting material such as a low softening point pitch obtained from the heavy oil. Further, by supporting a metal on the high softening point pitch, a carbonaceous material useful for exhibiting new functionality can be obtained industrially simply, efficiently, and by a stable method.

Further, in the method of the present invention, since the high softening point pitch having mesopores obtained by first shaping the starting material and solvent-extracting under specific conditions is used, a conventional high softening point pitch is produced. At the same time, it is possible to avoid the economic and technical problems that have become a problem at the same time, and it is possible to obtain a carbonaceous material in which a metal is uniformly dispersed without using an oxidizing agent such as nitric acid. Furthermore, in the method of the present invention, it is possible to control the pores and the crystal structure of the carbonaceous material by selecting the treatment conditions, the metal species and the like.

[Brief description of drawings]

FIG. 1 is an adsorption isotherm of high softening point pitch having mesopores obtained by using n-pentanol as an extraction solvent in Example 1.

2 is a pore distribution curve (DH method) of high softening point pitch having mesopores obtained by using n-pentanol as an extraction solvent in Example 1. FIG. The symbol "Rp" means the maximum radius.

FIG. 3 is a pore volume integral curve (DH method) of high softening point pitch having mesopores obtained by using n-pentanol as an extraction solvent in Example 1. The symbol "Rp" means the maximum radius.

FIG. 4 is an adsorption isotherm of a carbonaceous material in which cobalt was carried, infusibilized at 345 ° C., and carbonized at 1,000 ° C. in Example 7.

FIG. 5 is an adsorption isotherm of a carbonaceous material in which manganese was supported, infusibilized at 345 ° C., and carbonized at 1,000 ° C. in Example 7.

FIG. 6 is an observation result of a metal dispersed state by a SEM backscattered electron image of a carbonaceous material in which cobalt was carried, infusibilized at 345 ° C., and carbonized at 1,000 ° C. in Example 7. The white point in the figure is the reflected light of the metal.

FIG. 7 is an X-ray diffraction profile of a carbonaceous material graphitized without supporting a metal in Example 9.

FIG. 8 is an X-ray diffraction profile of a carbonaceous material supporting cobalt in Example 9 and graphitized.

9 is an X-ray diffraction profile of a carbonaceous material supporting manganese and graphitized in Example 9. FIG.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C10C 3/08 B01J 27/053 Z // B01J 27/053 27/122 Z 27/122 27/25 Z 27/25 31/04 Z 31/04 32/00 32/00 C04B 35/52 C 35/54 C

Claims (12)

[Claims] 1. A heavy oil having an H / C atomic ratio in the range of 0.8 to 1.2 and containing substantially no BTX solvent-insoluble matter, or a light component is distilled off from the heavy oil. The resulting low softening point pitch is used as a starting material, and particles having a diameter of 100 μm or less are used as the starting material.
Forming a powder or fibrous form into a shaped body, and contacting this shaped body with an organic solvent capable of leaving at least 10% by weight of it as an insoluble matter, and extracting 20 to 90% by weight of a light component of the shaped body. The temperature gradient method has a softening point of 150 ° C or higher and a weight loss by heating up to 300 ° C is 5% by weight.
A method for producing a high softening point pitch having mesopores having a pore volume of 100 mm ³ / g or more, which is as follows and has a pore volume calculated by the Dollimore-Heal method from an adsorption isotherm of nitrogen at a liquid nitrogen temperature. 2. The production method according to claim 1, wherein the method of shaping the starting material is pulverization, melt spinning or emulsification. 3. The production method according to claim 2, wherein the method of shaping the starting material is pulverization, melt spinning or membrane emulsification. 4. At least a heavy oil by-produced when naphtha or gas oil is pyrolyzed to produce olefins, or a heavy oil by-produced when fluidized catalytic cracking a petroleum fraction is used. The method according to any one of claims 1 to 3, wherein one kind of petroleum-based cracked heavy oil is used as a starting material. 5. An organic solvent for extracting a light component from a shaped material of a starting material is paraffin hydrocarbons, alcohols, ketones, or a mixed solvent obtained by mixing these.
Alternatively, the production method according to any one of claims 1 to 3, which is a mixed solvent of these and a BTX solvent. 6. The organic solvent is n-pentane, cyclopentane, n-hexane, isohexane, cyclohexane, n-heptane, isooctane, methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, n. -Pentanol, n-
The production method according to claim 5, which is at least one selected from hexanol, cyclohexanol, acetone, methyl ethyl ketone, diethyl ketone, methyl isopropyl ketone, and methyl isobutyl ketone, or a mixed solvent of these and a BTX solvent. 7. The high softening point pitch according to claim 1 is brought into contact with an anionic surfactant to obtain a high softening point pitch having an anionic surfactant adsorbed, and the anionic surfactant is A method for producing a metal-supported high softening point pitch, which comprises contacting the adsorbed high softening point pitch with an aqueous metal salt solution to replace the cations of the surfactant with the metal ion. 8. A metal-supported carbonaceous infusible product, characterized in that the metal-supported high softening point pitch according to claim 7 is heated in an atmosphere containing oxygen for infusibilization treatment. Method. 9. The infusible material according to claim 8 is heat-treated in an inert atmosphere at a temperature range of 500 to 3,000 ° C., or at least one oxidizing gas selected from steam and carbon dioxide gas is used. 500 to 1,500 in an atmosphere containing
A method for producing a carbonaceous material supporting a metal, which comprises performing heat treatment in a temperature range of ° C. 10. The high softening point pitch according to claim 1, or the infusible material according to claim 8 as a filler.
Using a metal having a high softening point pitch as a binder as described above, a molded body is formed by molding, infusibilizing, carbonizing or graphitizing the metal-containing carbonaceous material molded body Production method. 11. The carbon according to claim 10, wherein the binder used is the high softening point pitch carrying the metal according to claim 7, and the obtained carbonaceous material molded body is a molded body composed of homogeneous carbon. Method for manufacturing quality material molded body. 12. The method according to claim 7, wherein the metal salt used is a sulfate salt, a nitrate salt, a chloride salt or an acetate salt that produces a metal ion when dissolved in water.