JPH05320662A - Production of carbonaceous gel, its molding or carbonized or graphitized molding, and carbonaceous gel - Google Patents

Abstract

PURPOSE:To make the concentration of a hydrophilic bituminous material in a solution higher than that attained by the conventional process to thereby obtain efficiently a carbonaceous gel by subjecting a carbonaceous bituminous material to a treatment such as oxidation to convert it into a hydrophilic bituminous material containing functional groups determined according to the treatment, dissolving the hydrophilic material in a specified organic solvent and allowing the solution to gel as such. CONSTITUTION:A carbonaceous bituminous material is subjected to a treatment selected from among nitration, sulfonation, amination and a combination of at least two of them to obtain a hydrophilic bituminous material soluble in an organic solvent. This material is dissolved in an organic solvent having a dispersion solubility parameter of 8.0-10.0, a polar solubility parameter of 3.5-15.0 and a hydrogen bond solubility parameter of 2.5-15.0, and the resulting solution is allowed to gel as such to form a gel-like substance containing a large amount of the organic solvent. When this substance shows desired flow as its gelation progresses, it is molded in a desired shape and further allowed to gel into a solid, and this solid is dried to obtain a molding. This molding is further carbonized or graphitized to obtain a carbonized or graphitized product.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel gelled carbonaceous material using a carbonaceous bituminous material as a raw material, a carbonized gelled material molded product using the same, and a method for producing carbonized or graphitized products thereof. Furthermore, the present invention relates to a carbonaceous gelled substance itself, that is, to a novel carbonaceous material obtained by a completely different method from the conventional one.

[0002]

2. Description of the Related Art Heavy oil or pitch obtained by distilling and thermally decomposing heavy oil such as coal tar, asphalt, catalytic cracking residual oil of petroleum, mesophase pitch obtained by refining and heat treating these, mesophase Mesocarbon microbeads extracted as a solvent-insoluble matter from pitch, bulk mesophase showing the anisotropy of the whole obtained by further heat-treating mesophase pitch or the above heavy oil, raw coke obtained by heat-treating pitch, etc., Furthermore, carbonaceous bituminous materials, such as coal, are used for steelmaking electrodes,
It has been widely used as a raw material for binder pitch, blast furnace coke, and various graphite materials.

From these carbonaceous bituminous materials to various carbonaceous materials,
Research to manufacture graphite materials has been carried out for a long time, but it is an accumulation of empirical technology based on the knowledge obtained from appearance phenomena in the old days, and it is occurring inside carbonaceous bituminous matter. It was not to analyze reactions and behaviors and control them. However, the existence of the mesophase, which was clarified in the latter half of the 1960s, provides a clue to elucidate the reactions and behaviors that occur in these manufacturing processes, and the subsequent research is based on a mere accumulation of empirical techniques. It is no exaggeration to say that it has changed to a systematic study based on analysis of behaviors.

In recent years, it has become possible to produce high performance carbon fibers from mesophase pitch, and in order to obtain a suitable pitch for carbon fibers, how to control the structure and properties is important. It has become known to be the key. In addition, it was revealed that the mesocarbon microbeads collected from the mesophase pitch by solvent fractionation have the same reactivity as ordinary organic substances, and the separation ability as a packing material for liquid chromatography. The recognition that materials are materials with various functionalities is spreading.

Under such circumstances, control of the microscopic properties of carbonaceous or graphitic materials, which has been focused only on the recognition of macroscopic properties through the accumulation of empirical techniques and the handling as a solid, The research from a new aspect such as reaction analysis as a molecule has been actively conducted, and its application field is about to expand greatly as a new functional material.

However, the carbonaceous bituminous substances as described above are often solid at room temperature, and are solid when trying to carry out a certain reaction or when realizing a special shape or function. That was an obstacle. Usually, a method of heating to a molten state or dissolving it with an organic solvent has been adopted, but it has a very high softening point such as mesophase pitch, and is insoluble in solvents such as benzene and toluene. If you have a large amount of ingredients,
Operations that can be carried out in the state of being melted by heating, problems that the reaction is limited, and solvents such as benzene and toluene cannot be used, and highly soluble polar solvents such as pyridine and quinoline must be used. Therefore, in this case, there is a problem that the intended operation may not be carried out because the solvent is expensive or highly reactive.

As one of the attempts to solve such problems and to develop new utilization by treating carbonaceous bituminous substances by a completely different method, the method disclosed in JP-A-64-9288 is proposed. ing. In this method, when a functional group is introduced into the carbonaceous mesophase by nitration, sulfonation, amination, or oxidation reaction with nitric oxide, hydrogen peroxide, etc., part or all of the mesophase having this functional group becomes an alkaline solution. It is used to be soluble, and after dissolving the mesophase having a functional group in an alkaline solution, the insoluble matter is separated by filtration, and an acid is added to the alkaline solution of the soluble matter to make it acidic. It is a method of precipitating and recovering mesophase having a group. This method is a significant method in that it solubilizes a carbonaceous material that was not previously dissolved in a solvent such as water or alcohol into a solvent such as water or alcohol, and develops a new field of application of the carbonaceous material. It can be said to be one of the effective methods for doing this.

There is also an attempt to produce a new material by introducing the functional group into the carbonaceous mesophase and utilizing the property thereof, as disclosed in JP-A-63-139080 and JP-A-64-9.
No. 808 and JP-A-2-88414 propose a method for producing an elastic graphite body from a carbonaceous mesophase.
In these methods, the carbonaceous mesophase is oxidized with nitric acid, sulfuric acid or the like to introduce a functional group, and then the
When heated to a temperature of 400 ° C., the carbonaceous mesophase is remarkably foamed when the introduced functional group is decomposed and desorbed, and graphitization of this produces a highly elastic graphite material.

[0009]

The above-mentioned bank proposal is an effective method for utilizing carbonaceous bituminous material in a method different from the conventional one, but in the case of the method of Japanese Patent Laid-Open No. 64-9288. Is obtained by a method in which an acid is added to precipitate from a solution dissolved in an alkaline solution to cause precipitation, and although the particle size to be precipitated is small, it is still a solid. Limited to handling. Similarly, in each of the methods of JP-A-63-139080, JP-A-64-9808 and JP-A-2-88414, the product obtained by introducing a functional group is a solid and has a special shape. If you try to make something, you will also be limited to being solid.

The inventors of the present invention have also conducted research on the reaction of the new carbonaceous bituminous material and the method of utilizing the same, but it is to make it possible to handle the carbonaceous bituminous material or the reaction product in a free shape. Effectively utilize these reactions,
We have come to realize that it is extremely important for manufacturing new materials.

The inventors of the present invention have studied the oxidation reaction of the carbonaceous bituminous material and the properties of the alkali-soluble component obtained from the oxidation reaction of the carbonaceous bituminous material while proceeding with the research on the new utilization method of the carbonaceous bituminous material. In case of accident, the oxidized carbonaceous bituminous material is dissolved in an alkaline solution, and if this alkaline solution is left to stand, the solution viscosity increases with time, and finally it loses fluidity and becomes agar-like. I encountered the phenomenon of solidification. This indicates that the oxidized carbonaceous bituminous material has undergone some reaction in an alkaline solution and changed. JP-A 64-9288
The method of No. was to reprecipitate by adding an acid to a solution dissolved in an alkaline solution to obtain a solid powder, whereas the reaction occurs in the alkaline solution and solidifies at all. It was a new finding.

Further, the solidified product in this way is in a state of containing a large amount of the solvent (water or alcohol etc.) of the used alkaline solution, and when it is heated, it becomes fluid but is cooled. Then, it was recognized that it showed a reversible change of solidifying again. That is, it was considered that the sol-gel state was a fluid sol state at a high temperature, and was a kind of sol-gel state in which a gel state was lost with a large amount of solvent contained at a low temperature. Conventionally, gels of inorganic substances such as silica gel and alumina gel, polymer gels, and gels such as agar and gelatin have been known, but carbonaceous gels have not been known at all. Therefore, as a result of diligent studies on the phenomenon by the present inventors,
By effectively utilizing this gelling reaction and its process, it is possible to obtain a carbonaceous gelled substance which has never been obtained, and also to manufacture a new material by utilizing this carbonaceous gelled substance. Find what you can do,
I proposed this method earlier (Japanese Patent Application No. 3-258462).
issue).

However, when a carbonaceous gelled product is prepared using an alkaline solution as a solvent, the oxidized carbonaceous bituminous material (that is, hydrophilic bituminous material) to the alkaline solution is used.
Dissolved concentration of 1 to 20 wt% (preferably 1 to 15%)
Therefore, when the dissolved concentration is higher than this, the hydrophilic bituminous material is not completely melted and becomes a non-uniform gelled body.

Therefore, as a result of further diligent investigations by the present inventors on a method for producing a gelled product having a high concentration of hydrophilic bituminous material in a solution, when an organic solvent having a specific solubility parameter is used, The present invention has been completed by finding that an organic solvent solution of a highly concentrated hydrophilic bituminous material can be prepared, and that this solution gels as in the case of using an alkaline solution.

Therefore, in the present invention, in the method for producing a carbonaceous gelled product, the concentration of the hydrophilic bituminous material in the solution is remarkably increased to efficiently produce the carbonaceous gelled product. The purpose is to do.

[0016]

That is, the gist of the first invention is that a carbonaceous bituminous material can be treated with an organic solvent by oxidation, nitration, sulfonation, amination or a combination of at least two of these. A soluble hydrophilic bituminous material was used, and this had a dispersion dissolution parameter of 8.0 to 10.
0, the polar solubility parameter is 3.5 to 15.0,
In addition, the carbon is characterized by being a gel-like substance containing a large amount of an organic solvent by being dissolved in an organic solvent having a hydrogen bond solubility parameter of 2.5 to 15.0 and then undergoing a gelation reaction as a solution. It exists in the manufacturing method of a gelled substance.

Further, the gist of the second invention is that a hydrophilic bituminous material soluble in an organic solvent is obtained by subjecting a carbonaceous bituminous material to oxidation, nitration, sulfonation, amination or a combination of at least two of these. As a material, an organic solvent having a dispersion solubility parameter of 8.0 to 10.0, a polar solubility parameter of 3.5 to 15.0, and a hydrogen bond solubility parameter of 2.5 to 15.0 is used as a material. After dissolution
A gelling reaction is caused by reacting the solution as it is, and when it becomes a desired fluidity, it is molded into a desired shape,
Further, the present invention resides in a method for producing a carbonaceous gelled product, which comprises advancing a gelling reaction to solidify and drying the solidified product.

Further, the gist of the third invention is that a hydrophilic bituminous material soluble in an organic solvent is obtained by treating a carbonaceous bituminous material with oxidation, nitration, sulfonation, amination or a combination of at least two of these. As a material, an organic solvent having a dispersion solubility parameter of 8.0 to 10.0, a polar solubility parameter of 3.5 to 15.0, and a hydrogen bond solubility parameter of 2.5 to 15.0 is used as a material. After the solution is dissolved, the solution is reacted as it is to cause a gelation reaction, and when it becomes a desired fluidity, it is molded into a desired shape, and the gelation reaction is further proceeded to solidify, followed by drying the carbon. A method for producing a carbonized or graphitized product of a carbonaceous gelled body molded article, which is characterized in that the molded article is a carbonized gelled article, which is further carbonized or carbonized and graphitized.

A fourth aspect of the invention is a hydrophilic bituminous material soluble in an organic solvent, which is obtained by oxidizing, nitrating, sulfonation, aminating a carbonaceous bituminous material or a combination of at least two of these. And dissolved in an organic solvent having a dispersion solubility parameter of 8.0 to 10.0, a polar solubility parameter of 3.5 to 15.0, and a hydrogen bond solubility parameter of 2.5 to 15.0. rear,
The present invention resides in a gelled carbonaceous material characterized by being a gelled substance containing a large amount of an organic solvent, which is solidified by causing a gelling reaction by reacting the solution as it is.

More specifically, the present invention will be described in detail. The raw material carbonaceous bituminous materials used in the present invention include coal tar by-produced during coal carbonization, asphalt, which is a vacuum residue of petroleum, and catalytic cracking of petroleum. Decant oil, which is residual oil,
Isotropic pitch obtained by distilling and pyrolyzing heavy oil such as naphtha tar, which is a by-product of naphtha cracking, and pyrolysis tar, which is a by-product when pyrolyzing light oil fractions of petroleum, and this isotropic pitch. Mesophase pitch obtained by refining and heat treatment, mesocarbon microbeads extracted from the mesophase pitch as solvent-insoluble matter, bulk mesophase showing front anisotropy obtained by heat treatment of the mesophase pitch, the above heavy oil, pitch Coke obtained by heat-treating etc., pitch-like products obtained by thermally decomposing polyvinyl chloride (PVC), etc., and polycyclic aromatic compounds such as naphthalene, anthracene, etc. are polymerized in the presence of a catalyst. Pitch-like substances, and further those having a condensed polycyclic aromatic molecule such as coal or lignin as a main constituent component can be used, and generally, carbon is used. It can be used which is used as a raw material of the material.

The carbonaceous bituminous material used as a raw material in the present invention is first treated by oxidation, nitration, sulfonation or amination, or a treatment in which at least two of them are combined (hereinafter, these treatments are collectively referred to as "oxidation"). Processing, etc. "
Is introduced, and functional groups such as a nitro group, a sulfone group, a carbonyl group, a carboxyl group, a hydroxyl group, and an amino group are introduced depending on the treatment. In addition to being soluble in the specific organic solvent specified in, it is also hydrophilic, so it is referred to as "hydrophilic bituminous material.") If a light component is present in the carbonaceous bituminous material, oxidation treatment, etc. In this case, it is not preferable because it dissolves in a medium used for volatilization, decomposition or oxidation treatment and reduces the recovery rate of the hydrophilic bituminous material, and therefore the carbonaceous bituminous material usually has a boiling point of 300 ° C or higher. ,
It is preferable to use one having a softening point of 100 ° C. or higher.

Further, the carbonaceous bituminous material used as a raw material in the present invention includes raw coke obtained by heating heavy oil, pitch, etc. as described above. In some cases, the carbonization reaction proceeds too much and loses its activity as an organic substance, making it difficult to introduce a functional group during oxidation treatment or the like. Therefore, the carbonaceous bituminous material used in the present invention is required to have activity as an organic substance capable of sufficiently introducing a functional group by an oxidation treatment or the like, and usually the content of hydrogen is 2 wt% or more. Things are used.

In the practice of the present invention, the carbonaceous bituminous material as a raw material is made into a hydrophilic bituminous material by first introducing a functional group according to the treatment such as oxidation treatment as described above. For the oxidation treatment and the like, the carbonaceous bituminous materials described in JP-A-64-9288, JP-A-63-139080, JP-A-64-9808 and JP-A-2-88414 are used. A known oxidation treatment method, nitration treatment method, sulfonation treatment method, or amination treatment method for introducing a functional group can be adopted, but it is generally performed as follows.

As the treating agent used for the oxidation treatment, etc.,
Generally, in the case of oxidation treatment, hydrogen peroxide solution, a mixture of hydrogen peroxide solution and acetic acid, nitric oxide, ozone, etc. are used, in the case of nitration treatment, nitric acid etc. are used, and in the case of sulfonation treatment, sulfuric acid is used. Fuming sulfuric acid or the like is used, and in the case of amination treatment, a method of heating the product nitrated with the above nitrating agent in an acid or alkali using a metal catalyst is adopted. When at least two kinds of these treatments are combined, a mixed acid of nitric acid and sulfuric acid or the like is used.

In the method such as the oxidation treatment, for example, the treatment agent solution is stirred while maintaining it at a predetermined temperature, the carbonaceous bituminous material is gradually added thereto, and then the reaction is performed by stirring for a predetermined time. Method can be adopted. However, the reaction operation method is not limited to this, and generally used solid-liquid reaction equipment can be used. When the treating agent is a gaseous substance, a method of bringing the carbonaceous bituminous material into contact with the gaseous treating agent at a predetermined temperature is adopted.

Further, it is preferable to pulverize the carbonaceous bituminous material as a raw material in advance for the oxidation treatment etc. in order to shorten the reaction time. However, since the carbonaceous bituminous material is naturally finely pulverized as the reaction proceeds in the stirred reaction liquid, its particle size is not particularly limited, but considering the handling during the reaction operation, etc. Diameter 1 mm
It is preferable to pulverize to the following extent.

The addition amount of the carbonaceous bituminous material to the treatment agent solution naturally varies depending on the concentration of the treatment agent in the treatment agent solution, but even if a high concentration treatment agent solution is used, The amount of the bituminous material added should be 20 wt% or less, preferably 10 wt% or less. If the amount added is more than this, the fluidity of the mixture of the treatment agent solution and the carbonaceous bituminous material is lowered, and it becomes difficult to uniformly disperse the mixture in the treatment agent solution, and the reaction tends to be non-uniform. Further, the required amount of the treating agent varies depending on the type of treating agent and the type of carbonaceous bituminous material, and the amount of functional groups introduced varies depending on the ratio of the treating agent to the carbonaceous bituminous material. Therefore, the amount of the necessary treating agent is determined by analyzing the obtained hydrophilic bituminous material by elemental analysis, infrared absorption spectrum analysis, or the like to analyze the amount of the introduced functional group. It is desirable to determine in advance by a method such as measuring the amount of organic solvent-soluble components. Further, in order to introduce a sufficient functional group, it is desirable to carry out the oxidation treatment or the like in a state where a treatment agent in excess of the required treatment agent amount obtained by the above method is present.

The temperature of the oxidization treatment depends on the treating agent to be used, but for example, when nitric acid or a mixed acid of sulfuric acid and nitric acid is used, 0 to 150 ° C., sulfuric acid or a mixture of sulfuric acid and fuming sulfuric acid is used. 50 to 15 in case
In the case of 0 ° C., hydrogen peroxide solution or a reaction accelerator such as acetic acid added thereto, a temperature of 50 to 100 ° C. is adopted. The higher the temperature used, the easier the reaction proceeds, but when using a mixed acid of nitric acid and sulfuric acid, the reaction proceeds rapidly, and the reaction heat generated further promotes the reaction.
Since the temperature may become abnormally high, it is necessary to adjust the temperature used and the addition rate of the carbonaceous bituminous material so that abnormal reaction does not occur. On the contrary, if the reaction temperature used is too low, the reaction rate will be slow and the efficiency will be deteriorated.

The time required for the oxidation treatment depends on the reactivity of the carbonaceous bituminous material used, but when nitric acid, sulfuric acid, fuming sulfuric acid or a mixture thereof is used, it is several hours or less, usually 5 hours or less. is there. When hydrogen peroxide solution is used, it usually takes longer than this,
It may take several tens of hours, but it can be shortened by using an oxidation promoter such as acetic acid together.

After the reaction is carried out under a predetermined condition selected from the above-mentioned method and condition range, the reaction mixture is filtered as it is, put into a large amount of water to stop the reaction, and then filtered, or an alkali is used. Is added to neutralize and then the used treating agent solution is removed by a method such as filtration to obtain a carbonaceous bituminous material having a functional group introduced therein, that is, a hydrophilic bituminous material. It is also preferable to wash the hydrophilic bituminous material with water after the filtration. In addition, depending on the type of carbonaceous bituminous material used, it may be decomposed by this oxidation treatment and the like to produce a component soluble in the treatment agent solution, and the treatment agent solution generated by the filtration and washing operations as described above. It is preferable to remove the decomposition products, which are soluble components in water.

Further, a hydrophilic bituminous material obtained by reducing the nitro group to an amino group by subjecting the hydrophilic bituminous material into which a nitro group has been introduced by the above-mentioned method is also hydrophilic, which is a kind of hydrophilic bituminous material referred to in the present invention. Is. The reduction of the nitration product is achieved by heat treatment in an acid or an alkali, which is a usual reduction reaction, using a metal such as iron, zinc or tin as a catalyst.

The hydrophilic bituminous material which is the reaction product thus obtained is subsequently dissolved in an organic solvent. The present inventors have tried to prepare high-concentration carbonaceous gels with various solvents, and as a result, the dispersion solubility parameter is 8 or less, the polar solubility parameter is 3.5 or less, or the hydrogen bond solubility parameter is 2.5 or less. Solubility in hydrophilic carbonaceous bituminous substances is remarkably low in the solvent, and a carbonaceous gelled product cannot be obtained (does not gel), and the dispersion solubility parameter is 8.0 to 9.0, and the polar solubility parameter is 5 to 7. ,
When a solvent having a hydrogen bond solubility parameter of 4 to 6 is used, the solubility is highest, and a uniform and highly concentrated carbonaceous gelled product is obtained. It has been found that the properties are lowered and the concentration at which a uniform carbonaceous gel is obtained is lowered. This indicates that it is possible to produce a high-concentration carbonaceous gelled product in a specific region having a solubility parameter.

That is, the organic solvent used for dissolution in the present invention has a dispersion solubility parameter of 8.0 to 10.0 and a polar solubility parameter of 3.5 to 15.0 out of the solubility parameters showing the solubility of the solvent. And an organic solvent having a hydrogen bond solubility parameter of 2.5 to 15.0, such as formamide, N-methylformamide, N, N
-Dimethylformamide, dimethylacetamide, dimethyl sulfoxide, ethylene glycol and the like.

Here, the concept of solubility is related to the internal energy of the solvent and the solute, and δ = (ΔE / V) ^1/2 where δ: solubility parameter ΔE: molar energy of vaporization V: molar volume Hildebrand proposed that the solubility parameter is defined by the following relation, the closer the value of δ is, the more easily the two are dissolved. However, in the case of strong polar bonds and hydrogen bonds, this δ alone cannot explain the solubility of all solvents and solutes, and then Hansen proposed a three-dimensional solubility parameter for a much wider range of solubility. I can explain. What is the three-dimensional dissolution parameter?
(δ _d ), a polar solubility parameter (δ _p ), and a hydrogen bond solubility parameter (δ _h ), which are defined as satisfying the following relationship. δ = (δ _d ² + δ _p ² + δ _h ² ) ^1/2 Also, the value of each of these components is “Paint Flow and
Pigment Dispersion "Ed. TC Patton, Wiley-Inter
Science Pub., (1979), etc., describes the measurement and calculation methods. In addition, the "Coloring Materials Engineering Handbook" (edited by the Coloring Materials Association of Japan, Inc.) (Asakura Shoten) lists solubility parameters for typical solvents. Has been introduced. The dissolution parameters of typical solvents are shown in Table 1.

[0035]

[Table 1]

In the present invention, it is also possible to use a solvent in which the solubility parameter is out of the above range and the solvent in the above range is mixed to adjust the solubility parameter. For example, aromatic hydrocarbons such as benzene, alcohols such as methyl alcohol, ethyl alcohol and benzyl alcohol, ketones such as acetone and methyl ethyl ketone, and hetero element-substituted aromatic hydrocarbons such as nitrobenzene and chlorobenzene are hydrophilic by themselves. Since it has a low dissolving power for sexual bituminous materials and only a low-concentration solution can be obtained, it does not form a gel even if it is treated, but these solvents are mixed with the above-mentioned preferred solvent so that the solubility parameter falls within the above range. When adjusted, it can be used as a solvent for producing a gelled product.

The hydrophilic bituminous material has a functional group introduced therein and is soluble in an alkaline solution and an organic solvent. The kind of carbonaceous bituminous material to be used, the kind of treating agent, the reaction conditions and The amount of soluble components varies depending on the type of organic solvent, the concentration of the solution, and the melting temperature.

Components that are insoluble in the solution of the organic solvent can be removed by dissolving and then filtering, but in order to increase the amount of the carbonaceous gelation product of interest, the yield of soluble components is high. It is preferable to select the solvent so that the above conditions and to appropriately select the conditions such as the above-mentioned oxidation treatment. Further, when a solvent-insoluble matter is produced, when the amount of the insoluble component is small, it may be gelled as it is, but the desired carbonaceous gelled product, carbonaceous gelled product molded product or carbonization or graphitization thereof. In the case of a fiber, a membrane, a microsphere, or the like, which requires shape control on the order of micron, it is necessary to filter after dissolving in an organic solvent.

The method of dissolution is not particularly limited, and it is sufficient to add the hydrophilic bituminous material to the organic solvent and stir.
At this time, the higher the temperature, the faster the dissolution rate, and the stronger the stirring force, the shorter the dissolution will be. The melting temperature may be a temperature not lower than the freezing point of the organic solvent as a solvent and not higher than the boiling point, but 5 to 100 ° C. is usually sufficient. It is preferable to select an efficient temperature by the operation after dissolution. For example,
If the dissolution temperature is raised, the gelation reaction will proceed simultaneously with the dissolution, so the viscosity may have already risen after the dissolution, so if the filtration operation is attempted after the dissolution as described above, it will be dissolved at a low temperature. Preferably.

The solution of the hydrophilic bituminous material dissolved in the organic solvent in this manner is sealed so that the solvent does not volatilize, and the reaction is carried out as it is to cause a gelation reaction, and the viscosity gradually increases, Eventually, it loses fluidity and solidifies into a carbonaceous gel while still containing a large amount of organic solvent. At this time, the airtight container may be in an air atmosphere as it is, or may be sealed with an inert gas such as nitrogen,
It is also possible to pressurize in a pressure vessel to prevent the evaporation of the solvent.

The rate of this gelation reaction greatly varies depending on the concentration of the hydrophilic bituminous material, the solubility parameter of the organic solvent, and the reaction temperature. The higher the concentration of the hydrophilic bituminous material in the solution of the organic solvent, the faster the gelation reaction rate.However, if the concentration is remarkably high, the hydrophilic bituminous material will not be completely dissolved and gelation will occur with the insoluble matter contained. In order to form a uniform gel, it is necessary to select the concentration in consideration of the saturated dissolution concentration of the hydrophilic bituminous material in the solution of the organic solvent, the efficiency of the dissolution operation in the organic solvent, and the like. On the other hand, if the concentration is low, the gelation reaction rate will be remarkably slowed or the gel state will not be sufficient after the reaction, which is not preferable.

The dispersion and dissolution parameters are 8.0 to 10.
0, a polar solubility parameter is 3.5 to 15.0, and a hydrogen bond solubility parameter is from 2.5 to 15.0. The concentration of the blue-green material can be 10 to 60% by weight, preferably 20 to 50% by weight. This value is significantly higher than the concentration of the hydrophilic bituminous material of 1 to 20 wt% when the alkaline solution is used as the solvent.

The reaction temperature for gelation may be any temperature above the freezing point and below the boiling point of the organic solvent used,
The higher the temperature, the faster the gelling reaction. Usually 5-10
0 ° C, preferably 20 to 90 ° C is adopted. For example,
When a mixed solvent containing a volatile solvent such as methanol or acetone is used, if the reaction is carried out under pressure using a pressure vessel, the boiling temperature of the solvent will be higher, so a higher temperature may be adopted. it can.

Further, the reaction time required for the solution of the hydrophilic bituminous material in the organic solvent to undergo gelation reaction and finally to lose fluidity and solidify depends on the concentration of the hydrophilic bituminous material,
The time required for gelation becomes shorter as the reaction temperature becomes higher, although it depends largely on the solubility parameter of the organic solvent and the reaction temperature. For example, N-methylformamide is used as the organic solvent, and the concentration of hydrophilic bitumen is 350 g per solvent.
In the case of / l, the reaction temperature is set to 80 ° C and the reaction is carried out for 3 hours, and then gelation and solidification occur at the stage of cooling to 25 ° C. When the concentration of the hydrophilic bituminous material is 350 g / l using formamide as a solvent, gelation occurs during the reaction at 80 ° C. and the fluidity is lost.

Since the reaction rate of gelation and the like greatly vary depending on the conditions as described above, it is preferable to select appropriate conditions in consideration of the purpose, conditions of equipment, heat source, etc. and efficiency. When a heat source is not used, it can be dissolved in an organic solvent and then left standing at room temperature for a long time to obtain a carbonized gelled product. Alternatively, a method of reacting at high temperature until it solidifies upon cooling, then cooling and allowing to stand can be adopted.

Further, the temperature at which the obtained carbonaceous gelled product changes from a non-fluid gel state to a fluid sol state depends on the solvent used, the production conditions and the like. Therefore, the carbonaceous gelled material referred to in the present invention is a material that changes from a gel state having no fluidity to a sol state having fluidity depending on the temperature, and is a hydrophilic bituminous substance in an organic solvent at a certain temperature. Not only does this mean that the gelling reaction of the solution in which the material is dissolved loses fluidity and solidifies, but also that the gelling reaction has occurred and the viscosity has increased,
That is, it includes a material that loses fluidity and solidifies when cooled.

Further, the carbonaceous gelled product produced by using the organic solvent of the present invention, like the carbonaceous gelled product produced by using the alkaline solution, is completely fluid from the state of the solution of the organic solvent. Since the viscosity changes continuously until it is lost and solidified, the block, film,
It becomes possible to form it into a shape such as a sphere or a fiber. If the gelling reaction proceeds further after molding, it loses fluidity and solidifies,
A carbonaceous gelled product having a desired shape is obtained. It is also possible to form a gel having a desired fluidity by heating it into a sol state after gelling it so that it has no fluidity at room temperature.
Then, when dried, this product shrinks to lose the solvent and becomes a dried gelled product, that is, a carbonaceous gelled product molded product. Drying is generally carried out by heating under reduced pressure or considerable vacuum. In addition, this carbonaceous gelled product is a black pitch having a glassy luster,
It is optically isotropic when observed with a polarizing microscope.

Further, since the carbonaceous gelled product of the present invention has a high viscosity or is solidified while containing a large amount of an organic solvent, it considerably contracts when it is dried. Therefore, when a large-sized molded article is to be produced, the drying conditions should be selected with caution and the rapid evaporation of the organic solvent should be avoided, as in the generally known gel. However, when produced using the specific organic solvent of the present invention, the shrinkage rate is small because the concentration of the hydrophilic bituminous material is significantly higher than that of the carbonaceous gelled product produced using the alkaline solution. There is an advantage that.

As a method of molding into a desired shape, for example, in the case of a block shape, a solution of an organic solvent of a hydrophilic bituminous material may be placed in a predetermined container and reacted as it is to gel and solidify. Since it is in a solution state when handled, it can be easily filled even in a container or a mold having a complicated shape and a fine structure. Also, proceed with gelation reaction,
Those having a certain degree of viscosity can be applied to a substrate such as glass or a carbon material, and become a plate when a thick coating layer is formed and a film when a thin coating layer is formed.
Of course, a molding aid such as polyvinyl alcohol may be used when molding a fine shape such as a film.

As a method of molding the microspheres,
A method of adding the carbonaceous gel to silicone oil, fluorocarbon oil, hydrocarbon oil, etc., and stirring and dispersing these oils as a dispersion medium to make them spherical is preferable.
At this time, the organic solvent used to dissolve the hydrophilic bituminous material needs to be selected from those which are not compatible with the dispersion medium used here. For example, formamide is insoluble in silicone oils, thus choosing organic solvents and dispersion media that are not mutually soluble. The viscosity of the carbonaceous gel to be added, the amount and concentration to be added, the stirring speed, the particle size of the microspheres obtained by stirring power can be freely controlled,
It is possible to obtain microspheres of about 0.1 to 100 microns. Further, the method for molding the carbonaceous gelled body into a desired shape is not limited to the above, and generally used molding methods such as cast molding, rolling molding and extrusion molding can be adopted.

The dried carbonaceous gelled product thus obtained can be used as it is for the use of an ion exchanger or the like by utilizing its functional groups, but in the case of another use, It is also possible to carbonize and graphitize this to obtain a carbon material.

Also in the case of a carbonaceous gelled product using the organic solvent of the present invention, as in the case of using an alkaline solution.
Although some shrinkage occurs by heating up to 1000 ° C., carbonization occurs while maintaining almost the original shape.
No. 139080, JP-A-64-9808, JP-A-2
No significant foaming occurs as in the case of the method for producing a graphite material shown in -88414. Also, 1000 ℃
The structure after the heat treatment in (1) is optically isotropic like that before the heating. Thus, also in the case of the carbonaceous gelled product of the present invention, carbonization and graphitization can be carried out while maintaining a desired shape, and a carbon or graphite material having a desired shape can be obtained.

Furthermore, since the carbonaceous gelled material can be handled with various viscosities, it is possible to add other materials in an appropriate viscosity state, and after mixing, dissolving or dispersing the other materials. Further progress of gelation and solidification yields a composite material of the carbonaceous gel and other materials. As the composite additive for forming the composite material, there are inorganic materials such as alumina, silicon carbide, and boron carbide that are not dissolved in an organic solvent, metal materials such as iron, nickel, and aluminum, or organic polymer materials such as polyethylene and polypropylene. The shape of these materials may be fine powder or fibrous. Further, by adding a metal alkoxide, a metal salt or the like which is soluble in an organic solvent, a composite material in which a metal is uniformly dispersed can be obtained. The carbonaceous gelled body thus composited can be carbonized or graphitized as needed to obtain carbon or a graphite-based composite material.

Furthermore, it is presumed that the carbonaceous gelled product of the present invention has a functional group of the hydrophilic bituminous material modified,
It may be possible to react with a general monomer for polymer compounds, and it is useful for the development of new carbonaceous materials.

[0055]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples.

Example 1 Carbon content by elemental analysis 94.6 wt%, hydrogen 3.8 wt%
%, Nitrogen 1.0 wt% raw coke was crushed to 100 mesh or less to obtain a carbonaceous bituminous material as a starting material. This raw coke was gradually added to this mixed acid at a ratio of 100 cc of mixed acid of 70% concentrated sulfuric acid and 30% concentrated nitric acid to 5 g of raw coke while stirring, and was further oxidized by stirring at 80 ° C. for 3 hours. .. This treatment solution is heated to 1000 at room temperature.
The solution was added dropwise to cc of water with stirring and then filtered with a glass filter. Furthermore, the oxidized raw coke in the glass filter was thoroughly washed with water and then dried to obtain a hydrophilic bituminous material. Elemental analysis of the obtained hydrophilic bituminous material revealed that carbon was 52.4 wt%, hydrogen was 1.6 wt%, and nitrogen was 6.6.
It was wt%. Most of the rest is sulfur and oxygen.

In a 200 cc Erlenmeyer flask, 20 to 50 g of the hydrophilic bituminous material obtained by the above method and 100 cc of formamide or N, N-dimethylformamide as a solvent.
Then, the rotor of a magnetic stirrer coated with Teflon was placed therein, and the container was tightly closed and immersed in a water bath kept at 80 ° C., and the reaction was carried out for 3 hours while rotating with a rotating magnet from the lower part.

During this period, the contents were observed. As a result, the reaction conditions differed depending on the concentration of the hydrophilic bituminous material and the organic solvent used, and the gelation proceeded rapidly and the rotation of the rotor stopped within 3 hours. (A) Although the rotor did not stop for 3 hours, the Erlenmeyer flask was immediately removed from the 80 ° C. water bath and solidified into a gel immediately after cooling (B). After further reacting for 3 hours, it was cooled. However, the fluidity still remained, and there was a product (C) which was judged to have an insufficient reaction time of 3 hours.

Table 2 shows the difference between the respective situations when the above symbols (A) to (C) are distinguished. In the tables of the following examples, the meanings of the symbols (A), (B) and (C) are the same as in this example.

[0060]

[Table 2]

Example 2 As the organic solvent, mixed solvents of various mixing ratios of N, N-dimethylformamide and chlorobenzene were used.

In a 200 cc Erlenmeyer flask, 35 g of the same hydrophilic bituminous material as obtained in Example 1 and N, as a solvent,
100 cc of a mixed solvent of N-dimethylformamide and chlorobenzene was put, and a rotor of a magnetic stirrer coated with Teflon was put in the mixed solvent.
It was dipped in a water bath maintained at 1, and the reaction was performed for 3 hours while rotating from below with a rotating magnet.

During this period, as a result of observing the contents, it was found that the reaction situation varied depending on the mixing ratio of the above-mentioned two kinds of organic solvents. Further, when chlorobenzene alone was used as the solvent, the hydrophilic bituminous material was hardly dissolved, and a uniform carbonaceous gel was not obtained.

The difference between the mixing ratio of the solvent and each situation is
It was as shown in Table 3 when distinguished by the above-mentioned symbols (A) to (C).

[0065]

[Table 3]

Example 3 As an organic solvent, mixed solutions of N, N-dimethylformamide and benzyl alcohol in various mixing ratios were used.

In a 200 cc Erlenmeyer flask, 35 g of the same hydrophilic bituminous material as obtained in Example 1 and N as a solvent were used.
100 cc of a mixed solvent of N-dimethylformamide and benzyl alcohol was put, and a rotor of a magnetic stirrer coated with Teflon was put in the mixed solvent.
It was immersed in a water bath maintained at 0 ° C., and the reaction was carried out for 3 hours while rotating from below with a rotating magnet.

During this period, as a result of observing the contents, it was found that the reaction situation was different depending on the mixing ratio of the above two kinds of organic solvents. Further, when benzyl alcohol alone was used as a solvent, the hydrophilic bituminous material was hardly dissolved, and a uniform carbonaceous gel was not obtained.

The difference between the mixing ratio of the solvent and each situation is
It was as shown in Table 4 when distinguished by the above-mentioned symbols (A) to (C).

[0070]

[Table 4]

Example 4 As the organic solvent, mixed solvents of N, N-dimethylformamide and formamide in various mixing ratios were used.

In a 200 cc Erlenmeyer flask, 35 g of the same hydrophilic bituminous material as obtained in Example 1 and N, as a solvent,
Mixed solvent of N-dimethylformamide and formamide 1
00 cc was put therein, and a rotor of a magnetic stirrer coated with Teflon was put therein, and the container was tightly closed and immersed in a water bath kept at 80 ° C., and the reaction was carried out for 3 hours while rotating with a rotating magnet from the lower part.

During this period, as a result of observing the contents, it was found that the reaction situation was different depending on the mixing ratio of the above two kinds of organic solvents.

The difference between the mixing ratio of the solvent and each situation is
It was as shown in Table 5 when distinguished by the above-mentioned symbols (A) to (C).

[0075]

[Table 5]

Example 5 Glycerin was used as the organic solvent.

In a 200 cc Erlenmeyer flask, 35 g of the same hydrophilic bituminous material as obtained in Example 1 and 100 cc of glycerin as a solvent were placed, and the rotor of a magnetic stirrer coated with Teflon was placed in the flask, which was then sealed. It was immersed in a water bath maintained at 80 ° C., and the reaction was carried out for 3 hours while rotating it from below with a rotating magnet.

When glycerin is used as a solvent,
At a hydrophilic bituminous material concentration of 35 g / l, gelation proceeded and the rotor stopped during the reaction for 3 hours.

Comparative Example 1 Nitrobenzene was used as the organic solvent.

To a 200 cc Erlenmeyer flask, 35 g of the same hydrophilic bituminous material as obtained in Example 1 and 100 cc of nitrobenzene as a solvent were placed, and the rotor of a magnetic stirrer coated with Teflon was placed in the flask, which was then sealed. It was immersed in a water bath maintained at 80 ° C., and the reaction was carried out for 3 hours while rotating it from below with a rotating magnet.

When nitrobenzene was used as a solvent, the hydrophilic bituminous material was not sufficiently dissolved and remained non-uniform, and it did not gel and solidify even after cooling.

Example 6 As an organic solvent, N, N-dimethylformamide (80
%) And nitrobenzene (20%) mixed solvent was used.

In a 200 cc Erlenmeyer flask, 35 g of the same hydrophilic bituminous material as obtained in Example 1 and 100 cc of the above mixed solvent as a solvent were placed, and the rotor of a magnetic stirrer coated with Teflon was placed in the flask, followed by sealing. It was immersed in a water bath maintained at 80 ° C., and the reaction was carried out for 3 hours while rotating from below with a rotary magnet.

In the case of this mixed solvent, the fluidity still remained even after cooling after the reaction for 3 hours, and the reaction time of 3 hours was not sufficient.

Regarding Examples 2 to 6, Table 6 shows the dissolution parameters of mixed solvents having various mixing ratios.

[0086]

[Table 6]

Further, regarding Examples 2 to 6 and Comparative Example 1, the solubility parameter of the solvent used and the solubility parameter of the solvent were used for the conditions after the treatment with the hydrophilic bituminous material concentration of 350 g / l and the gelation reaction temperature of 80 ° C. for 3 hours. The difference in gelling state due to the difference is shown in FIG. That is, FIG.
Plots the polar solubility parameter on the vertical axis and the hydrogen bond solubility parameter on the horizontal axis for organic solvents with dispersion solubility parameters of 8 to 10, and the point is rotated within 3 hours after the rapid gelation. When the rotation of the child stopped (●), the rotor did not stop for 3 hours, but when the Erlenmeyer flask was taken out of the 80 ° C water bath and cooled, it immediately solidified into a gel (○). After the reaction for 3 hours, the fluidity still remained even after cooling, and it was judged that the reaction time of 3 hours was not sufficient (△). Also, the solubility was extremely low, and a carbonaceous gel was obtained. It is the figure which distinguished and plotted what was absent (x) with a symbol. The subscripts at each point are the mixing ratio (%) of another solvent added to dimethylformamide.

In FIG. 1, the region (A) shows the gelation rapidly progressing and the rotation of the rotor has stopped within 3 hours, and the region (B) shows that the rotor stops for 3 hours. However, when the Erlenmeyer flask was taken out of the 80 ° C. water bath and cooled, it immediately solidified into a gel, region (C)
After the reaction for 3 hours, the fluidity still remained after cooling, and it is judged that the reaction time of 3 hours was not sufficient.

That is, the polar solubility parameter is 3.5.
Hereinafter, in the region where the hydrogen bond solubility parameter is 2.5 or less, the solubility is extremely low and a carbonaceous gel cannot be obtained, and the polar solubility parameter is 5 to 7 and the hydrogen bond solubility parameter is 4 to 4. It can be seen that the region of 6 has the highest solubility and a high concentration of the carbonaceous gel is obtained.

Example 7 In a 200 cc Erlenmeyer flask, 30 g of the same hydrophilic bituminous material as obtained in Example 1 and 100 cc of formamide were placed, and the rotor of a magnetic stirrer coated with Teflon was placed in the flask and then sealed. It was immersed in a water bath maintained at 80 ° C. for 3 hours while rotating from below with a rotating magnet.

Then, 20 g of the above reaction mixture was added to 1000 cc of silicone oil which was kept at 90 ° C. and stirred.
The mixture was gradually added at 0 ° C., and stirring was continued for 1 hour. Then, the mixture was cooled to room temperature with stirring, the mixture was centrifuged, the dispersed carbonaceous gelled product was taken out, washed with benzene and acetone, and dried under reduced pressure at 40 ° C.

When the obtained carbonaceous gelled article was observed under a microscope, it was found to be a spherical body having a smooth surface of several to several tens of μ.

Further, as a result of similarly observing a product obtained by firing this product at 1000 ° C. in a nitrogen stream, it was confirmed that the original spherical shape was retained although the particle size was reduced.
It was confirmed that carbonization occurred without causing deformation such as melting and softening.

[0094]

Industrial Applicability The carbonaceous bituminous material and the reaction product obtained from the carbonaceous bituminous material are conventionally solids, and they are subject to the limitation of the field of use due to the handling as a solid and the production method as a solid. I didn't get it. The present inventors have previously proposed a novel carbonaceous gelled product and its use form. This is a newly found gelling reaction of hydrophilic bituminous material in an alkaline solution, and gelation. By effectively and effectively utilizing the reaction products, the limitation of being a solid, which has been a big problem in the past, is removed, and a carbonaceous bituminous material can be handled in a free shape. It has the effect of increasing the utility value of the reaction product and developing a new field of application of the carbonaceous material.

The present invention further improves on the above proposal and provides a method for producing a high-concentration carbonaceous gelled product by using an organic solvent having a specific solubility parameter. This is a markedly improved efficiency in producing the compound.

[Brief description of drawings]

FIG. 1 is a graph showing the relationship between the solubility parameter of an organic solvent used and the gelation state in Examples 2 to 6 and Comparative Example 1, and the vertical axis represents the polar solubility parameter (δp).
The horizontal axis is the hydrogen bond solubility parameter (δh).

Claims (4)

[Claims] 1. A hydrophilic bituminous material soluble in an organic solvent is obtained by treating a carbonaceous bituminous material with oxidation, nitration, sulfonation, amination, or a combination of at least two of these, and this is used as a dispersion solubility parameter. Is 8.0-1
0.0, the polar solubility parameter is 3.5 to 15.0, and the hydrogen bond solubility parameter is 2.5 to 15.
A method for producing a carbonaceous gelled product, which comprises dissolving in an organic solvent of 0 and then performing a gelling reaction as a solution to obtain a gelled substance containing a large amount of an organic solvent. 2. A hydrophilic bituminous material soluble in an organic solvent is prepared by subjecting a carbonaceous bituminous material to oxidation, nitration, sulfonation, amination, or a combination of at least two of these, to obtain a dispersion solubility parameter. Is 8.0-1
0.0, the polar solubility parameter is 3.5 to 15.0, and the hydrogen bond solubility parameter is 2.5 to 15.
After being dissolved in an organic solvent of 0, the solution is reacted as it is to cause a gelling reaction, and when it becomes a desired fluidity, it is molded into a desired shape, and the gelling reaction is further proceeded to solidify. A method for producing a carbonaceous gelled body molded article, comprising: 3. A carbonaceous bituminous material is treated with oxidation, nitration, sulfonation, amination or a combination of at least two of these to obtain a hydrophilic bituminous material soluble in an organic solvent, which is used as a dispersion solubility parameter. Is 8.0-1
0.0, the polar solubility parameter is 3.5 to 15.0, and the hydrogen bond solubility parameter is 2.5 to 15.
After being dissolved in an organic solvent of 0, the solution is reacted as it is to cause a gelling reaction, and when it becomes a desired fluidity, it is molded into a desired shape, and the gelling reaction is further proceeded to solidify. A method for producing a carbonized or graphitized product of a carbonaceous gelled body molded article, comprising the step of drying to obtain a carbonized gelated article formed body, and further subjecting this to carbonization treatment or carbonization and graphitization treatment. 4. A carbonaceous bituminous material is treated with oxidation, nitration, sulfonation, amination or a combination of at least two of these to obtain a hydrophilic bituminous material soluble in an organic solvent, which is used as a dispersion solubility parameter. Is 8.0-1
0.0, the polar solubility parameter is 3.5 to 15.0, and the hydrogen bond solubility parameter is 2.5 to 15.
A carbonaceous gelled product, which is a gel-like substance containing a large amount of an organic solvent, which is dissolved in an organic solvent of 0 and then reacted as it is to cause a gelling reaction to solidify.