JPH05112783A - Production of carbonaceous gel, molded product thereof and carbonized or graphitized product thereof and carbonaceous gel - Google Patents

Abstract

PURPOSE:To obtain a solid carbonaceous substance from a starting material handled in the form of a liquid, for example, in such a way that a solution prepared by dissolving a hydrophilic carbonaceous bitumen in an alkali solution is poured into a mold and allowing the solution to gel into a molding. CONSTITUTION:The title process for producing a carbonaceous gel comprises nitrating, sulfonating or aminating a carbonaceous bitumen into a hydrophilic carbonaceous bitumen, dissolving the bitumen in an alkali solution, and allowing the resulting alkali solution to gel. The title gel produced thereby.

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 it to a molten state or dissolving it in 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,
The operation that can be carried out in the state of being melted by heating, the problem that the reaction is limited, the solvent such as benzene and toluene cannot be used, and a highly soluble polar solvent such as pyridine and quinoline must be used. Therefore, 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. By utilizing the fact that it becomes soluble, after dissolving the mesophase having a functional group in an alkaline solution, the insoluble matter is separated by filtration, and the soluble solution is acidified by adding an acid to the alkaline solution. It is a method of precipitating and recovering mesophase having a functional 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,
If you try to make something with a special shape, you will still be constrained to be 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.

Therefore, it is an object of the present invention to remove the restriction imposed by the solid reaction product obtained from carbonaceous bituminous material and to make it easy to handle in a free shape. It aims to enhance the utility value of these reaction products and develop new fields of application of carbonaceous materials.

[0012]

The inventors of the present invention have been conducting research on new utilization methods of carbonaceous bituminous materials as described above, and have carried out oxidation reaction of carbonaceous bituminous materials and alkali-soluble substances obtained therefrom. While investigating the properties of the components, by chance, when the oxidized carbonaceous bituminous material was dissolved in an alkaline solution and the alkaline solution was left to stand, the solution viscosity increased with time and finally the fluidity I encountered a phenomenon of losing solids and solidifying into agar. This indicates that the oxidized carbonaceous bituminous material has undergone some reaction in the alkaline solution and changed. Whereas the method of JP-A-64-9288 described above was to re-precipitate by adding an acid to a solution dissolved in an alkaline solution to obtain a solid powder, the reaction was carried out with the alkaline solution as it was. What happened and solidified was a completely new finding.

Further, the solidified material in this way is in a state of containing a large amount of the solvent (water, alcohol, etc.) of the alkaline solution used, and becomes a fluidized state by heating, 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 with a large amount of solvent was lost at a low temperature. Heretofore, gels of inorganic substances such as silica gel and alumina gel, polymer gels, gels such as agar and gelatin have been known, but carbonaceous gels have not been known at all. Therefore, as a result of further diligent studies on this phenomenon, the present inventors have found that a carbonaceous gelation product which has never been obtained can be obtained by effectively utilizing this gelation reaction and its process. The present invention has been completed by finding that a new material can be produced by utilizing a gelled material.

That is, the gist of the first invention is that a hydrophilic bituminous material soluble in an alkaline solution is obtained by treating a carbonaceous bituminous material with oxidation, nitration, sulfonation, amination or a combination of at least two of these. A method for producing a carbonaceous gelled product is characterized in that a gelled substance containing a large amount of a solvent is obtained by dissolving the material in an alkaline solution and then subjecting it to a gelling reaction as it is in an alkaline solution.

Further, the gist of the second invention is a hydrophilic bituminous substance soluble in an alkaline solution by subjecting a carbonaceous bituminous material to oxidation, nitration, sulfonation, amination or a combination of at least two of these. As a material, after dissolving this in an alkaline solution, let the gelling reaction occur in the alkaline solution, and when it becomes the desired fluidity, mold it into a desired shape, further advance the gelling reaction and solidify it. The present invention resides in a method for producing a carbonaceous gelled body formed by drying.

Further, the gist of the third invention is that a hydrophilic bituminous material soluble in an alkaline solution 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, after dissolving this in an alkaline solution, let the gelling reaction occur in the alkaline solution, and when it becomes the desired fluidity, mold it into a desired shape, further advance the gelling reaction and solidify it. A method for producing a carbonized or graphitized product of a carbonaceous gelled body molding is characterized in that it is dried to obtain a carbonized gelled body formed body, and this is further carbonized or carbonized and graphitized.

A fourth aspect of the present invention is a hydrophilic bituminous material soluble in an alkaline solution by oxidizing, nitrating, sulfonation, aminating a carbonaceous bituminous material or a combination of at least two of these. And a gelled substance which is a gel-like substance containing a large amount of a solvent, which is obtained by dissolving this in an alkaline solution and then subjecting it to a gelling reaction as it is in an alkaline solution.

More specifically, the present invention will be described in detail. Examples of the carbonaceous bituminous material as a raw material 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, further coal, lignin, and the like, those having a condensed polycyclic aromatic molecule as a main constituent can be used, and generally, It can be used which are used as material cost of the raw materials.

The carbonaceous bituminous material used as a raw material in the present invention is first subjected to oxidative nitration, sulfonation or amination treatment, or a treatment in which at least two kinds thereof are combined (hereinafter, these treatments are collectively referred to as oxidization treatment). Etc.), and functional groups such as nitro group, sulfone group, carbonyl group, carboxyl group, hydroxyl group, amino group, etc. are introduced according to the applied treatment, but a light component in the carbonaceous bituminous material. Is present, it is not preferable because it will dissolve in the medium used for volatilization, decomposition or oxidation treatment during the oxidation treatment or the like and reduce the recovery rate of the hydrophilic bituminous material, and therefore it is not preferable. Is usually 300
It is preferable to use one having a boiling point of not lower than 0 ° C and a softening point of not lower than 100 ° C.

The carbonaceous bituminous material used as a raw material in the present invention also 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 carrying out the present invention, the carbonaceous bituminous material as a raw material is first made into a hydrophilic bituminous material by introducing a functional group according to the treatment by oxidation treatment or the like 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, hydrogen peroxide, a mixture of hydrogen peroxide and acetic acid, nitric oxide, ozone, etc. are used in the case of oxidation treatment, nitric acid, etc. are used in the case of nitration treatment, and sulfuric acid is used in the case of sulfonation treatment. , Fuming sulfuric acid, etc. are used, and in the case of the amination treatment, it is aminated by reducing the nitration product with the above nitrating agent. As the reduction treatment, the nitration product is treated with a metal catalyst. A method of heating in acid or alkali is used. When at least two kinds of these treatments are combined, a mixed acid of nitric acid and sulfuric acid or the like is used.

The oxidation treatment method is generally carried out by, for example, stirring the treatment agent solution while maintaining it at a predetermined temperature, gradually adding the carbonaceous bituminous material thereto, and then stirring the mixture for a predetermined time to cause a reaction. 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 in 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 amount of the carbonaceous bituminous material added 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 a method such as elemental analysis and infrared absorption spectrum analysis to analyze the introduced functional group, or the hydrophilic bituminous material. It is desirable to obtain it in advance by a method such as measuring the amount of alkali-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 also depends on the treating agent to be used. 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 method and range of conditions, the reaction mixture is filtered as it is, or the reaction mixture is poured into a large amount of water to stop the reaction and then filtered. Alternatively, by removing the treating agent solution used by a method such as adding an alkali to neutralize and then filtering, a carbonaceous bituminous material having a functional group introduced, that is, a hydrophilic bituminous material is obtained. Further, it is preferable to wash the hydrophilic bituminous material with water after the above-mentioned filtration, but it is not always an essential requirement since the operation of dissolving it in an alkali is performed thereafter. It is also possible to dissolve the hydrophilic bituminous material as it is by adding an alkali to the reaction mixture to neutralize the treating agent solution, and further adding an excess of alkali to adjust the pH. 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 produced by the filtration and washing operations as described above. It is preferable to remove decomposition products such as water-soluble components. When the reaction mixture is neutralized as it is and made alkaline, the decomposition products remain as they are, but if the amount of the decomposition products is not significantly large, the carbonaceous gel of the present invention is produced. The above is not a particular obstacle.

Further, a hydrophilic bituminous material in which a nitro group is introduced by the above-mentioned method is subjected to a reduction treatment to convert a nitro group into an amino group is also hydrophilic, which is a kind of the 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 alkaline solution.
This hydrophilic bituminous material has a functional group introduced and is soluble in an alkaline solution, but the type of carbonaceous bituminous material used, the type of treating agent, the reaction conditions and the molar concentration of the alkaline solution, the solubility The amount of soluble component varies depending on the temperature. Insoluble components in an alkaline solution can be removed by filtration after dissolution, but in order to increase the production amount of the target carbonaceous gelled product, the yield of soluble components should be increased as described above. It is preferable to appropriately select the conditions of. Further, when the amount of the insoluble component is small, it may be gelled as it is, but the target carbonaceous gelled body, carbonaceous gelled body molding or carbonaceous gelated body material is a fiber, film, or microsphere. When it is necessary to control the shape on the order of micron as in the case of the above, it is necessary to filter after dissolving in an alkaline solution.

As the alkaline solution used for dissolving the hydrophilic bituminous material, an aqueous solution of ammonium hydroxide, sodium hydroxide or potassium hydroxide or a polar organic solvent solution of alcohol can be used. Further, an aqueous solution or alcohol solution of amines such as hexamethylenediamine and triethanolamine can also be used, but considering the problem of no metal remaining in the carbonaceous gelation product and solvent recovery during drying, It can be said that it is most preferable to use an aqueous solution of ammonium hydroxide.

The method of dissolution is not particularly limited, and it is sufficient to add the hydrophilic bituminous material to the alkaline solution 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 temperature of dissolution may be a temperature above the freezing point of a polar organic solvent solution such as water or alcohol, which is a solvent, and below the boiling point, usually 5-10.
Although 0 ° C. is adopted, it is preferable to select a temperature that is efficient for the operation after dissolution. For example, if the dissolution temperature is raised, the gelation reaction may proceed simultaneously with the dissolution, and the viscosity may have already risen after the dissolution.Therefore, when attempting a filtration operation after dissolution as described above, a low temperature is used. It is preferable to dissolve in.

The solution of the hydrophilic bituminous material thus dissolved in the alkaline solution is sealed so that the water or polar organic solvent in the alkaline solution does not volatilize, and the reaction is carried out as it is to cause a gelling reaction. The viscosity gradually increases, and finally the fluidity is lost, and the carbonaceous gel is formed by solidifying while containing a large amount of water or a polar 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 gelling reaction greatly changes depending on the concentration of the hydrophilic bituminous material, the molar concentration of the alkaline solution, and the reaction temperature. The higher the concentration of the hydrophilic bituminous material in the alkaline solution, the faster the gelation reaction rate.However, if the concentration is remarkably increased, the hydrophilic bituminous material will not be completely dissolved and gelation will occur with insoluble matter, resulting in non-uniformity. Since it becomes a gelled substance, it is preferable to select the concentration in consideration of the saturated dissolution concentration of the hydrophilic bituminous material in the alkaline solution, the efficiency of the dissolution operation in the alkaline solution, and the like. Also, 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, and is usually 1 to 20 wt% with respect to the alkaline solution, preferably 2 to 15%.
wt% is adopted.

The reaction time required for gelation and solidification also depends on the molar concentration of the alkali in the alkaline solution. For the same hydrophilic bituminous material concentration, the higher the molar concentration, the longer the time required for gelation. It gets shorter. On the contrary, when the molar concentration is low, not only the gelation rate slows down,
If the molar concentration is remarkably reduced, the solubility of the hydrophilic bituminous material is reduced, and insoluble matter may be generated to fail to obtain a uniform gelled product. Therefore, the molar concentration of alkali in the alkaline solution is usually 0.1 mol / l or more, preferably 0.1 to 15 mol / l, in consideration of the time required for gelation and its efficiency. ..

Further, the reaction temperature for gelation may be a temperature not lower than the freezing point and not higher than the boiling point of a polar organic solvent solution such as water or alcohol as a solvent, and the higher the temperature, the faster the gelation reaction proceeds. Usually, 5 to 100 ° C., preferably 20 to 90 ° C. is adopted, but when the reaction is carried out under pressure using a pressure vessel, the boiling temperature of the solvent becomes high, so a higher temperature should be adopted. You can

Further, the reaction time required for the solution in which the hydrophilic bituminous material is dissolved in the alkaline solution to undergo gelation reaction and finally to lose fluidity and solidify is the concentration of the hydrophilic bituminous material, Although it varies greatly depending on the molar concentration of the alkali in the alkaline solution and the reaction temperature, one example is shown below. The concentration of the hydrophilic bituminous material is 4 wt%, the molar concentration of ammonia in the aqueous ammonia solution is 5.12 mol / l, and the reaction temperature is 25 ° C. In this case, the time required for gelation is about 16 days, the hydrophilic bituminous material concentration is 6 wt%, the ammonia molar concentration of the aqueous ammonia solution is 1.92 mol / l, and the reaction temperature is 25 ° C.
In case of, it is about 2 days. In addition, when the hydrophilic bituminous material concentration is 6 wt% and the molar concentration of ammonia in the aqueous ammonia solution is 1.92 mol / l, and the reaction temperature is 80 ° C., the solution is still fluid even after reacting for 3 hours. However, when the temperature is subsequently cooled to 25 ° C., it gels and solidifies. Further, when the hydrophilic bituminous material concentration was 6 wt% and the molar concentration of ammonia in the aqueous ammonia solution was 7.68 mol / l, and the reaction temperature was 80 ° C., gelation occurred within 3 hours and solidification also occurred at 80 ° C. It becomes a state.

Since the reaction rate of gelation and the like vary greatly depending on the conditions as described above, it is preferable to select appropriate conditions in consideration of conditions such as purpose, equipment and heat source, and efficiency. If a heat source is not used, it can be dissolved in an alkaline solution 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.

The carbonaceous gelled product obtained has a different transition temperature from a gel state having no fluidity to a sol state having fluidity depending on the production conditions, and the higher the concentration of the hydrophilic bituminous material, the more The higher the alkali concentration is, the more gel state is exhibited even at high temperature. Therefore, the carbonaceous gelled product referred to in the present invention changes from a gel state having no fluidity to a sol state having fluidity depending on the temperature thereof, and has a hydrophilic history in an alkaline solution at a certain temperature. Not only does this mean that the solution of the blue-green material has undergone a sufficient gelling reaction to lose fluidity and solidify, but it also has a viscosity that has increased due to a gelling reaction, that is, it loses fluidity when cooled. It also includes those that solidify. In addition, these are highly gelled or solidified ones that have not been heretofore available, because they have a high viscosity or are solidified while containing a large amount of water or a polar organic solvent in the alkaline solution used.

Further, since this carbonaceous gelled substance undergoes a continuous viscosity change from the state of an alkaline solution until it completely loses its fluidity and solidifies, the block, film, It becomes possible to form it into a shape such as a sphere or a fiber. When the gelling reaction is further promoted after the molding, the fluidity is lost and the mixture is solidified to obtain a carbonaceous gelled product having a desired shape.
Also, after gelling to make it not fluid at room temperature,
It is also possible to heat it to a sol state and mold it to a desired fluidity. Then, when dried, the product loses water or a polar organic solvent while shrinking to be a dried gelled product, that is, a carbonaceous gelled product molded product. This carbonaceous gelled product has a black pitch with a glassy luster and is optically isotropic when observed with a polarizing microscope.

Further, since the carbonaceous gelled product has a high viscosity or is solidified while containing a large amount of water or a polar organic solvent, it considerably contracts when it is dried. Therefore, when a large molded article is to be produced, the drying conditions should be selected with caution, as is the case with commonly known gels, and rapid evaporation of water or polar organic solvents should be avoided. Since the drying conditions remarkably differ depending on the size of the molded body, it cannot be unconditionally specified. Therefore, it is necessary to select appropriate conditions for each molded body.

As a method for molding into a desired shape, for example, in the case of a block shape, an alkaline solution of a hydrophilic bituminous material can be placed in a predetermined container and reacted as it is to gel and solidify. At this time, since it is in a solution state, it can be easily filled even in a container having a complicated shape and a fine structure. In addition, if the gelling reaction proceeds and the viscosity reaches a certain level, it can be applied to a substrate such as glass or carbon material.If a thick coating layer is made, a plate-shaped thin coating layer is made. If it does, it becomes a film. 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.
In this case, the viscosity of the carbonaceous gel to be added, the amount and concentration of the carbonaceous gel to be added, the stirring speed, and the particle size of the fine spheres obtained by the stirring force can be freely controlled, and the fine particles of about 0.1 to 100 microns can be controlled. You can get a sphere. Further, when this method is adopted, it is possible to remove water or the polar organic solvent in the alkaline solution at the same time as stirring, dispersing, and spheroidizing by raising the temperature of the medium, and therefore, from the dispersing medium. It is efficient because it is already a dried carbonaceous gelled body molded product when taken out. 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 carbonaceous gelled article thus obtained can be used as it is for the use of an ion exchanger or the like by utilizing its functional group, but in the case of another application, it is carbonized. It is also possible to graphitize it to obtain a carbon material.

Further, although the structure of the carbonaceous gelled product obtained by the method of the present invention, the reaction mechanism of gelation and the like have not been clarified yet, the carbonaceous bituminous material is treated with a hydrophilic bituminous material by an oxidation treatment or the like. It is also clear from the following test results that the properties of the gelled product and the gelled product in an alkaline solution are different.

That is, a hydrophilic bituminous material obtained by oxidizing raw coke with a mixed acid of sulfuric acid and nitric acid, and a dried carbonaceous gel material obtained by subjecting this to a gelation reaction in ammonia water and then drying. For, the behavior during heating was examined by a differential thermal balance. That is, 10 mg of the crushed sample was heated to 600 ° C. at a temperature rising rate of 10 ° C./min in a nitrogen stream, and the weight change and endothermic exothermic peak during this period were automatically recorded. The result is as shown in FIG. 1, and in FIG.
This curve is the heating loss curve, the upper two curves are the differential heat curves, the upward convex peak indicates exotherm, the downward convex peak indicates endotherm, and the solid line indicates the carbonaceous gel. It is the curve of the dry matter and the dotted line is the curve of the hydrophilic bituminous material. As is clear from FIG. 1, in the case of the hydrophilic bituminous material before gelation, a rapid heat loss was observed at a temperature of 200 to 400 ° C., and at this time, the exothermic peak of the sample was observed, but In the case of the dried carbonaceous gel product after the reaction in the solution, no rapid heat loss in this temperature range was observed, and no exothermic peak of the sample was observed. Loss on heating in this temperature range is considered to be elimination of functional groups introduced by oxidation treatment, etc., but such a difference in weight loss behavior indicates that some change has occurred in the functional groups due to gelation reaction. It is shown.

In order to further clarify the difference in the weight loss due to heating within the above temperature range, both of them are heated to about 140 to 235 ° C.
FIG. 2 shows the comparison of the weight loss when heated at the temperature of 3 hours. Fig. 2 shows the holding temperature during heating on the horizontal axis and
In the graph, the loss on heating after the retention of time is plotted on the vertical axis, the + symbol is the plot of the dried carbonaceous gel, and the □ symbol is the plot of the hydrophilic bituminous material. As is clear from FIG. 2, the weight loss due to heating at about 140 ° C. is larger in the dry carbonaceous gel,
On the contrary, when heated at 5 ° C., the hydrophilic bituminous material showed a larger weight loss. From this result, when the weight loss on heating in the range of 140 to 235 ° C is calculated and compared, the weight loss is about 13 wt% for the hydrophilic bituminous material, whereas it is only 5 wt% for the dried carbonaceous gel material. Is becoming

Furthermore, both of them are placed in a helium gas stream for 15 minutes.
After heating to 0 ° C. and holding for about 2.5 hours, and after confirming that the loss on heating had almost disappeared, when helium gas containing 3% of ammonia was replaced, the results were as shown in FIGS. 3 and 4. FIG. 3 is a diagram relating to a dried carbonaceous gel, and FIG. 4 is a diagram relating to a hydrophilic bituminous material. In both FIGS. 3 and 4, the horizontal axis indicates time, and The curve is the sample temperature, the central curve is a plot of the measured heating loss in mg units, and the lowermost curve is the measured heating loss calculated as a percentage (%) of the sample weight. It is a plot. This Figure 3
As is clear from FIG. 4 and FIG. 4, when heating in a helium gas containing 3% of ammonia, a new weight loss was observed in the case of the hydrophilic bituminous material, but in the case of the dried carbonaceous gel, No new heating loss was observed. Further, when the helium gas containing no ammonia was replaced again after about 4 hours, no weight loss was observed for both. This result is 150 ° C for hydrophilic bituminous material.
In the above, the active point that reacts with the ammonia gas is present, whereas this active point is not present in the dried carbonaceous gel material.

It is not clear yet what kind of structural difference between the two is the difference in behavior during heating.
The results of FIGS. 3 and 4 clearly show that they have different properties, and it is clear that the phenomenon of gelation is caused by some reaction.

Further, in the case of the carbonaceous gelled product of the present invention, although a slight shrinkage occurs by heating up to 1000 ° C., carbonization occurs while maintaining almost the original shape, and the above-mentioned JP-A-63- 139080, JP-A-64-9808,
It does not foam significantly as in the case of the method for producing a graphite material shown in JP-A-2-88414. Also,
The structure after the heat treatment at 1000 ° C. is optically isotropic as before the heating. Thus, in the case of a carbonaceous gelled product, carbonization and graphitization can be performed while maintaining a desired shape, and a carbon or graphite material having a desired shape, that is, the carbonaceous gelled product referred to in the present invention can be obtained. A carbonized or graphitized product is 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. Alumina, silicon carbide, which is not dissolved in an alkaline solution as a composite additive for forming a composite material,
There are inorganic materials such as boron carbide, metal materials such as iron, nickel and aluminum, and organic polymer materials such as polyethylene and polypropylene, and the shape of these materials may be differential or fibrous. Further, by adding a metal alkoxide, a metal salt or the like which is soluble in an alkaline solution, a composite material in which a metal is uniformly dispersed can be obtained. The thus-composited material can be carbonized and graphitized as required to obtain a carbonaceous gelled composite material.

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

[0053]

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. In the following examples, "%" means "% by weight" unless otherwise specified.

Example 1 This example shows an example of producing a carbonaceous gelled product near room temperature. Raw coke having a carbon content of 94.6%, hydrogen of 3.8% and nitrogen of 1.0% by elemental analysis was pulverized to 100 mesh or less to obtain a carbonaceous bituminous material as a starting material. 5 g of this raw coke was added to 7 g of concentrated sulfuric acid.
A mixed acid of 0% and concentrated nitric acid 30% in a ratio of 100 cc was gradually added to this mixed acid with stirring, and the mixture was further treated at 80 ° C. for 3 hours with stirring. This treatment liquid is 100 at room temperature.
The solution was added dropwise to 0 cc of water while 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%, hydrogen was 1.6%, and nitrogen was 6.6%.
Met. Most of the rest is sulfur and oxygen.

3 to 10 g of the hydrophilic bituminous material was added to 100 cc of an aqueous ammonium hydroxide solution having a different molar concentration, dispersed for 15 minutes by an ultrasonic cleaner at room temperature, and further dissolved by shaking for 12 hours. It was The obtained ammonium hydroxide aqueous solution was put into a 200 cc Erlenmeyer flask, and the reaction was carried out by putting it in a thermostat which was tightly closed and kept at 25 ° C. These contents gradually increased in viscosity and finally lost fluidity and solidified. The solidified product had a glassy luster, and when the weight was measured after solidification, it was confirmed that there was almost no change from that before the reaction and that the solidified product contained a large amount of water.

In order to examine the time required for this solidification, the Erlenmeyer flask is tilted after every predetermined time, and it is observed with the naked eye whether the contents flow, and after tilting the Erlenmeyer flask, about 1 minute The time required until the solidification was completed was defined as the time until the shape of the contents did not change at all.

Table 1 shows the difference between the molar concentration of ammonium hydroxide used and the amount of the hydrophilic bituminous material added until the completion of solidification.

[0058]

[Table 1]

Example 2 In this example, the progress of the gelation reaction near room temperature was traced from the change in viscosity. 6 g of a hydrophilic bituminous material obtained in the same manner as in Example 1 was added to 100 cc of an ammonium hydroxide aqueous solution having a molar concentration of 1.92, dispersed at room temperature for 15 minutes by an ultrasonic cleaner, and further shaken for 12 hours. It was then dissolved. The obtained ammonium hydroxide solution was put in a 200 cc Erlenmeyer flask, and the reaction was carried out by putting it in a thermostat bath which was tightly closed and kept at 25 ° C., and after a predetermined time, its viscosity was measured using a rotary viscometer. The result is as shown in FIG. 5. A rapid increase in viscosity was observed after a reaction time of 20 hours, and measurement was impossible with a viscometer used after 40 hours.

Then, in the same manner as in Example 1, when the state of gelation was visually confirmed by the tilt method, the reaction time was 5
In the case of 0 hours, the solidified so that the shape did not change at all for 1 minute even after tilting the Erlenmeyer flask.

Example 3 In this example, the gelling reaction was carried out at a relatively high temperature. In a 200 cc Erlenmeyer flask, 3 to 13 g of the hydrophilic bituminous material obtained in the same manner as in Example 1 and 100 cc of an aqueous solution of ammonium hydroxide having different molar concentrations were placed, and a rotor of a magnetic stirrer coated with Teflon was placed in the flask. , Tightly stopper and immerse in a water bath maintained at 80 ° C,
The reaction was carried out from the lower part for 3 hours while rotating with a rotating magnet.

During this period, as a result of observing the contents, the reaction situation varied depending on the hydrophilic bituminous material concentration and the molar concentration, and the gelation rapidly progressed and the rotation of the rotor stopped within 3 hours (A ) The rotor did not stop for 3 hours, but when the Erlenmeyer flask was taken out of the 80 ° C. water bath and immediately cooled, it solidified into a gel (B),
After the reaction for 3 hours and 3 hours, there was still fluidity even after cooling, and there was one (C) which was judged that the reaction time of 3 hours was not sufficient.

Table 2 shows the difference between the respective situations when distinguished by the symbols (A) to (C) as described above.

[0064]

[Table 2]

Example 4 In this example, a fine spherical body was produced as an example of a carbonaceous gelled body, a carbonaceous gelled body molded product, and a carbide thereof. As the carbonaceous bituminous material, mesophase pitch having a Mettler method softening point of 300 ° C. manufactured using coal tar as a raw material was used. This mesophase pitch has an anisotropy amount of almost 100% (area percentage of anisotropic phase), and carbon, hydrogen and nitrogen contents by elemental analysis are 93.2% and 4.
The content was 0% and 1.0%, the quinoline insoluble content was 0.5%, the pyridine insoluble content was 39.5%, and the xylene insoluble content was 95.3%.

This pitch was pulverized to 100 mesh or less, and 31% of hydrogen peroxide solution 2 was added to 10 g of pitch.
Put it in this hydrogen peroxide solution at a ratio of 00cc,
Oxidation treatment was carried out while stirring for 30 hours. After completion of the oxidation treatment, the mixture was cooled to room temperature, filtered with a glass filter, thoroughly washed with water, and dried under reduced pressure at 40 ° C. to obtain various hydrophilic bituminous materials.

Subsequently, 4 g of these hydrophilic bituminous materials were added to an ammonium hydroxide aqueous solution 1 having a molar concentration of 1.92 mol / l.
Each was added to 00 cc, and ultrasonically dispersed and shaken to dissolve in the same manner as in Example 1. These lysates were filtered with a glass filter, and the insoluble components remaining on the glass filter were thoroughly washed with water, dried and weighed. The amount of insoluble ammonium hydroxide solution was determined. It took about 30 hours to make almost all the bituminous material soluble in the aqueous ammonium hydroxide solution. The elemental analysis result of the hydrophilic bituminous material soluble in this ammonium hydroxide aqueous solution was as follows: carbon 66.7%, hydrogen 2.7.
%, And nitrogen was 1.8%.

[0068]

[Table 3]

4 g of the hydrophilic bituminous material obtained with the oxidation time of 30 hours was placed in 100 cc of an aqueous ammonium hydroxide solution having a molar concentration of 5.12 mol / l, dissolved in the same manner as in Example 1, and placed in a 200 cc Erlenmeyer flask. , After sealing
The mixture was placed in a constant temperature bath at 25 ° C. and reacted. The viscosity of the melt was measured with a rotary viscometer after every predetermined time, and it was confirmed that the viscosity gradually increased. Viscosity of 50 x 1 after reacting for 18 days
20 g of the carbonaceous gelation product having 0 ⁻³ Pa · s was added to 500 cc of olive oil kept at 90 ° C., and stirring was continued for 1 hour. Thereafter, the mixture was cooled with stirring, the mixture was centrifuged, and the dispersed carbonaceous gelled product was taken out, washed with benzene and acetone, and then dried. Observation of the obtained carbonaceous gelled article with a scanning electron microscope revealed that it was a spherical article with a smooth surface of 10 μm or less as shown in FIG. 6 (500 times) and FIG. 7 (2,010 times). It was confirmed that there is.

Further, the spherical substance was heat treated at a temperature of 1000 ° C. to obtain a carbonaceous gelled carbide, and its shape was confirmed with a scanning electron microscope. It was confirmed that they were held, and it was found that they were carbonized without causing deformation such as melting and softening.

The reaction time was 1 day, and the viscosity was 1 × 10 ^-3 Pa.
When spheroidization was performed by the same operation as above using the dissolved substance of s, the obtained spheres had wrinkles on the surface as shown in FIG. 8 (510 times) and FIG. 9 (2,040 times). It was something. Immediately after dissolving the hydrophilic bituminous material in the aqueous ammonium hydroxide solution, the viscosity of the dissolved material is also 1 × 10 ⁻³ P.
The desired gelling reaction did not proceed with the dissolved product having a reaction time of 1 a · s and a reaction time of 1 day, so that a spherical product having a desired smooth surface could not be obtained.

Example 5 In this example, a fine spherical body was manufactured as an example of a carbonaceous gelled body and a molded product of a carbonaceous gelated body. Example 1
6 g of hydrophilic bituminous material obtained in the same manner as in 1.
It was put in 100 cc of 92 mol / l ammonium hydroxide aqueous solution, and reacted in the same manner as in Example 3 while stirring at 80 ° C. for 3 hours. After reacting this at 80 ° C for 3 hours,
It had fluidity at 80 ° C, but when cooled, it gelled, lost fluidity, and solidified. This product was heated again to 80 ° C. so as to have fluidity, and 20 g thereof was put in 500 cc of olive oil at 90 ° C.
After stirring in olive oil at ℃ for 1 hour, cooling and centrifuging, the dispersed carbonaceous gel was taken out, washed with benzene and acetone, dried and observed under a microscope. The surface was smooth. It was confirmed that a fine spherical body was obtained.

Example 6 This example is an example in which sodium hydroxide was used as an alkali and a gelling reaction was carried out at a relatively high temperature. 200
In a cc Erlenmeyer flask, 8 to 14 g of the hydrophilic bituminous material obtained in the same manner as in Example 1 and 100 cc of a sodium hydroxide aqueous solution having a molar concentration of 0.20 mol / l were placed, and the rotor of a magnetic stirrer coated with Teflon was placed therein. After putting in, the container was sealed and 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.

During this period, as a result of observing the contents, Example 3
As in the case of using the ammonium hydroxide aqueous solution, the reaction situation varies depending on the hydrophilic bituminous substance concentration, and the rotation of the rotor is stopped within 3 hours due to rapid gelation (A), 3 hours During this period, the rotor did not stop, but when the Erlenmeyer flask was taken out of the 80 ° C water bath and immediately cooled, it solidified into a gel (B), and after 3 hours of reaction, it remained fluid even after cooling. Remained, and there was one (C) which was judged that the reaction time of 3 hours was not sufficient.

The state of gelation is summarized in the same manner as in Example 3 and is shown in Table 4.

[0076]

[Table 4]

Example 7 An isotropic pitch having a softening point of 260 ° C., a quinoline insoluble matter of 0% and a xylene insoluble matter of 61% was mixed with 100 g of a mixed acid of 70% concentrated sulfuric acid and 30% concentrated nitric acid per 5 g of this pitch. It was gradually added to the mixed acid with stirring, and further treated by stirring at 80 ° C. for 3 hours. Then these things 1
The reaction was stopped by pouring into 000 cc of water at room temperature, and these were filtered to obtain a hydrophilic bituminous material. Subsequently, 6 to 15 g of these hydrophilic bituminous materials were added to 100 cc of an ammonium hydroxide aqueous solution having a molar concentration of 1.92 mol / l and reacted in the same manner as in Example 3 at 80 ° C. with stirring.

During this period, the contents were observed in the same manner as in Example 3. As a result, the gelation rapidly proceeded and the rotation of the rotor was stopped within 3 hours (A). The rotation was continued for 3 hours. The child never stopped, but the Erlenmeyer flask was
It was judged that the reaction time of 3 hours was not sufficient, because it was solidified into a gel immediately after being taken out from the water bath at ℃ (C) and solidified into a gel immediately after cooling, and still had fluidity after cooling for 3 hours. Thing (C) was present.

Table 5 shows the difference between the respective situations when the above-mentioned symbols (A) to (C) are distinguished.

[0080]

[Table 5]

[0081]

Industrial Applicability The carbonaceous bituminous material, the hydrophilic bituminous material derived therefrom, and the material derived from the hydrophilic bituminous material are conventionally solids, and are handled as solids. There was no choice but to be restricted in various fields of use.

The present invention provides a novel carbonaceous gelled product and its utilization form, focusing on the gelling reaction of a hydrophilic bituminous material in a newly found alkaline solution. By effectively and effectively utilizing the gelation reaction product, various restrictions due to being a solid, which was a big problem in the past, were removed, and the carbonaceous bituminous material could be handled in any shape. It is intended to increase the utility value of carbonaceous bituminous materials and enable the development of new fields of application.

[Brief description of drawings]

FIG. 1 shows the results of measurement of the heat loss and endothermic exothermic peaks of a dried carbonaceous gel and a hydrophilic bituminous material by a differential thermal balance.

FIG. 2 shows the measurement results of the weight loss due to heating of the dried carbonaceous gel material and the hydrophilic bituminous material.

FIG. 3 shows the measurement results of the heating loss in a heated helium gas stream and a helium gas stream containing ammonia of a dried carbonaceous gel.

FIG. 4 shows the measurement results of heating loss of a hydrophilic bituminous material in a heated helium flow and in a helium flow containing ammonia.

FIG. 5 shows the measurement results of the viscosity change with the passage of reaction time of a solution prepared by dissolving a hydrophilic bituminous material in an ammonium hydroxide aqueous solution in Example 2.

FIG. 6 is a scanning electron micrograph (500 times) of the spherical carbonaceous gelled product molding of the present invention obtained in Example 4.

FIG. 7 is a scanning electron micrograph (2,010) of the spherical carbonaceous gelled product molding of the present invention obtained in Example 4.
Times).

FIG. 8 is a scanning electron micrograph (5) of spherical carbonaceous particles prepared by using an alkaline aqueous solution of a hydrophilic bituminous material in which a gelling reaction has not progressed for the purpose of comparison in Example 4.
10 times).

9 is a scanning electron micrograph (2,040 times) of spherical carbonaceous particles prepared using an alkaline aqueous solution of a hydrophilic bituminous material in which a gelling reaction has not progressed for the purpose of comparison in Example 4. FIG. Is.

Claims (4)

[Claims] 1. A hydrophilic bituminous material soluble in an alkaline solution is obtained by subjecting a carbonaceous bituminous material to oxidation, nitration, sulfonation, amination, or a combination of at least two of these, and converting this into an alkaline solution. A method for producing a carbonaceous gelled product, which comprises forming a gel-like substance containing a large amount of a solvent by performing a gelling reaction in an alkaline solution after dissolution. 2. A hydrophilic bituminous material soluble in an alkaline solution is obtained by subjecting a carbonaceous bituminous material to oxidation, nitration, sulfonation, amination, or a combination of at least two of these, which is then converted into an alkaline solution. After dissolution, a gelling reaction is caused as it is in an alkaline solution, and when it becomes a desired fluidity, it is molded into a desired shape, further progresses the gelling reaction to solidify, and the carbon is characterized by drying. Of producing a highly gelled molded article. 3. A hydrophilic bituminous material soluble in an alkaline solution is obtained by treating a carbonaceous bituminous material with oxidation, nitration, sulfonation, amination, or a combination of at least two of these, and using this as an alkaline solution. After dissolution, the gelling reaction takes place in the alkaline solution as it is, and when it becomes the desired fluidity, it is molded into the desired shape, and the gelling reaction is further advanced to solidify it, and this is dried to form a carbonaceous gel. A method for producing a carbonized or graphitized product of a carbonaceous gelled body molded article, which comprises subjecting the molded article to a carbonization treatment or carbonization treatment or graphitization treatment. 4. A hydrophilic bituminous material soluble in an alkaline solution is obtained by subjecting a carbonaceous bituminous material to oxidation, nitration, sulfonation, amination, or a combination of at least two of these, which is then converted into an alkaline solution. A carbonaceous gelled product, which is a gel-like substance containing a large amount of a solvent, obtained by a gelling reaction of an alkaline solution after dissolution.