JPH0712923B2 - Method for producing carbonaceous mesophase molded article - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a carbonaceous mesophase molded article useful as a separating agent for ions and the like, an adsorbent, and the like.

(Prior Art) A general carbon material is produced by kneading aggregate coke powder with a binder, molding and firing. Since the kneaded product with the binder is in a semi-solid state, the carbon material produced has a simple shape such as a cylinder or a square. Therefore,
Machining is mainly performed to obtain a carbon material having a desired shape. Primary fired products rarely become products as they are, and most of them are commercialized by processing.

The carbonaceous mesophase and raw coke produced in the transition stage (carbonization process) to carbon by heat treatment of heavy bituminous materials such as pitch are lumps and granular solids, but they can be pressure molded as they are because they are organic substances. A high-density carbon material is mainly manufactured by firing this molded body.

(Problems to be Solved by the Invention) Although the carbonaceous mesophase and raw coke are still organic substances as described above, the shape that can be formed is as simple as general carbon materials because they are lumpy or granular. However, it is not possible to make a molded product with a complicated shape. Further, although it is an organic substance, there is no solvent to dissolve it, and it does not melt even if it is heated unless special treatment is performed.

Under these circumstances, the carbonaceous mesophase and green coke have not been found to have particularly large applications other than the raw material for producing the high-density carbon material by pressure-molding the mesophase. Therefore, the present inventors have previously found that an amphiphilic carbonaceous mesophase soluble in water or an organic solvent can be produced by introducing a hydrophilic group into the carbonaceous mesophase insoluble in water or an organic solvent. It was This makes it possible to handle solid carbonaceous mesophases like liquids,
Moreover, they have found that chemical modification can be easily performed, and have completed the present invention.

(Means for Solving Problems) That is, the gist of the present invention is that, when a carbonaceous mesophase molded article is produced by molding a carbonaceous mesophase molded article, an amphipathic property having a hydrophilic group soluble in water or an organic solvent. The present invention relates to a method for producing a carbonaceous mesophase molded article, which comprises subjecting a carbonaceous mesophase to crosslinking treatment.

Hereinafter, the present invention will be described in detail.

In the present invention, an amphipathic carbonaceous mesophase is used as the carbonaceous mesophase for molding.

This amphiphilic carbonaceous mesophase is meant to be a carbonaceous mesophase soluble in both water and an organic solvent, and can be obtained from the carbonaceous mesophase as a raw material by the following method. The carbonaceous mesophase of this raw material is an aromatic system such as quinoline or anthracene oil, which is a good solvent for the heavy bituminous substance and has an optically anisotropic phase observed by a polarization microscope at room temperature. What is separated as an insoluble component of oil, or what is converted from a heavy bituminous product to a full-weight anisotropic phase is used. The optically anisotropic phase in the heat-treated heavy bituminous material is simply referred to as an anisotropic phase. Originally, carbonaceous mesophase is used as a general term including the optically anisotropic phase produced by heat treatment of heavy bituminous material that is an optically isotropic phase and the one obtained by separating it. Means an optically anisotropic phase that does not substantially contain an optically isotropic phase as the carbonaceous mesophase of the raw material.

(1) Preparation of raw material carbonaceous mesophase The preparation of carbonaceous mesophase is performed by heat treatment and separation of a heavy bituminous material such as tar or pucci. Examples of heavy bituminous products used are coal tar, coal tar pitch and coal liquefaction in coal systems. In petroleum oil, distillate residue oil of crude oil, tar by-produced by thermal decomposition of naphtha,
It is a heavy component of tar, oil sands and oil shale, which are by-products of the fluid catalytic cracking (FCC) method. In addition, synthetic polymers such as polyvinyl chloride (PVC) can also be used.

These heavy bituminous products are heat treated at temperatures in the range of about 350-500 ° C, preferably 400-500 ° C. The temperature and the holding time are determined by the properties of the obtained carbonaceous mesophase, especially the elemental analysis value thereof. That is, among the constituent elements, it is preferable that the content of hydrogen be 15% by weight or more. The yield of amphiphilic carbonaceous mesophase decreases from a carbonaceous mesophase having a hydrogen content below this value.

When the heat-treated heavy bitumen contains an optically isotropic phase, aromatic oils such as quinoline and anthracene oils are added and heated to dissolve and disperse. Then, the soluble component is separated by filtration and centrifugation to obtain a carbonaceous mesophase as an insoluble component, or the heavy bituminous material is heated and melted, and this is allowed to stand to precipitate an anisotropic phase, A carbonaceous mesophase is obtained by separating this. When substantially all of the heat-treated heavy bituminous material has an optically anisotropic phase, it is directly used as a carbonaceous mesophase. When this carbonaceous mesophase contains a component soluble in quinoline and aromatic oil, it may be treated with these solvents.

(2) Production of amphiphilic carbonaceous mesophase A hydrophilic group is introduced into the obtained carbonaceous mesophase. As this hydrophilic group, a nitro group, a sulfonic acid group,
Examples thereof include a hydroxyl group, a carboxylic acid group and an amino group.
Examples of treatment methods such as nitration, sulfonation, oxidation and amination for introducing these groups are as follows.

(A) Nitration treatment It is general to use a mixed acid of concentrated sulfuric acid and concentrated nitric acid or concentrated nitric acid as a reaction reagent. The mixing ratio of sulfuric acid, which is a mixed acid, and nitric acid is preferably 2: 1 to 1: 2 mol ratio. Add 20ml or more of mixed acid to 1g of carbonaceous mesophase, and add 10g at 0-150 ℃
~ Process for about 300 minutes. At this time, either stirring or standing may be performed. After a lapse of time, transfer to a large amount of water to stop the reaction.

(B) Sulfonation treatment Generally, a mixture of concentrated sulfuric acid and fuming sulfuric acid is used as a reaction reagent. When only concentrated sulfuric acid is used, sulfonic acid groups are introduced, but this is not preferable because the yield of the amphoteric carbonaceous mesophase is very low. The mixing ratio of fuming sulfuric acid to concentrated sulfuric acid is about 10 to 100% (volume ratio).
A mixture of 20 ml or more is added to 1 g of carbonaceous mesophase, and the mixture is treated at 50 to 150 ° C for 30 minutes or more. After the treatment, it is filtered as it is or transferred to a large amount of water to stop the reaction.

(C) Oxidation treatment For this treatment, a method used for surface oxidation treatment of solid carbon such as a gas phase method using nitric oxide, ozone, water vapor, etc. and a liquid phase method using hydrogen peroxide or hydrogen peroxide and acetic acid etc. It is common to choose from. For example, in the case of liquid phase method,
20 ml or more of hydrogen peroxide with a concentration of 30-35% is added to 1 g of carbonaceous mesophase and heat-treated at 80-100 ° C for 60 minutes or more. In the case of, 1 g of carbonaceous mesophase is suspended in acetic acid, and 20 ml or more of hydrogen peroxide having a concentration of 30 to 35% is added dropwise while stirring. After adding the whole amount, heat-treat at 80 to 100 ° C for 60 minutes or more.

(D) Amination treatment The introduction of an amino group is carried out by converting the above-mentioned nitration treatment into a amino group by reduction treatment. The nitrated product used is a nitrated carbonaceous mesophase or an amphipathic carbonaceous mesophase obtained from the present invention. The reduction treatment of these nitration products is carried out by heating treatment at a temperature of about 100 ° C. in an ordinary reduction reaction with a metal powder such as iron, zinc, tin and an acid or alkali. By this treatment, the nitro group can be converted stoichiometrically into an amino group.

By the above method, a nitro group and a carboxylic acid group are introduced in (a), a sulfonic acid group is introduced in (b), a hydroxyl group and a carboxylic acid group are introduced in (c), and an amino group is introduced in (d). When these reactants are transferred to a large amount of water to stop the reaction and allowed to stand, the carbonaceous mesophase precipitates.
The color of the supernatant depends on the reaction conditions. That is, when treated under mild conditions, it is hardly colored,
Colors slightly when conditions are severe. This means that the pH of the supernatant liquid is about 2 or less when the reaction product is transferred to water, and the amount of the carbonaceous mesophase component soluble in water is considered to be small.

In the present invention, the hydrophilic group-introduced carbonaceous mesophase is dissolved in water or an organic solvent, and the desired amphiphilic carbonaceous mesophase is obtained from the resulting solution.

When dissolved in water, after the above reaction, an aqueous alkaline solution is added to the suspension in water to adjust the pH. The alkali used is preferably an alkali metal salt or an aqueous ammonia solution. The amount of carbonaceous mesophase dissolved when an aqueous alkaline solution was added was determined by the reaction conditions such as nitration reaction and the pH of the suspension.
Depends on. The more severe the reaction conditions, the more the total amount of carbonaceous mesophase is solubilized in the low pH region. After adjusting the pH to 4 to 14 with the above alkaline aqueous solution, the undissolved carbonaceous mesophase is removed by filtration, centrifugation, or the like. The pH of the suspension is 12
Even if it is above, the amount of dissolution does not change significantly.

The alkali-soluble matter thus obtained is adjusted to pH by adding acid.
Is precipitated in a more acidic region, the amphiphilic carbonaceous mesophase is obtained by collecting it. The pH value in the acidic region for precipitation varies depending on the reaction conditions. For example, in the nitration reaction, when the reaction was carried out at 100 ° C., the pH was about 2 and the supernatant liquid after the precipitation was settled by standing was almost colorless.
When the reaction is carried out at 0 ° C., the supernatant is colored even if the pH is adjusted to 1 or less, and complete precipitation cannot be achieved. In addition, in the case of an oxidation treatment product with hydrogen peroxide, it hardly precipitates at a pH of 2, and when it is 1 or less, it precipitates and precipitates as the supernatant becomes colorless, but there are components that cannot be precipitated when the reaction conditions are severe.

On the other hand, in the treatment with an organic solvent, the one after the above reaction treatment is directly transferred to the organic solvent, or after the reaction treatment, it is suspended in water, and the carbonaceous mesophase from which the reaction reagent is removed by filtration, centrifugation, etc. Add to organic solvent and dissolve. The organic solvent used is selected from those having polar groups such as ketones, esters, ethers, alcohols, organic acids, nitrogen-containing compounds and sulfoxides.

For example, ketones and esters are acetone, methyl ethyl ketone and ethyl acetate, ethers are tetrahydrofuran, dioxane and diethylene glycol dimethyl ether, alcohols are methanol, ethanol, ethylene glycol and glycerin, and organic acids are formic acid, acetic acid and phenol. , Cresol, the nitrogen-containing compound is ethylenediamine, aniline, pyridine, dimethylformamide, and nitromethane, and the sulfoxide is dimethylsulfoxide, which can be appropriately selected depending on the kind of introduced hydrophilic group.

Almost all of the above-mentioned carbonaceous mesophase introduced with a hydrophilic group is dissolved in these organic solvents, but the kind of reaction,
Depending on the conditions, undissolved carbonaceous mesophase may remain. At this time, the undissolved carbonaceous mesophase is removed by filtration, centrifugation, or the like. When the organic solvent is dissolved in an organic solvent, the amphiphilic carbonaceous mesophase is obtained by removing the organic solvent by distillation or the like.

The yield of the amphipathic carbonaceous mesophase thus obtained is that there is almost no undissolved carbonaceous mesophase,
In addition, when the total amount is precipitated in the acidic region, it becomes 100% or more.
This is due to the introduction of functional groups, and the rate of increase is usually 30-40%. The term “dissolution” as used in the present invention means that the carbonaceous mesophase as solid particles is treated and dissolved in an alkaline aqueous solution or an organic solvent to separate it from undissolved carbonaceous mesophase by filtration. Indicates that the carbonaceous mesophase component in the solution is a true solution or a colloidal state when the dissolution operation is performed.

(3) Amphiphilic carbonaceous mesophase The obtained amphiphilic carbonaceous mesophase is in a muddy or slurry state when it contains water, but becomes a lump when dried. The fracture surface of this agglomerate exhibits a black glassy mirror surface, which is different from that of the carbonaceous mesoface having a gray-black diffuse reflection surface. Further, the lumps are completely dissolved when added again to the alkaline aqueous solution or the organic solvent, and are precipitated when the pH is lowered by the acid or the solvent is removed.

Observation with a polarizing microscope shows that the raw material carbonaceous mesophase has optical anisotropy, while it exhibits isotropicity, indicating that the molecules are not oriented (the substance of the mesophase is considered unchanged). .

The elemental composition contains many hetero elements such as oxygen, nitrogen and sulfur. Since these amounts differ depending on the reaction, they will be described in detail in Examples. In addition, when the functional group was examined by infrared absorption spectrum, it was about 30 in the carbonaceous mesophase.
30 cm ^-1, whereas the absorption spectrum attributable to aliphatic hydrogen absorption and about 2920 cm ^-1 attributable to the aromatic hydrogens 750～900Cm ^-1 is observed, aromatics amphiphilic carbonaceous mesophase Absorption of and aliphatic hydrogen is very weak, and in some cases almost never observed. Along with that, about 1700 cm ^-1 carbonyl group, 3500-3000 cm ^-1 hydroxyl group, about 1560, 1340 cm
^-1 nitro group, 1230, sulfonic acid group near 1180 cm ^-1 , 34
A new absorption attributed to the amino group at 10,3500 cm ^-1 appears.

When heat-treated in an inert gas, it is carbonized without passing through the liquid phase (solid-state carbonization). The yield of carbonized product when heat-treated to 1000 ° C is about 50 to 70% by weight. This value is low compared to that of the carbonaceous mesophase which is about 90% by weight. This is due to the elimination of the introduced functional group, and when we examined the weight change during the heating process with a thermobalance, it was about 25
There is a large amount of weight loss at 0 to 350 ° C, which is considered to be due to elimination of the functional group introduced in this temperature range.

Next, the amphipathic carbonaceous mesophase is subjected to a crosslinking treatment. This cross-linking treatment does not cause modification of the carbonaceous mesophase in an atmosphere and at a temperature (usually 400 ° C or lower, preferably 200 ° C or lower).
It can be performed under the conditions of.

For example, in the case of a chemical method, the hydrophilic group can be appropriately selected depending on the kind of hydrophilic group that the amphiphilic carbonaceous mesophase has, the use of the resulting molded article, etc., but the hydrophilic group is a hydroxyl group, a carboxyl group, an amino group, etc. When it has active hydrogen, it is generally subjected to crosslinking treatment by a condensation reaction or an addition reaction type ionic mechanism. The cross-linking agent is selected from polyvinyl alcohol (PVA), polyvinyl chloride (PVC), polyvinylidene chloride, epoxy, etc.

The following is an example of the case where a film is obtained by a cross-linking treatment by a chemical method. In the amphipathic carbonaceous mesophase, the hydrophilic group introduced as described above differs depending on the preparation method. For example, the groups introduced by nitration reaction are nitro group, carboxylic acid group, and hydroxyl group, and by sulfonation reaction, only sulfonic acid group is introduced. Thus, since the hydrophilic groups are different, it is necessary to use a cross-linking agent that reacts with these hydrophilic groups. When PVA is used as the cross-linking agent, an ether bond is generated by a dehydration reaction between the hydroxyl group of PVA and the hydroxyl group of the amphiphilic carbonaceous mesophase, and cross-linking occurs. Since the amphiphilic carbonaceous mesophase is soluble in water at pH 4 to 14 as described above,
When preparing an amphipathic carbonaceous mesophase, if one dissolved in an alkaline solution is used, add PV to this aqueous solution.
Add powder A as it is or dissolved in water. When the amphipathic carbonaceous mesophase precipitated with an acid is used, an alkaline aqueous solution is added to dissolve it.
At this time, PVA may be added either before or after the addition of the alkaline aqueous solution. The acid is then added to bring the pH below about 2. As a result, the amphipathic carbonaceous mesophase gels. It is preferably heated to a temperature above about 30 ° C. The heated product is filtered to remove water and excess PVA, and formed into a film. Then, put it together with the filter paper in an acidic aqueous solution with a pH of about 1 or less and heat it to about 70-100 ° C.
Allow the reaction to proceed to some extent. By this heat treatment, the shape of the film is maintained even if it is peeled from the filter paper.
If the film is peeled from the filter paper, keep it on a plate made of a material such as polytetrafluoroethylene (“Teflon”) that does not adhere even when dried, at about 50 to 100 ° C for several hours. . By this operation, the dehydration reaction is completely performed. The film obtained by such a method does not dissolve even when placed in an alkaline aqueous solution.

As described above, the kind of the cross-linking agent can be selected depending on the kind of the hydrophilic group that the amphiphilic carbonaceous mesophase has, but if it has a group that reacts with the hydrophilic group, that kind,
The reaction conditions are not particularly limited.

Further, the crosslinking is generally performed after molding from the viewpoint of moldability and the like, but is not necessarily limited to this.

In the present invention, the shape of the molded body can be selected arbitrarily, and in addition to the film (thin film) as described above, a plate-like shape,
The block shape or the like can be obtained according to the purpose by a conventional method such as a casting method in the molding method itself.

Further, in the present invention, when a carbon molded body is formed, by applying a magnetic field (for example, 1 to 10 KG),
Since the molecules can be oriented parallel to the magnetic field direction,
It is possible to obtain a molded product having a more ordered molecular arrangement.

(Examples) Hereinafter, the present invention will be described in more detail with reference to Examples and Examples.

Reference Example 1 Coal tar pitch (softening point 78 ° C, benzene insoluble content 38.1
Wt%, quinoline insoluble matter 3.8% by weight) was put into about twice the amount of quinoline and heated to 90 ° C. to dissolve and disperse. This was filtered under reduced pressure with a glass filter (No. 4). The filtrate was distilled under reduced pressure to obtain a pitch containing no quinoline-insoluble component as the residue. About 400 g of this pitch was put in a 500 ml cylindrical container made of glass and heat-treated at 430 ° C. for a predetermined time in a nitrogen gas stream while stirring. This heat treatment time was adjusted so that the amount of quinoline-insoluble component in the heat-treated pitch was about 30, 50 and 90% by weight. That is, 30% by weight
Was 25 minutes, 50% by weight was 45 minutes, and 90% by weight was 120 minutes. The heat-treated pitch was added to about twice the amount of quinoline and heated to 90 ° C. to dissolve and disperse. An insoluble component was settled in the centrifuge, and the supernatant was removed. New quinoline was added to the precipitate, heated to 90 ° C., and then sedimented by a centrifuge. By repeating this operation, the insoluble component was washed until the quinoline was slightly colored (5 to 8 times). Then, it was washed several times with benzene and further washed with acetone to remove quinoline, and dried to obtain an insoluble component. The amount of the insoluble component obtained in this way, with respect to the heat treatment pitch,
They were 29.1, 50.6 and 86.7% by weight, respectively. Of these insoluble components, those of 29.1 and 50.6% by weight were further put in about 3 times the amount of quinoline, heated to about 300 ° C., and kept under reflux of quinoline (boiling point of quinoline: 238 ° C.) for 3 hours. This was thoroughly washed with quinoline at 90 ° C. Then benzene,
It was washed with acetone to remove quinoline and dried. The insoluble component thus obtained was used as a carbonaceous mesophase. Hereinafter, these carbonaceous mesophases will be referred to as CP (30) 238Q1, CP (50) 238Q1 and CP (90) 90Q1, respectively, where CP is an abbreviation for coal tar pitch and the value in parentheses is heat treated at 90 ° C. The amount of quinoline insoluble component in the prepared pitch, and the following numerical values and symbols are abbreviations of temperature and quinoline insoluble component when the carbonaceous mesophase was prepared.

Furthermore, the same raw coulter pitch as above is used at 450 ° C.
Then, the whole was solidified by heat treatment for 180 minutes and 300 minutes. Grind this as it is, or heat it at 450 ° C for 300 minutes and heat it to about 300 ° C in about 3 times the amount of quinoline,
The quinoline insoluble component obtained by treating the quinoline under reflux for 3 hours was used as a carbonaceous mesophase. In addition, these carbonaceous mesophases are CP (450 to 180) and CP (450 to 30), respectively.
0) and CP (450-300) 238Q1.

The carbonaceous mesophase obtained by the above operation was crushed to 42 mesh (0.35 mm) or less, and the following experiment was conducted using this. Table 1 shows the elemental composition of the carbonaceous mesophase.

(A) Nitration reaction 1 g of carbonaceous mesophase was placed in an Erlenmeyer flask having a capacity of 200 ml, 20 ml of a mixed acid of 97% concentrated sulfuric acid and 68% concentrated nitric acid was added thereto, and then heated in an oil bath at 100 ° C. for 60 minutes. Immediately after the lapse of time, the reaction mixture was taken out from the oil bath and transferred into about 300 ml of water to stop the reaction. To this, add 1N NaOH aqueous solution to adjust the pH to 12
Adjusted to. Then, insoluble components were precipitated in this solution by a centrifuge, and the supernatant was filtered under reduced pressure with a membrane filter having an opening of 0.45 μm. All the insoluble components were washed out with a pH = 12 aqueous solution of NaOH on a filter, filtered, and finally the insoluble components were washed with a small amount of distilled water, dried and weighed.
Aqueous HCl solution is added to the solution that has passed through the filter to adjust the pH to 0.7.
Adjusted to ~ 1.0. Soluble components precipitated and settled out when left standing overnight, so the precipitate was settled with a centrifuge, and the supernatant was filtered under reduced pressure with a 0.45 μm membrane filter, and the precipitate was washed with an aqueous solution of pH = 1. The entire amount was washed out on the filter and dried. The precipitate was in a muddy state at the stage of filtration and became granular by drying.

The same operation as above was carried out with a mixed acid in which the reaction temperature, time and the mixing ratio of concentrated sulfuric acid and concentrated nitric acid were changed, and the carbonaceous mesophase used as the soluble component was the component that passed through a membrane filter with an opening of 0.45 μm. The difference in the amount of the insoluble component from the amount of was calculated as a percentage with respect to the carbonaceous mesophase, and this value was taken as the dissolution rate. In addition, the results obtained are summarized in Table 2 in which the soluble component is deposited by pH adjustment and the dried deposit, that is, the amount of the amphiphilic carbonaceous mesophase is used as the deposit.

Next, 1 g of carbonaceous mesophase of CPBM (50) 238QI was placed in an Erlenmeyer flask, and it was mixed with 97% concentrated sulfuric acid and 64% concentrated nitric acid 70: 3.
20 ml of mixed acid of 0 (volume ratio) was added, and the mixture was treated at 100 ° C. for 60 minutes. After cooling to room temperature, it was transferred to 300 ml of water. Since the pH of this aqueous solution was about 1.5, the pH was adjusted to 10, 8, 6, 4, and 2 by adding a 1N NaOH aqueous solution. After centrifugal sedimentation, the supernatant was filtered under reduced pressure with a 0.45 μm membrane filter and the precipitate was adjusted to pH with HCl or NaOH.
The whole amount was washed out on the filter with each adjusted aqueous solution, washed with a small amount of distilled water, dried and weighed. The filtrate was adjusted to pH = 0.7 to 10 with an aqueous solution of HCl, allowed to stand for a whole day and night, and then the precipitate was centrifugally sedimented, filtered under reduced pressure with a similar filter, dried and weighed.

The amount of insoluble components, the dissolution rate, and the amount of precipitates thus obtained are summarized in Table 3.

Furthermore, CPBM (50) 238QI was used as a carbonaceous mesophase, 1 g of which was collected in an Erlenmeyer flask, and 20 ml of a mixed acid of 97% concentrated sulfuric acid and 64% concentrated nitric acid at 70:30 (volume ratio) was added,
It was treated at 60 ° C for 60 minutes. Then, transfer to about 300 ml of water, 1
After adjusting the pH to 12 with a specified NaOH aqueous solution, the opening is 0.45 μm
It was filtered under reduced pressure with a membrane filter. The obtained filtrate was allowed to stand overnight for one day, but no precipitate was observed. Then, it was transferred to a centrifuge tube and spun down by a centrifuge at 13,000 rpm for 60 minutes, but in this case as well, there was no sedimentation.

Six of these filtrates were prepared, and an aqueous HCl solution was added to each to adjust the pH to 8, 6, 4, 3, 2, and 1, and then allowed to stand overnight. As a result, no appearance of sedimentation was observed at pH = 4 or above, but precipitates were sedimented at pH = 3, but the supernatant liquid was a very dark reddish brown. Below pH = 2, the precipitate was completely separated, and the supernatant liquid was slightly yellow.

As a carbonaceous mesophase to investigate the effect of grain size
CP- (90) 90QI 24-42 mesh (0.35-0.7mm) and 1
4 to 24 mesh (0.7 to 1.17 mm), 97% concentrated sulfuric acid and 64
It was treated in a mixed acid of 70% (volume ratio) of% concentrated nitric acid at 100 ° C. for 60 minutes. Then, the amount of insoluble components, the dissolution rate, and the amount of precipitates were determined by the same operation as in the case of Table 2 above, and the results are shown in Table 4.

(B) Sulfonation CPBM (50) 238QI was used as a carbonaceous mesophase, 1 g of which was placed in an Erlenmeyer flask, and 20 ml of a mixed acid of 97% concentrated sulfuric acid and 30% fuming sulfuric acid was added thereto. Then, after holding for 60 minutes in an oil bath heated to 100 ° C., it was taken out from the oil bath and cooled to room temperature. This was gradually transferred to 300 ml of water, and 1N aqueous NaOH solution was added until the pH reached 12. And
Insoluble components on the 0.45 μm membrane filter
After washing with a pH = 12 aqueous NaOH solution, a small amount of distilled water was used for washing, drying and weighing. The filtrate was adjusted to pH 0.7 with the addition of an aqueous HCl solution.
After adjusting to ~ 1.0, it was left to stand overnight. After confirming that the precipitate had settled, the precipitate was settled by a centrifuge, and the supernatant was filtered under reduced pressure with a 0.45 μm filter. An aqueous HCl solution having a pH of 1 was added to the sediment in the centrifuge tube, and the mixture was stirred and then subjected to centrifugal sedimentation. After repeating this operation several times, the whole amount was transferred onto a filter, filtered under reduced pressure, and dried. The filtered product was in the form of mud, and the dried product was in the form of particles of 1 to 5 mm.

Further, 1 g of the same carbonaceous mesophase as described above was placed in an Erlenmeyer flask, 20 ml of 30% fuming sulfuric acid was added thereto, and the mixture was treated at 100 ° C. for 60 minutes. Then, after cooling to room temperature, opening 0.5
The mixture was filtered under reduced pressure with a membrane filter made of polytetrafluoroethylene (“Teflon”) having a thickness of μm. After transferring to the filter with a small amount of 30% fuming sulfuric acid, wash with a small amount of distilled water.
It was dried and weighed.

The amount of insoluble components, the dissolution rate and the amount of precipitates thus obtained are summarized in Table 5.

(C) Oxidation treatment (1) Method using hydrogen peroxide CPBM (50) 238QI was used as a carbonaceous mesophase.
Put 1g of this in a 200ml Erlenmeyer flask and add 35% to it.
Hydrogen peroxide (H ₂ O ₂ ) water having a concentration was added, and the mixture was treated for 60 minutes and 180 minutes in a 100 ° C. oil bath equipped with a reflux condenser. After the lapse of time, the mixture was cooled to room temperature and transferred into 300 ml of water. Since the pH of this aqueous solution was about 2.3, the pH was adjusted to 12, 10, 8, 6, and 4 with a 1N aqueous NaOH solution, and the mixture was allowed to stand overnight. Then, insoluble components were settled by a centrifugal settler, and the supernatant was filtered under reduced pressure with a membrane filter having an opening of 0.45 μm. The precipitate was washed with an aqueous solution of the same pH, then the whole amount was transferred onto a filter, washed with a small amount of distilled water, dried and weighed. The filtrate is an aqueous HCl solution and has a pH of 0.7 to 1.0.
After allowing the mixture to stand still for 24 hours, the precipitate was settled with a centrifugal settler, filtered with a 0.45 μm filter, washed, dried and weighed.

The amount of insoluble components, the dissolution rate, and the amount of precipitates thus obtained are summarized in Table 6.

Treat with hydrogen peroxide at 100 ° C for 180 minutes in the same manner as above, and adjust the pH.
= 12, then add aqueous HCl to the filtered filtrate, p
H was adjusted to 8, 6, 4, 2 and 1. This was left standing overnight and the sedimentation state was examined. As a result, at pH / 2 or higher, the whole was black and the bottom was examined by inclining, but no sediment was found. In the case of pH = 1, the appearance of a precipitate was observed, but the supernatant was dark reddish yellow and was sedimented and separated by a centrifuge, but the supernatant had the same hue.

(2) Method using hydrogen peroxide and acetic acid 1 g of carbonaceous mesophase and 25 ml of glacial acetic acid similar to the above 300 m
It was put in an Erlenmeyer flask of l, and 20 ml of 35% hydrogen peroxide solution was added dropwise thereto while stirring. Then, a cooling tube was attached and the mixture was treated at 100 ° C. for 60 minutes. After processing, about 300 ml
The mixture was transferred to water, and the pH was adjusted by adding 1N NaOH aqueous solution, and the insoluble component was precipitated by a centrifuge. The supernatant is filtered under reduced pressure with a 0.45 μm membrane filter, and all insoluble components are washed out on the filter with the same pH aqueous solution.
After washing, it was washed with a small amount of distilled water, dried and weighed.
The pH of the filtrate was adjusted to 7.7 to 1.0 with an aqueous HCl solution, allowed to stand overnight and then the precipitate was settled with a centrifuge, and the supernatant was 0.45 μm.
Filtered under reduced pressure with a filter of No. 3, and then the whole amount of the precipitate was transferred onto the filter, washed, dried and weighed.

Table 7 shows the amounts of insoluble components, the dissolution rates, and the amounts of precipitates thus obtained.

(D) Amination treatment CPBM (50) 238QI was used as the carbonaceous mesophase, 1 g of which was placed in an Erlenmeyer flask, and 20 ml of a mixed acid of 97% concentrated sulfuric acid and 68% concentrated nitric acid at 70:30 (volume ratio) was added thereto. After that, 100 ℃, 60
Heated for minutes. Then, the reaction was stopped by transferring into about 300 ml of water. Since the treated product settles by leaving it to stand, the supernatant was removed by decantation, the precipitate was filtered under reduced pressure, washed with a small amount of water, and then dried to obtain a nitrate. Collect 1g of this in a 300ml Erlenmeyer flask, add 2g of tin powder and 100ml of acetic acid, and add 20ml of 36% hydrochloric acid while stirring.
Was gradually added. After adding all the hydrochloric acid, 60 in a boiling water bath.
Heated for minutes. After cooling to room temperature, it was filtered under reduced pressure, washed with a small amount of water, and dried. The yield of this product is 87.3%,
The elemental composition is carbon 73.6%, hydrogen 2.3%, nitrogen 6.1%, sulfur 0.
It was 8% and oxygen 16.7%. Further, from the infrared absorption spectrum, in the nitration, absorptions attributable to stretching vibrations of N = 0 at 1540 and 1380 cm ^-1 were observed, whereas in the reduced treatment, these absorptions were not observed. 3500
broad absorption of cm ^-1 and about 700～900Cm ^-1 was observed, which is attributed to the absorption of the amine.

0.5 g of the reduced product was put in 100 ml of a pH = 12 aqueous solution of NaOH, stirred, and then filtered under reduced pressure with a membrane filter having an opening of 0.45 μm, and the product on the filter was washed with a small amount of water and dried. A hydrochloric acid aqueous solution was added to the filtrate to adjust the pH to 1, and the mixture was allowed to stand for one day and night, then filtered under reduced pressure with a membrane filter having an opening of 0.45 μm, washed with a small amount of water, and then dried. As a result, the amount of insoluble components on the filter is 0.1%, and the dissolution rate is 99.9%. The amount of precipitate was 91.6%. The elemental composition of the precipitate was carbon 73.3%, hydrogen 2.4%, nitrogen 6.1%, sulfur 0.8%, oxygen 16.8%, and the infrared spectrum was similar to that of the reduction treated product.

Reference Example 2 Carbonaceous mesophase used in Reference Example 1, CPBM (50) 238Q
I was treated with a mixed acid of 97% sulfuric acid and 67% nitric acid at 70:30 (volume ratio) at 100 ° C for 60 minutes. Transfer this to a large amount of water,
The product was directly filtered under reduced pressure with a membrane filter having an opening of 0.45 μm. Then, it was washed with distilled water until the pH of the filtrate reached 4, and then dried. The yield was 138.6 wt%.

0.5 g of this and 50 ml of methyl ethyl ketone (MEK) were placed in an Erlenmeyer flask with a capacity of 200 ml, tightly packed, and shaken at 30 ° C. for 5 hours. Then, it was filtered under reduced pressure with a membrane filter made of "Teflon" having an opening of 0.5 µm, finally washed with a small amount of MEK, dried and weighed. As a result, there was no insoluble component remaining on the filter, and the entire amount was solubilized.

Table 8 shows the results of determining the amount of insoluble components by changing the organic solvent by the same method.

Further, the amount of insoluble components was determined by the same method for the oxide obtained in Experiment No. 33 (100 ° C., 180 minutes, pH 12) in Table 6 (Table 8).

Reference Example 3 Uncalcined coke (called green coke or raw coke) produced by an industrial-scale lade coker as a carbonaceous mesophase and 600, 7 of this in a nitrogen stream.
The ones heat-treated at 00 and 800 ° C. for 60 minutes were used. The elemental analysis values are shown in Table 9.

Grind these to 100-270 mesh (0.05-0.15mm),
1 g of the mixture was treated in 20 ml of a mixed acid of 97% concentrated sulfuric acid and 67% concentrated nitric acid at 70:30 (volume ratio) at 100 ° C for 60 minutes. Then, by the same operation as in Table 2 of Reference Example 1, the amount of insoluble components, the dissolution rate, and the amount of precipitates were obtained. The results are shown in Table 9.

Reference Example 4 As a raw material for preparing a carbonaceous mesophase, 10 mm of tar produced as a by-product during thermal decomposition of naphtha, a heavy petroleum-based bituminous product, was used.
The pitch of the residue distilled to 250 ° C. under reduced pressure of Hg was used. About 400 g of this pitch was put in a glass cylindrical container having a capacity of 500 ml and heat-treated at 430 ° C. for 90 minutes. Then, after dissolving and dispersing at 90 ° C. in about 3 times amount of quinoline, insoluble components were settled with a centrifuge, and the supernatant was removed by decantation,
A new quinoline was added to the insoluble component and heated to 90 ° C, and the insoluble component was settled by a centrifuge. This operation was repeated until the quinoline was slightly colored to wash the insoluble components, then washed with benzene and acetone to remove the quinoline, and dried. The quinoline-insoluble component thus obtained was used as a carbonaceous mesophase. The yield was 38.3% by weight, and the elemental analysis values were carbon 93.9% by weight, hydrogen 4.4% by weight, nitrogen 0.1% by weight,
The sulfur was 0.2 wt% and the oxygen was 1.3 wt%.

This carbonaceous mesophase was crushed to 0.15-0.35 mm,
In the same manner as in Example 1, 1 g was treated in 20 ml of a mixed acid of 97% sulfuric acid and 67% nitric acid (70:30, volume ratio) at 100 ° C. for 60 minutes to carry out a nitration reaction. Transfer the reaction product to approximately 300 ml of water and
The pH was adjusted to 12 with a specified NaOH aqueous solution, and the insoluble component was precipitated with a centrifuge. The supernatant is filtered under reduced pressure with a 0.45 μm membrane filter, and then the insoluble components are adjusted to the same pH.
The whole amount was transferred onto a filter with an aqueous solution, and finally washed with a small amount of distilled water, dried and weighed. The filtrate is an aqueous HCl solution and the pH is 0.7.
After adjusting to ˜1.0 and leaving it to stand overnight, the precipitate was settled with a centrifuge. The precipitate is washed with an aqueous solution of HCl having a pH of 1 to give 0.4
It was filtered with a 5 μm filter, dried and weighed.

As a result of obtaining the dissolution rate from the amount of the insoluble component thus obtained, the amount of the insoluble component is about 0.1% by weight or less, which is a trace level,
The dissolution rate was 100% by weight, and the amount of precipitate was 135.8% by weight.

Example 1 The elemental composition of the amphipathic carbonaceous mesophase obtained in Table 6, Experiment No. 33 of Reference Example 1 was carbon 58.4%, hydrogen 2.5%, nitrogen 0.5%, sulfur 0.4%, oxygen 28.3%. The total ion exchange capacity, strong acid amount, and weak acid amount of this amphiphilic carbonaceous mesophase were determined to be 6.72, 2.58, and 4.14 meq / g, respectively, using 0.1N sodium hydroxide and 0.1N sodium hydrogen carbonate aqueous solution. A strong acid amount corresponds to a carboxyl group, and a weak acid amount corresponds to a hydroxyl group.

0.03g of this amphiphilic carbonaceous mesophase and PVA (polymerization degree 20
00) 0.02 g was placed in a 200 ml Erlenmeyer flask, and 3 ml of a 1N aqueous sodium hydroxide solution was added thereto, and the mixture was stirred and dissolved. Then, 6 ml of a 1N aqueous hydrochloric acid solution was added, and the mixture was heated at 70 ° C. for 6 minutes. This was filtered into a film by using a Teflon membrane filter (filtering area 96 cm ² ) having openings of 0.5 μm. Then, it was transferred to a beaker containing 1N hydrochloric acid aqueous solution together with filter paper, heated at 90 ° C. for 60 minutes, and then heated and boiled on an electric stove. Since the film is peeled from the filter paper by this operation, after cooling, it was spread on a Teflon plate and dried at 80 ° C. for 3 hours in a dryer. This was a black, slightly flexible, smooth surface film about 50 μm thick. It was very flexible when placed in water. The total ion exchange capacity is 2.33.
It was meq / g.

Example 2 The elemental composition of the amphiphilic carbonaceous mesophase obtained in Table 2 of Reference Example 1 and Experiment No. 2 was as follows: carbon 51.6%, hydrogen 2.0%, nitrogen 6.2%, sulfur 1.0%, oxygen 31.0%. Absorption spectrum showed absorption of nitro group, carbonyl group, and hydroxyl group. The total ion exchange capacity was 5.83 meq / g.

0.3g of this amphiphilic carbonaceous mesophase was added to 0.5g of epoxy resin (“Araldide M”) and mixed well,
It was applied thinly on a "Teflon" plate. Then, it was heat-treated at 180 ° C. for 8 hours. After cooling, it had hardened and was peeled off from the "Teflon" plate with a knife. This was a film with a surface gloss.

(Effects of the Invention) According to the present invention, a carbonaceous mesophase that is originally solid can be formed into a free shape similar to a liquid, and a molded body having a function of ion exchange can be manufactured.

Front page continuation (51) Int.Cl. ⁶ Identification number Office reference number FI Technical indication location B01J 47/12 A C04B 35/52 C10C 3/02 6958-4H (72) Inventor Hidemasa Honda Suginami-ku, Tokyo 3-29-23 Wada Examiner Noriko Kuriyama

Claims (1)

[Claims] 1. An amphiphilic carbonaceous mesophase soluble in water and an organic solvent, which is obtained by introducing a hydrophilic group into a carbonaceous mesophase when the carbonaceous mesophase is produced by molding a carbonaceous mesophase. A method for producing a carbonaceous mesophase molded article, which comprises a cross-linking treatment.