JPH0249095A - Production of carbon material - Google Patents

Abstract

PURPOSE:To obtain a carbon material readily convertible into a mesophase with a high fixed carbon content and hardly any portion insoluble in quinoline by mixing specific pitch with a Lewis acid in a consolute solvent at a specific ratio and reacting both under specified conditions. CONSTITUTION:(A) Pitch having >=0.6 aromatic carbon ratio (fa) and (B) a Lewis acid catalyst consisting of BF3, HF.BF3, anhydrous AlCl3, anhydrous CuCl2, anhydrous ZnCl2, anhydrous SnCl2, etc., are added and mixed with a consolute solvent, such as o-dichlorobenzene, at 0.3-5.0 molar ratio to react the pitch in the mixture at 100-300 deg.C temperature. The Lewis acid and consolute solvent are then removed from the above-mentioned reaction product to afford the objective modified pitch for carbon materials.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method of reacting pitch in the presence of a co-soluble solvent and a Lewis acid to obtain modified pitch useful as various carbon materials.

The modified pitch of the present invention has a low softening point, low quinolinous content, and high specific carbon content, and can be easily converted into a metsu phase by heat treatment, so it can be used as a carbon-carbon composite material. It can be used for a variety of purposes, including artificial graphite electrodes, impregnating materials for high-grade carbon materials such as carbon and graphite molded products, raw materials for mesophase pitch-based carbon Wi&I, and mixed materials for modifying various pitches.

The present invention also relates to a method for producing spherical mesocarbon microbeads by heat-treating modified pitch obtained by reacting pitch in the presence of a co-soluble solvent and a Lewis acid at 200 to 380°C. The invention particularly relates to a method for producing uniformly sized mesocarbon microbeads with a high yield of more than about 60% and an average particle size of 0.5 to 20 μm.

Mesocarbon microbeads are spherical carbon particles with highly condensed polycyclic aromatic hydrocarbons arranged in a certain direction, and have chemical, electrical, and magnetic properties unique to carbon. It also has good sinterability in the carbonization process, so it can be used as an industrial material such as conductive fillers, binderless isotropic high-density carbon materials, catalyst supports, and chromatogram fillers. , Nuso carbon microhi~
(ft! is used after carbonization).

[Support 1] High-grade carbon materials such as carbon/#2 composite materials, artificial graphite electrodes, and carbon/graphite molded products are usually used as aggregates and caking materials such as coke molded products. It is manufactured by mixing pi-sochi, molding, firing, and graphitization. Among these, materials requiring particularly high density and high strength are graphitized after repeating pitch impregnation to #E formation several times after firing. The purpose of impregnating baked products with Bi-Sochi is to connect aggregates together, and to reduce the porosity, increase density and strength, and increase electrical conductivity and thermal conductivity of the resulting carbon material. impregnation (
This ability is essential to the production of high-grade carbon materials.

This pitch-based impregnating material is produced by using petroleum-based or coal-based pitch as a raw material, and typically performing a polycondensation reaction and removing low-boiling salts by heat treatment.

In addition, pitch-based impregnating materials are required to have the following properties depending on their purpose.

(1) Quinoline (: low soluble content (tl+) (2)
Low softening point (3) ri! , high constant carbon content (4) high content of β-resin (・＼difference between insoluble content and soluble content of quinoline) (5) low ash content (6) low content of low boiling point components. Among the properties, it is particularly important to have a low content of old, a low softening point, and a high fixed carbon content.

However, in conventional pitch-based impregnating materials, lowering the softening point in order to improve impregnability results in a significant decrease in fixed carbon content. I had to repeat it several times.

In addition, if we try to manufacture impregnating pitch with a high identified carbon content in order to reduce the number of times of pitch impregnation and demolishing, this will result in an increase in the 01 component and an increase in the soft 1 hit point, resulting in a significant decrease in impregnating properties. A solvent extraction operation was required for removal.

In addition, in the production of pitch-based charcoal fibers, there is a problem in that when high-performance carbon fibers are used, the softening point of the raw material pitch increases by 60%, resulting in a decrease in spinnability. was there.

Furthermore, according to the conventional method for producing mesocarbon microbeads, it has been difficult to produce mesocarbon microbeads having a diameter of 51 tm or less.

Furthermore, when attempting to increase the yield of optically anisotropic spherules during the reaction process, the spherules coalesce and settle to form a bulk mesophase.1. -There was a problem that it was difficult to separate the small spheres.

Several techniques are known in which the quality of the product is modified by coexisting a Lewis acid during mesophase 1 production of pitch. Japanese Patent Publication No. 53-7533 discloses that a Lewis acid catalyst such as AlCl3 is directly added to petroleum-based tar or pitch having a softening point of 120° C. or less to produce a mixture with a softening point of 120° C. or less.
After heat treatment at a temperature of 300 °C and removal of catalyst 350
Perform second stage heat treatment at ~500″C, 200~:30
A method of manufacturing a mesoface pitch with a soft 1 hit point of 0(I is disclosed.

This mesophase hitch is said to be preferable as a raw material for carbon fibers because the flow characteristics of the non-mesophase component are close to those of the mesophase component, so even if the mesophase ratio is 1 degree, the spinnability is poor.

However, in order to completely dissolve the solid Lewis acid, it was necessary to increase the temperature of the first stage heat treatment. Note that nothing is disclosed about the production of metsucarbon microbeads.

Furthermore, JP-A No. 5,612 discloses a mesophase pitch having a camelliad-shaped molecule, which is prepared by polymerization of an aromatic hydrocarbon containing two or more fused rings. The molecules of this mesoface pitch are elongated and have an overall shape close to an ellipsoid, with more than 60% of the bonds connecting the integrated rings being arranged by coupling (bonds that are not closed).

The polymerization reaction is catalyzed by a weak Lewis acid, such as anhydrous AlCl3, with a second component that acts to reduce the activity of A ICI . AlC as a weak Lewis acid
It is said that CuCl2 is preferable, and orthodichlorobenzene, nitrobenzene, and trichlorobenzene are preferable as the solvent. Mesophase pitch obtained by heat-treating pitch from which the catalyst has been removed is said to have good spinnability, probably because the molecule is long, and has a low softening point, so it is said to have good moldability at one temperature. It can be said that this mesophase pitch has a higher crystalline perfection than the fM mesophase pitch, but the layered thickness of the molecules is smaller. It is also said that this mesophase pitch has different characteristics from mesophase pitch produced using a strong Lewis acid without a second component.

This method complicates the adjustment of the catalyst system and suppresses mesophase growth. Further, the production of mesocarbon microbeads is not disclosed.

As a method for producing mesocarbon microbeads, for example, as disclosed in Japanese Patent Publication No. 50-39833,
Conventionally, petroleum-based or coal-based pitches were heated at 350 to 500°C.
, a method of heat treatment at a relatively slow temperature increase rate (10° C./min or less) is used.

The problem with this method is that it is difficult to produce mesocarbon microbeads with a uniform particle size at a high yield; even if high-quality pitch containing no free carbon is used as a raw material, the yield is only 10 Vo % or less.

When producing Ia mesocarbon micropieces, the problem of long reaction times can be solved by making the temperature inside the reactor uniform and efficiently discharging by-product low-boiling components out of the system. Japanese Patent Publication No. 53-9599 heats the pitch in a reactor by blowing superheated steam into it, and at the same time generates optically anisotropic small spheres in a relatively short period of time by stirring strongly, and extracts mesocarbon from the reaction product. Discloses a technology for manufacturing microbeads.

The problem with this technique is that it is difficult to avoid the problem of optically anisotropic small spheres colliding and aggregating due to strong stirring.

This patent solves the problem of rIII foam by keeping the yield of optically anisotropic spherules low, just over 10%.

Therefore, there is a problem that there are many pitch spears that have to be discarded and the cost is high.

As a method for producing mesocarbon microbeads with a uniform particle size, Japanese Patent Publication Sho SQ-+7O43 discloses performing heat treatment of the pitch twice in order to obtain optically anisotropic spherules. This method removes the optically anisotropic spherules that precipitate during the second heat treatment and collects only the optically anisotropic spherules that remain floating after the second heat treatment. The aim is to make the particle size uniform and obtain small spheres with high roundness.

Although the carbon microbeads produced by this method are said to have good quality such as uniform particle size and roundness, and are easy to use, the yield of mesocarbon microheath from the raw material Bi-Sochi is still around 10%. Therefore, there is a problem that the cost is high.

[Problems to be Solved by the Invention] The object of the present invention is to produce a modified pitch for various carbon materials that has a low softness point, a low 01 component, and a high fixed carbon content.

In addition, the present invention solves the problems of the conventional production method of mesocarbon microbeads, which are low yield and high cost. f:2 from 0.571m
Mesocarbon microbeads with a uniform particle size and an average particle size of 0.071 or less are produced with a high yield of about 60% or more. The purpose is to create.

[Means for Solving the Problems] The present invention includes a pitch having an aromatic carbon ratio fa of 0.6 or more and a Lewis acid in a co-dissolved solvent for the Lewis acid and the pitch.
The molar ratio of the Lewis acid to the pitch is 0.3 to 5.0
, the molar ratio of the co-soluble solvent to the pitch is 2.5 to 5.
Modified pitch for carbon materials, characterized in that the pitch in the mixture is reacted at a temperature of 100 to 300°C, and then the Lewis acid and co-soluble solvent are removed from the reaction product. This is a manufacturing method.

The pitch used in the present invention has an aromatic carbon ratio (ratio of carbon forming aromatic rings to total carbon) fa of 0.6.
This is from E. The raw material for the raw pitch is preferably a petroleum-based or coal-based high boiling point distillate, but this does not preclude the use of low boiling point raw materials. For example, there is no particular problem in using a raw material with a boiling point similar to that of kerosene. As raw materials, pure substances with a high aromatic S* ratio, such as naphthalene, anthracene, phenanthrene, etc., can be used alone or in combination.

The Lewis acid catalyst used in the present invention is BF, )IF-BF
3, Anhydrous A I CI 3, Anhydrous CuCl2, Anhydrous Zn
Any solvent such as Cl 2 or anhydrous 5nC12 may be used as long as it has a solvent that is co-soluble with the raw material pitch.

Anhydrous AC+3 is preferable from the viewpoint of microbead production speed, but when it is necessary to completely remove the catalyst from one reaction product, a vaporizing catalyst is preferable, especially HF/BF.
is preferable because IF enhances its function as a catalyst, can be expected to be effective as a solvent, and can be easily recovered and reused.

The co-soluble solvent used in the present invention preferably has a boiling point of 100 to
It is a compound that does not react to decompose Lewis acids at 350°C, most preferably 150 to 250°C, and is easily separated from reaction products. These are preferably aromatic compounds having neutral or acidic substituents, most preferably containing one or more compounds selected from the group of dichlorobenzene, nitrobenzene, and tricumyl-benzene as a main component. It is something to do. Furthermore, even basic compounds such as pyridine and quinoline, which do not destroy the structure of the Lewis acid when they react with it and do not produce water upon neutralization, simply weaken the catalytic effect. So it is usable.

Various effects can be obtained by using co-soluble solvents.

First, since both the pitch and the Lewis acid are dissolved, the two come into contact with each other in liquid form, and the efficiency of the reaction is extremely high, and uniform modified pitch can be obtained.

Next, even a pitch with a high softening point of, for example, 250'(''') can be used as a raw material by dissolving it in a co-soluble solvent, making it possible to select a wide range of raw materials depending on the quality of the desired product.

In particular, in the case of HF-BF without a co-solubilizing solvent, raw materials with very high softening points cannot be used due to the limited solvency of HF, and if IF is used as a solvent, the amount of HF used will be very high. The pressure in the ring 2 system becomes high, making it difficult to separate and recover 11F and BF. On the other hand, if a co-soluble solvent exists, the amount of HF used can be significantly reduced.

Furthermore, there is an advantage that the reaction temperature can be lowered. In other words, even pitches with high softening points become liquid even at low temperatures when dissolved in a co-soluble solvent. If you want to make it liquid, you have to raise the temperature above this, but if you use a co-soluble solvent, you can make it liquid at a lower temperature.

The mixing ratio of pitch, Lewis acid, and co-soluble solvent during the reaction is:
Preferably, the molar ratio is 1:0.3 to 5:2.5 to 5 degrees. Special Publication No. 53-7533 has a softening point of 1.
A Lewis acid catalyst such as AlCl3 is directly added to petroleum tar or pitch at 20"C or less, and heat treated at a temperature of 200 to 300C north of the softening point of the compound. After removing the catalyst, 350 ~ 500 ° (= second stage heat treatment, 2
A method of manufacturing mesoface pitch with a softening point of 00-300C is disclosed.

This mesophase pitch is said to be preferable as a raw material for carbon fibers because the flow characteristics of the non-mesophase component are close to those of the mesophase component, so even if the mesophase ratio is low, the spinnability is excellent.

However, in order to completely dissolve the solid Lewis acid, it was necessary to increase the temperature of the first stage heat treatment. Note that nothing is disclosed about the production of mesocarbon microbeads.

Further, JP-A-185612 discloses a mesophase pitch having camellia cylindrical molecules produced by polymerization of aromatic hydrocarbons containing two or more condensed rings. In this mesophase pitch molecule, more than 60% of the bonds connecting the condensed rings are formed by coupling (bonds that are not closed).

It is elongated and its overall shape is close to an ellipsoid.

This polymerization reaction is catalyzed by a weak Lewis acid such as aqueous AlCl3 with a second component which acts to reduce the activity of 111CI. As a weak Lewis acid, AlCl-
1.CuCl2 is preferred, and as the solvent, orthodichlorobenzene, nitrobenzene, and trichlorohensen are preferred. Mesoface pitch, which is obtained by heat-treating pitch from which the catalyst has been removed, has good spinnability, probably due to its elongated molecules, and has a low softening point, so it is said to have good moldability at low temperatures. This mesophase pitch is said to have a higher crystalline perfection than the conventional mesocarbon Sochi, but the thickness of the 111 layer of molecules is smaller. It is also said that this mesophase pitch has different characteristics from mesophase pitch produced using a strong Lewis acid without a second component.

This method complicates the adjustment of the catalyst system and suppresses mesophase growth. Further, the production of mesocarbon microbeads is not disclosed.

As a method for producing mesocarbon microbeads, for example, as disclosed in Japanese Patent Publication No. 50-39633,
Conventionally, petroleum-based or coal-based pitches were heated at 350 to 500°C.
, a method of heat treatment at a relatively slow temperature increase rate (10° C./min or less) is used.

The problem with this method is that it is difficult to produce mesocarbon microbeads with uniform particle size at a high yield, and even if high-quality pitch containing no free carbon is used as a raw material, the yield is loVol% It was below.

When producing mesocarbon microbeads, it is thought that the problem of long reaction times can be solved by making the temperature inside the reactor uniform and efficiently discharging by-product low-boiling components out of the system. In Japanese Patent Publication No. 53-9599, optically anisotropic small spheres are produced in a relatively short period of time by heating the pitch in a reactor by blowing a-hot steam into it, and at the same time stirring it strongly. Discloses a technology for producing carbon microbeads.

The problem with this technique is that it is difficult to avoid the problem of optically anisotropic small spheres colliding and aggregating due to strong stirring.

This patent solves the problem by keeping the yield of optically anisotropic spherules low, just over 10%.

Therefore, there is a problem that many pitch spears are discarded and the cost is high.

As a method for producing mesocarbon microbeads having a uniform particle size, Japanese Patent Publication No. 17043/1983 discloses that heat treatment of the pitch is performed twice in order to obtain optically anisotropic small spheres. This method removes the optically anisotropic spherules that precipitate during the second heat treatment, and collects only the optically anisotropic spherules that remain floating after the second heat treatment. The aim is to make the particle size of the small spheres uniform and to obtain small spheres with high roundness.

Mesocarbon microbeads produced by this method are said to have good particle size uniformity, high quality, and are easy to use, but the yield of mesocarbon microbeads from Iq material pitch is still only about 10%. Although it varies depending on conditions such as the type of pitch and the molar ratio of Lewis acid, for example, in the case of modified pitch using 1.35 mol of AlC11 per 1 mol of pitch, if the heat treatment temperature is 250°C or less, Ilt
It is advantageous to produce optically anisotropic small spheres with an average particle diameter of tm or less, and at 250 to 300°C, it is easy to produce an average particle diameter of 1 to 5/1 m, and at 300 to 350°C, it is 5 to 20 μm. It is easy to produce particles with the average particle size of rinsing.

Furthermore, in the case of HF-BF, there is a tendency that a slightly higher temperature is required than in the case of AlCl3.

The method for collecting the optically anisotropic spherules from the reaction product after the heat treatment is preferably a method of extracting the remaining isotropic components with a solvent. It is also possible to separate the liquid by separating the liquid by specific gravity or lowering the temperature to assimilate only the optically anisotropic spherules, but the isotropic components tend to stick to the spherules and remain, resulting in a low yield. Although it is excellent, the quality is 12
Not even one sushi was good.

Quinoline is conventionally often used as a solvent for extraction of optically anisotropic microspheres. In the case of the present invention, since the optically anisotropic microspheres obtained and the isotropic component of the matrix have good solubility, the use of quinoline results in a low yield of microspheres. As the solvent used for extracting the optically anisotropic microspheres of the present invention, it is preferable to use toluene or benzene, xylene, trichlorobenzene, nitrohensen, or 0-dichlorobenzene, which have a similar solubility to toluene.

Example 1 Petroleum pitch (initial distillation 460°C to final distillation 560°C) produced by thermal catalytic cracking (FCC) of de-6R vacuum gas oil,
A sample with a softening point of 72°C (using a Mettler softening point measurement device #) and a number average molecular weight of 400 was placed in a 2008 glass Maruki flask, and monohydric A I C1, 5]O was added as a Lewis acid catalyst.
g, 0-dichlorobenzene as a co-soluble solvent looo
ml was added and the reaction was carried out for 26 hours at a temperature of 180°C (τ solvent 1 batch). (The molar ratio of pitch, Lewis acid and co-soluble solvent was I: 1.35: 17.155) After the reaction, the solvent was removed. Removal by vacuum distillation under nitrogen atmosphere gave a solid residue. The solid residue was washed with distilled water and IN dilute hydrochloric acid, and anhydrous AlCl was hydrolyzed and removed to obtain modified pitch.

This modified pitch was obtained in approximately the same amount as the raw material pitch before reaction. The softening point of this modified pitch was 176°C. 100g of the modified pitch was taken, placed in a stainless steel reactor with an internal volume of 5001, and nitrogen was flowed at a rate of fE t 2N I (standard state liter)/min to 300g. A pitch product was obtained by heat treatment for 30 minutes while stirring at T. The yield was 98% based on the raw material modified pitch.

When pitch products are observed under a polarizing microscope, the average diameter is 3~
It contained optically anisotropic small spheres with a uniform particle size of 5 μm. This pitch product was dissolved in trichlorobenzene and filtered to obtain mesocarbon microbeads at a yield of % by weight as insoluble matter.

Example 2 When the modified pitch of Example 1 was heat-treated at a temperature of 330°C and a heat-treatment time of 60 minutes, the yield of the pitch product obtained was 95%, with a small optical anisotropy contained. The average diameter of the spheres was 6.2 .mu.-, and the yield of mesocarbon microbeads contained as trichlorobenzene-insoluble matter was 80% by weight.

Example 3 The heat treatment temperature of the modified pitch of Example 1 was 250°C, IIJ
I2! What is the yield of the pitch product obtained when the L processing time is increased to 60 minutes? , 18% in Eastern Europe, the average diameter of the optically anisotropic spherules contained was 0.777111, and the yield of mesocarbon microbeads obtained as trichlorohensen insoluble matter was 5 coul%.

Example 4 Thermal catalytic cracking of desulfurized vacuum gas oil (softening point of petroleum pitch by-produced by FCO: 130°C (using a Mettler softening point measurement device)) Anhydrous and anhydrous pitch was prepared using an average fraction of 100 in the same molar ratio as in Example 1. A ICI and 0-dichlorobenzene were added, and the reaction was carried out for 2 hours under solvent reflux at a temperature of 180°C.

After the reaction was completed, 0-dichlorobenzene and anhydrous AI CI3 were removed in the same manner as in Example 1 to obtain a modified pitch.

This modified pitch was obtained in approximately the same amount as the raw material pitch before reaction. The softening point of this modified pitch was xvs'c.

When the heat treatment temperature of this modified pitch was 250°C and the heat treatment time was 60 minutes, the yield of the obtained pitch product was 9811%, and the average diameter of the optically anisotropic small spheres contained was 4.5%. The yield of mesocarbon microbeads obtained as trichlorobenzene-insoluble matter was 69% by weight.

Comparative Example l The raw material pitch of Example 1 was immediately put into a stainless steel reactor without performing a reaction using a Lewis acid catalyst, and heat-treated at 380° C. for 12 hours while stirring while flowing nitrogen @ 2 Nl/ml 1 nt'. , a pitch-like material was obtained.

The yield was 92% based on the raw material pitch. When this pitch-like material was treated with trichlorobenzene in the same manner as in Example 1, the solubility of the isotropic pitch was poor and it was difficult to isolate mesocarbon microbeads. When this pitch-like material was dissolved using quinoline instead of trichlorobenzene and filtered, mesocarbon microbeads were obtained as insoluble matter at a yield of 16.3% by weight.

Example 5 IP with Lewis acid of Example 1! When the modified pitch was heat-treated at 420°C for 1 hour after washing and removing the Lewis acid, mesoface pitch with a softening point of 248°C and substantially 100% fluidity was obtained.

Example 6 200g of petroleum pitch with a softening point of 8iL3℃ (Mettler Softening Point Measuring Instrument r # Jfl), luene insoluble content 20.9%, quinoline soluble content 0.31%, and average molecular weight 9450. Glass round bottom flask (capacity 2000ml)
) and anhydrous A I C1 as a Lewis acid catalyst.
og, 0-dichlorbe and nzene as co-soluble solvents.
Add 00 ml and heat at 180' (26 mL) under solvent depletion.
Allowed time to react. (The molar ratio of pitch and Lewis-1 co-soluble solvent was I: 1.52: After the reaction was completed, the solvent was removed by vacuum distillation under an atmosphere of 9 atoms to obtain an isoisomer residue. This solid residue was mixed with water and IN Wash with dilute hydrochloric acid and wash with sanmizu AICI.
q was hydrolyzed and removed to obtain modified pitch. The softening point of this modified pitch was r8ot;

Take +00g of this modified pitch, ? ￥fJI500ml
into a stainless steel reactor, and nitrogen was added at a flow rate of 2Nl/w+
Heat treatment was performed at 340° C. for 60 minutes with stirring while flowing the mixture under an in-flow condition to obtain a pitch product. The yield is based on the raw material modified pitch! It was 15% by weight.

When the pitch product is observed under a polarizing microscope, it has an average diameter of 8.
It contained optically anisotropic spherules of 2Bta.

When this pitch product was dissolved in trichlorobenzene and insoluble materials were filtered off, mesocarbon microheath was obtained with a yield of 73%.

Example 7 Using the same material pitch as in Example 1, reacting with different types and ratios of Lewis acid and co-soluble solvent, and removing the Lewis acid and co-soluble solvent to obtain an optical difference. We generated oriented spherules and made mesocarbon microbeads. Table 1 shows the reaction conditions and product characteristics.
Shown below.

Table 1 Reaction conditions for pitch using Lewis acid and characteristics of the product (symbol) IIcB Nidichlorol (N8: Nitokuchi Hensen Table 1 Reaction conditions for pitch using Lewis acid and characteristics of the product (continued) Example 8 Desulfurization The softening point of petroleum-based pitch (initial distillation 1N 30°C to stationary 560°C) produced by thermal catalytic cracking (FCC) of vacuum gas oil is 72'(': (using Mettler softening point tide measuring device)) with a number average molecular weight of 400. .5 mol stainless steel 155
The mixture was placed in a 00m autoclave, and 1.25 mol of 0-dichlorobenzene was added and dissolved, and then cooled to 5°C. Next, 2.5 mol of HF was added in a cooled state, the inside was replaced with nitrogen, 30.5 mol of BH was blown in, and the temperature was increased at a rate of 3.
The temperature was raised at a rate of °C/sin, and the reaction was carried out at 180 °C for 2 hours.

After the reaction was completed, the mixture was cooled to room temperature.

The temperature was raised to 200° C. while purging with nitrogen, and 0-dichlorobenzene and HF/RF3 were simultaneously collected from the system. After this 0-dichlorobenzene and HF/BF3 removal operation, the modified pitch was taken out. The yield of this modified pitch was 100%.

The modified pitch obtained here had a softening point of 114°C.

50 g of the obtained modified pitch was placed in a 3501 stainless steel reactor, and nitrogen was passed through it at a flow rate of 2 Nl/win.
A pitch product was obtained by heat treatment at 50"C for 1 hour with stirring.The yield was 97% of sales based on the modified pitch.The average particle size of the optically anisotropic small spheres contained was ,?,f
It was iILm.

This raw pitch Fig was dissolved in trichlorobenzene and filtered to obtain metsucarbon microheath with a yield of 65% as insoluble matter.

Example 9 Thermal contact molecules of desulfated IF eaves oil (softening point 130 as a by-product due to FC□): (using Mettler softening point measurement device)
Using a semi-uniform molecule 1k (5 (10 h oil amount 11 ICL pitch), reaction was carried out using II + ".HF3 as a Lewis acid and 〇-dichlorohensen as a co-soluble solvent, and the Lewis acid and co-soluble solvent were removed. Optically anisotropic spherules were produced from the resulting modified pitch to produce mesocarbon microheats.In this case, the reaction temperature, heat treatment temperature and time were varied.The reaction conditions and the properties of the product are shown below. Shown in 2.

Pitch reaction conditions and product characteristics (symbols) according to Table HF-BF3 OCR: Dichlorobenzene Example 10 Softening point of petroleum pitch produced by thermal catalytic cracking (FCC) of desulfurized vacuum gas oil: 130°C (Mettler softening point Measuring device used) 6 moles of average molecular weight @500 were put into a SUS autoclave, 17.8 moles of 0-dichlorobenzene was added and dissolved, and then cooled to 5°C.
After adding 12 moles of F and substituting the inside with nitrogen, 1 mole of 8F3 was blown into the reactor, and the temperature was raised at a temperature increase rate of 1.5°C/win to react at 160°C for 3 hours.

After the reaction was completed, it was cooled to room temperature.

The temperature was raised to 200°C while purging with nitrogen, and O-dichlorobenzene and HF/BF3 were collected from the system at the same time.

After cooling to room temperature, the modified pitch was taken out. The yield of this modified pitch was 100%, and the softening point was 151°C.

When this modified pitch was heat treated at 400°C for 2.5 hours, the mesophase content was 100%, and the softening point of this mesophase was 267°C.

This mesophase was spun at 285°C, made infusible by a conventional method, and carbonized at 2500°C. The obtained carbon fiber has a tensile strength of 362 kg f/mm2 and an elastic modulus of 77×
It showed 10"kgf/+u+2.

Example 11 5 mol of petroleum pitch produced by M catalytic cracking (FCC) of desulfurized vacuum gas oil, softening point 200°C (using Mettler softening point measurement H), number average molecular t598, SUS!
1 Place in an autoclave and add 0-dichlorobenzene 17
．． After adding and dissolving 8 mol, the mixture was cooled to 5°C.

Next, 25 moles of HF was added in a cooled state, and after replacing the inside with nitrogen, 5 moles of 8F3 was blown in, and the heating rate was 1.
The temperature was raised at a rate of 5°C/s and reacted at 160°C for 3 hours.

After the reaction was completed, it was cooled to room temperature.

Removal of 0-dichlorobenzene and HF/FIF was performed under reduced pressure, and 0-dichlorobenzene and HF/8F3 were removed under reduced pressure.
was collected outside the system at the same time. After cooling to room temperature, the modified pitch was taken out. The yield of this modified pitch was 100%, and the softening point was 232°C.

When this modified pitch was heat treated at 400°C for 2 hours, the mesophase content was 100%, and the softening point of this mesophase was 270°C.

The mesophase was spun at 288°C, made infusible by a conventional method, and carbonized at 2500°C. The obtained carbon fiber is
Tensile strength 370kg, f/mm2, elastic modulus 80X 1
03 kgf/mm'.

Example 12 Desulfurization reduction - Petroleum pitch produced by thermal catalytic cracking of gas oil (1" (j:)) has a softening point of 72°C (using a Mettler softening point measurement device) and is heated at a mesophase content of 10% by heat treatment in a nitrogen atmosphere. Pitch A with a softening point of 190°C was created.The same heat treatment as before was continued to create pitch B with a mesophase content of 100% and a softening point of 278°C.

Modified pitch created in Example 10 (softening point 151'C)
was added at 20% to pitch A and heat-treated at 400°C for 2 hours, resulting in a pitch with a mesophase content of 90%, and the softening point of the pitch was 262°C.

In addition, the modified pitch prepared in Example 10 (softening point 151°C
) was added at 20% to pitch B and 0.5% was added at 380°C.
After heat treatment for a period of time, a pitch with a mesophase content of 100% was obtained, and its softening point was 270°C.

[Operations and Effects of the Invention] The present invention relates to a method of reacting pitch in the presence of a co-soluble solvent and a Lewis acid to obtain a modified pitch useful as various carbon insert materials.

The reformed pitch of the present invention has a softening point of 1 degree and has a high identified carbon content despite having a low quinolinated content, and is easily converted into mesophase by heat treatment, making it a carbon-carbon composite. It can be used for a variety of purposes, including artificial graphite electrodes, impregnating materials for high-grade carbon materials such as carbon and graphite molded products, raw materials for mesophase pitch carbon fibers, and mixed materials for modifying various pitches.

Furthermore, the present invention can produce grains with an average particle size of 0 from petroleum-based pitch, coal-based pitch, or a mixture thereof with a high yield of 60% or more.
．． The present invention relates to a method for producing mesocarbon microbeads with a uniform particle size of 5 to 20III+.

Mesocarbon microbeads are spherical carbon materials with a structure in which highly condensed polycyclic aromatic hydrocarbons are arranged in a certain direction, and have chemical, electrical, and magnetic properties unique to carbon. Mesocarbon micro is used as an industrial material such as conductive filler, binderless isotropic high-density carbon material, catalyst support, and glomatogram filler because it has good emotional properties in the carbonization process. The beads can be used in their F1 form or after carbonization.

Procedural amendment 1 Indication of the case 1999 Patent Application No. 117468 3 Person making the amendment IfI relationship with the case Patent applicant address
3-6 Kioicho, Chiyoda-ku, Tokyo Name (Name) Betka Co., Ltd. 4 Agent

Claims (1)

[Claims] 1. A pitch having an aromatic carbon ratio fa of 0.6 or more and a Lewis acid are mixed in a co-dissolved solvent for the Lewis acid and the pitch, and the molar ratio of the Lewis acid to the pitch is 0.3-5.0,
The molar ratio of the co-soluble solvent to the pitch is 2.5 to 50.
Modified pitch for carbon materials, which is characterized in that the pitch is mixed in a circular motion, the pitch in the mixture is reacted at a reaction temperature of 100 to 300°C, and then the Lewis acid and co-soluble solvent are removed from the reaction product. Production method. 2. Pitch with aromatic carbon ratio fa of 0.6 or more and HF・
FB_3 in a co-soluble solvent, HF, B for the pitch
The molar ratio of F_3 and the co-soluble solvent is 1 to 5 and 0.
3-1, 2.5-50, reaction temperature 1
A method for producing modified pitch for carbon materials, which comprises reacting pitch in a mixture at 00 to 300°C, and then removing HF, BF_3, and a co-soluble solvent from the reaction product. 3. The modified pitch for carbon material according to claim 1 or 2 is heat-treated at 200 to 380°C to generate optically anisotropic small spheres, and these are separated from the optically isotropic component. A method for producing mesocarbon microbeads. 4. Patent claim 1 for mesophase-containing pitch produced using pitch with an aromatic carbon ratio fa of 0.6 or more as a raw material.
Alternatively, a method for producing a low softening point mesophase pitch, which comprises mixing the modified pitch for carbon materials according to 2 and heat-treating the mixture. 5. A method for producing mesophase pitch-based carbon fiber, characterized in that the pitch produced by the method according to claim 1, 2 or 4 is used as a raw material.