JPS58214531A - Preparation of pitch for producing pitch type carbon fiber - Google Patents

Abstract

PURPOSE:To make it possible to obtain a pitch having improved spinning property, by using a hydrogenated condensed bi- or polycyclic aromatic compound as a solvent in a hydrogenating step of a heavy bituminous material. CONSTITUTION:100-300pts.wt. mixture of hydrogenated condensed bi- or polycyclic aromatic compound, preferably anthracene oil, creosote oil, absorption oil or naphthalane oil which is a distillation oil of coal tar or light oil formed in the thermal cracking of naphtha as a by-product, is added to 100pts.wt. pitch in a heavy bituminous oil, and the resultant mixture is then treated at 400- 500 deg.C under the autogenous pressure and then heat-treated at 450 deg.C or above to give a pitch for spinning. The resultant pitch is then made infusible and carbonized to afford the aimed carbon fibers. Preferably, 50-100pts.wt. solvent is added, and the resultant mixture is treated in the presence of a hydrogenation catalyst at 50kg/cm<2> or higher pressure of hydrogen at 360-500 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention consists of a first step in which a coal-based petroleum pitch such as coal tar pitch or naphtha tar pitch is used as a raw material, and is subjected to a mild hydrogenation treatment, and then a hydrogenation process under reduced pressure or normal pressure.
This invention relates to a method for producing pitch for producing high-density carbon fiber ## with excellent spinnability, which is made of a second culm treated at a temperature of 0° C. or higher.

This is an improved version of the mild hydrotreating method used in the special E No. 1 culm.

Conventionally, carbon fiber has heat resistance, insulation properties, and chemical resistance.

Utilizing its characteristics of excellent rigidity, electrical conductivity, and light weight, it is widely used in heat insulating materials, sealing materials, electrical equipment parts, Wt structural members, friction materials, aluminum electrodes, and the like.

Carbon fibers are mainly produced by firing fibers such as acrylonitrile and cellulose, but these raw materials have the disadvantages of high cost and low carbonization yield. On the other hand, each rare pitch available in large quantities is a by-product of the coal-oil industry.

A method of manufacturing carbon fiber using this raw material has been proposed, but it is difficult to spin due to lightening point, viscosity, etc., and the quality of the carbon fiber obtained is low. The reality is that there are still many problems that need to be resolved.

In order to solve these problems, there has been a method using a pitch-like substance obtained by hydrogenating or heat treating a specific condensed polycyclic aromatic compound (Japanese Patent Publication No. 45-28015,
(Japanese Patent Publication No. 49-8654) 9 A method using petroleum tar or pitch obtained by removing the Lewis acid catalyst and subjecting it to a second heat treatment (Japanese Patent Publication No. 55-7555), M
A method for producing carbon fibers by forming mesoface pitch with a predetermined mesoface content by rolling and using this as a raw material (Japanese Patent Application Laid-open No. 11350/1983, Japanese Patent Publication No. 54-18
10), a method using mesophase pitch having a specific composition and specific properties (Japanese Patent Application Laid-Open No. 54-55625, US Pat. No. 4,787,541), etc., but these methods have not been effective. However, it is not possible to obtain carbon fibers with properties comparable to those made from acridinitrile, so to date there is no known practical method for obtaining high-performance grade carbon fibers from pitch-like materials. Ta.

The present inventors believe that in order to produce high-quality pitch-based carbon fiber from mesoface pitch, it is essential to produce pitch with excellent spinnability.

Unlike carbon fibers made from polyacrylonitrile, pitch molding requires the molecules that make up pitch to be aligned parallel to the fiber axis during spinning, and subsequent infusibility, carbonization, or graphite death immediately It is quite difficult to correct the alignment of irregular molecules. In other words, it is based on the idea that the arrangement of one molecule is mostly determined during spinning. Based on this idea, we previously proposed a method for producing pitch-based carbon fiber navy blue using brimesophase as a raw material as a method for producing pitch with excellent spinnability.
6-117470). Among these, primesophase is a precursor of mesophase, and is a quinoline-soluble component that is optically isotropic. After spinning it into a fiber, it is first processed through primary treatment. It refers to something that changes to optical anisotropy. Then, as a method for producing this brimethophase, the first step is to treat pitch with tetofhydroquinoline at 380 to 500°C, or with aromatic swelling hydrogen such as naphthalene at 450°C or higher under hydrogen pressure. and the treated product under reduced pressure or normal pressure.
He proposed a method consisting of a second culm treated with a culm or higher (patent application 117470/1982) and published on May 12, 1983.
1 dea). In these methods, the first step is to carry out a thermal decomposition reaction of high molecular weight components in the peach and to stabilize the radio produced thereby by hydrogenation, thereby substantially reducing the molecular weight. For this purpose, it is necessary to be a good solvent for pitch and to have hydrogen donating properties. By the way, tetralin, which is known as a hydrogen donor, is a solvent, but it is not a good solvent for pitch, so when pitch is treated with it, coke, which is a polymerization product of pitch, is easily generated. do. The above-mentioned tetofhydroquinoline can be easily produced by hydrogenation of quinoline, and since quinoline is a good solvent for pitches, it was most suitable as a treatment agent for the first culm. but,
Although quinoline can be produced synthetically, it is mostly produced by separating basic components from coal tar.

It has the disadvantage that it is difficult to obtain in large quantities due to the wear and tear, and it is also expensive. On the other hand, in the case of aromatic hydrogenated hydrogen such as naphthalene, the hydrogenation reaction occurs at a treatment temperature of 450° C. or higher, and this reaction rate must be increased.

It also has the disadvantage of requiring high temperatures. After searching for a solvent that eliminates these drawbacks and has the same effect as tetrahydroquinoline, we found that distilled oil of coal tar, such as antoph7ine oil, which is a mixture of fused polycyclic aromatic hydrogenated compounds of 2 gJ or more. The present inventors have discovered that light oil, which is produced as a by-product during the thermal decomposition of naphtha, is effective.9 The present invention has been completed.

The present invention prepares pitch for spinning through a first culm in which pitches are subjected to a mild hydrogenation treatment and a second process in which the treated product is treated at high temperature for a short time under reduced pressure or normal pressure. This relates to a mild hydrogenation treatment method in the process, and will be explained in detail below.

The raw material heavy bituminous material may be any of the Ishijisaku 9 petroleum products, but
In particular, the heavy parts of heavy bituminous materials, ie, pitches, are suitable. These pitches are coal tar pitch, which is the distillation residue of coal tar if it is an Ishiji type, or the distillation residue of the by-product tar during naphtha thermal decomposition if it is an old method liquefied 9 petroleum type.

Fluid catalytic cracking method (FCC method) F? −Therefore, it is advantageous□
Decomposed tar from tar-like substances produced by oil, asphalt, which is a residue from distillation of crude oil, and pitch produced by thermal decomposition of this are used. These pitches may be used alone or in combination.

The condensed polycyclic aromatic hydrocarbons with two or more rings used as solvents include ansifcene oil, which is a distillate of coater, creosote oil, naphthalene oil, and absorption oil, as well as heavy oil, which is a by-product during naphtha thermal decomposition. This is the light oil fraction in the fraction.

There are two methods for treating pitches and solvents: That is, in the first method, the solvent is hydrogenated in advance, and the hydrogenated solvent and pitches are heated under an autogenous pressure of 400 to 500
Treat at ℃. The second method is to add a solvent to pitches, further add an iron-based compound, cobalt-molybdenum-alumina or nickel-molybdenum-alumina as a catalyst, and carry out the process under pressure of water gas.

The first method is hydrogenation treatment of the solvent in the presence of a catalyst at a hydrogen gas pressure of 50 to 200
Kp/country 9 Reaction flow rate carried out at 2300-400°C varies depending on the catalyst. For example, when a commercially available cobalt-molybdenum-alumina desulfurization catalyst is used as the catalyst.

The hydrogenation reaction occurs at about 320℃, but considering the reaction rate, it is better to be at about 350 to 380℃.
As time passes, the amount of hydrogen absorbed decreases. Hydrogen consumption is 1
~Shigeko Sanju-ru. In addition, when iron oxide (F@t's) among iron-based compounds is used as a catalyst, the hydrogenation reaction is approximately 3
Occurs at temperatures above 80°C. At 400°C, hydrogen absorption ends in a fairly short time. When a nickel-molybdenum/L/l catalyst is used, the hydrogenation reaction occurs from about 500°C.

The hydrogenation solvent used in the present invention is preferably one in which the amount of hydrogen consumed in the hydrogenation reaction is 1 to 3 by weight per 1 # of solvent.

100M of the hydrogenated solvents prepared in this way
Add 100 to 300 weight to the bearing part. This is placed in a closed container 1, for example, an autoclave, and the air inside is replaced with an inert gas such as nitrogen gas or hydrogen.

Then, it is heated to 400-500°C while stirring. It is good if the time to maintain this temperature is within 60 minutes.

Then, the treated product is filtered, centrifuged, etc. to remove solid matter. This removal process is not necessarily necessary if the raw material Piena is purified by removing solid matter in advance. The treated product from which the solid matter has been removed is used as it is, or the residue after recovering the solvent by distillation or the like is used as the raw material for the second culm.

The recovered solvent is again hydrogenated and reused.

2nd method This method uses a hydrogenated solvent or an unhydrogenated solvent, and hydrogenates the pitch using hydrogen released from the solvent. By treating the pitch under pressure, hydrogenation of the solvent and hydrogenation of the pitch are performed simultaneously. That is, to 100 parts by weight of pitch, add 50 to 100 parts by weight of solvent,
Hydrogenation of molybdenum-amina etc. as a catalyst for hydrogenation #! 1. The solid acid catalyst for sulfur is an iron-based compound with a pitch of 5 to 10 times the weight and a hydrogen pressure of 50 to 20.
Process with 0 immediate/α21360-5001c. A treatment time of 60 minutes or less is sufficient. Solids and catalysts are removed from the treated product by filtration and centrifugation. Next, this is used as it is, or the residue after recovering the solvent by distillation is used as a raw material for the second step. Since the recovered solvent is hydrogenated, it can be reused or used as a solvent in the first method.

In this method, the amount of solvent is less than 50 parts by weight, which poses a problem in terms of economy during the recovery operation. The catalyst is preferably an iron-based compound, especially iron oxide, but iron ore powder, bauxite,
Alternatively, red mud can be used.

Solid acid catalysts such as cobalt-molybdenum-alumina are good when processed at temperatures around 400°C.

It is not very suitable for processing at high temperatures of about 500°C.

This is because although it accelerates the decomposition of pitches, it also tends to generate coke on the catalyst, and as is well known, when coke is generated, the catalyst activity decreases.

The pitches treated by the first or second method described above are subjected to the following second step.

``In the second step, the processed material in the first culm is treated at a high temperature of 450° C. or higher, preferably at a temperature of 450 to 530° C., for a short period of time within 60 minutes. This treatment may be carried out under normal pressure or reduced pressure. When carrying out under normal pressure, an inert gas such as nitrogen gas or water vapor may be blown in to stir the treated material and remove light oil components. It is preferable to carry out the process under reduced pressure at a pressure of 30 Hp or less.1゜Through this treatment of the second culm, the light oil content is removed, and the residual pitch undergoes decomposition and polymerization reaction, resulting in a pitch suitable for spinning. becomes. In order to produce pitch with excellent spinnability, it is necessary to select a temperature of 1 hour and to effectively remove light oil components. Temperature and time are the first
The processing conditions in the process are involved. If the treatment temperature in the first step is as low as 400°C, the polymerization reaction will occur rapidly.
The selection range for temperature and time becomes narrower. Furthermore, if light oil components are insufficiently removed, they will separate during yarn wandering and the spinnability will deteriorate.

The pitch obtained by this 21st process has excellent spinnability and usually has a softening point of 300° C. or less and a fixed carbon width of about 90°. It contains primesophase or mesophase as a quinoline-soluble component. Spinning is possible if the content of mesophase is in the range of 0 to 90%, but particularly excellent spinnability is obtained when the mesophase content is about 70% or less.

Spinning can be either melt spinning or blow spinning. When performing melt spinning, a pitch is placed in a spinner with a nozzle diameter of 0.3 to 0.5 mm, and the pitch is approximately 70 to 14 mm above the softening point.
Heat to a temperature 0°C higher, apply pressure from the top of the pitch, and thread 8 threads. The winding speed can be 1000 m/min or more. The spun fibrous peach is about SOO in the air.
After oxidation and infusibility treatment with , C, 1
Carbonize by heating to 000-1500°C. Then, if necessary, it is heated to 2000° C. or higher to graphitize it.

The structure of spun fibrous pitch observed under a polarized light microscope is optically isotropic when the spinning pitch consists only of pre-mesophase, but when it contains mesophase, the molecules of this mesophase are arranged parallel to the fiber axis direction. It is a mixture of optically anisotropic parts and optically isotropic parts. This situation does not change even with infusibility treatment, but about 6
The entire fiber becomes optically anisotropic by carbonization treatment at 00°C or higher. Along with this, the meat fibers obtained by carbonization treatment of 1000 tl' have a diameter of 20 μm or less 1 Usually a, oltm
Tensile strength 200KF/2 or more, elongation rate 1.2-1.
79! , primary fibers with an elastic modulus of 12 to 17 L/2 are obtained at a yield of about 90 g based on the spinning pitch. Furthermore, when fired at high temperature, both strength and modulus of elasticity increase, and 2
When graphitized at 800℃, the tensile strength is 300Kf/m.
m2 or more 9 elastic modulus 50 / resistance 2 or more.

The present invention has the great advantage of providing the same effect through the same operation as the tetrahydroquinoline used in the earlier invention (Japanese Patent Application No. 117,470/1983), and being industrially available in large quantities and at low cost.

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

1 Reference Example Industrially produced anthothusene oil was distilled under reduced pressure, and 7:
A fraction having a pressure-equivalent boiling point of about 550° C. or lower was collected.

When this fraction was analyzed using a gas chromatograph, naphthalene to pyrene was detected.

The main ingredients are naphthalene, methylnaphthalene, acenabutene, anthronine (phenanthrene), carbacy,
Methyl antofcene, fluorene.

They were fluofunten and pirene.

This antotsucene oil 200# was placed in an autoclave with an internal volume of 500 f111, 5 tons of cobalt-molybdenum-alumina was added as a catalyst, and the initial pressure of hydrogen was 50 rp7. z
Heat under pressure. The internal pressure increased as the temperature rose, but when the temperature of the contents reached approximately 320°C, the pressure stopped increasing and began to decrease from around 525°C. Therefore, hydrogen is supplied from a hydrogen gas reservoir.

It was set to 100KG+/II2. While maintaining this pressure, the temperature continued to rise until the content temperature reached 380°C, and this temperature was maintained for 90 minutes. Immediately after the lapse of time, it was taken out of the furnace and cooled to room temperature. The amount of residual hydrogen was determined from the amount of gas in the autoclave and the hydrogen concentration, and the amount of hydrogen consumed was determined from the amount of pressure drop in the hydrogen gas reservoir.
It was 1.53 weight against f.

The catalyst was removed from the Naihayamono by filtration to obtain hydrogenated anthracite oil. When this was analyzed by gas chromatography and compared with the raw material anthracene oil, the presence of six new components was recognized. this house.

One component was tetralin, but the other components are unknown; one component has a boiling point of about 240°C and two components have a boiling point of about 250°C.

Fluorene (boiling point 298°C) and anthracene (boiling point 34°C)
A component with a boiling point between Pazo/I/ (boiling point 555°C) and fluoranthene (boiling point 384°C) was selected. Since the peak areas of these components varied depending on the reaction conditions, they were presumed to be hydrogenated aromatic hydrocarbons.

In the same manner as above, nickel-molybdenum was used as a catalyst.
Hydrogenation treatment was carried out using alumina or red mud under various conditions. In the case of nickel-molybdenum-amina, the decrease in hydrogen pressure became noticeable from about 30° C. and became rapid above about 330° C.

In the case of the red part, a decrease in hydrogen pressure was observed from about 375℃,
When the temperature reached 400°C, it became rapid. Even when hydrotreating using these catalysts, the changes in the components in the product were similar to those in the case of cobalt-molybdenum-alumina. The hydrogenation reaction occurs when the hydrogen pressure is 501f/α2 or more, but as the pressure increases, the amount of hydrogen consumed increases under the same hydrogenation conditions.

The above hydrogenation reaction involves taleosote oil and absorption oil.

The same applies to naphthalene oil or light oil, which is a mixture of methyl- and di-substituted benzenes and naphthalenes having ethyl groups, and mono- and di-substituted naphthalenes having methyl and ethyl groups in heavy oils produced as by-products during defroster preheating decomposition.

Hydrogenation was performed using anthracene oil under 9 different conditions, and the hydrogen consumption per 1 ton of anthracene oil and the peak area ratio of tetralin and naphthalene determined by - on the gas chromatograph were calculated as the amount of tetralin produced. Shown in 1.

The amount of tetralin produced and the amount of hydrogen consumed have an LX@ relationship as shown in FIG. Therefore, if you know the amount of tetralin produced, you can know the amount of hydrogen consumed, so below,
In the examples, the hydrogen calibration of the pitch was determined from the relationship shown in FIG.

Table 1 Note 1) CoMo is cobalt-molybdenum, NiMo is nickel-molybdenum.

Example 1 2fI with the properties shown in Table 2! ! - Luther μ
Pitch was used as the raw material. These pitches are about 200~
500 F into an autoclave with an internal volume of 21.

Pre-hydrogenated anthracene oil from 300 to 4
After adding 00, the inside of the autoclave was replaced with Arbo9. While stirring this, the average temperature rate is 2.5
Heat treatment was performed at 400°C or higher at a rate of °C/min.

After maintaining the predetermined temperature for a predetermined time, the autoclave was immediately taken out of the furnace and cooled to room temperature. The generated gas was analyzed using a gas analyzer to determine the amount of hydrogen gas. Solid matter was precipitated from the treated product using a centrifugal precipitator, and the supernatant was filtered under reduced pressure using qualitative filter paper. To collect pitch attached to solid materials.

Fresh anthracene oil was added to the solid, which was thoroughly washed, then benzene was added to remove the anthracene oil, and then dried. The filtrate is under reduced pressure of IQWRlRHp, and the content is 290%
Distillation was carried out until c □ was reached, and anthracene oil was recovered. This distillation residue pitch was used as a raw material for producing pitch for subsequent spinning. Incidentally, a small amount of the treated product after the autoclave treatment was collected and analyzed by gas chromatography to determine the peak area ratio of tetralin and naphthalene. Next, the hydrogen consumption amount was determined from the difference in the peak area ratio of tetralin and naphthalene in the hydrogenated anthracene oil used as the raw material. Next, the amount of hydrogen in the generated gas was subtracted from this hydrogen f4*maximum 1, and this value was taken as the hydrogen consumption amount of the pitch.

Table 3 summarizes the results of processing under various conditions according to the above method.

Table 2 Using the residual pitch in Table 3, pitch for spinning was prepared in the following manner.

Approximately 1,001 pieces of residual pitch were placed in a cylindrical container (capacity: 300 m/cm) made of 300 ml glass, and the container was placed in the upper part of a furnace that had been preheated to approximately 490° C. for preheating. This preheating melted the pitch until it reached approximately 300°C). to this,
Insert the glass tube to the bottom of the container.

, tt purity nitrogen gas was blown for 1 to 2 minutes.

First, the pitch was placed in a furnace, and after the temperature of the pitch reached 470° C., it was maintained at this temperature for a predetermined period of time. After time tU
The container was immediately removed from the oven and cooled to room temperature. During this process, nitrogen gas continued to flow.

The spilled oil was collected in a trap. Also, the time to reach 470°C from about 0°C is about ±→- minutes, which is 1. 5I
0 Furthermore, when performing under reduced pressure, connect the distilled oil outlet of the 5-ton cylinder container to a vacuum bonder via a trap.
The same operation as above is carried out under a reduced pressure of 30 to Hp or less.9 Normally, 10 to Ht is used.

The pitch obtained by the above operation was used as spinning pitch.

Yield of pitch obtained by processing under various conditions.

The notes are summarized in Table 4.

The spinning pitch of this spinning pitch is 20 inner rods with a nozzle having a diameter of 0.3 mm or 0.5 mm, and a length of 150 mm.
The spinning pitch was about 102 people ps0.
The pitch extruded from the nozzle is rolled onto a drum.
I did it using the following method. The winding speed of the drum is usually set to 1000.
m/min, and the spinability of the spear was easily evaluated by winding the yarn without breaking for at least several minutes. Those with a winding speed of 1000 m/min or less,
Alternatively, even if the speed was 1000 m/min, if thread breakage frequently occurred, it was evaluated as difficult.

The results are shown in Table 4. Furthermore, this spun fibrous pitch was heated at 5°C/min from room temperature to 200°C in air.
The temperature was raised to 300°C at a rate of 2°C/min and held for 15 minutes to perform infusibility treatment. Then, in an argon stream.

Heating to 1000℃ at a temperature increase rate of 25℃/win,
The carbon fibers were obtained by holding for 5 minutes and performing a legalization treatment. Fiber diameter and tensile strength of this carbon fiber (average It of 10 fibers)
These are also shown in Table 4E.

Example 2 The same coal tar pitches A, B and naphsatar μ as in Example 1 were mixed under a reduced pressure of 10 tmHIi at a temperature of 290°C.
Residue pitch after vacuum distillation (below).

↑7 Sutter μ pitch) was used as the raw material pitch. Nafu Kui tar pitch has a softening point of 113℃, pen-12in insoluble separation,
Both amounts of quinoline dissolved therein were 0.54 wt%.

These pitches of about 4007F were put into a 2J autoclave, and the andobutsen oil used in the voice example, the light oil in the heavy oil by-produced during Naf'M decomposition, and the hydrogenated oil of antotsusen oil (actual M number 9 in Table 1) were added. ) and red mud as a catalyst.

Approximately 2 Of cobalt-molybdenum-alumina or nickel-molybdenum-alumina was added. Then, while stirring under a pressure of hydrogen initial pressure 759/z2, Example 1
Heat to 360-460℃ in the same manner as above, and heat to 10-6℃.
It was held for 0 minutes. Immediately after the time elapsed, the autoclave was taken out of the furnace and cooled to room temperature. From the thus obtained treated product, pitch for spinning was prepared in the same manner as in Example 1. Table 5 summarizes the results of processing the raw materials Pi and Chi under various conditions, and Table 6 shows the properties of the spinning pitch and the results of producing subelementary fibers using this pitch in the same manner as in Example 1. .

The spinning pitch numbered 12.15 in Table 6 is one in which the raw pitch is treated at a temperature of 400°C or lower, but the spinnability of this pitch is inferior to that treated at a temperature of 400°C or higher. Since there is no big difference in hydrogen consumption, in order to produce pitch with excellent spinnability, it is necessary not only to increase the hydrogen consumption of raw material pitch but also to increase the amount of hydrogen consumed by raw material pitch.

It can be said that it is necessary to cause a thermal decomposition reaction of a pitch of C or higher. In the treatment of raw material pitch, when highly active cobalt-molybdenum-alumina or nickel-molybdenum-alumina is used as a catalyst.

If no solvent is added to the raw pitch, approximately 420 t: l! A large amount of coke, which is insoluble in the ¥3, is produced, but when a solvent is added, as shown in Table 5, even at 460°C, the solid content is only slightly larger than the amount of quinolinine dissolved in Table 1. , it can be said that almost no coke is produced. Prior invention of treating raw material pitch with tetrahydroquinoline or quinoline (Patent application 117/1982)
470)', it is not possible to use a highly active catalyst and treat at high temperatures as described above. This is because a denitrification reaction occurs and the loss of tetrahydroquinoline or quinoline increases. Regarding this point 1, in the case of the present invention, l
Since the I9 nitrogen reaction was very low, it became possible to use highly active catalysts. Furthermore, the ability to use a highly active catalyst has the advantage of easily increasing hydrogen consumption. This is because when spun fibrous pitch is oxidized and infusible with air, the oxidation weight increase increases and infusibility becomes easier.

[Brief explanation of the drawing]

FIG. 1 shows the relationship between hydrogen consumption and tetralin production when anthracene oil is hydrotreated. Patent applicant Makoto Ishiita, Director of the Agency of Industrial Science and Technology - Figure 1 Hydrogen consumption (wt%) Procedural amendment (method) % formula % 1. Indication of the case Patent Application No. 98194 of 1981 2
, Title of the invention: Method for adjusting pitch for manufacturing pitch-based carbon fibers 3, Relationship with the case of the person making the amendment Patent applicant: 1-3-1 Kasumigaseki, Chiyoda-ku, Tokyo (114) Director of the Agency of Industrial Science and Technology Makoto Ishizaka - 1972 Year 9
September 9th (Shipping date: September 28th, 1982)

Claims (1)

[Claims] 1. A method for spinning by the first step of treating the FIJ pre-bituminous material and the second step of treating the hydrogenated heavy bituminous material at a temperature of 450° C. or higher under reduced pressure or normal pressure. After producing pitch, spinning this pitch, and infusible treatment,
Carbonized pitch-based carbon fiber 1111! In the method of producing heavy bituminous materials, hydrogenation treatment in the 11th culm
A pitch system characterized by adding 100 to 300 p of a hydrogenated mixture of fused polycyclic aromatic compounds having two or more rings to the base and treating it under autogenous pressure at a temperature of 400 to 500°C. Method for preparing pitch for carbon fiber Ijll manufacturing. 2. When the hydrogenated mixture of fused polycyclic aromatic compounds with 2 or more rings is hydrogenated in the presence of a catalyst, the hydrogen consumption amount is 1 to 3 double cyclones. - The method according to claim 1. 3. Pitch for spinning is produced by the first step of treating the ffi pre-bituminous material and the second step of treating the hydrogenated heavy bituminous material at a temperature of 450° C. or higher under reduced pressure or normal pressure. In the method of manufacturing pitch-based carbon fiber by spinning pitch, infusible treatment, and then carbonization treatment, the hydrogenation treatment in the first culm was performed on 100 heavy bituminous materials. A mixture of fused polycyclic aromatic compounds with more than one ring or a mixture of fused polycyclic aromatic compounds with more than one ring
Add 0-1-100 parts by weight and further in the presence of a hydrogenation catalyst* 360~
A method for preparing pitch for producing pitch-based secondary fiber #, characterized by processing at a temperature of 500°C. 4. Anthra7 oil, which is a distilled oil of coal tar, which is a mixture of fused polycyclic aromatic compounds having two or more rings. The method according to claims 2 and 3, which is creosote oil, absorption oil, naphthalene oil, and light oil produced as a by-product during naphtha thermal decomposition. 5. The method according to claims 2 and 5, wherein the hydrogenation catalyst is a nickel-molybdenum-alumina, copper-molybdenum-aluminum, or iron-based compound.