KR101537869B1

KR101537869B1 - Method for manufacturing isotropic pitch having high softening point

Info

Publication number: KR101537869B1
Application number: KR1020130158040A
Authority: KR
Inventors: 이주형; 윤광의; 송영석; 이현철; 김명수; 유미정
Original assignee: 오씨아이 주식회사
Priority date: 2013-12-18
Filing date: 2013-12-18
Publication date: 2015-07-17
Also published as: WO2015093846A1; KR20150075123A

Abstract

(a) preparing a mixed solution obtained by mixing a carbonaceous raw material containing at least one selected from the group consisting of a coal-based carbonaceous raw material, a petroleum-based carbonaceous raw material and a combination thereof with an organic solvent; (b) adding an acid or an oxidizing agent to the mixture of the carbonaceous raw material and the organic solvent; And (c) heat treating the resultant product of step (b) to obtain a pitch, wherein a high softening point isotropic pitch is produced.

Description

METHOD FOR MANUFACTURING ISOTROPIC PITCH HAVING HIGH SOFTENING POINT [0002]

To a method of producing a high softening point isotropic pitch.

Generally, a method of producing a high softening point isotropic pitch is a method in which a heat treatment is performed in an inert gas atmosphere using a carbonaceous raw material as a starting material, a method in which air is blown in air, a reaction additive such as a nitro compound, And a heat treatment is performed by adding a halogen compound (chlorine (Cl ₂ ), bromine (Br ₂ ), iodine (I ₂ ), thionyl chloride (SOCl ₂ ), sulfuryl chloride (SO ₂ Cl ₂ ) Method.

Among the above methods, the heat treatment in the inert atmosphere is performed at a low temperature to suppress the radical reaction. The heat treatment time is very long and the amount of the pitch obtained is 20 to 40 wt% Is 10 to 25% by weight based on the raw material.

In addition, the heat treatment method in which a nitro compound is added is problematic in that the production cost is increased due to the expensive nitro compound and the process is complicated. On the other hand, in the heat treatment method in which a catalyst such as aluminum chloride is added, Due to problems, commercial technology is difficult to apply.

In addition, a method of adding a halogen compound to heat treatment is to use a petroleum heavy oil having a high yield rate of isotropic pitch with high softening point but a low degree of aromatization when using coal tar, coal tar pitch, or FCC-DO (fluidized catalytic cracking- (Anthracene, methylnaphthalene, etc.) as raw materials, the yield is lowered to less than 30% by weight.

One embodiment of the present invention can be made of a carbon material having excellent mechanical properties because it can obtain an isotropic pitch with a high softening point at a high yield, a high carbonization yield when used as a carbon precursor, and uniform physical properties. Thereby providing a method of manufacturing an isotropic pitch.

In one embodiment of the invention,

(a) preparing a mixed solution obtained by mixing a carbonaceous raw material containing at least one selected from the group consisting of a coal-based carbonaceous raw material, a petroleum-based carbonaceous raw material and a combination thereof with an organic solvent;

(b) adding an acid or an oxidizing agent to the mixture of the carbonaceous raw material and the organic solvent; And

(c) heat treating the result of step (b) to obtain a pitch.

The carbonaceous raw material may be at least one selected from the group consisting of coal-based coal tar, coal-based coal tar pitch, petroleum heavy oil, heavy oil, hydrocarbonaceous material containing the maximum amount of the hydrocarbonaceous material in the composition, And may include at least one selected.

The method of manufacturing the high softening point isotropic pitch may further include removing ash or insoluble solid carbon from the carbonaceous raw material before the step (a).

The carbonaceous raw material may have a softening point of 20 to 60 캜.

The organic solvent may have a polarity index of 3 to 6.

The organic solvent may include at least one selected from the group consisting of ethanol, methanol, isopropyl alcohol, tetrahydrofuran, dichloromethane, chloroform, and combinations thereof.

In the step (a), the organic solvent may be mixed in an amount of 5 to 200 parts by weight based on 100 parts by weight of the carbonaceous raw material.

The step (a) may be carried out at 20 to 90 ° C.

The viscosity of the mixed solution may be 0.1 to 30 cp at 60 ° C.

The acid is an inorganic acid solution containing at least one selected from the group consisting of nitric acid, sulfuric acid, hydrochloric acid, and combinations thereof, and the oxidizing agent may be hydrogen peroxide, peracetic acid, oxone, ammonium persulfate, sodium persulfate, and potassium persulfate.

In the step (b), the acid or the oxidizing agent may be added to the mixed solution at a content ratio of 0.1 to 50 parts by weight based on 100 parts by weight of the carbonaceous raw material.

The step (c) may be heat-treated at 100 to 300 ° C.

The step (c) may be heat treated for 10 minutes to 300 minutes.

The method of manufacturing the high softening point isotropic pitch may further include removing low-volatile matter from the result of step (c).

The softening point of the isotropic pitch obtained by the method for producing a high softening point isotropic pitch may be 250 to 300 캜.

The isotropic pitch at a high softening point can be obtained at a high yield by the above-mentioned method of producing a high softening point isotropic pitch.

The high softening point isotropic pitch produced by the method of producing a high softening point isotropic pitch is a precursor of carbon material and has a high carbonization yield when used.

In addition, the high softening point isotropic pitch produced by the method of producing a high softening point isotropic pitch can uniformly realize physical properties of the obtained isotropic pitch, so that the carbon material produced therefrom has improved mechanical properties.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention. The present invention may be embodied in many different forms and is not limited to the embodiments described herein.

In one embodiment of the invention,

(c) heat treating the result of step (b) to obtain a pitch.

The method of producing a high softening point isotropic pitch is a method of obtaining an isotropic pitch at a high softening point by polymerizing a component having a high molecular weight by using a carbonaceous raw material.

Specific examples of the carbon material obtained by using the high softening point isotropic pitch produced by the method of producing a high softening point isotropic pitch as the precursor include carbon fiber, carbon-carbon composite material, secondary battery electrode material, high purity graphite and the like The isotropic pitch obtained by the above production method can be used as a precursor for producing carbon materials in various fields.

The carbonaceous raw material may be a mixture of hydrocarbon materials containing a maximum content of coal-based coal tar, coal-based coal tar pitch, petroleum heavy oil, petroleum heavy oil, Raw materials, and the like, and may include a combination of at least one of these.

For example, the mixed material of the hydrocarbon material includes at least one of aromatic hydrocarbon compounds such as naphthalene, methylnaphthalene, and anthracene as main components, and various materials obtained as an intermediate product during a treatment process such as coal, It can be used as raw material.

The carbonaceous raw material can improve the physical properties of finally obtained isotropic pitch by removing the ash or insoluble solid carbon before the step (a).

Accordingly, the method of producing a high softening point isotropic pitch may further comprise removing ash or insoluble solid carbon from the carbonaceous raw material before the step (a).

The carbonaceous raw material may be a material having a softening point of 20 to 60 캜.

The prepared carbonaceous raw material is mixed with an organic solvent to prepare a mixed solution.

By mixing the carbonaceous raw material with an organic solvent to prepare a mixed solution, the carbonaceous raw material can be homogeneously mixed with an acid or an oxidizing agent when mixed with an acid or an oxidizing agent in step (b) ), The yield of the isotropic pitch can be increased by causing the reaction to occur uniformly during the heat treatment.

The organic solvent may be used without limitation as long as it is a substance capable of dissolving the carbonaceous raw material. However, when the carbonaceous raw material is a mixture of various components, an organic solvent capable of dissolving the main component of the carbonaceous raw material may be used, and some insoluble components may be contained in the mixed solution.

As the organic solvent, an organic solvent having a polarity index of 3 to 6 may be used. When the polarity of the organic solvent is lower than 3, the solubility with acid is lowered. When the polarity is higher than 6, the solubility of the carbonaceous raw material deteriorates. Therefore, the organic solvent having the polarity in the above range dissolves the carbonaceous material uniformly Is suitable for preparing the mixed solution.

The organic solvent may be, for example, ethanol, methanol, isopropyl alcohol, tetrahydrofuran, dichloromethane, chloroform, or the like, or a combination of at least one of them.

In the step (a), the carbonaceous raw material and the organic solvent may be mixed at 20 ° C to 90 ° C to prepare a mixed solution.

When 100 g of pitch is used in the step (a), the organic solvent may be added at a rate of 0.1 to 100 ml / min. By adding an organic solvent at the above-mentioned range and mixing with the carbonaceous raw material, the carbonaceous raw material can be dissolved well in the organic solvent, and a more homogeneous mixed solution can be produced.

In the step (a), the organic solvent may be mixed in an amount of 5 to 200 parts by weight based on 100 parts by weight of the carbonaceous raw material. By mixing in the above-mentioned range, the mixed solution has an appropriate viscosity and can be mixed well with an acid or an oxidizing agent in step (b).

Specifically, the viscosity of the mixed solution may be 0.1 to 30 cp at 60 ° C. If the mixed solution has a viscosity within the range, it can be mixed well with an acid or an oxidizing agent in the step (b).

In the step (b), when the mixed solution is mixed with an acid or an oxidizing agent and then heat-treated in the step (c), an isotropic pitch having a high softening point is obtained by a reaction in which the carbonaceous raw material is polymerized in a high molecular weight.

In the step (b), both the acid or the oxidizing agent serve to oxidize the pitch, the pitch is oxidized to cause an alkylation reaction (dealkylation), and an oxygen-containing structure is formed. Thereby forming radicals. The molecular weight of the generated pitch is increased due to polycondensation of the formed radical.

In the step (b), an acid or an oxidizing agent is added to the mixed solution in which the carbonaceous raw material is uniformly dissolved in the organic solvent through the step (a), whereby the carbonaceous raw material is converted into a component having a high molecular weight The polymerization reaction can occur uniformly and an isotropic pitch at a high softening point can be obtained at a high yield. That is, in order to overcome the fact that the physical properties of an uneven homogeneous pitch, which is a disadvantage of an acid and an oxidizing agent, which is a method of obtaining a high high softening point yield compared to an oxidation reaction using conventional air, The present invention provides a production method having uniform physical properties while having a high yield ratio of high softening point pitch.

The acid may be, for example, an inorganic acid solution such as nitric acid, sulfuric acid, hydrochloric acid, or the like, or a combination thereof.

The oxidizing agent may be, for example, hydrogen peroxide, peracetic acid, oxone, ammonium persulfate, sodium persulfate, or potassium persulfate.

In the step (b), the acid or the oxidizing agent may be added to the mixed solution at a content ratio of 0.1 to 50 parts by weight relative to 100 parts by weight of the carbonaceous raw material. By adding the acid or the oxidizing agent to the mixed solution so as to have the above content ratio, it is possible to increase the yield of the obtained isotropic pitch at a high softening point.

In the step (c), the heat treatment may be performed at 100 to 300 ° C. It is possible to increase the yield of the isotropic pitch at a high softening point obtained by performing the heat treatment within the above temperature range.

Also, in the step (c), the heat treatment may be performed for 10 minutes to 300 minutes. The yield of the isotropic pitch at the high softening point obtained by performing the heat treatment within the time range can be increased.

The softening point of the finally obtained isotropic pitch can be further increased by removing the low-volatile matter material with respect to the isotropic pitch of the high softening point obtained in the step (c).

Accordingly, the method for producing a high softening point isotropic pitch may further include removing low-volatile matter from the result of step (c) after step (c). Specifically, the low volatiles can be distilled off from the product of step (c).

The softening point of the finally obtained isotropic pitch can be freely adjusted according to the degree of removal of the low-volatile matter substance.

For example, the softening point of the isotropic pitch obtained by the method of producing the high softening point isotropic pitch may be 250 to 300 캜.

The yield of the high softening point isotropic pitch produced by the method of producing a high softening point isotropic pitch is higher than the yield of isotropic pitch obtained by another manufacturing method under the condition having the same softening point and has a uniform physical property. This is because, as described above, by using an organic solvent having an appropriate polarity, the carbonaceous raw material is more homogeneously mixed with an acid or an oxidizing agent and then heat-treated to have homogeneous physical properties. However, by the polymerization reaction of the pitch by an acid and an oxidizing agent, This is because it is possible to increase the production yield of softening point pitch.

In general, the yield of the pitch obtained from the coal-based raw material is low in the petroleum-based raw material. The method of producing a high softening point isotropic pitch can produce an isotropic pitch with a good yield in both the petroleum raw material and the coal raw material.

Hereinafter, specific embodiments of the present invention will be described. However, the embodiments described below are only intended to illustrate or explain the present invention, and thus the present invention should not be limited thereto.

( Example )

Example One

Coal-based coal tar pitch was used as the carbonaceous raw material. 50 g of ethanol was added to 100 g of a soft pitch having a softening point of 35 캜 and sufficiently stirred at 80 캜. The viscosity of the obtained mixed solution was 4 cp at 60 占 폚. Thereafter, 10 g of 60 wt% nitric acid was added at a rate of 1 ml / min or less, followed by heat treatment at 200 DEG C for 1 hour. Thereafter, the low molecular weight material was removed by vacuum distillation to prepare a high softening point isotropic pitch. The softening point of the pitch at this time and the pitch production yield are shown in Table 1 below. Table 1 shows the yields of carbon fiber fabrication using carbon fiber prepared by the following method using the prepared high softening point isotropic pitch.

Manufacture of carbon fiber

The high softening point isotropic pitch obtained in the above process was continuously spinned at a melt temperature of 320 DEG C with a nozzle having a diameter of 0.3 mm (winding speed: 600 m / min) to obtain pitch fibers.

The obtained pitch fiber was infused in air at a heating rate of 1 占 폚 / min to 150-350 占 폚, and the unfused fiber was fired at 1000 占 폚 for 1 minute in a nitrogen atmosphere to produce carbon fibers.

Example 2

Coal-based coal tar pitch was used as the carbonaceous raw material. 30 g of tetrahydrofuran was added to 100 g of a soft pitch having a softening point of 35 캜 and sufficiently stirred at 60 캜. The viscosity of the obtained mixed solution was 6 cp at 60 占 폚. Subsequently, 8 g of sulfuric acid at a concentration of 95 wt% was added at a rate of 1 ml / min or less, and then heat treatment was performed at 180 캜 for 1 hour. Subsequently, low molecular weight substances were removed by vacuum distillation to prepare a high softening point isotropic pitch. The softening point and yield of the pitch at this time are shown in Table 1 below.

Carbon fibers were prepared in the same manner as in Example 1 with the high softening point isotropic pitch obtained in the above process.

Example 3

Petroleum heavy oil (heavy oil) was used as the carbonaceous raw material. 40 g of ethanol was added to 100 g of heavy oil and the mixture was sufficiently stirred at 80 ° C. The viscosity of the obtained mixed solution was 5 cp at 60 占 폚. Subsequently, 8 g of sulfuric acid at a concentration of 95 wt% was added at a rate of 1 ml / min or less, and then heat-treated at 180 ° C. for 1 hour. Subsequently, low molecular weight substances were removed by vacuum distillation to prepare a high softening point isotropic pitch. The softening point and yield of the pitch at this time are shown in Table 1 below.

Comparative Example One

A coal-based coal tar pitch having a softening point of 35 캜, which is the same carbonaceous raw material as in Example 1, was used. 100 g of pitch was heated to a temperature of 340 캜, and then heat treatment was performed for 3 hours while air was injected at a rate of 300 ml / min. Subsequently, low molecular weight substances were removed by vacuum distillation to prepare a high softening point isotropic pitch. The softening point and yield of the pitch at this time are shown in Table 1 below.

Comparative Example 2

A coal-based coal tar pitch having a softening point of 35 캜, which is the same carbonaceous raw material as in Example 1, was used. 100 g of pitch was added with 10 g of 60% concentration of nitric acid at a rate of 1 ml / min or less while stirring at 80 캜 without adding an organic solvent. Thereafter, heat treatment was performed at 200 ° C for 1 hour. Subsequently, low molecular weight substances were removed by vacuum distillation to prepare a high softening point isotropic pitch. The softening point and yield of the pitch at this time are shown in Table 1 below.

Comparative Example 3

Petroleum heavy oil which is the same carbonaceous raw material as in Example 3 was used. 8 g of 95 wt% sulfuric acid was added at a rate of 1 ml / min or less while stirring at 80 占 폚 with no organic solvent added, and then heat treatment was performed at 180 占 폚 for 1 hour. Subsequently, low molecular weight substances were removed by vacuum distillation to prepare a high softening point isotropic pitch. The softening point and yield of the pitch at this time are shown in Table 1 below.

Item The softening point of the obtained pitch [占 폚] The yield (A) of the obtained pitch [%] Carbon fiber production yield (B) [%] Overall yield (A / 100 x B / 100 x 100) [%] Example 1 278 54 80 43.2 Example 2 281 62 81 50.2 Example 3 279 43 78 33.5 Comparative Example 1 280 45 75 33.8 Comparative Example 2 282 50 73 36.5 Comparative Example 3 281 40 72 28.8

As shown in Table 1, both Examples 1-3 and Comparative Examples 1-3 obtained an isotropic pitch at a high softening point.

Example 1-2 is obtained by obtaining a high softening point isotropic pitch from the coal-based raw material, and it can be confirmed that the yield of the pitch obtained in comparison with Comparative Example 1-2 in which a high softening point isotropic pitch is obtained from the coal-based raw material is likewise improved.

Example 3 is obtained by obtaining a high softening point isotropic pitch from the petroleum-based raw material, and it can be confirmed that the yield of the pitch obtained in comparison with Comparative Example 3 in which a high softening point isotropic pitch is obtained from the petroleum-based raw material is likewise improved.

In addition, it can be confirmed that the production yield of carbon fiber of Example 1-3 is superior to that of Comparative Example 1-3.

The overall yield is shown as a percentage by multiplying the yield (A) of the obtained pitch and the carbon fiber production yield (B), and it can be compared with Example 1-2 and Comparative Example 1-2 in the case of being made of a coal-based raw material . As a result, it can be confirmed that the results of Example 1-2 are superior, and in addition, Example 3 and Comparative Example 3, which are made of a petroleum-based raw material, can be compared. As a result, Can be confirmed.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, And falls within the scope of the invention.

Claims

(a) preparing a mixed solution obtained by mixing a carbonaceous raw material containing at least one selected from the group consisting of a coal-based carbonaceous raw material, a petroleum-based carbonaceous raw material and a combination thereof with an organic solvent;
(b) adding an acid to the mixture of the carbonaceous raw material and the organic solvent; And
(c) heat treating the result of step (b) to obtain a pitch,
The organic solvent has a polarity index of 3 to 6,
The step (a) is carried out at 20 to 90 ° C,
In the step (b), the acid is added to the mixed solution at a content ratio of 0.1 to 50 parts by weight relative to 100 parts by weight of the carbonaceous raw material
Method of manufacturing high softening isotropic pitch.

The method according to claim 1,
The carbonaceous raw material may be at least one selected from the group consisting of coal-based coal tar, coal-based coal tar pitch, petroleum heavy oil, heavy oil, hydrocarbonaceous material containing the maximum amount of the hydrocarbonaceous material in the composition, And a method of producing a high softening point isotropic pitch comprising at least one selected.

The method according to claim 1,
Further comprising the step of removing ash or insoluble solid carbon from the carbonaceous raw material prior to the step (a).

The method according to claim 1,
Wherein the carbonaceous raw material has a softening point of 20 to 60 캜.

delete

The method according to claim 1,
Wherein the organic solvent comprises at least one selected from the group consisting of ethanol, methanol, isopropyl alcohol, tetrahydrofuran, dichloromethane, chloroform, and combinations thereof.

The method according to claim 1,
In the step (a), the organic solvent is mixed at a content ratio of 5 to 200 parts by weight based on 100 parts by weight of the carbonaceous raw material.

delete

The method according to claim 1,
Wherein the viscosity of the mixed solution is 0.1 to 30 cp at 60 캜.

The method according to claim 1,
Wherein the acid is an inorganic acid solution containing at least one selected from the group consisting of nitric acid, sulfuric acid, hydrochloric acid, and combinations thereof.

delete

The method according to claim 1,
Wherein the step (c) is heat-treated at 100 to 300 ° C.

The method according to claim 1,
Wherein the step (c) is heat-treated for 10 minutes to 300 minutes.

The method according to claim 1,
Further comprising the step of removing low-volatile matter from the result of step (c).

The method according to claim 1,
Wherein the softening point of the obtained isotropic pitch is 250 to 300 占 폚.