KR101927615B1 - Manufacturing method of petroleum-based binder pitch with high quinoline-insoluble content - Google Patents

Abstract

A process for producing a petroleum-based binder pitch having a high content of quinoline insoluble components is disclosed.
A method of manufacturing a petroleum-based binder pitch according to the present invention comprises the steps of: a first step of activating a carbonaceous material by applying an ultrasonic wave in a state in which a carbonaceous material is supported on an acid solution; A second step of reacting the carbon material activated through the first step with fluorine gas to introduce a fluorine functional group onto the surface of the carbon material; And a third step of mixing a carbonaceous material having a fluorine functional group introduced into the surface thereof with a petroleum residue oil through a second step and heat treating the carbonaceous material to produce a petroleum binder pitch.

Description

[0001] The present invention relates to a method for producing a petroleum-based binder pitch having a high content of quinoline-insoluble components,

The present invention relates to a method of producing a petroleum-based binder pitch, and more particularly, to a method of producing a petroleum-based binder pitch by subjecting a carbonaceous material to ultrasonic treatment in a state of being supported on an acid solution, Based binder component having a quinoline-insoluble component.

Carbon materials are used in various industrial fields because of their high specific strength, high conductivity and excellent thermal shock resistance. Precursors of such carbon materials include polyacrylonitrile (PAN), phenol resin, and pitch. The pitch among the precursors is an aggregate of aromatic organic molecules of a condensed platelet structure capable of being graphitized, and is largely divided into coal-based and petroleum-based pitches. The petroleum pitch is produced by heat treatment of the petroleum residue obtained after the crude oil refining process, and then solidified through a condensation reaction, aromatization reaction and the like. The petroleum pitch thus prepared is used as a binder for the production of a carbon compact.

Quinoline insoluble matters of about 10% are present in the case of the coal-based binder pitch, but quinoline insoluble matters of about 1% are present in the case of the petroleum-based binder pitch, so that in the case of the carbon molded article produced by using the petroleum-based binder pitch, Is lowered and the physical properties are lowered.

It is an object of the present invention to provide a method for producing a petroleum-based binder pitch having a quinoline insoluble component of about 10 wt%, which is known to be ideal by a simple process.

In order to achieve the above-mentioned object, the present invention provides a method of producing a petroleum-based binder pitch having a high quinoline insoluble component. In the method of producing a petroleum-based binder pitch according to an embodiment of the present invention, A first step of activating the carbonaceous material by applying ultrasonic waves in one state; A second step of reacting the carbon material activated through the first step with fluorine gas to introduce a fluorine functional group onto the surface of the carbon material; And a third step of mixing a carbonaceous material having a fluorine functional group introduced into its surface with a petroleum residue oil through a second step and then heat-treating the carbonaceous material to produce a petroleum binder pitch.

The carbon material may be selected from the group consisting of carbon black, carbon nanotubes, graphene, activated carbon, and mixtures thereof.

In the third step, the carbon material is preferably mixed with 0.5 to 2 wt% of the entire mixture.

The heat treatment in the third step is preferably performed in a temperature range of 300 to 400 ° C.

The heat treatment is preferably performed in an inert gas atmosphere.

According to the present invention described above, the carbon material having the fluorine functional group introduced on the surface thereof is reacted with the fluorine gas by applying the ultrasonic wave to the carbon material while the carbon material is supported on the acid solution, A petroleum-based binder pitch having a quinoline insoluble component of about 10 wt%, which is known to be ideal, can be produced.

Also, according to the present invention, by using a carbonaceous material, which is the same component as the petroleum residue oil, as a component mixed in a petroleum residue oil in order to increase the quinoline insoluble component, the conventional additive material acts as an impurity, .

Therefore, the carbon formed body manufactured using the petroleum-based binder pitch according to the present invention can obtain a good yield and secure a stable physical property.

Fig. 1 shows the content of quinoline insoluble components in the petroleum-based binder pitches prepared in Examples and Comparative Examples of the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will now be described in detail with reference to the accompanying drawings.

The present invention provides a method for producing a petroleum-based binder pitch having a high content of quinoline insoluble components. In the method for producing a petroleum-based binder pitch according to an embodiment of the present invention, ultrasonic waves are applied in a state of holding a carbon material in an acid solution A first step of activating the carbonaceous material; A second step of reacting the carbon material activated through the first step with fluorine gas to introduce a fluorine functional group onto the surface of the carbon material; And a third step of mixing a carbonaceous material having a fluorine functional group introduced into its surface with a petroleum residue oil through a second step and then heat-treating the carbonaceous material to produce a petroleum binder pitch.

The carbon material may be selected from the group consisting of carbon black, carbon nanotubes, graphene, activated carbon, and mixtures thereof. However, it is preferable to use carbon black having excellent surface activity and adsorption power, but it is not limited thereto.

In the first step, the carbon material is activated by applying ultrasonic waves while the carbon material is supported on the acid solution. This is to facilitate the process of introducing the fluorine functional group in the subsequent second step.

Any of the acid solutions may be used, and the ultrasonic treatment is preferably performed in the range of 20 to 40 kHz for 0.1 to 1 hour. The ultrasonic treatment range is an optimal value selected by repeated experiments, but it is not limited thereto.

The activated carbon material through the first step reacts with the fluorine gas in the second step, and a fluorine functional group is introduced into the surface of the carbon material.

The fluorine gas can be introduced from various materials including pure fluorine and fluorine, and for example, fluorine, boron trifluoride, nitrogen trifluoride, and mixtures thereof can be used. That is, the fluorine gas referred to herein is a concept that refers to various materials including pure fluorine gas and fluorine.

The process of introducing the fluorine functional group in the second step is preferably performed after repeating the process of injecting and discharging the inert gas several times in order to minimize undesired side reactions.

The process of introducing the fluorine functional group in the second step may be performed at room temperature and may be performed for 0.1 to 1 hour in the range of 0.1 to 1 bar pressure of the fluorine gas in the reactor. Also, the process of introducing the fluorine functional group in the second step may be performed using a mixed gas of an inert gas and a fluorine gas. In this case, the partial pressure of the fluorine gas is preferably in the range of 0.1 to 1 bar.

When the pressure (or partial pressure) of the fluorine gas and the reaction time are less than the lower limit, there is a possibility that the introduction of the fluorine functional group into the carbon material may be insufficient, and the fluorine gas pressure (or partial pressure) There is no difference in the amount of the fluorine functional groups to be introduced and the undesirable structural deformation due to the overfire may occur, which is not preferable.

When the process of the second step is performed as described above, sufficient fluorine functional groups are introduced into the surface of the carbonaceous material. In the third step, the carbon material into which the fluorine functional group has been introduced is mixed with the oil residues and heat-treated to prepare a binder pitch.

The carbon material into which the fluorine functional group is introduced in the third step is preferably mixed with 0.5 to 2 wt% of the carbon material to which the fluorine functional group is introduced. When the mixing ratio of the carbon material into which the fluorine functional group is introduced is less than the lower limit, It is difficult to fully expect the formation and growth effect of the quinoline insoluble component due to the presence of the fluorine functional group. When the mixing ratio of the carbon material into which the fluorine functional group is introduced exceeds the upper limit value, the quinoline insoluble component may grow more than necessary.

The heat treatment is preferably performed at a temperature in the range of 300 to 400 ° C. If the heat treatment temperature is lower than the lower limit value, the energy for thermal polymerization may not be sufficient. If the heat treatment temperature exceeds the upper limit value, It is not preferable because there is a concern that structural strain may occur.

The heat treatment is preferably performed in an inert gas atmosphere in order to minimize undesired side reactions.

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

Example  : Manufacture of Petroleum Binder Pitch

Carbon black was supported on a nitric acid solution, and ultrasonic waves of 30 kHz were then applied at room temperature for 10 minutes to activate the carbon black. The carbon black was then washed with distilled water and dried in an oven at 100 ° C.

In the state that the dried carbon black was put in the fluorination reactor, nitrogen gas was injected into the fluorination reactor, and the exhaust gas was decompressed and exhausted three times. Then, the nitrogen gas and the fluorine gas were injected under the same partial pressure, and the fluorine treatment was performed for 0.5 hours under the pressure of 1 bar inside the fluorination reactor.

Next, the carbon black to which the fluorine functional group was introduced was mixed with the petroleum residue oil, and the mixture was heat-treated at 350 DEG C for 4 hours while nitrogen was supplied at a rate of 1 liter / min to prepare a petroleum binder pitch and then the mixture was naturally cooled.

The carbon black into which the fluorine functional groups had been introduced was mixed so as to have a ratio of 1 wt% and 1.5 wt% in the total weight of the carbon black and the petroleum residue mixture, respectively. This was mixed with Example 1 (carbon black content 1 wt%) and Example 2 Carbon black content of 1.5 wt%).

Comparative Example  1, 2

A petroleum binder pitch was prepared in the same manner as in the above example except that the content of the carbon black into which the fluorine functional group was introduced was changed. Comparative Example 1 (carbon black content: 0.1 wt%) and Comparative Example 2 Black content 3 wt%).

Comparative Example  3

A petroleum-based binder pitch was prepared in the same manner as in Example 1 except that carbon black was supported on a nitric acid solution and then activated by ultrasonic waves to obtain a comparative example 3 (carbon black content 1 wt%).

Comparative Example  4

And a pure carbon black not subjected to a fluorine treatment were used in place of the carbon black used in Example 1. The petroleum binder pitch was prepared as Comparative Example 4 (carbon black content 1 wt%).

Comparative Example  5

Only petroleum residues were heat-treated in the same manner as in the above example without using carbon black to prepare a petroleum-based binder pitch.

Quinoline insoluble content

The content of quinoline insoluble components in the petroleum-based binder pitches prepared according to Examples and Comparative Examples was measured and shown in the following Table and FIG. The content of the quinoline insoluble component was measured by the method of ASTM D 4746-14.

The quinoline insoluble component in the binder pitch improves the density and compressive strength of the carbon formed body produced by increasing the residual carbon content during the high temperature heat treatment and suppressing cracking and volume expansion by providing a root of volatilization in the process of manufacturing carbon molded bodies such as artificial graphite . It is known that the content of quinoline insoluble components in the binder pitch is in the range of 5 to 15%, ideally about 10%.

As can be seen from the above table and FIG. 1, the content of quinoline insoluble components in the petroleum-based binder pitches prepared according to the examples of the present invention is about 10%. Compared with Comparative Example 5 in which a petroleum-based binder pitch was produced using only pure petroleum residues without using carbon black, the content of quinoline insoluble components was 0.8%. Compared with the content of quinoline insoluble components in the present invention Can be ideally controlled.

In the case of Comparative Example 1 and Comparative Example 2 in which the pitch of the petroleum binder was produced through the same procedure as that of the Example of the present invention except for the content of carbon black, the content of quinoline insoluble components was less than expected or too high , It can be confirmed that the content of quinoline insoluble components can be adjusted to an ideal range by controlling the content of carbon black in which a fluorine functional group is introduced by reacting with fluorine gas by ultrasonic wave in the state of being supported in an acid solution.

Although the present invention has been described with reference to the accompanying drawings and the preferred embodiments and test examples, the present invention is not limited thereto but is limited by the following claims. Accordingly, those skilled in the art will appreciate that various modifications and changes may be made thereto without departing from the spirit of the following claims.

Claims (6)

A first step of activating the carbonaceous material by applying ultrasonic waves in a state in which the carbonaceous material is supported on the acid solution;
A second step of reacting the carbon material activated through the first step with fluorine gas to introduce a fluorine functional group onto the surface of the carbon material; And
And a third step of preparing a petroleum binder pitch by mixing the carbonaceous material having a fluorine functional group introduced on the surface thereof with the petroleum residue oil in a proportion of 1 to 1.5 wt% Based binder pitch.
The method according to claim 1,
Wherein the carbon material is selected from the group consisting of carbon black, carbon nanotubes, graphene, activated carbon, and mixtures thereof.
3. The method of claim 2,
Wherein the carbon material is carbon black.
delete The method according to claim 1,
Wherein the heat treatment in the third step is performed in a temperature range of 300 to 400 ° C.
6. The method of claim 5,
Wherein the heat treatment is performed in an inert gas atmosphere.

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