KR101804298B1 - Method of manufacturing binder pitch from petroleum by-product - Google Patents

Abstract

The present invention relates to a process for producing a solid component by a first heat treatment at a temperature of 340 ° C to 420 ° C (step 1); (Step 2) of extracting the gasoline fraction by subjecting the solid matter produced in step 1 to a second heat treatment at a temperature of 700 ° C to 900 ° C; And a third step of heat treating the petroleum fractions extracted in step 2 at a temperature of 150 to 250 ° C. to prepare a binder pitch (step 3). The binder pitch manufacturing method according to the present invention can produce a binder pitch having a softening point of 100 ° C to 150 ° C from petroleum-based low-grade raw materials and can omit the secondary softening point adjusting step for softening point control.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a method for producing a binder pitch from a petroleum chemical by-

The present invention relates to a method for producing binder pitch from petrochemical by-products.

Generally, petroleum-based low-grade raw materials (PFO, NCB-Oil, FCC-DO, VR, etc.) are obtained as a by-product of petroleum refining process and are used as fuels for most ships and power generation facilities due to low utilization value. It is easy to form a carbon structure and various application studies have been made.

The binder pitch is used as a raw material in the production of artificial graphite, a carbon compact, a graphite compact and the like. The binder pitch is mixed with coke, carbon powder or the like to improve the bonding force, and injection, extrusion, molding press, cold isostatic pressing, HIP A molded product can be produced by a method such as molding.

The conventional petroleum-based binder pitch has a softening point (150 DEG C to 200 DEG C) higher than that of coal binder (100 DEG C to 150 DEG C) because it is difficult to control the low boiling point gasoline fraction (boiling point 250 DEG C or less) possessed by the raw material. Therefore, in the mixing process of the coke or the graphite powder with the binder pitch, a higher mixing temperature than that of the coal binder is required, so that the process cost and the inter-mixture pitch are overproduced There are disadvantages. Further, due to the problem of having a high softening point as described above, there is a problem in that a secondary softening point adjustment step such as thin layer evaporation (TLE) for additional softening point control must be performed.

The present inventors have been studying a method for producing a binder pitch from a petrochemical by-product. The inventors of the present invention produced a solid component through a first heat treatment using a petroleum chemical by-product and then subjected to a second heat treatment in the solid component, Min and a third heat treatment using the extracted petroleum fractions to finally produce a binder pitch. The softening point of the binder pitch thus prepared exhibits a softening point of 100 to 150 ° C. And completed the present invention.

Korea Patent No. 0146869

It is an object of the present invention to provide a method for producing a binder pitch having a softening point of 100 ° C to 150 ° C from petrochemical by-products.

In order to achieve the above object,

Treating the petrochemical by-product at a temperature of 340 ° C to 420 ° C to produce a solid component (Step 1);

(Step 2) of extracting the gasoline fraction by subjecting the solid matter produced in step 1 to a second heat treatment at a temperature of 700 ° C to 900 ° C; And

(3) heat treating the petroleum fractions extracted in the step (2) at a temperature of 150 ° C to 250 ° C to prepare a binder pitch (step 3).

In addition,

Which is manufactured from the petrochemical by-product by the above-

And has a softening point of 100 캜 to 150 캜.

Further,

Treating the petrochemical by-product at a temperature of 340 ° C to 420 ° C to produce a solid component (Step 1);

(Step 2) of extracting the gasoline fraction by subjecting the solid matter produced in step 1 to a second heat treatment at a temperature of 700 ° C to 900 ° C;

(3) heat treating the petroleum fractions extracted in the step (2) at a temperature of 150 ° C to 250 ° C to prepare a binder pitch having a softening point of 100 ° C to 150 ° C; And

And a step (step 4) of preparing a carbon compact by using the binder pitch produced in the step 3.

The binder pitch manufacturing method according to the present invention can produce a binder pitch having a softening point of 100 ° C to 150 ° C from petroleum-based low-grade raw materials and can omit the secondary softening point adjusting step for softening point control.

The present invention

Treating the petrochemical by-product at a temperature of 340 ° C to 420 ° C to produce a solid component (Step 1);

(Step 2) of extracting the gasoline fraction by subjecting the solid matter produced in step 1 to a second heat treatment at a temperature of 700 ° C to 900 ° C; And

(3) heat treating the petroleum fractions extracted in the step (2) at a temperature of 150 ° C to 250 ° C to prepare a binder pitch (step 3).

Hereinafter, the method of producing the binder pitch according to the present invention will be described in detail for each step.

First, in the method of manufacturing the binder pitch according to the present invention, step 1 is a step of preparing a solid component by first heat-treating the petrochemical by-product at a temperature of 340 to 420 ° C.

In the step 1, a low-boiling (low-molecular weight, mainly aliphatic compound) component not participating in the reaction is extracted from the petroleum-derived byproduct and a primary heat treatment is performed at a temperature of 340 ° C to 420 ° C to induce polymerization of aromatic components .

Specifically, the petroleum-based low-grade feedstock of step 1 may be pyrolyzed fuel oil (PFO), heavy oil, superheavy oil, VR, atmospheric residuum, fluid catalytic cracking decant oil (FCC-DO) Ethylene bottle oil (EBO) or the like can be used.

The first heat treatment of step 1 is preferably performed at a temperature of 340 to 420 캜, and may be performed at a temperature of 340 to 380 캜, and at a temperature of 380 to 420 캜. In addition, the first heat treatment of step 1 is preferably performed for 30 minutes to 6 hours, more preferably for 1 hour to 3 hours.

If the primary heat treatment in step 1 is carried out at a temperature of less than 340 ° C., there is a problem that the finally produced binder pitch has a softening point at room temperature of 50 ° C. or lower and a solidification pitch of 420 ° C. There is a problem that an insoluble matter such as coke or the like is formed and the pitch can not be manufactured.

In addition, the first heat treatment is preferably performed in an inert gas atmosphere, and the inert gas atmosphere may be a nitrogen atmosphere, an argon atmosphere, or the like.

Further, the solid content of the step 1 has a softening point of more than 150 ° C and 250 ° C or less, and a solid content having a softening point of a high temperature can be obtained.

Next, in the method of manufacturing the binder pitch according to the present invention, the step 2 is a step of performing a secondary heat treatment of the solid component produced in the step 1 at a temperature of 700 ° C to 900 ° C to extract the gasoline component.

In the step 2, the solid component having the high softening point prepared in the step 1 is used to extract the gasoline component through a secondary heat treatment at a high temperature. The gasoline fraction extracted in the step 2 is not a low boiling point but a gasoline fraction having a high boiling point generated during a secondary heat treatment at a high temperature.

Specifically, the second heat treatment of step 2 is preferably performed at a temperature of 700 ° C to 900 ° C, and may be performed at a temperature of 700 ° C to 800 ° C, and may be performed at a temperature of 800 ° C to 900 ° C . In addition, the second heat treatment of step 2 is preferably performed for 10 minutes to 4 hours, more preferably 20 minutes to 3 hours, most preferably 30 minutes to 2 hours.

If the secondary heat treatment in step 2 is carried out at a temperature of less than 700 ° C., the gasoline fraction is not sufficiently extracted and the final binder pitch can not be obtained. If the temperature is higher than 900 ° C. There is a problem that the gasoline fractions can not be separated from the solid component due to cracking of the molecules due to cracking of the gasoline components.

Also, the secondary heat treatment is preferably performed in an inert gas atmosphere, and the inert gas atmosphere may be a nitrogen atmosphere, an argon atmosphere, or the like.

Next, in the method for producing a binder pitch according to the present invention, step 3 is a step of preparing a binder pitch by subjecting the petroleum fractions extracted in step 2 to a tertiary heat treatment at a temperature of 150 ° C to 250 ° C.

In the step 3, the gasoline fraction extracted in the step 2 is subjected to a tertiary heat treatment so as to finally obtain a binder pitch, thereby finally producing a binder pitch having a low softening point.

Specifically, the third heat treatment in step 3 is preferably performed at a temperature of 150 ° C to 250 ° C, at a temperature of 150 ° C to 200 ° C, and at a temperature of 200 ° C to 250 ° C . In addition, the third heat treatment of step 3 is preferably performed for 10 minutes to 4 hours, more preferably 20 minutes to 3 hours, most preferably 30 minutes to 2 hours.

If the third heat treatment in step 3 is carried out at a temperature lower than 150 ° C., there is a problem that a pitch having a softening point of less than 100 ° C. is produced and a pitch not solidified at room temperature is produced. There is a problem that a pitch having a softening point exceeding 150 DEG C is produced.

In addition, the third heat treatment is preferably performed in an inert gas atmosphere, and the inert gas atmosphere may be a nitrogen atmosphere, an argon atmosphere, or the like.

Further, the final binder pitch prepared through the above step has a softening point of 100 ° C to 150 ° C. As described above, the binder pitch manufacturing method according to the present invention can produce a binder pitch having a softening point of 100 ° C to 150 ° C from the petroleum-based low-grade raw material, and can omit the secondary softening point adjusting step for controlling the softening point .

In addition,

Which is manufactured from the petrochemical by-product by the above-

And has a softening point of 100 캜 to 150 캜.

The binder pitch according to the present invention is a binder pitch having a softening point of 100 ° C to 150 ° C, which is produced from a petroleum chemical by-product. The binder pitch is used as a raw material in the production of artificial graphite, carbon compact, graphite compact, Powder or the like to improve the bonding force, and the molded product can be produced by a method such as injection, extrusion, molding press, cold isostatic pressing, HIP molding, or the like.

Further,

Treating the petrochemical by-product at a temperature of 340 ° C to 420 ° C to produce a solid component (Step 1);

(Step 2) of extracting the gasoline fraction by subjecting the solid matter produced in step 1 to a second heat treatment at a temperature of 700 ° C to 900 ° C;

(3) heat treating the petroleum fractions extracted in the step (2) at a temperature of 150 ° C to 250 ° C to prepare a binder pitch having a softening point of 100 ° C to 150 ° C; And

And a step (step 4) of preparing a carbon compact by using the binder pitch produced in the step 3.

Hereinafter, the method for producing the carbon material according to the present invention will be described in detail for each step.

First, in the method of manufacturing the binder pitch according to the present invention, step 1 is a step of preparing a solid component by first heat-treating the petrochemical by-product at a temperature of 340 to 420 ° C.

In the step 1, a low-boiling (low-molecular weight, mainly aliphatic compound) component not participating in the reaction is extracted from the petroleum-derived byproduct and a primary heat treatment is performed at a temperature of 340 ° C to 420 ° C to induce polymerization of aromatic components .

Specifically, the petroleum-based low-grade feedstock of step 1 may be pyrolyzed fuel oil (PFO), heavy oil, superheavy oil, VR, atmospheric residuum, fluid catalytic cracking decant oil (FCC-DO) Ethylene bottle oil (EBO) or the like can be used.

The first heat treatment of step 1 is preferably performed at a temperature of 340 to 420 캜, and may be performed at a temperature of 340 to 380 캜, and at a temperature of 380 to 420 캜. In addition, the first heat treatment of step 1 is preferably performed for 30 minutes to 6 hours, more preferably for 1 hour to 3 hours.

If the primary heat treatment in step 1 is carried out at a temperature of less than 340 ° C., there is a problem that the finally produced binder pitch has a softening point at room temperature of 50 ° C. or lower and a solidification pitch of 420 ° C. There is a problem that an insoluble matter such as coke or the like is formed and the pitch can not be manufactured.

In addition, the first heat treatment is preferably performed in an inert gas atmosphere, and the inert gas atmosphere may be a nitrogen atmosphere, an argon atmosphere, or the like.

Further, the solid content of the step 1 has a softening point of more than 150 ° C and 250 ° C or less, and a solid content having a softening point of a high temperature can be obtained.

Next, in the method of manufacturing the binder pitch according to the present invention, the step 2 is a step of performing a secondary heat treatment of the solid component produced in the step 1 at a temperature of 700 ° C to 900 ° C to extract the gasoline component.

In the step 2, the solid component having the high softening point prepared in the step 1 is used to extract the gasoline component through a secondary heat treatment at a high temperature. The gasoline fraction extracted in the step 2 is not a low boiling point but a gasoline fraction having a high boiling point generated during a secondary heat treatment at a high temperature.

Specifically, the second heat treatment of step 2 is preferably performed at a temperature of 700 ° C to 900 ° C, and may be performed at a temperature of 700 ° C to 800 ° C, and may be performed at a temperature of 800 ° C to 900 ° C . In addition, the second heat treatment of step 2 is preferably performed for 10 minutes to 4 hours, more preferably 20 minutes to 3 hours, most preferably 30 minutes to 2 hours.

If the secondary heat treatment in step 2 is carried out at a temperature of less than 700 ° C., the gasoline fraction is not sufficiently extracted and the final binder pitch can not be obtained. If the temperature is higher than 900 ° C. There is a problem that the gasoline fractions can not be separated from the solid component due to cracking of the molecules due to cracking of the gasoline components.

Also, the secondary heat treatment is preferably performed in an inert gas atmosphere, and the inert gas atmosphere may be a nitrogen atmosphere, an argon atmosphere, or the like.

Next, in the method for producing a binder pitch according to the present invention, step 3 is a step of preparing a binder pitch by subjecting the petroleum fractions extracted in step 2 to a tertiary heat treatment at a temperature of 150 ° C to 250 ° C.

In the step 3, the gasoline fraction extracted in the step 2 is subjected to a tertiary heat treatment so as to finally obtain a binder pitch, thereby finally producing a binder pitch having a low softening point.

Specifically, the third heat treatment in step 3 is preferably performed at a temperature of 150 ° C to 250 ° C, at a temperature of 150 ° C to 200 ° C, and at a temperature of 200 ° C to 250 ° C . In addition, the third heat treatment of step 3 is preferably performed for 10 minutes to 4 hours, more preferably 20 minutes to 3 hours, most preferably 30 minutes to 2 hours.

If the third heat treatment in step 3 is carried out at a temperature lower than 150 ° C., there is a problem that a pitch having a softening point of less than 100 ° C. is produced and a pitch not solidified at room temperature is produced. There is a problem that a pitch having a softening point exceeding 150 DEG C is produced.

In addition, the third heat treatment is preferably performed in an inert gas atmosphere, and the inert gas atmosphere may be a nitrogen atmosphere, an argon atmosphere, or the like.

Further, the final binder pitch prepared through the above step has a softening point of 100 ° C to 150 ° C. As described above, the binder pitch manufacturing method according to the present invention can produce a binder pitch having a softening point of 100 ° C to 150 ° C from the petroleum-based low-grade raw material, and can omit the secondary softening point adjusting step for controlling the softening point .

Next, in the method for producing a carbon material according to the present invention, Step 4 is a step of producing a carbon compact by using the binder pitch produced in Step 3 above.

The step 4 is a step of preparing a carbon compact by using the binder pitch produced through the steps 1 to 3. Specifically, the step 4 is a mixing step of mixing the binder pitch and the coke, A molding process for forming a molded body through extrusion, molding or the like, an impregnation process for filling pores or voids formed in the molding process by impregnating pitch, or the like.

As a result, it is possible to manufacture a carbon compact having no pores and excellent density and strength.

Hereinafter, examples and experimental examples of the present invention will be described in more detail.

However, the following Examples and Experimental Examples are merely illustrative of the present invention, and the present invention is not limited by the following Examples and Experimental Examples.

≪ Example 1 > Preparation of binder pitch 1

Step 1: Pyrolyzed fuel oil (PFO) was charged into an autoclave reactor and then subjected to a first heat treatment at 420 ° C for 3 hours in a nitrogen gas atmosphere to prepare a solid.

Step 2: The solid component produced in step 1 was subjected to a secondary heat treatment in a nitrogen gas atmosphere at 900 DEG C for 1 hour in a nitrogen atmosphere to extract volatile components.

Step 3: The volatile components extracted in step 2 were subjected to a third heat treatment at a temperature of 250 캜 in a nitrogen gas atmosphere to prepare a binder pitch.

≪ Example 2 > Preparation of binder pitch 2

A binder pitch was prepared in the same manner as in Example 1, except that the first heat treatment was performed at a temperature of 380 ° C in the step 1 of Example 1.

≪ Example 3 > Preparation of binder pitch 3

A binder pitch was prepared in the same manner as in Example 1, except that the first heat treatment was performed at a temperature of 340 ° C in Step 1 of Example 1.

≪ Example 4 > Preparation of binder pitch 4

A binder pitch was prepared in the same manner as in Example 1 except that the second heat treatment was performed at a temperature of 700 ° C in the step 2 of Example 1.

≪ Example 5 > Preparation of binder pitch 5

The binder pitch was prepared in the same manner as in Example 1 except that the second heat treatment was performed at a temperature of 800 ° C in the step 2 of Example 1.

≪ Example 6 > Preparation of binder pitch 6

A binder pitch was prepared in the same manner as in Example 1 except that the third heat treatment was performed at a temperature of 150 ° C in the step 3 of Example 1.

≪ Example 7 > Preparation of binder pitch 7

A binder pitch was prepared in the same manner as in Example 1 except that the third heat treatment was performed at a temperature of 200 ° C in the step 3 of Example 1.

≪ Comparative Example 1 &

A binder pitch was prepared in the same manner as in Example 1, except that the first heat treatment was performed at a temperature of 300 ° C in the step 1 of Example 1 above.

≪ Comparative Example 2 &

A binder pitch was prepared in the same manner as in Example 1 except that the first heat treatment was performed at a temperature of 450 ° C in the step 1 of Example 1.

≪ Comparative Example 3 &

A binder pitch was prepared in the same manner as in Example 1 except that the second heat treatment was performed at a temperature of 500 ° C in the step 2 of Example 1.

≪ Comparative Example 4 &

A binder pitch was prepared in the same manner as in Example 1, except that the second heat treatment was performed at a temperature of 1100 캜 in the step 2 of Example 1.

≪ Comparative Example 5 &

A binder pitch was prepared in the same manner as in Example 1 except that the third heat treatment was carried out at a temperature of 100 ° C in the step 3 of Example 1.

≪ Comparative Example 6 >

A binder pitch was prepared in the same manner as in Example 1 except that the third heat treatment was performed at a temperature of 300 ° C in Step 3 of Example 1.

EXPERIMENTAL EXAMPLE 1 Analysis of Softening Point of Binder Pitch

In order to confirm the softening point of the binder pitch according to the present invention, the softening points of the binder pitches prepared in Examples 1 to 7 and Comparative Examples 1 to 6 were analyzed, and the results are shown in Table 1 below.

Step 1 Step 2 Step 3 Softening point
(° C) Temperature
(° C) time
(h) Temperature
(° C) time
(h) Temperature
(° C) time
(h) Example 1 420 3 900 One 250 One 149 Example 2 380 3 900 One 250 One 132 Example 3 340 3 900 One 250 One 111 Example 4 420 3 700 One 250 One 125 Example 5 420 3 800 One 250 One 132 Example 6 420 3 900 One 150 One 115 Example 7 420 3 900 One 200 One 126 Comparative Example 1 300 3 900 One 250 One Liquid product Comparative Example 2 450 3 900 One 250 One > 300 Comparative Example 3 420 3 500 One 250 One 59 Comparative Example 4 420 3 1100 One 250 One Comparative Example 5 420 3 900 One 100 One 53 Comparative Example 6 420 3 900 One 300 One 204

As shown in Table 1, the softening point of the binder pitch produced by the production method according to the present invention is at least 111 ° C to 149 ° C, which indicates a softening point suitable for use as a binder pitch.

On the other hand, in the case where the first heat treatment temperature was 300 ° C (Comparative Example 1), the solidified pitch was produced and the liquid phase. When the first heat treatment temperature was 450 ° C (Comparative Example 2), the softening point exceeded 300 ° C, It can be confirmed that the same insoluble matter is formed. In addition, it can be seen that a pitch with a very low softening point is formed when the secondary heat treatment temperature is 500 ° C (Comparative Example 3). In the case where the secondary heat treatment temperature is 1100 ° C (Comparative Example 4) It was impossible. Further, when the third heat treatment temperature is 100 ° C, it can be seen that a very low softening point is formed, and when the third heat treatment temperature is 300 ° C, a pitch having a softening point exceeding 200 ° C is produced .

As described above, the binder pitch manufacturing method according to the present invention can produce a binder pitch having a softening point of 100 ° C to 150 ° C from the petroleum-based low-grade raw material, and can omit the secondary softening point adjusting step for controlling the softening point .

Claims (10)

Treating the petrochemical by-product at a temperature of 340 ° C to 420 ° C to produce a solid component (Step 1);
(Step 2) of extracting the gasoline fraction by subjecting the solid matter produced in step 1 to a second heat treatment at a temperature of 700 ° C to 900 ° C; And
(3) heat-treating the petroleum fractions extracted in the step (2) at a temperature of 150 ° C to 250 ° C to produce a binder pitch.
The method according to claim 1,
The petrochemical by-products of step 1 above are pyrolyzed fuel oil (PFO), heavy oil, superheated oil, reduced pressure residual oil (VR), normal pressure residual oil, fluid catalytic cracking decant oil (FCC-DO) wherein the binder is at least one selected from the group consisting of polyvinyl alcohol, polyvinyl alcohol, and polyvinyl alcohol.
The method according to claim 1,
Wherein the first heat treatment of step 1 is performed for 30 minutes to 6 hours.
The method according to claim 1,
Wherein the solid content of the step (1) has a softening point of more than 150 ° C but not more than 250 ° C.
The method according to claim 1,
Wherein the second heat treatment of step 2 is performed for 10 minutes to 4 hours.
The method according to claim 1,
Wherein the third heat treatment of step 3 is performed for 10 minutes to 4 hours.
The method according to claim 1,
Wherein the binder pitch of step 3 has a softening point of 100 占 폚 to 150 占 폚.
The method according to claim 1,
Wherein the heat treatment is performed in an inert gas atmosphere.
delete Treating the petrochemical by-product at a temperature of 340 ° C to 420 ° C to produce a solid component (Step 1);
(Step 2) of extracting the gasoline fraction by subjecting the solid matter produced in step 1 to a second heat treatment at a temperature of 700 ° C to 900 ° C;
(3) heat treating the petroleum fractions extracted in the step (2) at a temperature of 150 ° C to 250 ° C to prepare a binder pitch having a softening point of 100 ° C to 150 ° C; And
And a step (4) of producing a carbon compact by using the binder pitch produced in the step (3).