JP7555374B2 - Method for producing heterophasic binder pitch and heterophasic binder pitch produced therefrom - Google Patents

Description

The present invention relates to a method for producing a heterophase binder pitch that has a heterophase texture in which an anisotropic texture is uniformly dispersed in an isotropic matrix, and that does not significantly change the softening point and selectively increases only the carbonization yield, and to the heterophase binder pitch produced from the method.

Pitch is a residue resulting from the thermal decomposition of solid organic substances or tar distillation at room temperature. It is composed of numerous highly directional hydrocarbon compounds and heterocyclic compounds, and does not have a constant melting point but rather shows a wide softening range.

The pitch has the property that when it melts and cools, it solidifies without going through a crystallization step.

Binder pitch is a secondary material used together with the main material, coke, when making artificial graphite compacts such as isotropic graphite blocks and electrode rods.

The usual method for producing binder pitch involves heat treating medium oil in an inert atmosphere at a temperature of 300-500°C for a certain period of time to remove volatile components and induce a polycondensation reaction of the remaining components to produce a binder pitch with optical isotropy.

The biggest problem with petroleum-based binder pitch produced by these manufacturing methods is the low carbonization yield, which results in low density and low strength of the graphite block, and this is known to be the most difficult problem to solve.

Through various research, the applicant has developed a technology for producing binder pitch from medium-strength petroleum oil, which has a heterophase structure in which anisotropic texture is uniformly dispersed within an isotropic matrix.

As a result, the applicant has produced a pitch whose softening point does not change significantly and which selectively increases only the carbonization yield. When this pitch is used as a binder pitch in the production of graphite compacts, the applicant has acquired a manufacturing process technology for the binder pitch which results in a significantly increased density of the compacts, thus completing the present invention.

Korean Patent Publication No. 1993-0005525 (Patent Publication Date: June 22, 1993)

Therefore, the object of the present invention is to provide a method for producing a heterophase binder pitch that can solve the problem of low density/low strength of graphite blocks due to the low carbonization yield of binder pitch by producing a heterophase binder pitch with a high carbonization yield, and when the heterophase binder pitch is used to produce graphite blocks, it is possible to produce compacts with high density.

Another object of the present invention is to provide a heterophase binder pitch that has a uniformly dispersed anisotropic texture in an isotropic matrix, does not significantly change the softening point, and selectively increases only the carbonization yield.

The problems that the present invention aims to solve are not limited to those mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.

In order to solve the above problems, according to one aspect of the present invention,
A method for producing a heterophase binder pitch having a heterophase texture in which an anisotropic texture is uniformly dispersed in an isotropic matrix, comprising:
hydrotreating the middle oil to obtain a hydrotreated feed;
thermally polymerizing the resulting hydrogenated feedstock to produce a primary pitch;
thin-film distillation of the produced primary pitch to remove low boiling point components and obtain an anisotropic pitch enriched in mesogen components;
A step of extracting the anisotropic pitch with a solvent, filtering and drying the anisotropic pitch to separate only the mesogen component in the anisotropic pitch;
mixing the separated mesogenic component with a basic isotropic pitch.

According to one embodiment of the present invention, the basic isotropic pitch is
Thermally polymerizing the medium oil under normal and elevated pressure to produce an isotropic pitch;
and subjecting the isotropic pitch to thin film distillation.

According to one embodiment of the present invention, the hydrotreatment comprises:
A reaction temperature of 350°C to 500°C;
A reaction time of 10 minutes to 10 hours; or
The mixing ratio (weight ratio) of medium oil to organic solvent is 1:0.5 to 1:4.

According to one embodiment of the present invention, the organic solvent may include a hydrogen donor solvent including tetralin or tetrahydroquinoline.

According to one embodiment of the present invention, the thermal polymerization is
A reaction temperature of 400°C to 500°C;
A reaction time of 10 minutes to 10 hours; or
The inert gas flow rate can be set to 100 mL/min/kg to 5000 mL/min/kg.

According to one embodiment of the present invention, the thin film distillation comprises:
A treatment temperature of 250°C to 400°C;
A processing time of 5 to 60 minutes, or
The pressure can be set to 1 hPa to 100 hPa.

According to one embodiment of the present invention, the anisotropic pitch obtained from the thin film distillation has
Softening point 250℃~350℃;
Anisotropic content between 70% and 100%, or
The manufacturing yield may be between 15% and 25%.

According to one embodiment of the invention, the extraction of the solvent comprises:
Mixing ratio (weight ratio) of anisotropic pitch:solvent=1:2 to 1:40;
Extraction time of 5 minutes to 24 hours; or
The extraction can be carried out using THF (tetrahydrofuran) as an extraction solvent.

According to one embodiment of the present invention, the step of mixing the basic isotropic pitch and the mesogen comprises:
Basic isotropic pitch:mesogen mixing ratio=95:5 to 60:40;
Mixing temperature 200°C to 400°C; or
The mixing time can be from 5 minutes to 2 hours.

According to another aspect of the present invention,
The present invention provides a heterophase binder pitch produced by the method for producing a heterophase binder pitch.

According to one embodiment of the present invention, the microstructure of the heterophase binder pitch may have a morphology in which anisotropic globules are uniformly dispersed within an isotropic matrix.

According to one embodiment of the present invention, the softening point of the heterophase binder pitch may be 50°C to 200°C.

According to one embodiment of the present invention, the anisotropic content of the heterophase binder pitch may be between 0% and 30%.

According to one embodiment of the present invention, the carbonization yield of the heterophase binder pitch may be 25% to 50%.

The present invention solves the problem of low density/low strength of graphite blocks due to low carbonization yield by producing a heterophase binder pitch with a high carbonization yield, and provides a method for producing a heterophase binder pitch that can produce a high density molded body when a graphite block is produced using the heterophase binder pitch. This provides excellent process stability and low production costs, making it economical.

In addition, the present invention provides a heterophase texture in which anisotropic texture is uniformly dispersed within an isotropic matrix, and the softening point does not change significantly, and the heterophase binder pitch selectively increases only the carbonization yield, so it has the advantages of excellent physical properties and a wide range of applications.

It should be understood that the effects of the present invention are not limited to the effects described above, but include all effects that can be inferred from the configuration of the invention described in the detailed description of the present invention or the claims.

1 is a process flow diagram for a heterophase binder pitch according to one embodiment of the present invention. 1 is a polarized microscope image of FCC-DO basic isotropic pitch according to one embodiment of the present invention. 1 shows a polarizing microscope image of FCC-DO pitch containing up to 20% anisotropic globules in an isotropic matrix according to an embodiment of the present invention. 13 is a polarizing microscope image of FCC-DO pitch containing anisotropic globules within 20% in an isotropic matrix according to another embodiment of the present invention. 1 is a polarized microscope image of hydrogenated FCC-D anisotropic pitch according to one embodiment of the present invention. 3 is a polarizing microscope image of a binder pitch obtained by mixing FCC-DO basic isotropic pitch according to an embodiment of the present invention with THFI, a mesogen component, in a weight ratio of 9:1. 3 is a polarizing microscope image of a binder pitch obtained by mixing FCC-DO basic isotropic pitch according to an embodiment of the present invention with THFI, a mesogen component, in a weight ratio of 8:2. 3 is a polarizing microscope image of a binder pitch obtained by mixing FCC-DO basic isotropic pitch according to an embodiment of the present invention with THFI, a mesogen component, in a weight ratio of 7:3.

Below, a preferred embodiment of the present invention will be described in detail with reference to the accompanying drawings.

The advantages and features of the present invention and the method of achieving the same will become clearer with reference to the following detailed description of the embodiments together with the accompanying drawings.

However, the present invention is not limited to the embodiments disclosed below, but may be embodied in various different forms. However, the embodiments are provided to fully disclose the present invention and fully inform those skilled in the art of the scope of the invention, and the present invention is defined only by the scope of the claims.

In addition, when explaining the present invention, if it is determined that related publicly known technologies etc. may obscure the gist of the present invention, detailed explanations of such technologies will be omitted.

The present invention is explained in detail below.

<Method for producing heterophase binder pitch>
The present invention provides a method for producing a heterophase binder pitch with a high carbonization yield, which solves the problem of low density/low strength of a graphite block due to a low carbonization yield, and which can produce a molded product having a high density when a graphite block is produced using the heterophase binder pitch.

The method for producing the heterophase binder pitch of the present invention comprises the steps of:
A method for producing a heterophase binder pitch having a heterophase texture in which an anisotropic texture is uniformly dispersed in an isotropic matrix, comprising:
hydrotreating the middle oil to obtain a hydrotreated feed;
thermally polymerizing the resulting hydrogenated feedstock to produce a primary pitch;
thin-film distillation of the produced primary pitch to remove low boiling point components and obtain an anisotropic pitch enriched in mesogen components;
A step of extracting the anisotropic pitch with a solvent, filtering and drying the anisotropic pitch to separate only the mesogen component in the anisotropic pitch;
mixing the separated mesogenic component with a basic isotropic pitch.

Here, the heterophase binder pitch may be a heterophase texture in which an anisotropic texture is uniformly dispersed in an isotropic matrix.

The medium oil is a medium oil or residual oil generated in the crude oil refining process, and may be a petroleum-based raw material such as FCC-DO (fluidized catalytic cracking-decant oil), which is the residual oil of a fluidized bed reactor, PFO (pyrolysis fuel oil) and EBO (ethylene bottom oil), which are the residual oil of a naphtha cracker, VR (vacuum residue), which is the residue of a vacuum distillation tower, DAO (de-asphalted oil), which is obtained by removing asphaltene from these medium oils, or coal-based raw material such as coal tar, which is a by-product of the coal carbonization process.

Here, the basic isotropic pitch is
Thermally polymerizing the medium oil under normal and elevated pressure to produce an isotropic pitch;
and subjecting the isotropic pitch to thin film distillation.

Here, the thin-film distillation may be thin-film evaporation (TFE) or thin-layer evaporation (TLE).

The hydrotreatment is further carried out as follows:
A reaction temperature of 350°C to 500°C;
A reaction time of 10 minutes to 10 hours; or
The mixing ratio (weight ratio) of medium oil to organic solvent is 1:0.5 to 1:4.

Here, if the reaction temperature of the hydrogenation process is less than 350°C, the efficiency of the hydrogenation process decreases, and if the reaction temperature of the hydrogenation process is more than 500°C, the economic efficiency may decrease.

In addition, if the reaction time of the hydrogenation treatment is less than 10 minutes, the efficiency of the hydrogenation treatment may be negligible, and if the reaction time of the hydrogenation treatment is more than 10 hours, there may be a problem of reduced economic efficiency.

Furthermore, if the mixing ratio (weight ratio) of the medium oil to the organic solvent during the hydrotreating process is less than 1:0.5, the efficiency of the hydrotreating process decreases, and if the mixing ratio (weight ratio) of the medium oil to the organic solvent during the hydrotreating process exceeds 1:4, problems such as increased production costs may occur.

The organic solvent may include a hydrogen donor solvent, such as tetralin or tetrahydroquinoline.

Here, the organic solvent is not limited to the above, and any hydrogen donor solvent can be used.

The thermal polymerization is
A reaction temperature of 400°C to 500°C;
A reaction time of 10 minutes to 10 hours; or
The inert gas flow rate can be set to 100 mL/min/kg to 5000 mL/min/kg.

Here, if the reaction temperature of the thermal polymerization is less than 400°C, the efficiency of the thermal polymerization decreases, and if the reaction temperature of the thermal polymerization is more than 500°C, the economic efficiency decreases.

In addition, if the reaction time of the thermal polymerization is less than 10 minutes, the efficiency of the thermal polymerization may be negligible, and if the reaction time of the thermal polymerization is more than 10 hours, there may be a problem of reduced economic efficiency.

If the flow rate of the inert gas during the thermal polymerization is less than 100 mL/min/kg, the thermal polymerization efficiency decreases, and if the flow rate of the inert gas during the thermal polymerization exceeds 5,000 mL/min/kg, problems such as increased production costs may occur.

The thin film distillation further comprises:
A treatment temperature of 250°C to 400°C;
A treatment time of 5 to 60 minutes; or
The pressure can be set to 1 hPa to 100 hPa.

The thin film distillation is a method for separating desired substances with high purity by forming a thin film and then evaporating it. It is a suitable method for separating heat-sensitive substances and substances with high boiling points.

Here, if the thin film distillation processing temperature is less than 250°C, the thin film distillation efficiency decreases, and if the thin film distillation processing temperature exceeds 400°C, a problem may occur in which a non-uniform heterophase binder pitch is produced.

In addition, if the processing time of the thin film distillation is less than 5 minutes, the thin film distillation efficiency may be negligible, and if the processing time of the thin film distillation is more than 60 minutes, there may be a problem of reduced economic efficiency.

If the pressure during the thin film distillation exceeds 100 hPa, the thin film distillation efficiency decreases, and if the pressure during the thin film distillation is less than 1 hPa, a problem may occur in which a non-uniform heterophase binder pitch is produced.

The anisotropic pitch obtained by the thin film distillation is
Softening point 250℃~350℃;
anisotropic content of 70% to 100%; or
The manufacturing yield may be between 15% and 25%.

Here, the extraction of the solvent is
Mixing ratio (weight ratio) of anisotropic pitch:solvent=1:2 to 1:40;
Extraction time of 5 minutes to 24 hours; or
The extraction can be carried out using THF (tetrahydrofuran) as an extraction solvent.

Here, if the mixing ratio (weight ratio) of anisotropic pitch:solvent during the solvent extraction is less than 1:2, the efficiency of the solvent extraction decreases, and if the mixing ratio (weight ratio) of anisotropic pitch:solvent exceeds 1:40, there may be a problem of reduced economic efficiency.

In addition, if the processing time for the solvent extraction is less than 5 minutes, the efficiency of the solvent extraction may be negligible, and if the processing time for the solvent extraction is more than 24 hours, there may be a problem of reduced economic efficiency.

The extraction solvent may be ethers including diethyl ether or ketones including MEK.

The mixing step of the basic isotropic pitch and the mesogen comprises:
Basic isotropic pitch:mesogen mixing ratio=95:5 to 60:40;
Mixing temperature 200°C to 400°C; or
The mixing time can be from 5 minutes to 2 hours.

Here, in the step of mixing the separated mesogen component with basic isotropic pitch, if the mixing ratio of basic isotropic pitch:mesogen is less than 95:5, the production efficiency of the binder pitch decreases, and if the mixing ratio of basic isotropic pitch:mesogen is more than 60:40, a problem of producing a non-uniform heterophase binder pitch may occur.

In addition, in the step of mixing the separated mesogen component with the basic isotropic pitch, if the mixing temperature is less than 200°C, the production efficiency of the anisotropic pitch may be negligible, and if the mixing temperature exceeds 400°C, a problem may occur in which a non-uniform heterophase binder pitch is produced.

In addition, in the step of mixing the separated mesogen component with the basic isotropic pitch, if the mixing time is less than 5 minutes, the production efficiency of the binder pitch decreases, and if the mixing time exceeds 2 hours, a problem of producing a non-uniform heterophase binder pitch may occur.

The carbonization yield of the heterophase binder pitch may be 25% to 50%.

Figure 1 is a process flow diagram for heterophase binder pitch according to one embodiment of the present invention.

Referring to FIG. 1, the raw material medium oil (S100) can be thermally polymerized (S110) and then thin-film distilled (TFE or TLE) (S120) to produce basic isotropic pitch (S125).

The raw material, medium oil (S100), is then hydrogenated (S130), thermally polymerized (S140), and thin-film distilled (TFE or TLE) (S150) to produce anisotropic pitch (S160).

Then, the anisotropic pitch (S160) is subjected to solvent extraction (S170) with THF (tetrahydrofuran) solvent to produce THFI (S180), a mesogen component that is insoluble in THF.

Finally, THFI (S180), a mesogenic component that is insoluble in THF, can be mixed (S190) with basic isotropic pitch (S125) to produce binder pitch (S200).

<Heterophase binder pitch>
The present invention provides a heterophase binder pitch produced by the above-mentioned method for producing a heterophase binder pitch.

In particular, the present invention provides a heterophase binder pitch that has a uniformly dispersed anisotropic texture in an isotropic matrix, does not significantly change the softening point, and selectively increases only the carbonization yield.

Here, the microstructure of the heterophase binder pitch may have a morphology in which anisotropic globules are uniformly dispersed within an isotropic matrix.

The softening point of the heterophase binder pitch may be from 50°C to 200°C.

The anisotropic content of the heterophase binder pitch may be 0% to 30%.

The carbonization yield of the heterophase binder pitch may be 25% to 50%.

The present invention will be described in more detail below with reference to examples. However, the following examples are intended to more specifically explain the present invention, and the scope of the present invention is not limited to the following examples. The following examples may be modified or altered as appropriate by those skilled in the art within the scope of the present invention.

<Preparation Example> Manufacturing of FCC-DO isotropic pitch 1) Thermal polymerization 100g of FCC-DO as a raw material was put into an autoclave reactor (volume 150mL) and then completely sealed. Then, the mixture was stirred at a speed of 100 rpm and heated to 390°C at a speed of 10°C/min, and thermal polymerization was carried out by maintaining the temperature for 6 hours. Then, heating was stopped and the internal temperature of the reactor was allowed to drop to room temperature, and the reaction product, the thermally polymerized FCC-DO, was collected.

2) Thin-film evaporation
The FCC-DO thermal polymer obtained by thermal polymerization was placed in a rotary thin-film evaporator, heated to 300° C. under a reduced pressure of 10 hPa, and then subjected to thin-film distillation for 30 minutes to obtain FCC-DO basic isotropic pitch.

The softening point of the FCC-DO basic isotropic pitch obtained by thin-film distillation was 97°C, and the carbonization yield was 23.2%. Observation of the microstructure of the FCC-DO basic isotropic pitch using a polarizing microscope showed a 100% isotropic structure. The polarizing microscope image is shown in Figure 2.

<Example>
Comparative Example 1: Production of 410°C thermal polymerization, 20% anisotropy, FCC-DO pitch Thermal polymerization and thin-film distillation were carried out under the same conditions as in Preparatory Example, except that the thermal polymerization temperature was changed to 410°C, to produce an FCC-DO pitch in which anisotropic spheres were contained in an isotropic matrix at 20% or less (410°C thermal polymerization, 20% anisotropy, FCC-DO pitch).

The resulting 410°C thermally polymerized, 20% anisotropic, FCC-DO pitch had a softening point of 100°C and a carbonization yield of 30.0%. Observation under a polarizing microscope showed that the microstructure was an isotropic matrix containing up to 20% anisotropic spheres, with some of the spheres being uniformly dispersed, but most of them exhibiting an agglomerated form. The polarizing microscope image is shown in Figure 3.

Comparative Example 2: Production of 430°C thermal polymerization, 20% anisotropy, FCC-DO pitch Thermal polymerization and thin-film distillation were carried out under the same conditions as in Preparatory Example, except that the thermal polymerization temperature was changed to 430°C, to produce an FCC-DO pitch in which anisotropic spheres were contained in an isotropic matrix at 20% or less (430°C thermal polymerization, 20% anisotropy, FCC-DO pitch).

The resulting 430°C thermally polymerized, 20% anisotropic, FCC-DO pitch had a softening point of 110°C and a carbonization yield of 39.2%. Observation under a polarizing microscope showed that the microstructure was an isotropic matrix containing up to 20% anisotropic globules, and the globules were not uniformly dispersed but mostly existed in agglomerates. The polarizing microscope image is shown in Figure 4.

Example 1: Preparation of heterophase binder pitch mixed at 9:1 1) Hydrogenation 50g of FCC-DO and 50g of tetralin were added to an autoclave reactor (volume 150mL) and then completely sealed. Then, the mixture was stirred at a speed of 100 rpm and heated to 370°C at a speed of 10°C/min, and the temperature was maintained for 1 hour to carry out a hydrogenation reaction. Then, heating was stopped and the internal temperature of the reactor was allowed to drop to room temperature, after which the reaction product, FCC-DO and tetralin hydride, was collected.

To separate tetralin from the reaction products FCC-DO and tetralin hydride, the FCC-DO and tetralin hydride were placed in a rotary evaporator and treated at 150°C for 1 hour. As a result, 50g of hydrogenated FCC-DO from which tetralin had been removed was obtained. To carry out the subsequent steps, the above procedure was repeated once more to prepare a total of 100g of hydrogenated FCC-DO from which tetralin had been removed.

2) Thermal Polymerization 100 g of hydrogenated FCC-DO from which tetralin had been removed was added to an autoclave reactor (volume 150 mL), and nitrogen gas was introduced at a rate of 200 mL/min. The mixture was stirred at a rate of 100 rpm and heated to 390°C at a rate of 5°C/min, and thermal polymerization was carried out while maintaining the temperature for 6 hours. Thereafter, heating was stopped and the internal temperature of the reactor was allowed to drop to room temperature. Then, the introduction of nitrogen gas and stirring were stopped, and the hydrogenated FCC-DO thermal polymer, which was the reaction product, was recovered.

3) Thin-film distillation The hydrogenated FCC-DO thermal polymer obtained by thermal polymerization was placed in a rotary thin-film distillation apparatus, heated to 390° C. under a reduced pressure of 10 hPa, and maintained for 30 minutes to obtain a hydrogenated FCC-DO anisotropic pitch.

The softening point of the hydrogenated FCC-DO anisotropic pitch obtained by thin-film distillation was 284°C, and the microstructure was observed under a polarizing microscope, revealing an anisotropic structure of approximately 93%. The polarizing microscope image is shown in Figure 5.

4) Solvent Extraction To separate the mesogen component, the 93% hydrogenated FCC-DO anisotropic pitch was mixed with an organic solvent, tetrahydrofuran (THF), in a weight ratio of 1:9 and stirred at a temperature of 50° C. for 24 hours.

Then, the components that were not soluble in THF solvent (insoluble matter) were filtered out by vacuum filtration, and the insoluble matter was collected and then dried for 12 hours in a convection oven at 60°C. The dried insoluble matter corresponds to the mesogenic component and was named THFI.

The component that dissolves in THF solvent was named THFS.

5) Mixing The basic isotropic pitch obtained in Preparation Example and the mesogen component THFI were mixed in a weight ratio of 9:1, and the mixture was heated to 350° C. at a heating rate of 5° C./min, and then stirred for 30 minutes.

The softening point of the heterophase binder pitch obtained from the 9:1 mixture was 106°C, and the carbonization yield was 35.5%. Observation under a polarizing microscope showed that it contained 7.7% anisotropic structure, and exhibited a uniformly dispersed morphology in the form of small spheres without aggregation. The polarizing microscope image is shown in Figure 6.

Example 2: Preparation of 8:2 mixed heterophase binder pitch
The basic isotropic pitch obtained from Preparation Example and THFI obtained from Example 1 were mixed in a weight ratio of 8:2, and the mixture was heated to 350° C. at a heating rate of 5° C./min, and then stirred for 30 minutes.

The softening point of the heterophase binder pitch obtained from the 8:2 mixture was 118°C, and the carbonization yield was 38.7%. Observation under a polarizing microscope showed that it contained 10.3% anisotropic structure, and exhibited a uniformly dispersed morphology in the form of small spheres without aggregation. The polarizing microscope image is shown in Figure 7.

Example 3: Preparation of a heterophase binder pitch mixed at a ratio of 7:3 The basic isotropic pitch obtained from Preparatory Example and THFI obtained from Example 1 were mixed at a weight ratio of 7:3, heated to 350° C. at a heating rate of 5° C./min, and stirred for 30 minutes.

The softening point of the heterophase binder pitch obtained from the 7:3 mixture was 122°C, and the carbonization yield was 40.8%. Observation under a polarizing microscope showed that it contained 16.8% anisotropic structure, and exhibited a uniformly dispersed morphology in the form of small spheres without aggregation. The polarizing microscope image is shown in Figure 8.

Example 4: Manufacturing of graphite block compact 1 The binder pitch obtained in the present invention was applied to the manufacturing of a graphite block. The FCC-DO basic isotropic pitch obtained in the preparation example and needle coke (particle size 0.1 to 2 mm) were mixed in a weight ratio of 25:75, and then kneaded at 180°C for 2 hours.

The kneaded sample was then placed in a cylindrical mold with a diameter of 1 cm and pressed with a weight of 1 ton for 10 minutes at 150°C. A cylindrical molded body with a press diameter of 1 cm was obtained, which was heated to 800°C at a rate of 1°C/min in a furnace under a nitrogen atmosphere and maintained at that temperature for 30 minutes in order to perform carbonization heat treatment.

Then, the graphitization heat treatment was performed at 2,800°C. The graphitization heat treatment conditions were as follows: after reaching 2,800°C, the maintenance time was 10 minutes, the heating rate was 10°C/min, and the gas used to maintain the inert atmosphere was argon gas.

After graphitization, the final compact obtained showed perfect patterning without any breaks or cracks and had a measured density of 1.16 g/ ^cm3 .

Example 5: Manufacture of graphite block compact 2 A compact was manufactured in the same manner as in Example 4, but the binder pitch used was the pitch obtained in Example 1. Carbonization and graphitization were also carried out under the same conditions. After graphitization, the final compact obtained showed a perfect pattern without any breaks or cracks, and the measured density was 1.22 g/ ^cm3 .

Example 6: Manufacture of graphite block compact 3 A compact was manufactured in the same manner as in Example 4, but the binder pitch used was the pitch obtained in Example 2. Carbonization and graphitization were also carried out under the same conditions. After graphitization, the final compact obtained showed a perfect pattern without any breaks or cracks, and the measured density was 1.24 g/ ^cm3 .

Example 7: Manufacture of graphite block compact 4 A compact was manufactured in the same manner as in Example 4, but the binder pitch used was the pitch obtained in Example 3. Carbonization and graphitization were also carried out under the same conditions. After graphitization, the final compact obtained showed a perfect pattern without any breaks or cracks, and the measured density was 1.19 g/ ^cm3 .

As can be seen from the results of Examples 4 to 7 above, the binder pitch produced according to the present invention not only exhibits a higher carbonization yield than existing binder pitches, but also realizes a higher density of the compact when used to produce graphite compacts compared to existing binder pitches.

So far, we have described the method for producing heterophase binder pitch according to the present invention and specific examples of the heterophase binder pitch produced from the method, but it is obvious that various modifications of the implementation are possible within the limits of the scope of the present invention.

Therefore, the scope of the present invention should not be limited to the described embodiments, but should be determined not only by the scope of the claims described below, but also by equivalents to these claims.

In other words, it should be understood that the above-described embodiments are illustrative in all respects and not limiting, and the scope of the present invention is indicated by the claims set forth below rather than by the detailed description, and all modifications or variations that come within the meaning and scope of the claims and their equivalent concepts should be interpreted as being included in the scope of the present invention.

Claims (9)

A method for producing a heterophase binder pitch having a heterophase texture in which an anisotropic texture is uniformly dispersed in an isotropic matrix, comprising:
hydrotreating the middle oil to obtain a hydrotreated feed;
thermally polymerizing the resulting hydrogenated feedstock to produce a primary pitch;
thin-film distillation of the produced primary pitch to remove low boiling point components and obtain an anisotropic pitch enriched in mesogen components;
A step of extracting the anisotropic pitch with a solvent, filtering and drying the anisotropic pitch to separate only the mesogen component in the anisotropic pitch;
and homogeneously mixing the separated mesogenic component with an isotropic pitch. The isotropic pitch is
Thermally polymerizing the medium oil under normal and elevated pressure to produce an isotropic pitch;
and subjecting the isotropic pitch to thin-film distillation.
A method for producing the heterophase binder pitch according to claim 1. The hydrotreatment is
A reaction temperature of 350°C to 500°C;
A reaction time of 10 minutes to 10 hours; and
The mixing ratio (weight ratio) of medium oil to organic solvent is 1:0.5 to 1:4.
A method for producing the heterophase binder pitch according to claim 1. The organic solvent contains a hydrogen donor solvent containing tetralin or tetrahydroquinoline.
A method for producing the heterophase binder pitch according to claim 3. The thermal polymerization is
A reaction temperature of 400°C to 500°C;
A reaction time of 10 minutes to 10 hours; and
The inert gas flow rate is 100 mL/min/kg to 5000 mL/min/kg.
A method for producing the heterophase binder pitch according to claim 1. The thin film distillation comprises:
A treatment temperature of 250°C to 400°C;
A treatment time of 5 to 60 minutes; and
It is characterized by being carried out under pressure conditions of 1 hPa to 100 hPa,
A method for producing the heterophase binder pitch according to claim 1. The anisotropic pitch obtained from the thin film distillation is
Softening point 250℃~350℃;
anisotropic content of 70% to 100%; and
The production yield is 15% to 25%.
A method for producing the heterophase binder pitch according to claim 1. The solvent extraction is
Mixing ratio (weight ratio) of anisotropic pitch:solvent=1:2 to 1:40;
Extraction time: 5 minutes to 24 hours; and
The extraction is carried out under the condition of an extraction solvent of THF (tetrahydrofuran),
A method for producing the heterophase binder pitch according to claim 1. The step of mixing the isotropic pitch with the mesogen comprises:
Mixing ratio of isotropic pitch:mesogen = 95:5 to 60:40;
Mixing temperature: 200°C to 400°C;
The mixing time is 5 minutes to 2 hours.
A method for producing the heterophase binder pitch according to claim 1.