KR20220105211A - The manufacturing method for petroleum-based high softening point pitch - Google Patents

Abstract

The present invention relates to a method for manufacturing petroleum-based high softening point pitch. More specifically, the method includes the steps of: performing an oxidation heat-treatment process on petroleum-based residue oil using an oxidation heat-treatment device including an oxidation reactor; and performing a reduced pressure heat-treatment process on the oxidation heat-treated petroleum-based residue oil, wherein the ratio of the height and diameter of the oxidation reactor is 0.5 to 2, and the quinoline insoluble content (QI) content of the petroleum-based high softening point pitch is 0.001 to 0.5 wt% relative to the total weight of the petroleum-based high softening point pitch.

Description

Manufacturing method of petroleum-based high softening point pitch {THE MANUFACTURING METHOD FOR PETROLEUM-BASED HIGH SOFTENING POINT PITCH}

The present invention relates to a method for producing a petroleum-based high softening point pitch, and more particularly, to a method for producing a high-purity petroleum-based high softening point pitch capable of suppressing the generation of quinoline insolubles (QI) in the oxidation heat treatment step. .

The high softening point pitch is used as a raw material or precursor material for various carbon materials, such as carbon fiber, activated carbon, anode materials for secondary batteries, and graphite materials. In order to produce a high softening point pitch, a method of manufacturing through an oxidation process and a heat treatment process using a coal-based or petroleum-based material as a raw material is generally known.

When a high softening point pitch is used as a raw material for a secondary battery anode material, the lower the content of quinoline insoluble content, inorganic impurities such as metals, or heteroatoms such as nitrogen and sulfur contained in the high softening point pitch, the better the battery capacity and lifespan characteristics It is known to be effective in improving and improving output characteristics. Since petroleum-based raw materials contain virtually no quinoline-insoluble matter, the high softening point pitch prepared from petroleum-based materials has a relatively small amount of quinoline insoluble content compared to high softening point pitches prepared from coal-based materials. , some quinoline insolubles are produced in its manufacturing process. When the high softening point pitch is used as a raw material for a secondary battery negative electrode material, the quinoline insoluble content generated in the manufacturing process has a problem of lowering the performance of the secondary battery.

Conventional technology for producing high softening point pitch using petroleum-based raw materials or coal-based raw materials has high quinoline insoluble content in the manufactured high softening point pitch, or risks such as boron compounds, hydrofluoric acid, peroxide-based compounds, etc. in the production of high softening point pitch As a method of using a material, there is a problem in that it is difficult to economically manufacture a high softening point pitch. In particular, when manufacturing a high softening point pitch using a petroleum-based raw material, a method for suppressing the formation of quinoline insoluble content on the manufacturing process is not suggested.

The problem to be solved by the present invention is to provide an economical method for producing a petroleum-based high softening point pitch.

The problem to be solved by the present invention is to provide a method for producing a high-quality petroleum-based high softening point pitch in which the content of quinoline insoluble (QI) is significantly reduced.

According to the concept of the present invention, a method for producing a petroleum-based high softening point pitch includes the steps of performing an oxidation heat treatment process on petroleum residue using an oxidation heat treatment apparatus including an oxidation reactor, and the oxidation heat treatment of the petroleum residue oil Including the step of performing a reduced pressure heat treatment process, wherein the ratio of the height to the diameter of the oxidation reactor is 0.5 to 2, and the quinoline insoluble (QI) content of the petroleum-based high softening point pitch is the total of the petroleum-based high softening point pitch. It may be 0.001 wt% to 0.5 wt% based on the weight.

The method for producing a petroleum-based high softening point pitch according to the present invention can significantly reduce the quinoline insoluble content formed in the manufacturing process, and thus it is possible to manufacture a high-quality petroleum-based high softening point pitch with a low impurity content.

The method for producing a petroleum-based high softening point pitch according to the present invention does not require a catalyst and high pressure conditions, so a separate process for removing the catalyst is not required and an expensive high pressure vessel may not be used. In addition, since peroxide-based compounds are not used, there is no risk of explosion during the manufacturing process and no environmental pollution occurs. Accordingly, it is possible to economically manufacture high-quality petroleum-based high softening point pitch.

Since the petroleum-based high softening point pitch produced by the method for producing a petroleum-based high softening point pitch according to the present invention is significantly reduced in quinoline insoluble content, the capacity, lifespan and charging/discharging efficiency of the secondary battery to which the petroleum-based high softening point pitch is applied is improved can be

1 is a flowchart for explaining a method for manufacturing a petroleum-based high softening point pitch according to an embodiment of the present invention.
2 is a schematic diagram for explaining an oxidation heat treatment apparatus according to an embodiment of the present invention.
3 is a photograph of the shape of a negative active material prepared using a petroleum-based high softening point pitch prepared according to embodiments of the present invention.
Figure 4 is a schematic process diagram for explaining a method for manufacturing a petroleum-based high softening point pitch according to an embodiment of the present invention.

In order to fully understand the configuration and effect of the present invention, preferred embodiments of the present invention will be described with reference to the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below, and may be embodied in various forms and various modifications may be made. However, it is provided so that the disclosure of the present invention is complete through the description of the present embodiments, and to fully inform those of ordinary skill in the art to which the present invention belongs, the scope of the invention.

In this specification, when a component is referred to as being on another component, it may be directly formed on the other component or a third component may be interposed therebetween. In addition, in the drawings, the thickness of the components is exaggerated for effective description of technical content. Parts indicated with like reference numerals throughout the specification indicate like elements.

In various embodiments of the present specification, terms such as first, second, third, etc. are used to describe various components, but these components should not be limited by these terms. These terms are only used to distinguish one component from another. The embodiments described and illustrated herein also include complementary embodiments thereof.

The terminology used herein is for the purpose of describing the embodiments and is not intended to limit the present invention. In this specification, the singular also includes the plural, unless specifically stated otherwise in the phrase. As used herein, 'comprises' and/or 'comprising' does not exclude the presence or addition of one or more other elements.

1 is a flowchart for explaining a method for manufacturing a petroleum-based high softening point pitch according to an embodiment of the present invention.

2 is a schematic diagram for explaining an oxidation heat treatment apparatus according to an embodiment of the present invention.

Figure 4 is a schematic process diagram for explaining a method for manufacturing a petroleum-based high softening point pitch according to an embodiment of the present invention.

1, 2, and 4, the method for producing a petroleum-based high softening point pitch according to an embodiment of the present invention is petroleum-based using an oxidation heat treatment apparatus 1 including an oxidation reactor 100. It may include a step (S1) of performing an oxidation heat treatment process on the resid, and a step (S2) of performing a reduced pressure heat treatment process on the oxidative heat treatment petroleum-based residue oil.

The petroleum residue may have a higher carbonization yield and aromatic ratio than light oil. Accordingly, the petroleum residue may be suitably used as a raw material for a carbon material. The petroleum residue may have different chemical and physical properties depending on process conditions. The petroleum residue may include a reactive material. For example, the reactive material in the petroleum residue may include at least one of indene, an indene derivative, styrene, and a styrene derivative.

For example, the petroleum residue is pyrolysis fuel oil (PFO), naphtha cracking bottom oil (NCB), ethylene residue oil (EBO, Ethylene Bottom Oil), FCC-DO (Fluid Catalytic). Cracking-Decant Oil), RFCC-DO (Residue Fluid Catalytic Cracking-Decant Oil), Aromatic Extract (AE), and may include at least one of hydrotreated petroleum residual oil.

Before performing the oxidation heat treatment process, performing a pre-treatment process on the petroleum residue, and may further include injecting the petroleum residue on which the pre-treatment process has been performed into the oxidation reactor. By the pretreatment process, the petroleum residue may be used as a raw material for producing the high softening point pitch. More specifically, by the pretreatment process, the light oil in the petroleum residue may be removed. In general, the physical properties of the high softening point pitch can be easily changed according to the various physical properties of the raw material used for the production of the high softening point pitch. According to the present invention, as the light oil in the petroleum residue is removed by the pretreatment process, the physical properties of the high softening point pitch may be relatively uniformly maintained. Accordingly, the subsequent oxidation heat treatment process or the vacuum heat treatment process can be easily performed. In addition, as reactive substances such as indene, indene derivative, styrene, or styrene derivative contained in the light oil are removed by the pretreatment process, quinoline insoluble content generated in the oxidation heat treatment reaction (Quinoline Insoluble) , QI) can be reduced. In the present specification, the quinoline insoluble (QI) may mean solid particles that are not soluble in the quinoline solvent. In general, when the high softening point pitch is prepared from the petroleum residue, quinoline insolubles (QI) may be formed in the manufacturing process. Unlike the present invention, when a high softening point pitch having a high content of quinoline insoluble (QI) is used as a raw material for a secondary battery anode material, the performance of the secondary battery may be deteriorated.

The heat treatment apparatus 1 includes an oxidation reactor 100 , an oxidizing gas supply unit 110 , an inert gas supply unit 120 , a gas supply unit 130 , a stirring unit 140 , an electric heater 150 , and first to third Flow measurement units 161 , 162 , 163 , first to third flow control valves 171 , 172 , 173 , circulation pump 180 , heating jacket 190 , upper temperature sensor 200 , central temperature sensor 210 , and a lower temperature sensor 220 .

The oxidizing gas supply unit 110 may supply the oxidizing gas to the gas supply unit 130 . For example, the oxidizing gas may include at least one of air, oxygen, and ozone. For example, as the oxidizing gas, air in the atmosphere may be directly used.

The inert gas supply unit 120 may supply an inert gas to the gas supply unit 130 . For example, the inert gas may include at least one of nitrogen and argon.

The gas supply unit 130 may be disposed between the oxidizing gas supply unit 110 and the oxidation reactor 100 and between the inert gas supply unit 120 and the oxidation reactor 100 . The oxidizing gas or the inert gas may be charged into the oxidation reactor 100 through the gas supply unit 130 . In some embodiments, the oxidizing gas may be charged alone into the oxidation reactor 100 . In another embodiment, the oxidizing gas and the inert gas may be charged into the oxidation reactor 100 . In this case, the oxidizing gas may be diluted with the inert gas. For example, the concentration of oxygen may be adjusted by diluting oxygen with nitrogen.

The flow rate of the oxidizing gas may be 0.01 L/min to 1 L/min compared to 1 kg of the petroleum residue. On the other hand, when the flow rate of the oxidizing gas exceeds 1 L/min compared to 1 kg of the petroleum residue, the concentration of oxygen reacting with the vaporized aromatic hydrocarbon increases and the quinoline insoluble content (QI) formed on the inner wall of the oxidation reactor ) may increase.

The first flow rate measuring unit 161 may be disposed between the oxidizing gas supply unit 110 and the gas supply unit 130 , and between the inert gas supply unit 120 and the gas supply unit 130 . A second flow rate measuring unit 162 may be disposed. The first flow rate control valve 171 may be disposed between the first and second flow rate measurement units 161 and 162 and the gas supply unit 130 . The flow rate of the oxidizing gas supply unit 110 may be measured by the first flow rate measurement unit 161 , and the flow rate of the inert gas supply unit 120 may be measured by the second flow rate measurement unit 162 . have. The flow rate of the oxidizing gas or the inert gas charged into the gas supply unit 130 may be adjusted by the first flow rate control valve 171 .

The oxidation reactor 100 may be a reactor in which an oxidation heat treatment process is performed on the petroleum residue. An oxidation heat treatment process may be performed on petroleum residues using the oxidation heat treatment apparatus 1 including the oxidation reactor 100 . The oxidation heat treatment process may include heating the petroleum residue and the oxidizing gas, which are reactants of the oxidation heat treatment process.

For example, the temperature of the reactant in the oxidation heat treatment process may be 250 °C to 400 °C. In the present specification, the temperature of the reactant of the oxidation heat treatment process may mean a temperature of a portion filled with the reactant of the oxidation heat treatment process, for example, it may mean a temperature measured by the lower temperature sensor 220 . On the other hand, when the temperature of the reactant in the oxidation heat treatment process is less than 250 ° C., the molecular weight of the petroleum residue does not sufficiently increase, so a problem in that the yield of the final product, the high softening point pitch, is lowered may occur. In addition, when the temperature of the reactant in the oxidation heat treatment process exceeds 400 °C, the content of the quinoline insoluble in the reactant in the oxidation heat treatment process is rapidly increased, and coking may occur.

For example, the execution time of the oxidation heat treatment process may be 1 hour to 20 hours. If the duration of the oxidation heat treatment process is less than 1 hour, the oxidation reaction may not sufficiently occur. In addition, when the duration of the oxidation heat treatment process exceeds 20 hours, an excessive polymerization reaction may be induced, and the physical properties of the final product, a high softening point pitch, may be altered. In particular, when the oxidation reaction proceeds excessively, the oxygen content of the prepared high softening point pitch may be high. Accordingly, the performance of the secondary battery may be deteriorated when it is subsequently used as a raw material for a secondary battery negative electrode material. In addition, when the petroleum residue is heat-treated under high temperature conditions or oxidation reaction conditions, and excessive polymerization of aromatic compounds proceeds, the petroleum residue may be converted into an insoluble material.

For example, the ratio (L/D) of the height (L) to the diameter (D) of the oxidation reactor 100 may be 0.5 to 2. When performing an oxidation heat treatment reaction on the petroleum residue, the petroleum oil may be exposed to an oxidizing gas while flowing out. When the oxidative heat treatment process is performed by mixing the petroleum residue and the oxidizing gas, aromatic hydrocarbons volatilized at high temperature react with the oxidizing gas so that quinoline insolubles (QI) are adsorbed on the inner wall of the oxidation reactor 100 can be For example, the amount of the quinoline insoluble component (QI) adsorbed from the inner wall of the oxidation reactor 100 may be greater than the amount generated inside the reactant of the oxidation heat treatment process.

According to the present invention, as the ratio (L/D) of the height (L) to the diameter (D) of the oxidation reactor 100 is 0.5 to 2, the amount of impurities in the petroleum-based high softening point pitch is reduced and oxidation The heat treatment reaction can be efficiently performed. On the other hand, when the ratio (L/D) of the height (L) to the diameter (D) of the oxidation reactor 100 exceeds 2, the area inside the reactor in which the quinoline insoluble content is formed is increased, resulting in petroleum-based high The amount of impurities in the softening point pitch may be increased. In addition, when the ratio (L/D) of the height (L) to the diameter (D) of the oxidation reactor 100 is less than 0.5, heat transfer inside the reactor according to the temperature gradient as the diameter (D) of the oxidation reactor increases It may be difficult, and thus the efficiency of the oxidation reaction may be reduced.

The upper temperature sensor 200 , the central temperature sensor 210 , and the lower temperature sensor 220 may be disposed in the oxidation reactor 100 . The upper temperature sensor 200 may be disposed above the oxidation reactor 100 . The lower temperature sensor 220 may be disposed at a lower portion in the oxidation reactor 100 . The central temperature sensor 210 may be disposed between the upper temperature sensor 200 and the lower temperature sensor 220 .

The central part temperature sensor 210 may control the temperature of the central part in the oxidation reactor 100 . The lower temperature sensor 220 may control the temperature of the lower portion in the oxidation reactor 100 . The upper temperature sensor 200 may control the temperature of the upper portion in the oxidation reactor 100 . For example, the temperature of the upper part of the oxidation reactor may be maintained at 250 °C to 370 °C, or 280 °C to 360 °C. In the present specification, the upper portion in the oxidation reactor may mean a portion in which the reactant of the oxidation heat treatment process is not filled. To this end, a heating unit for independently heating the upper and lower portions of the oxidation reactor 100 may be further included. On the other hand, when the upper temperature in the oxidation reactor 100 exceeds 370° C., the rate of the polymerization reaction caused by the volatilized aromatic hydrocarbon and the oxidizing gas may be rapidly increased. Accordingly, the amount of the quinoline insoluble (QI) adsorbed in the oxidation reactor 100 may increase rapidly.

In general, in order to increase the softening point of the high softening point pitch, which is the final product, a catalyst may be used under high pressure conditions, and in order to reduce the quinoline insoluble (QI) content in the high softening point pitch, an oxidizing gas and a peroxide-based compound are mixed can be However, when the catalyst is used under high pressure conditions, an expensive high-pressure vessel is required as well as a separate process for removing the catalyst, so the cost of producing a high softening point pitch may increase. In addition, when the peroxide-based compound is additionally added to the oxidizing gas, there may be a risk of explosion during the manufacturing process due to the high reactivity of the peroxide-based compound, and the cost of the peroxide-based compound, the cost of managing dangerous substances, and the cost of wastewater treatment can increase Accordingly, the economical efficiency for manufacturing a large-scale high softening point pitch may be reduced.

According to the present invention, the molecular weight of the petroleum residue may be increased by the oxidation heat treatment process, and the yield of the final product, the high softening point pitch, may be improved. In particular, high-pressure conditions may not be required in the oxidative heat treatment process, and a catalyst may not be used, so it is possible to manufacture an economical and high-quality petroleum-based high softening point pitch. Furthermore, according to the present invention, before the oxidation heat treatment process is performed or while the oxidation heat treatment process is performed, the peroxide-based compound may not be charged into the oxidation reactor 100 . As peroxide-based compounds are not used, the manufacturing process can be economical, and the risk of explosion during the manufacturing process can be prevented.

The stirring unit 140 may be disposed in the oxidation reactor 100 . The reactants of the oxidation heat treatment process may be smoothly mixed by the stirring unit 140 .

Heating jackets 190 may be disposed on the outer wall of the oxidation reactor 100 to cover a portion of the outer wall of the oxidation reactor 100 . The heating jackets 190 may perform a function of insulating, insulating, or keeping the oxidation reactor 100 .

The circulation pump 180 may be connected to the oxidation reactor 100 . For example, the circulation pump 180 may be connected to the lower portion of the oxidation reactor 100 . A reactant of the oxidation heat treatment process may be injected into the electric heater 150 by the circulation pump 180 . The electric heater 150 may be connected to the circulation pump 180 . That is, the circulation pump 180 may be disposed between the oxidation reactor 100 and the electric heater 150 . The third flow rate measurement unit 163 and the second flow rate control valve 172 may be disposed between the circulation pump 180 and the electric heater 150 . The third flow rate measurement unit 163 may be disposed adjacent to the circulation pump 180 , and the second flow rate control valve 172 may be disposed adjacent to the electric heater 150 . The third flow rate measurement unit 163 may measure the flow rate of the reactant in the oxidation heat treatment process injected into the electric heater 150 . The second flow rate control valve 172 may control the flow rate of the reactant of the oxidation heat treatment process injected into the electric heater 150 . The electric heater 150 may heat a reactant of the oxidation heat treatment process. The reactant of the oxidation heat treatment process heated by the electric heater 150 may be injected back into the oxidation reactor 100 . For example, the reactant of the oxidation heat treatment process heated by the electric heater 150 may be connected to the upper portion of the oxidation reactor 100 . A third flow rate control valve 173 may be disposed between the electric heater 150 and an upper portion of the oxidation reactor 100 . The flow rate of the reactant in the oxidation heat treatment process injected into the upper portion of the oxidation reactor 100 may be controlled by the third flow rate control valve 173 .

The oxidative heat treatment of the petroleum-based residue oil may be produced by an oxidative heat treatment process, petroleum-based pitch. Hereinafter, petroleum-based pitch in the present specification may refer to petroleum-based residual oil subjected to oxidation heat treatment by the oxidation heat treatment process. A reduced pressure heat treatment process may be performed on the petroleum-based pitch. The reduced pressure heat treatment process may include heating the petroleum pitch under reduced pressure conditions. The reduced pressure heat treatment process may be performed in a reduced pressure heat treatment apparatus.

In the present invention, by the reduced pressure heat treatment process, the heavy oil of the petroleum pitch can be removed, the softening point can be increased, and the content of toluene insolubles can be increased to increase the carbonization yield of the pitch. have. On the other hand, unlike the present invention, when the atmospheric heat treatment process or the pressure heat treatment process is performed on the petroleum pitch instead of the reduced pressure heat treatment process, it may be difficult to remove the heavy oil, and the softening point of the pitch increases it may not be

For example, the pressure of the reduced pressure heat treatment process may be 1 torr to 300 torr, 1 torr to 200 torr, or 1 torr to 100 torr. For example, the heat treatment temperature of the reduced pressure heat treatment process may be 300 °C to 430 °C. On the other hand, when the heat treatment temperature of the reduced pressure heat treatment process is less than 300 ° C, it may be difficult to remove heavy oil, and the production of toluene insoluble content is lowered, so that it may be difficult to manufacture a high-quality pitch with a high softening point. In addition, there may be a limit in increasing the softening point of the petroleum pitch because the heavy oil in the pitch is not sufficiently removed. When the heat treatment temperature of the reduced pressure heat treatment process is higher than 430° C., coking phenomenon of the petroleum-based pitch may occur to form coke, and the content of quinoline insolubles (QI) may be rapidly increased.

For example, the execution time of the reduced pressure heat treatment process may be 1 hour to 20 hours, or 2 hours to 10 hours. If the execution time of the reduced pressure heat treatment process is less than 1 hour, the heavy oil may not be sufficiently removed, and it may be difficult to prepare a pitch having a high softening point. In addition, a toluene-insoluble component may not be sufficiently generated due to a lack of thermal polymerization reaction time, and a low-quality, high softening point pitch with a low carbonization yield may be manufactured. If the execution time of the reduced pressure heat treatment process exceeds 20 hours, excessive polymerization may proceed and toluene insoluble content may be excessively generated, and the operation cost of the process and the manufacturing cost of the product may increase due to the increase in the process time. have.

The reduced pressure heat treatment process may further include mixing inert gas or steam. By the reduced pressure heat treatment process, the heavy oil of the petroleum pitch can be effectively removed from the reduced pressure heat treatment apparatus. For example, the inert gas may include at least one of nitrogen and argon.

For example, the flow rate of the inert gas or steam may be 0.01 L/min to 2.0 L/min compared to 1 kg of the petroleum pitch. Unlike the present invention, when an oxidizing gas is charged during the reduced pressure heat treatment process, the quinoline insoluble component may be rapidly formed by the oxidation reaction at a high temperature. Therefore, according to the present invention, an inert gas or steam may be charged during the reduced pressure heat treatment process. In particular, when an inert gas or steam is heated and charged, the heavy oil can be more effectively removed.

In the method for producing a petroleum-based high softening point pitch according to the present invention, after the reduced-pressure heat treatment process, an atmospheric heat treatment process may be further performed on the petroleum-based pitch. By the atmospheric heat treatment process, the content of toluene insolubles in the petroleum-based high softening point pitch may be increased. For example, the heat treatment temperature of the atmospheric pressure heat treatment process may be 300 °C to 430 °C. On the other hand, when the heat treatment temperature of the atmospheric pressure heat treatment process is less than 300 °C, it may be difficult to generate a heavy toluene insoluble component. In addition, when the heat treatment temperature of the atmospheric pressure heat treatment process is higher than 430° C., the coking phenomenon of petroleum-based pitch may occur to form coke, and the content of quinoline insolubles may be rapidly increased.

For example, the execution time of the atmospheric pressure heat treatment process may be 30 minutes to 20 hours. On the other hand, when the execution time of the atmospheric pressure heat treatment process is less than 30 minutes, the heat treatment reaction time is too short, so that the toluene insoluble content may not be sufficiently generated. When the execution time of the atmospheric pressure heat treatment process exceeds 20 hours, the operating cost of the process and the manufacturing cost of the product may increase due to the increase in the operating time.

The petroleum-based high softening point pitch manufactured by the manufacturing method of the petroleum-based high softening point pitch according to the present invention, for example, may have a softening point of 150 °C to 300 °C. For example, the quinoline insoluble (QI) content of the petroleum-based high softening point pitch may be 0.5 wt% or less, and may be 0.001 wt% to 0.5 wt%, based on the total weight of the petroleum-based high softening point pitch. That is, according to the present invention, the petroleum-based high softening point pitch can have a high softening point and, at the same time, the content of quinoline insolubles can be significantly reduced.

According to the present invention, petroleum-based high softening point pitch can be manufactured through an oxidative heat treatment process and a reduced pressure heat treatment process using petroleum residue as a raw material, and the petroleum-based high softening point pitch is a raw material of carbon material or graphite material, carbon material or It may be used as a precursor material for graphite material. For example, the carbon material or graphite material may include carbon fiber, activated carbon, a secondary battery negative electrode material, and the like.

In general, when petroleum-based high softening point pitch is used as a raw material for a secondary battery anode material, the performance of the secondary battery may be deteriorated due to quinoline insoluble content. That is, the lower the content of quinoline insoluble content, inorganic impurities such as metals, or heteroatoms such as nitrogen and sulfur in the petroleum-based high softening point pitch, the battery capacity can be improved, and the lifespan characteristics and output characteristics can be improved. .

The petroleum-based high softening point pitch produced by the method for manufacturing a petroleum-based high softening point pitch according to the present invention has a high softening point and at the same time has a remarkably low content of quinoline insoluble content, The performance of the secondary battery manufactured by using it can be improved.

In some embodiments, the petroleum-based high softening point pitch may be used as a binder material or a coating material of an anode material (eg, a natural graphite anode material or an artificial graphite anode material). In another embodiment, it may be used as a carbon-based negative electrode material by performing a carbonization process on a petroleum-based high softening point pitch.

In addition, the petroleum-based high softening point pitch prepared by the present invention may be used as a precursor material for carbon fibers through a carbonization process and a graphitization process. When the petroleum-based high softening point pitch according to the present invention is used as a precursor material of the carbon fiber, the high softening point and carbonization yield of the petroleum-based high softening point pitch, and the low quinoline insoluble content, the tensile strength of the produced carbon fiber, and the tensile strength Physical properties such as elastic modulus may be improved.

In addition, the petroleum-based high softening point pitch prepared by the present invention may be used as a precursor material for activated carbon through a carbonization process and an activation process. The petroleum-based high softening point pitch according to the present invention has a high softening point, carbonization yield, mechanical properties, and low impurity content, so that the prepared activated carbon may have improved specific surface area and mechanical strength.

Example

Example 1

Pyrolysis fuel oil (PFO) was used as the petroleum residue, and air was used as the oxidizing gas. Pyrolysis fuel oil (PFO) was injected into an oxidation reactor having a height (L) and a diameter (D) ratio (L/D) of 1.6. The oxidation heat treatment process was performed by charging air at a flow rate of 0.5 L/min compared to 1 kg of pyrolysis fuel oil (PFO). The temperature of the reactants in the oxidation heat treatment process is 370 °C, and the temperature at the top in the oxidation reactor is 350 °C. The oxidation heat treatment process was performed for 4 hours.

Thereafter, the pressure was reduced to 80 torr, and a reduced pressure heat treatment process was performed at 400° C. for 10 hours to prepare a petroleum-based high softening point pitch. The softening point of the prepared petroleum-based high softening point pitch was 251 ° C., the content of quinoline insolubles was 0.08 wt% based on the total weight of the petroleum-based high softening point pitch, and the coking value was 65 wt%.

Example 2

Pyrolysis fuel oil (PFO) was used as the petroleum residue, and air was used as the oxidizing gas. Pyrolysis fuel oil (PFO) was injected into an oxidation reactor having a height (L) and a diameter (D) ratio (L/D) of 1.6. The oxidation heat treatment process was performed by charging air at a flow rate of 0.2 L/min compared to 1 kg of pyrolysis fuel oil (PFO). The temperature of the reactants in the oxidation heat treatment process is 370 °C, and the temperature at the top in the oxidation reactor is 350 °C. The oxidation heat treatment process was performed for 4 hours.

Thereafter, the pressure was reduced to 80 torr, and a reduced pressure heat treatment process was performed at 400° C. for 10 hours to prepare a petroleum-based high softening point pitch. The softening point of the prepared petroleum-based high softening point pitch was 254 ° C., the content of quinoline insolubles was 0.02 wt% based on the total weight of the petroleum-based high softening point pitch, and the coking value was 64 wt%.

Example 3

Pyrolysis fuel oil (PFO) was used as the petroleum residue, and air was used as the oxidizing gas. Pyrolysis fuel oil (PFO) was injected into an oxidation reactor having a height (L) and a diameter (D) ratio (L/D) of 1.6. The oxidation heat treatment process was performed by charging air at a flow rate of 0.5 L/min compared to 1 kg of pyrolysis fuel oil (PFO). The temperature of the reactants in the oxidation heat treatment process is 370 °C, and the temperature at the top in the oxidation reactor is 360 °C. The oxidation heat treatment process was performed for 4 hours.

Thereafter, the pressure was reduced to 80 torr, and a reduced pressure heat treatment process was performed at 400° C. for 10 hours to prepare a petroleum-based high softening point pitch. The softening point of the prepared petroleum-based high softening point pitch was 254 ° C., the content of quinoline insolubles was 0.24 wt% based on the total weight of the petroleum-based high softening point pitch, and the coking value was 68 wt%.

Comparative Example 1

Pyrolysis fuel oil (PFO) was used as the petroleum residue, and air was used as the oxidizing gas. Pyrolysis fuel oil (PFO) was injected into an oxidation reactor having a height (L) and diameter (D) ratio (L/D) of 2.5. The oxidation heat treatment process was performed by charging air at a flow rate of 0.5 L/min compared to 1 kg of pyrolysis fuel oil (PFO). The temperature of the reactants in the oxidation heat treatment process is 370 °C, and the temperature at the top in the oxidation reactor is 360 °C. The oxidation heat treatment process was performed for 4 hours.

Thereafter, the pressure was reduced to 80 torr, and a reduced pressure heat treatment process was performed at 400° C. for 10 hours to prepare a petroleum-based high softening point pitch. The softening point of the prepared petroleum-based high softening point pitch was 245 ° C., the content of quinoline insolubles was 0.76 wt% based on the total weight of the petroleum-based high softening point pitch, and the coking value was 66 wt%.

Comparative Example 2

Pyrolysis fuel oil (PFO) was used as the petroleum residue, and air was used as the oxidizing gas. Pyrolysis fuel oil (PFO) was injected into an oxidation reactor having a height (L) and a diameter (D) ratio (L/D) of 1.6. The oxidation heat treatment process was performed by charging air at a flow rate of 0.5 L/min compared to 1 kg of pyrolysis fuel oil (PFO). The temperature of the reactants in the oxidation heat treatment process is 380 °C, and the temperature at the top in the oxidation reactor is 380 °C. The oxidation heat treatment process was performed for 4 hours.

Thereafter, the pressure was reduced to 80 torr, and a reduced pressure heat treatment process was performed at 400° C. for 10 hours to prepare a petroleum-based high softening point pitch. The softening point of the prepared petroleum-based high softening point pitch was 244 ° C., the content of quinoline insolubles was 1.06 wt% based on the total weight of the petroleum-based high softening point pitch, and the coking value was 64 wt%.

Comparative Example 3

Pyrolysis fuel oil (PFO) was used as the petroleum residue, and air was used as the oxidizing gas. Pyrolysis fuel oil (PFO) was injected into an oxidation reactor having a height (L) and a diameter (D) ratio (L/D) of 1.6. The oxidation heat treatment process was performed by charging air at a flow rate of 1.5 L/min compared to 1 kg of pyrolysis fuel oil (PFO). The temperature of the reactants in the oxidation heat treatment process is 370 °C, and the temperature at the top in the oxidation reactor is 360 °C. The oxidation heat treatment process was performed for 4 hours.

Thereafter, the pressure was reduced to 80 torr, and a reduced pressure heat treatment process was performed at 400° C. for 10 hours to prepare a petroleum-based high softening point pitch. The softening point of the prepared petroleum-based high softening point pitch was 248 ° C., the content of quinoline insolubles was 0.93 wt% based on the total weight of the petroleum-based high softening point pitch, and the coking value was 58 wt%.

The ratio (L/D) of the height (L) to the diameter (D) of the oxidation reactor in the oxidation heat treatment process in Examples 1 to 3 and Comparative Examples 1 to 3, the upper part of the oxidation reactor The temperature, the flow rate of the oxidizing gas, and the physical properties of the prepared petroleum-based high softening point pitch are shown in Table 1 below.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Ratio (L/D) of height (L) to diameter (D) of oxidation reactor 1.6 1.6 1.6 2.5 1.6 1.6 Upper temperature in reactor (°C) 350 350 360 360 380 360 Flow rate of oxidizing gas compared to 1kg of petroleum residue (L/min) 0.5 0.2 0.5 0.5 0.5 1.5 Softening point of petroleum-based high softening point pitch (℃) 251 254 254 245 244 248 QI content (wt%) of petroleum-based high softening point pitch 0.08 0.02 0.24 0.76 1.06 0.93 Coking Value (wt%) of petroleum-based high softening point pitch 65 64 68 66 64 58

Referring to Table 1, the petroleum-based high softening point pitch of Examples 1 to 3 has a high softening point of 200 ° C. or higher, a quinoline insoluble content of 0.5 wt% or less, and a high coking value of 60% or more. can be checked

On the other hand, Comparative Example 1 used the same petroleum residue as Example 1 as a raw material, but as the L/D of the oxidation reactor increases, the adsorption amount of quinoline insoluble content inside the oxidation reactor may increase, and the As a result, it can be confirmed that the impurity content of the petroleum-based high softening point pitch is high.

In Comparative Example 2, the same petroleum residue as Example 1 was used as a raw material and an oxidation reactor of the same size was used. As it increases, the amount of quinoline insoluble content may be increased, and as a result, it can be confirmed that the impurity content of the petroleum-based high softening point pitch is high.

In Comparative Example 3, the same petroleum residue as Example 1 was used as a raw material and an oxidation reactor of the same size was used, but as the flow rate of the oxidizing gas charged into the oxidation reactor increased, the aromatic hydrocarbon material was volatilized. As the amount of oxygen reacts increases, the content of quinoline insolubles produced by polymerization may increase, and as a result, it can be confirmed that the impurity content of the petroleum-based high softening point pitch is high.

Experimental example

Experimental Example 1 : Preparation of secondary battery using petroleum-based high softening point pitch prepared according to Example 1

A secondary battery was manufactured by using the petroleum-based high softening point pitch prepared according to Example 1 as a coating material for a secondary battery negative electrode material.

Specifically, 5 g of the petroleum-based high softening point pitch prepared according to Example 1 was mixed with 95 g of spherical natural graphite having an average diameter of 15 μm. Then, the petroleum-based high softening point pitch was coated on the surface of natural graphite using a mechanical stirrer. After the coating was completed, heat treatment was performed at 1,100° C. for 1 hour to prepare an anode active material.

The shape photograph of the negative active material prepared using the petroleum-based high softening point pitch prepared according to Example 1 is shown in FIG. 3 . It can be seen that the petroleum-based high softening point pitch is uniformly coated on natural graphite.

With the anode active material prepared using the petroleum-based high softening point pitch prepared according to Example 1, a composition for an anode slurry was prepared. Specifically, negative electrode active material: carbon black: carboxymethyl cellulose: styrene butadiene = 91: 5: 2: 2 by weight ratio of the negative electrode active material, carbon black, carboxymethyl cellulose, and styrene butadiene are mixed with water to a composition for a negative electrode slurry was prepared. The negative electrode slurry composition was coated on a copper current collector, dried and rolled in an oven at 110° C. for about 1 hour to prepare a negative electrode for a secondary battery.

Thereafter, the anode for the secondary battery, the separator, the electrolyte, and the lithium electrode were stacked in this order to prepare a coin cell type secondary battery. At this time, the electrolyte was a solvent in which the weight ratio of ethylene carbonate: dimethyl carbonate was 1:1, and 1.0 M LiPF ₆ was added.

Experimental Example 2 : Preparation of secondary battery using petroleum-based high softening point pitch prepared according to Comparative Example 2

A secondary battery was prepared by using the petroleum-based high softening point pitch prepared according to Comparative Example 2 as a coating material for a secondary battery negative electrode material.

Instead of using the petroleum-based high softening point pitch prepared according to Example 1, a petroleum-based high softening point pitch prepared according to Comparative Example 2 was used, except for this, substantially the same as in Experimental Example 1 A secondary battery was manufactured by the method.

Experimental Example 3 : Measurement of charge/discharge capacity and initial efficiency of secondary batteries

The performance of the secondary battery prepared by using each of the petroleum-based high softening point pitches prepared according to Example 1 and Comparative Example 2 as a coating material for a secondary battery negative electrode material was measured.

Specifically, charge/discharge capacity and initial efficiency were measured for each of the prepared secondary batteries according to the following conditions. Specifically, it was charged to 0.01 V with a constant current of 0.2 C, and charged to 0.01 C with a constant voltage of 0.01 V. Then, it was discharged to 1.5 V with a constant current of 0.2 C. The 1st cycle, 50th cycle, and 100th cycle were repeated to measure initial efficiency and discharge capacity according to each cycle, which are shown in Table 2 below.

Initial Efficiency (%) Discharge capacity (mAh/g) 1st cycle 50th cycle 100th cycle Example 1 90 361 358 356 Comparative Example 2 87 358 343 332

Referring to Table 2, when the petroleum-based high softening point pitch prepared according to Comparative Example 2 was used as a coating material of natural graphite, the petroleum-based high softening point pitch prepared according to Example 1 was used as a coating material of natural graphite. It can be seen that the discharge capacity is small compared to the case of use, and the initial efficiency is also lowered. This may be understood because the petroleum-based high softening point pitch prepared according to Comparative Example 2 has a higher content of quinoline insolubles than the pitch prepared according to Example 1.

Above, although embodiments of the present invention have been described with reference to the accompanying drawings, those of ordinary skill in the art to which the present invention pertains can implement the present invention in other specific forms without changing its technical spirit or essential features. You will understand that there is Therefore, it should be understood that the embodiments described above are illustrative in all respects and not restrictive.

Claims (15)

performing an oxidation heat treatment process on petroleum residues using an oxidation heat treatment apparatus including an oxidation reactor; and
In the method for producing a petroleum-based high softening point pitch comprising the step of performing a reduced pressure heat treatment process on the oxidative heat treatment of the petroleum residue,
The ratio of the height to the diameter of the oxidation reactor is 0.5 to 2,
The quinoline insoluble (QI) content of the petroleum-based high softening point pitch is 0.001 wt% to 0.5 wt% based on the total weight of the petroleum-based high softening point pitch. The method of claim 1,
Before performing the oxidation heat treatment process, further comprising the step of charging an oxidizing gas to the oxidation reactor,
The flow rate of the oxidizing gas is 0.01 L/min to 1 L/min compared to 1 kg of the petroleum residue,
The temperature of the upper part in the oxidation reactor is a method of producing a petroleum-based high softening point pitch maintained at 250 ℃ to 370 ℃. The method of claim 1,
The oxidation heat treatment apparatus includes an upper temperature sensor disposed above the oxidation reactor; and
Further comprising a heating unit for independently heating the upper and lower portions of the oxidation reactor,
The upper temperature sensor is a method of manufacturing a petroleum-based high softening point pitch for controlling the temperature of the upper portion in the oxidation reactor. The method of claim 1,
The oxidation heat treatment apparatus is a method for producing a petroleum-based high softening point pitch further comprising a gas supply for supplying an oxidizing gas or an inert gas to the oxidation reactor. 5. The method of claim 4,
The oxidizing gas comprises at least one of air, oxygen, and ozone;
The inert gas is a method for producing a petroleum-based high softening point pitch comprising at least one of nitrogen and argon. The method of claim 1,
The petroleum residues include Pyrolysis Fuel Oil (PFO), Naphtha Cracking Bottom Oil (NCB), Ethylene Bottom Oil (EBO), and Fluid Catalytic Cracking-Decant (FCC-DO). Oil), RFCC-DO (Residue Fluid Catalytic Cracking-Decant Oil), Aromatic Extract (AE), and a method for producing a petroleum-based high softening point pitch comprising at least one of hydrotreated petroleum residue. The method of claim 1,
Before performing the oxidation heat treatment process,
performing a pretreatment process on the petroleum residue; and
Further comprising injecting the petroleum residue on which the pretreatment process has been performed into the oxidation reactor,
Method for producing a petroleum-based high softening point pitch in which the light oil in the petroleum residue is removed by the pretreatment process. The method of claim 1,
The temperature of the reactants of the oxidation heat treatment process is 250 ℃ to 400 ℃,
A method for producing a petroleum-based high softening point pitch, wherein the oxidative heat treatment process is performed for 1 hour to 20 hours. The method of claim 1,
The pressure of the reduced pressure heat treatment process is 1 torr to 300 torr,
The heat treatment temperature of the reduced pressure heat treatment process is 300 ℃ to 430 ℃,
A method of producing a petroleum-based high softening point pitch of 1 hour to 20 hours for the execution time of the reduced pressure heat treatment process. The method of claim 1,
The reduced pressure heat treatment process further comprises incorporating an inert gas or steam,
The inert gas is a method for producing a petroleum-based high softening point pitch comprising at least one of nitrogen and argon. The method of claim 1,
After performing the reduced pressure heat treatment process, further comprising performing an atmospheric heat treatment process on the petroleum residue,
A method for producing a petroleum-based high softening point pitch in which the content of toluene insolubles of the high softening point pitch is increased by the atmospheric pressure heat treatment process. 12. The method of claim 11,
The heat treatment temperature of the atmospheric pressure heat treatment process is 300 ℃ to 430 ℃,
A method for producing a petroleum-based high softening point pitch, wherein the execution time of the atmospheric heat treatment process is 30 minutes to 20 hours. The method of claim 1,
The softening point of the high softening point pitch is a method of producing a petroleum-based high softening point pitch of 150 ℃ to 300 ℃. The method of claim 1,
A method for producing a petroleum-based high softening point pitch in which a peroxide-based compound is not charged into the oxidation reactor. The method of claim 1,
The temperature of the upper portion in the oxidation reactor is lower than the temperature of the reactants of the oxidation heat treatment process of the petroleum-based high softening point pitch.

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