WO2024034929A1 - Method for producing petroleum-based high-softening point pitch - Google Patents

Method for producing petroleum-based high-softening point pitch Download PDF

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WO2024034929A1
WO2024034929A1 PCT/KR2023/010870 KR2023010870W WO2024034929A1 WO 2024034929 A1 WO2024034929 A1 WO 2024034929A1 KR 2023010870 W KR2023010870 W KR 2023010870W WO 2024034929 A1 WO2024034929 A1 WO 2024034929A1
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softening point
heat treatment
petroleum
high softening
point pitch
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PCT/KR2023/010870
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French (fr)
Korean (ko)
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이현철
권한솔
송영석
이주형
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오씨아이 주식회사
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Publication of WO2024034929A1 publication Critical patent/WO2024034929A1/en

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
    • C10C3/00—Working-up pitch, asphalt, bitumen
    • C10C3/002—Working-up pitch, asphalt, bitumen by thermal means
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
    • C10C3/00—Working-up pitch, asphalt, bitumen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
    • C10C3/00—Working-up pitch, asphalt, bitumen
    • C10C3/02—Working-up pitch, asphalt, bitumen by chemical means reaction
    • C10C3/04—Working-up pitch, asphalt, bitumen by chemical means reaction by blowing or oxidising, e.g. air, ozone

Definitions

  • the present invention relates to a method for producing petroleum-based high softening point pitch and the high softening point pitch produced thereby.
  • High softening point pitch is used as a raw material or precursor material for various carbon materials and graphite materials such as carbon fiber, activated carbon, and secondary battery anode materials.
  • carbon materials and graphite materials such as carbon fiber, activated carbon, and secondary battery anode materials.
  • coal-based or petroleum-based materials are used as raw materials and undergo an oxidation process and heat treatment. Manufacturing methods through processes are generally known.
  • high softening point pitch When using high softening point pitch as a raw material for secondary battery anode materials, the lower the content of quinoline insoluble substances, 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 performance and output characteristics. Since petroleum-based raw materials have virtually no quinoline-insoluble substances, high softening point pitch made from petroleum-based materials has the advantage of having a relatively small amount of quinoline-insoluble substances compared to high softening point pitch made from coal-based materials.
  • the purpose of the present invention is to provide a method for producing petroleum-based high softening point pitch with improved production yield while having a high softening point and significantly lowering the content of quinoline insoluble substances by using raw materials containing petroleum residues.
  • Another object of the present invention is to provide a method for economically and safely producing high-quality petroleum-based high softening point pitch.
  • an oxidation heat treatment step of charging an oxidizing gas to a raw material containing petroleum residue and heating it; And a reduced pressure heat treatment step of heating the result of the oxidation heat treatment step under reduced pressure conditions, wherein the oxidation heat treatment step is a method of producing a petroleum-based high softening point pitch performed in an oxidation heat treatment device that satisfies the following condition (1). can be provided.
  • D1 is the diameter of the oxidation reactor
  • D2 is the diameter of the oil pipe for charging the oxidizing gas.
  • the method for producing petroleum-based high softening point pitch according to the present invention can efficiently proceed with the heat treatment step, easily increase the softening point of the pitch in the heat treatment step, and at the same time significantly reduce quinoline insoluble substances formed in the manufacturing process. , there is an advantage in being able to manufacture high quality petroleum-based high softening point pitch with high manufacturing yield.
  • the petroleum-based high softening point pitch produced according to the method for producing the petroleum-based high softening point pitch according to the present invention has a low quinoline insoluble content, so when a negative electrode material for a secondary battery containing high softening point pitch is used, the capacity of the secondary battery, Lifespan and charge/discharge efficiency can be improved.
  • FIG. 1 is a flowchart illustrating a method of manufacturing petroleum-based high softening point pitch according to an embodiment of the present invention.
  • Figure 2 is a schematic process diagram for explaining a method of manufacturing petroleum-based high softening point pitch according to an embodiment of the present invention.
  • first, second, and third are used to describe various components, but these components should not be limited by these terms. These terms are merely used to distinguish one component from another.
  • a method for producing petroleum-based high softening point pitch can be provided.
  • the method for producing a petroleum-based high softening point pitch includes an oxidizing heat treatment step (S1) of charging an oxidizing gas to a raw material containing petroleum residue and heating it; and a reduced pressure heat treatment step (S2) of heating the result of the oxidation heat treatment step under reduced pressure conditions.
  • the oxidation heat treatment step in the manufacturing method of high softening point pitch is performed by charging an oxidizing gas into a raw material containing petroleum residue and heating it.
  • the content of quinoline insoluble content is reduced by controlling the size and degree of dispersion of the gas bubbles of the oxidizing gas without using substances that cause process hazards such as peroxide-based compounds.
  • the present invention was completed by focusing on the fact that the high softening point range of the desired pitch can be achieved, and the manufacturing yield of the high softening point pitch can also be increased.
  • the oxidizing gas introduced into the raw material containing petroleum residue has the problem that the oxidation reaction rate becomes slower as the droplet size of the gas increases, and the problem that the oxidation reaction rate becomes slower as the gas droplet size becomes larger, and that the oxidizing gas introduced into the raw material containing petroleum residue oil is
  • the residence time on the raw material solution containing oxalic acid was shortened, and also, if the droplet size of the oxidizing gas was too small, it was confirmed that there was a problem in that the oxidation reactivity increased and the quinoline insoluble component increased.
  • the present invention has devised a method of controlling the droplet size of the oxidizing gas charged in the oxidation heat treatment step.
  • the purpose of the present invention could be achieved by controlling the droplet size of the oxidizing gas by adjusting the ratio of the diameters of the 'reactor' and the 'oxidizing gas charging pipe' of the oxidation heat treatment device that performs the oxidation heat treatment step, which is achieved through oxidation heat treatment. It can be specified as the following condition (1) regarding the device.
  • D1 is the diameter of the oxidation reactor
  • D2 is the diameter of the oil pipe for charging the oxidizing gas.
  • the droplet size and dispersibility of the oxidizing gas can be adjusted by the ratio of the diameter (D1) of the oxidation reactor and the diameter (D2) of the pipe into which the oxidizing gas is charged.
  • D1/D2 can be adjusted from the perspective of solving the above problems and achieving the purpose of the present invention.
  • D1/D2 may be, for example, 40-100, for example, 40-80, or for example, 45-70.
  • the droplet size of the oxidizing gas is related to the area of the pipe, if the value of D1/D2 is less than 40, there may be a problem that occurs when the droplet size of the oxidizing gas is too small, and if it is greater than 100, the droplet size of the oxidizing gas may be small. There may be problems that occur when is too large.
  • the number of oil pipes for charging the oxidizing gas is not limited.
  • it may be single or plural, but the number of oil pipes can be adjusted in consideration of the flow rate.
  • the number of oil pipes can be adjusted in consideration of the flow rate.
  • the number of related pipes may be plural, 1 to 20, or 1 to 10, but is not limited thereto.
  • the softening point of the petroleum-based high softening point pitch produced by the method for producing the petroleum-based high softening point pitch according to the present invention may be, for example, 150 to 300°C, and is preferably 200 to 300°C.
  • the content of quinoline insoluble content (QI) contained in the petroleum-based high softening point pitch produced by the method for producing the petroleum-based high softening point pitch according to the present invention may be, for example, 1% or less, and preferably 0.001 to 1%.
  • QI quinoline insoluble content
  • the production yield of the high softening point pitch can be increased, and specifically, it exhibits a softening point of 200 to 300°C, for example, 20 to 50%, for example, 30 to 50%. It could be manufactured with a high manufacturing yield of %.
  • the present invention is significant in that it is possible to produce petroleum-based high softening point pitch with high yield without including the halogen compounds used conventionally as additives. Meanwhile, the production yield of high softening point pitch is calculated according to the following equation (1).
  • Manufacturing yield (%) (Weight of manufactured high softening point pitch / Weight of input raw material) ⁇ 100
  • the petroleum residue used as the raw material is not particularly limited as long as it is used in the present technical field, but for example, the petroleum residue is pyrolysis fuel oil (PFO), naphtha cracking residue oil. (Naphtha Cracking Bottom Oil, NCB), Ethylene Bottom Oil (EBO), FCC-DO (Fluid Catalytic Cracking-Decant Oil), RFCC-DO (Residue Fluid Catalytic Cracking-Decant Oil), and aromatic extract (Aromatic It may include one or more types selected from the group consisting of Extract, AE).
  • PFO pyrolysis fuel oil
  • NCB Naphtha Cracking Bottom Oil
  • EBO Ethylene Bottom Oil
  • FCC-DO Flud Catalytic Cracking-Decant Oil
  • RFCC-DO Residue Fluid Catalytic Cracking-Decant Oil
  • Aroma Extract Aromatic It may include one or more types selected from the group consisting of Extract, AE).
  • the hydrotreated petroleum residue can be used as a raw material
  • the raw material containing the petroleum residue may also include petroleum residue and hydrotreated petroleum residue.
  • the process temperature of the oxidation heat treatment step (S1) is the temperature of the reactant in the oxidation heat treatment step, and is preferably 250 to 400°C, 300 to 400°C, or 300 to 350°C. If the temperature of the reactants in the oxidation heat treatment process is less than 250°C, the molecular weight of the petroleum residue may not increase sufficiently, which may result in a decrease in the yield of the final product, high softening point pitch. In addition, when the temperature of the reactant of the oxidation heat treatment process exceeds 400°C, the content of quinoline insoluble matter in the reactant of the oxidation heat treatment process may rapidly increase, resulting in a coking phenomenon. In addition, when the petroleum residue is heat-treated under high temperature conditions or oxidation reaction conditions, and excessive polymerization of aromatic compounds occurs, the petroleum residue may be converted into an insoluble material.
  • the process time of the oxidation heat treatment step (S1) may preferably be 1 to 20 hours, 5 to 20 hours, or 10 to 15 hours, but is not necessarily limited thereto. If the process time of the oxidation heat treatment step is less than 1 hour, the oxidation reaction may not sufficiently occur. In addition, if the process performance time of the oxidation heat treatment step exceeds 20 hours, excessive polymerization may occur and the physical properties of the final product, high softening point pitch, may be deteriorated. In particular, if the oxidation reaction proceeds excessively, the oxygen content of the produced high softening point pitch may be high. Accordingly, the performance of the secondary battery may deteriorate when it is later used as a raw material for a secondary battery negative electrode material.
  • the charging flow rate of the oxidizing gas may preferably be 0.01 to 2 L/min, 0.3 to 2 L/min, and 0.5 to 2 L/min relative to 1 kg of petroleum residue oil. It may be L/min, and may be 0.3 to 1 L/min. If the flow rate of the oxidizing gas is less than 0.01 L/min relative to 1 kg of petroleum residue oil, the crosslinking reaction may not sufficiently occur, which may reduce the yield and quality of the product.
  • the oxidizing gas may include one or more types selected from the group consisting of air, oxygen, and ozone.
  • the oxidizing gas may directly use air in the atmosphere.
  • the oxidizing gas since the oxidizing gas can be used by diluting an inert gas, the oxidizing gas may further include an inert gas for dilution.
  • the inert gas for dilution may include one or more types selected from the group consisting of nitrogen and argon.
  • a catalyst in order to increase the softening point of the final product, high softening point pitch, a catalyst can be used under high pressure conditions, and in order to reduce the quinoline insoluble content (QI) content in the high softening point pitch, peroxide is used together with an oxidizing gas.
  • QI quinoline insoluble content
  • the molecular weight of petroleum residue can be increased by the oxidation heat treatment process, and the yield of high softening point pitch, which is the final product, can be improved.
  • high pressure conditions may not be required and a catalyst may not be used, so economical and high-quality petroleum-based high softening point pitch can be produced.
  • a peroxide-based compound may not be used as the oxidation reactor before or while the oxidation heat treatment process is performed.
  • the manufacturing process can be economical and the risk of explosion during the manufacturing process can be prevented.
  • oxidation heat-treated petroleum residue can be produced into petroleum pitch through the oxidation heat treatment step (S1). Therefore, in this specification, 'petroleum-based pitch' may refer to petroleum-based residue oil subjected to oxidation heat treatment in the oxidation heat treatment step (S1).
  • a reduced pressure heat treatment step (S2) may be performed in which the petroleum pitch resulting from the oxidation heat treatment step (S1) is heated under reduced pressure conditions.
  • the reduced pressure heat treatment process may be performed in a reduced pressure heat treatment apparatus.
  • the reduced pressure heat treatment device in which the reduced pressure heat treatment step (S2) is performed includes a sampling device for the reactants to control the rate of increase in softening point of the initial reactants, a device for controlling the amount of oil flowing out of the off gas of the reactor, and a device for controlling the amount of oil flowing out of the reactor. It may include a device for regulating internal pressure.
  • the reduced pressure heat treatment step (S2) the heavy oil of the petroleum pitch can be removed, the softening point can be increased, and the content of toluene insoluble content can be increased to increase the carbonization yield of the pitch. .
  • the petroleum-based pitch is subjected to an atmospheric pressure heat treatment step or a pressure heat treatment step rather than a reduced pressure heat treatment step, removal of heavy oil may be difficult, and the softening point of the pitch may not increase. This may cause problems.
  • the process pressure of the reduced pressure heat treatment step (S2) is preferably 1 to 300 torr, 1 to 100 torr, 1 to 200 torr, 50 to 250 torr, and 80 to 100 torr. It may be 80 to 150 torr, but it is not necessarily limited thereto.
  • the process heat treatment temperature of the reduced pressure heat treatment step (S2) may preferably be 300 to 430°C, 200 to 400°C, or 300 to 350°C. If 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 matter may be reduced, making it difficult to manufacture high-quality, high softening point pitch. In addition, there may be a limit to increasing the softening point of petroleum-based pitch because the heavy oil in the pitch is not sufficiently removed. If the heat treatment temperature of the reduced pressure heat treatment process is higher than 430°C, coking of the petroleum pitch may occur and coke may be formed, and the content of quinoline insoluble matter (QI) may rapidly increase.
  • QI quinoline insoluble matter
  • the process time of the reduced pressure heat treatment step (S2) is preferably 1 to 20 hours, 4 to 20 hours, 5 to 15 hours, or 5 to 12 hours. If the reduced pressure heat treatment process is performed for less than 1 hour, heavy oil may not be sufficiently removed, making it difficult to manufacture pitch with a high softening point. In addition, due to insufficient thermal polymerization reaction time, toluene insoluble matter may not be sufficiently generated, and low-quality, high softening point pitch with low carbonization yield may be produced. If the performance time of the reduced pressure heat treatment process exceeds 20 hours, excessive polymerization may proceed and excessive toluene insoluble matter may be generated, and the operation cost of the process and the manufacturing cost of the product may increase due to the increase in process time. there is.
  • an inert gas or steam may be mixed, and the inert gas may include at least one selected from the group consisting of nitrogen and argon, thereby reducing the heavy weight of the petroleum pitch. Oil can be removed more effectively. In particular, when inert gas or steam is heated and charged, heavy oil can be removed more effectively.
  • the flow rate of the inert gas or steam may be 0.01 to 2.0 L/min relative to 1 kg of petroleum pitch, but is not limited thereto.
  • the reduced pressure heat treatment step (S2) of the present invention is characterized in that no oxidizing gas is charged. If, unlike the present invention, an oxidizing gas is charged in the reduced pressure heat treatment step (S2), there is a problem in that quinoline insoluble matter is rapidly formed due to an oxidation reaction at high temperature.
  • the softening point of the petroleum-based high softening point pitch produced by the method for producing the petroleum-based high softening point pitch according to the present invention may be, for example, 150 to 300°C, and is preferably 200 to 300°C.
  • the content of quinoline insoluble content (QI) contained in the petroleum-based high softening point pitch produced by the method for producing the petroleum-based high softening point pitch according to the present invention may be, for example, 1% or less, and preferably 0.001 to 1%. For this purpose, the production of quinoline insoluble substances can be suppressed.
  • the oxidation heat treatment step can be performed more efficiently by controlling the droplet size or dispersion of the oxidizing gas.
  • the droplet size of the inert gas introduced to remove oil in the reduced pressure heat treatment step can be adjusted, thereby effectively increasing the softening point of the final product, high softening point pitch. It is possible to produce high-quality petroleum-based high softening point pitch with high yield by suppressing the formation of quinoline insoluble substances.
  • the petroleum-based high softening point pitch of the present invention can be used as a raw material for carbon materials or graphite materials, or as a precursor material for carbon materials or graphite materials.
  • petroleum-based high softening point pitch can be used as a precursor material for carbon fiber through a carbonization process and a graphitization process.
  • the petroleum-based high softening point pitch of the present invention can be used as a binder material or coating material for anode materials (e.g., natural graphite anode materials, artificial graphite anode materials, etc.).
  • anode materials e.g., natural graphite anode materials, artificial graphite anode materials, etc.
  • the petroleum-based high softening point pitch can be used as a carbon-based anode material by performing a carbonization process, and it can be used as a precursor material for carbon fiber through a carbonization process and a graphitization process.
  • petroleum-based high softening point pitch manufactured by the method for manufacturing petroleum-based high softening point pitch according to the present invention is used as a raw material for a secondary battery anode material, the performance of the produced secondary battery can be improved.
  • pyrolysis fuel oil (PFO) as petroleum residue is placed in an oxidation reactor with a diameter (D1) of 220 mm, and air is used as the oxidizing gas, and the flow rate is 1.0 L compared to 1 kg of petroleum residue.
  • the oxidation heat treatment reaction was performed by charging at a rate of /min.
  • the diameter (D2) of the oil pipe for charging the oxidizing gas was 1/8 inch, so the ratio of the diameter of the oil pipe to the oxidation reactor (D1/D2) was 69, and the number of oil pipes was 4.
  • the temperature of the reactant in the oxidation heat treatment step was 300°C, and the oxidation heat treatment process was performed for 10 hours.
  • the pressure was reduced to 200 torr, and a reduced pressure heat treatment step was performed at 400°C for 10 hours to prepare a petroleum-based high softening point pitch.
  • the softening point of the produced petroleum-based high softening point pitch was 242°C, the content of quinoline insoluble substances was 0.08%, and the production yield calculated according to equation (1) of the present invention was 28%.
  • pyrolysis fuel oil (PFO) as petroleum residue is placed in an oxidation reactor with a diameter (D1) of 300 mm, and air is used as the oxidizing gas, and the flow rate is 0.5 L compared to 1 kg of petroleum residue.
  • the oxidation heat treatment reaction was performed by charging at a rate of /min.
  • the diameter (D2) of the oil pipe for charging the oxidizing gas was 1/4 inch, so the ratio of the diameter of the oil pipe to the oxidation reactor (D1/D2) was 47, and the number of oil pipes was 8.
  • the temperature of the reactant in the oxidation heat treatment step was 320°C, and the oxidation heat treatment process was performed for 8 hours.
  • the softening point of the produced petroleum-based high softening point pitch was 245°C, the content of quinoline insoluble substances was 0.04%, and the production yield calculated according to equation (1) of the present invention was 30%.
  • pyrolysis fuel oil (PFO) as petroleum residue is placed in an oxidation reactor with a diameter (D1) of 220 mm, and air is used as the oxidizing gas, and the flow rate is 1.0 L compared to 1 kg of petroleum residue.
  • the oxidation heat treatment reaction was performed by charging at a rate of /min.
  • the diameter (D2) of the oil pipe for charging the oxidizing gas was 1/8 inch, so the ratio of the diameter of the oil pipe to the oxidation reactor (D1/D2) was 69, and the number of oil pipes was 8.
  • the temperature of the reactant in the oxidation heat treatment step was 300°C, and the oxidation heat treatment process was performed for 10 hours.
  • the pressure was reduced to 200 torr, and a reduced-pressure heat treatment was performed at 400°C for 10 hours to prepare a petroleum-based high softening point pitch.
  • the softening point of the produced petroleum-based high softening point pitch was 255°C
  • the content of quinoline insoluble substances was 0.03%
  • the production yield calculated according to equation (1) of the present invention was 31%.
  • pyrolysis fuel oil (PFO) as petroleum residue is placed in an oxidation reactor with a diameter (D1) of 220 mm, and air is used as the oxidizing gas, and the flow rate is 1.0 L compared to 1 kg of petroleum residue.
  • the oxidation heat treatment reaction was performed by charging at a rate of /min.
  • the diameter (D2) of the oil pipe for charging the oxidizing gas was 1/4 inch, so the ratio of the diameter of the oil pipe to the oxidation reactor (D1/D2) was 35, and the number of oil pipes was 4.
  • the temperature of the reactant in the oxidation heat treatment step was 300°C, and the oxidation heat treatment process was performed for 10 hours.
  • the pressure was reduced to 200 torr, and a reduced-pressure heat treatment was performed at 400°C for 10 hours to prepare a petroleum-based high softening point pitch.
  • the softening point of the produced petroleum-based high softening point pitch was 185°C, the content of quinoline insoluble material was 0.05%, and the production yield calculated according to equation (1) of the present invention was 18%.
  • pyrolysis fuel oil (PFO) as petroleum residue is placed in an oxidation reactor with a diameter (D1) of 220 mm, and air is used as the oxidizing gas, and the flow rate is 1.0 L compared to 1 kg of petroleum residue.
  • the oxidation heat treatment reaction was performed by charging at a rate of /min.
  • the diameter (D2) of the oil pipe for charging the oxidizing gas was 1/16 inch, so the ratio of the diameter of the oil pipe to the oxidation reactor (D1/D2) was 139, and the number of oil pipes was 4.
  • the temperature of the reactant in the oxidation heat treatment step was 300°C, and the oxidation heat treatment process was performed for 10 hours.
  • the pressure was reduced to 200 torr, and a reduced-pressure heat treatment was performed at 400°C for 10 hours to prepare a petroleum-based high softening point pitch.
  • the softening point of the produced petroleum-based high softening point pitch was 242°C, the content of quinoline insoluble material was 1.5%, and the production yield calculated according to equation (1) of the present invention was 28%.
  • Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Oxidation reactor diameter (D1)/ Ratio of pipe diameter (D2) 69 47 69 35 139 Number of related connections (units) 4 4 8 4 4 Softening point of high softening point pitch (°C) 242 245 255 185 242 High softening point pitch Quinoline insoluble content (%) 0.08 0.04 0.03 0.05 1.5 High softening point pitch Manufacturing yield (%) 28 30 31 18 28
  • the petroleum-based high softening point pitch of Examples 1 to 3 has a high softening point of 200 °C or more, a low quinoline insoluble content of 1% or less, and a high softening point pitch production yield of 25% or more. I was able to confirm that I had it.
  • Comparative Example 1 used the same raw materials as Example 1 except that the ratio of the oxidation reactor diameter (D1) / pipe diameter (D2) was 34, and the same oxidation heat treatment and reduced pressure heat treatment were performed in the same oxidation reactor. High softening point pitch was manufactured under these conditions. It was confirmed that the softening point of the high softening point pitch produced in Comparative Example 1 was not sufficiently increased, and the manufacturing yield was also low.
  • Comparative Example 2 used the same raw materials as Example 1 except that the ratio of the oxidation reactor diameter (D1) / pipe diameter (D2) was 139, and the same oxidation heat treatment and reduced pressure heat treatment operating conditions were used in the same oxidation reactor.
  • High softening point pitch was manufactured. It can be seen that the softening point of the high softening point pitch prepared in Comparative Example 2 was sufficiently increased and the production yield was high, but a high content of quinoline insoluble matter was produced.

Abstract

A method for producing petroleum-based high-softening point pitch of the present invention comprises: an oxidation heat treatment step of introducing an oxidizing gas to a raw material containing petroleum-based residues, followed by heating; and a reduced-pressure heat treatment step of heating the resultant product of the oxidation heat treatment step under reduced-pressure conditions, wherein the oxidation heat treatment step is performed in an oxidation heat treatment apparatus satisfying the following condition (1). Condition (1): 40 ≤ D1/D2 ≤ 100 (where, D1 represents the diameter of an oxidation reactor; and D2 represents the diameter of a flow duct for introducing the oxidizing gas)

Description

석유계 고연화점 피치의 제조방법Manufacturing method of petroleum-based high softening point pitch
본 발명은 석유계 고연화점 피치의 제조방법 및 이에 의해 제조된 고연화점 피치에 관한 것이다. The present invention relates to a method for producing petroleum-based high softening point pitch and the high softening point pitch produced thereby.
고연화점 피치는 탄소섬유, 활성탄, 이차전지 음극재 등 다양한 탄소재 및 흑연재의 원료 혹은 전구체 물질로 사용되고 있으며, 고연화점 피치를 제조하기 위해서 석탄계 또는 석유계 물질을 원료로 사용하여 산화공정 및 열처리 공정을 통해 제조하는 방법이 일반적으로 알려져 있다.High softening point pitch is used as a raw material or precursor material for various carbon materials and graphite materials such as carbon fiber, activated carbon, and secondary battery anode materials. To produce high softening point pitch, coal-based or petroleum-based materials are used as raw materials and undergo an oxidation process and heat treatment. Manufacturing methods through processes are generally known.
고연화점 피치를 이차전지 음극재의 원료로 사용할 시에 고연화점 피치에 포함되어 있는 퀴놀린 불용성 물질, 금속 등의 무기질 불순물, 혹은 질소, 황 등의 이종원자들의 함량이 적을수록 전지의 용량 개선, 수명특성 향상, 출력특성 향상 등에 효과가 좋은 것으로 알려져 있다. 석유계 원료는 퀴놀린 불용분 물질이 사실상 없기 때문에 석유계 물질을 원료로 제조된 고연화점 피치는 석탄계 물질을 원료로 제조된 고연화점 피치에 비해서는 상대적으로 퀴놀린 불용성 물질이 양이 적은 장점이 있다.When using high softening point pitch as a raw material for secondary battery anode materials, the lower the content of quinoline insoluble substances, 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 performance and output characteristics. Since petroleum-based raw materials have virtually no quinoline-insoluble substances, high softening point pitch made from petroleum-based materials has the advantage of having a relatively small amount of quinoline-insoluble substances compared to high softening point pitch made from coal-based materials.
종래의 석유계 원료 혹은 석탄계 원료를 사용하여 고연화점 피치를 제조하는 기술(예컨대, KR1997-0036066A, KR2000-0026341A, KR2014-0090062A, JP1995-194966A 등)은 고연화점 피치의 제조 수율을 높이기 위해서 할로겐 화합물, 퍼옥사이드계 화합물 등 위험한 물질을 사용하는 방법으로 경제적이고 안전한 공정의 구현에 어려움이 있거나, 또는 제조된 고연화점 피치의 퀴놀린 불용분 함량이 높다는 문제점이 있다.Conventional technology for producing high softening point pitch using petroleum-based raw materials or coal-based raw materials (e.g., KR1997-0036066A, KR2000-0026341A, KR2014-0090062A, JP1995-194966A, etc.) uses halogen compounds to increase the production yield of high softening point pitch. , there are difficulties in implementing an economical and safe process by using dangerous substances such as peroxide-based compounds, or there is a problem that the produced high softening point pitch has a high quinoline insoluble content.
또한, 고연화점 피치의 제조 공정에 있어서, 퀴놀린 불용성 물질의 형성을 억제하기 위하여 효과적으로 산화 공정을 수행하는 방법, 고연화점 피치의 연화점을 효과적으로 높이기 위한 방법, 고연화점 피치의 제조 수율을 높이기 위한 방법 등은 제시되어 있지 않아 개발이 필요한 실정이다.In addition, in the manufacturing process of high softening point pitch, a method of effectively performing an oxidation process to suppress the formation of quinoline insoluble substances, a method of effectively increasing the softening point of high softening point pitch, a method of increasing the production yield of high softening point pitch, etc. has not been presented, so development is necessary.
본 발명의 목적은 석유계 잔사유를 포함하는 원료를 사용하여 연화점이 높고, 퀴놀린 불용성 물질의 함량을 현저히 낮추면서도, 제조 수율이 향상된 석유계 고연화점 피치의 제조방법을 제공하는 것이다.The purpose of the present invention is to provide a method for producing petroleum-based high softening point pitch with improved production yield while having a high softening point and significantly lowering the content of quinoline insoluble substances by using raw materials containing petroleum residues.
본 발명의 다른 목적은 우수한 품질의 석유계 고연화점 피치를 경제적이고 안전하게 제조하는 방법을 제공하는 것이다.Another object of the present invention is to provide a method for economically and safely producing high-quality petroleum-based high softening point pitch.
본 발명의 목적은 이상에서 언급한 목적으로 제한되지 않으며, 언급되지 않은 본 발명의 다른 목적 및 장점들은 하기의 설명에 의해서 이해될 수 있고, 본 발명의 실시예에 의해 보다 분명하게 이해될 것이다. 또한, 본 발명의 목적 및 장점들은 특허 청구 범위에 나타낸 수단 및 그 조합에 의해 실현될 수 있음을 쉽게 알 수 있을 것이다.The object of the present invention is not limited to the object mentioned above, and other objects and advantages of the present invention that are not mentioned can be understood through the following description and will be more clearly understood by the examples of the present invention. Additionally, it will be readily apparent that the objects and advantages of the present invention can be realized by the means and combinations thereof indicated in the patent claims.
상기 목적을 달성하기 위하여, 본 발명에 따르면, 석유계 잔사유를 포함하는 원료에 산화성 기체를 장입하여 가열하는 산화 열처리 단계; 및 상기 산화 열처리 단계의 결과물을 감압 조건에서 가열하는 감압 열처리 단계;를 포함하고, 상기 산화 열처리 단계는, 하기 조건 (1)을 만족하는 산화 열처리 장치에서 수행되는 석유계 고연화점 피치의 제조방법을 제공할 수 있다.In order to achieve the above object, according to the present invention, an oxidation heat treatment step of charging an oxidizing gas to a raw material containing petroleum residue and heating it; And a reduced pressure heat treatment step of heating the result of the oxidation heat treatment step under reduced pressure conditions, wherein the oxidation heat treatment step is a method of producing a petroleum-based high softening point pitch performed in an oxidation heat treatment device that satisfies the following condition (1). can be provided.
조건 (1): 40 ≤ D1/D2 ≤ 100Condition (1): 40 ≤ D1/D2 ≤ 100
상기 조건 (1)에서, D1은 산화 반응기의 직경이고, D2는 산화성 기체를 장입하는 유관의 직경임.In the above condition (1), D1 is the diameter of the oxidation reactor, and D2 is the diameter of the oil pipe for charging the oxidizing gas.
본 발명에 따른 석유계 고연화점 피치의 제조 방법은 열처리 단계를 효율적으로 진행할 수 있고, 열처리 단계에서 피치의 연화점을 상승시키기 용이하며, 이와 동시에 제조 공정에서 형성되는 퀴놀린 불용성 물질을 현저히 감소시킬 수 있고, 제조 수율이 높은 고품질의 석유계 고연화점 피치를 제조할 수 있는 이점이 있다.The method for producing petroleum-based high softening point pitch according to the present invention can efficiently proceed with the heat treatment step, easily increase the softening point of the pitch in the heat treatment step, and at the same time significantly reduce quinoline insoluble substances formed in the manufacturing process. , there is an advantage in being able to manufacture high quality petroleum-based high softening point pitch with high manufacturing yield.
또한, 본 발명에 따른 석유계 고연화점 피치의 제조 방법에 따라 제조된 석유계 고연화점 피치는 퀴놀린 불용분 함량이 적어, 고연화점 피치를 포함하는 이차전지용 음극재를 사용하면, 이차전지의 용량, 수명 및 충ㆍ방전 효율이 향상될 수 있다.In addition, the petroleum-based high softening point pitch produced according to the method for producing the petroleum-based high softening point pitch according to the present invention has a low quinoline insoluble content, so when a negative electrode material for a secondary battery containing high softening point pitch is used, the capacity of the secondary battery, Lifespan and charge/discharge efficiency can be improved.
상술한 효과와 더불어 본 발명의 구체적인 효과는 이하 발명을 실시하기 위한 구체적인 사항을 설명하면서 함께 기술한다.In addition to the above-described effects, specific effects of the present invention are described below while explaining specific details for carrying out the invention.
도 1은 본 발명의 일 구현예에 따른 석유계 고연화점 피치를 제조하는 방법을 설명하기 위한 순서도이다.1 is a flowchart illustrating a method of manufacturing petroleum-based high softening point pitch according to an embodiment of the present invention.
도 2는 본 발명의 일 구현예에 따른 석유계 고연화점 피치를 제조하는 방법을 설명하기 위한 개략적인 공정도이다.Figure 2 is a schematic process diagram for explaining a method of manufacturing petroleum-based high softening point pitch according to an embodiment of the present invention.
전술한 목적, 특징 및 이점은 이하에서 상세하게 설명되며, 이에 따라 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자가 본 발명의 기술적 사상을 용이하게 실시할 수 있을 것이다. 본 발명을 설명함에 있어서 본 발명과 관련된 공지 기술에 대한 구체적인 설명이 본 발명의 요지를 불필요하게 흐릴 수 있다고 판단되는 경우에는 상세한 설명을 생략한다. 후술되는 용어들은 본 발명에서의 기능 및 작용을 고려하여 기재된 용어들로서, 각 용어의 의미는 본 명세서 전반에 걸친 내용을 토대로 해석되어야 할 것이다.The above-described objects, features, and advantages will be described in detail below, so that those skilled in the art will be able to easily implement the technical idea of the present invention. In describing the present invention, if it is determined that a detailed description of known technologies related to the present invention may unnecessarily obscure the gist of the present invention, the detailed description will be omitted. The terms described below are terms written in consideration of the function and operation in the present invention, and the meaning of each term should be interpreted based on the content throughout the present specification.
본 명세서에서, 어떤 구성요소가 다른 구성요소 상에 있다고 언급되는 경우에 그것은 다른 구성요소 상에 직접 형성될 수 있거나 또는 그들 사이에 제3의 구성요소가 개재될 수도 있다는 것을 의미한다. 또한, 도면들에 있어서, 구성요소들의 두께는 기술적 내용의 효과적인 설명을 위해 과장된 것이다. 명세서 전체에 걸쳐서 동일한 참조번호로 표시된 부분은 동일한 구성요소들을 나타낸다.In this specification, when an element is referred to as being on another element, it means that it may be formed directly on the other element or that a third element may be interposed between them. Additionally, in the drawings, the thickness of components is exaggerated for effective explanation of technical content. Parts indicated with the same reference numerals throughout the specification indicate the same elements.
본 명세서의 다양한 실시예들에서 제1, 제2, 제3 등의 용어가 다양한 구성요소들을 기술하기 위해서 사용되었지만, 이들 구성요소들이 이 같은 용어들에 의해서 한정되어서는 안 된다. 이들 용어들은 단지 어느 구성요소를 다른 구성요소와 구별시키기 위해서 사용되었을 뿐이다. In various embodiments of the present specification, terms such as first, second, and third are used to describe various components, but these components should not be limited by these terms. These terms are merely used to distinguish one component from another.
본 명세서에서 사용된 용어는 실시예들을 설명하기 위한 것이며 본 발명을 제한하고자 하는 것은 아니다. 본 명세서에서, 단수형은 문구에서 특별히 언급하지 않는 한 복수형도 포함한다. 본 명세서에서 사용되는 '포함한다', '함유한다'등의 기재는 언급된 구성요소는 하나 이상의 다른 구성요소의 존재 또는 추가를 배제하지 않는다.The terminology used herein is for describing embodiments and is not intended to limit the invention. As used herein, singular forms also include plural forms, unless specifically stated otherwise in the context. As used herein, descriptions such as 'includes' and 'contains' do not exclude the presence or addition of one or more other components.
본 명세서에서 '%'는 다른 언급이 없는 한 '중량%'로 해석될 수 있다.In this specification, '%' can be interpreted as 'weight%' unless otherwise specified.
이하에서, 본 발명을 구체적으로 설명한다.Below, the present invention will be described in detail.
본 발명의 일 양태에 따르면, 석유계 고연화점 피치의 제조 방법을 제공할 수 있다.According to one aspect of the present invention, a method for producing petroleum-based high softening point pitch can be provided.
도 1 및 도 2를 참조하면, 본 발명의 일 실시예에 따른 석유계 고연화점 피치의 제조 방법은, 석유계 잔사유를 포함하는 원료에 산화성 기체를 장입하여 가열하는 산화 열처리 단계(S1); 및 상기 산화 열처리 단계의 결과물을 감압 조건에서 가열하는 감압 열처리 단계(S2);를 포함할 수 있다. Referring to Figures 1 and 2, the method for producing a petroleum-based high softening point pitch according to an embodiment of the present invention includes an oxidizing heat treatment step (S1) of charging an oxidizing gas to a raw material containing petroleum residue and heating it; and a reduced pressure heat treatment step (S2) of heating the result of the oxidation heat treatment step under reduced pressure conditions.
< 산화 열처리 단계 (S1) >< Oxidation heat treatment step (S1) >
고연화점 피치의 제조방법 중 산화 열처리 단계에서는 석유계 잔사유를 포함하는 원료에 산화성 기체를 장입하여 가열함으로써 수행된다. 본 발명의 산화 열처리 단계에서는, 이하에서 상세히 설명하는 것처럼 퍼옥사이드계 화합물과 같은 공정 위험성을 초래하는 물질을 사용하지 않고, 산화성 기체의 기체 방울의 크기 및 분산 정도를 조절함으로써 퀴놀린 불용분의 함량을 낮출 수 있고, 목적하는 피치의 고연화점 범위를 달성할 수 있으며, 고연화점 피치의 제조 수율도 높일 수 있음에 착안하여, 본 발명을 완성하였다.The oxidation heat treatment step in the manufacturing method of high softening point pitch is performed by charging an oxidizing gas into a raw material containing petroleum residue and heating it. In the oxidation heat treatment step of the present invention, as described in detail below, the content of quinoline insoluble content is reduced by controlling the size and degree of dispersion of the gas bubbles of the oxidizing gas without using substances that cause process hazards such as peroxide-based compounds. The present invention was completed by focusing on the fact that the high softening point range of the desired pitch can be achieved, and the manufacturing yield of the high softening point pitch can also be increased.
구체적으로, 본 발명자들이 예의 연구한 결과, 석유계 잔사유를 포함하는 원료에 투입되는 산화성 기체는, 기체의 방울 크기가 클수록 산화 반응속도는 느려지는 문제점과, 높은 반응 온도에서 원료로서 석유계 잔사유가 포함된 원료 용액 상에서의 체류시간이 작아지는 문제점이 있었고, 또한, 산화성 기체의 방울 크기가 너무 작을 경우 산화 반응성이 커져 퀴놀린 불융분 성분이 증가하는 문제점이 있음을 확인할 수 있었다.Specifically, as a result of intensive research by the present inventors, the oxidizing gas introduced into the raw material containing petroleum residue has the problem that the oxidation reaction rate becomes slower as the droplet size of the gas increases, and the problem that the oxidation reaction rate becomes slower as the gas droplet size becomes larger, and that the oxidizing gas introduced into the raw material containing petroleum residue oil is There was a problem in that the residence time on the raw material solution containing oxalic acid was shortened, and also, if the droplet size of the oxidizing gas was too small, it was confirmed that there was a problem in that the oxidation reactivity increased and the quinoline insoluble component increased.
또한, 이하에서 자세히 설명되는 감압 열처리 단계에서도 고연화점 피치의 연화점을 높이기 위해서 고비점 물질을 효과적으로 제거해야 하는데, 일반적으로 불활성 기체를 투입하는 방법을 사용한다. 이 때 불활성 기체의 표면적이 클수록 즉, 기체 방울의 크기가 작을수록 연화점 증가가 잘 이루어지는 반면, 유관의 압력이 증가된다는 단점이 있으며, 나아가 표면적이 너무 크면 연화점 증가가 어렵다는 문제점이 있다.In addition, in the reduced pressure heat treatment step described in detail below, high boiling point substances must be effectively removed to increase the softening point of the high softening point pitch, and a method of introducing an inert gas is generally used. At this time, the larger the surface area of the inert gas, that is, the smaller the size of the gas bubble, the easier it is to increase the softening point. However, there is a disadvantage in that the pressure in the oil pipe increases. Furthermore, if the surface area is too large, it is difficult to increase the softening point.
상기 문제점들을 해결하기 위한 수단으로써, 본 발명에서는 산화 열처리 단계에서 장입되는 산화성 기체의 방울 크기를 제어하는 방법을 안출하였다. 즉, 산화 열처리 단계를 수행하는 산화 열처리 장치의 '반응기' 및 '산화성 기체 장입 유관'의 직경의 비율을 조절함으로써 산화성 기체의 방울 크기를 조절하여 본 발명의 목적을 달성할 수 있었으며, 이는 산화 열처리 장치에 관한 하기 조건 (1)로 구체화할 수 있다. As a means to solve the above problems, the present invention has devised a method of controlling the droplet size of the oxidizing gas charged in the oxidation heat treatment step. In other words, the purpose of the present invention could be achieved by controlling the droplet size of the oxidizing gas by adjusting the ratio of the diameters of the 'reactor' and the 'oxidizing gas charging pipe' of the oxidation heat treatment device that performs the oxidation heat treatment step, which is achieved through oxidation heat treatment. It can be specified as the following condition (1) regarding the device.
조건 (1): 40 ≤ D1/D2 ≤ 100 Condition (1): 40 ≤ D1/D2 ≤ 100
상기 조건 (1)에서, D1은 산화 반응기의 직경이고, D2는 산화성 기체를 장입하는 유관의 직경이다.In the above condition (1), D1 is the diameter of the oxidation reactor, and D2 is the diameter of the oil pipe for charging the oxidizing gas.
이와 같이, 산화성 기체의 방울 크기 및 분산성은 산화 반응기의 직경(D1)과 산화성 기체를 장입하는 유관의 직경(D2)의 비율로 조절될 수 있다. 구체적으로, 산화성 기체의 방울 크기가 클수록 산화 반응속도는 느려지고, 용액 상에서의 체류시간이 작아지는 문제점이 있었고, 또한, 산화성 기체의 방울 크기가 너무 작을 경우 산화 반응성이 커져 퀴놀린 불융분 성분이 증가하는 문제점이 있으므로, 상기 문제점들을 해결하여 본 발명의 목적을 달성하기 위한 관점에서, D1/D2를 조절할 수 있다. D1/D2는 예를 들어 40~100일 수 있고, 예를 들어 40~80일 수 있고, 예를 들어 45~70일 수 있다. 산화성 기체의 방울 크기는 유관의 면적과 관계가 있기 때문에, 상기 D1/D2의 값이 40 미만이면 산화성 기체의 방울 크기가 너무 작을 때 발생하는 문제점이 있을 수 있고, 100 초과이면 산화성 기체의 방울 크기가 너무 클 때 발생하는 문제점이 있을 수 있다.In this way, the droplet size and dispersibility of the oxidizing gas can be adjusted by the ratio of the diameter (D1) of the oxidation reactor and the diameter (D2) of the pipe into which the oxidizing gas is charged. Specifically, there was a problem that the larger the droplet size of the oxidizing gas, the slower the oxidation reaction rate and the shorter the residence time in the solution. Additionally, if the droplet size of the oxidizing gas was too small, the oxidation reactivity increased and the quinoline insoluble component increased. Since there is a problem, D1/D2 can be adjusted from the perspective of solving the above problems and achieving the purpose of the present invention. D1/D2 may be, for example, 40-100, for example, 40-80, or for example, 45-70. Since the droplet size of the oxidizing gas is related to the area of the pipe, if the value of D1/D2 is less than 40, there may be a problem that occurs when the droplet size of the oxidizing gas is too small, and if it is greater than 100, the droplet size of the oxidizing gas may be small. There may be problems that occur when is too large.
상기 산화 열처리 장치에 있어서, 산화성 기체를 장입하는 유관의 수는 제한 없으며, 예를 들어 단수 또는 복수일 수 있으나, 유량을 고려하여 유관의 개수를 조절할 수 있다. 예를 들어, 유관의 개수가 많을수록 산화성 기체의 분산성을 높일 수는 있으나, 유량이 적으면서 유관의 개수가 많아지면 일부 유관에는 유량이 흐르지 않을 수도 있는 문제점이 있을 수 있다. 이러한 관점에서, 특별한 제한이 있는 것은 아니지만, 예를 들어, 유관의 수는 복수일 수 있고, 1~20개일 수 있고, 1~10개일 수 있으나, 이에 한정되는 것은 아니다.In the oxidation heat treatment apparatus, the number of oil pipes for charging the oxidizing gas is not limited. For example, it may be single or plural, but the number of oil pipes can be adjusted in consideration of the flow rate. For example, as the number of oil pipes increases, the dispersibility of the oxidizing gas can be improved, but if the flow rate is low and the number of oil pipes increases, there may be a problem in that the flow rate may not flow in some pipes. In this respect, there is no particular limitation, but for example, the number of related pipes may be plural, 1 to 20, or 1 to 10, but is not limited thereto.
본 발명에 따른 석유계 고연화점 피치의 제조방법으로 제조된 석유계 고연화점 피치의 연화점은, 예를 들어 150~300℃일 수 있고, 바람직하게는 200~300℃인 것을 목적으로 한다.The softening point of the petroleum-based high softening point pitch produced by the method for producing the petroleum-based high softening point pitch according to the present invention may be, for example, 150 to 300°C, and is preferably 200 to 300°C.
본 발명에 따른 석유계 고연화점 피치의 제조방법으로 제조된 석유계 고연화점 피치에 포함된 퀴놀린 불용분(QI)의 함량은, 예를 들어 1% 이하일 수 있고, 바람직하게는 0.001~1%인 것을 목적으로 한다.The content of quinoline insoluble content (QI) contained in the petroleum-based high softening point pitch produced by the method for producing the petroleum-based high softening point pitch according to the present invention may be, for example, 1% or less, and preferably 0.001 to 1%. The purpose is to
본 발명의 석유계 고연화점 피치의 제조방법에 따르면, 고연화점 피치의 제조 수율을 높일 수 있으며, 구체적으로는 200~300℃의 연화점을 나타내면서 예를 들어 20~50%, 예를 들어 30~50%의 높은 제조 수율로 제조할 수 있었다. 본 발명에서는 종래에 사용된 할로겐 화합물을 첨가제로서 포함하지 않으면서 석유계 고연화점 피치를 높은 수율로 제조할 수 있다는 점에서 의의가 있다. 한편, 고연화점 피치의 제조 수율은 하기 식 (1)에 따라 계산한다.According to the method for producing a petroleum-based high softening point pitch of the present invention, the production yield of the high softening point pitch can be increased, and specifically, it exhibits a softening point of 200 to 300°C, for example, 20 to 50%, for example, 30 to 50%. It could be manufactured with a high manufacturing yield of %. The present invention is significant in that it is possible to produce petroleum-based high softening point pitch with high yield without including the halogen compounds used conventionally as additives. Meanwhile, the production yield of high softening point pitch is calculated according to the following equation (1).
식 (1) : 제조 수율(%) = (제조된 고연화점 피치의 중량 / 투입되는 원료의 중량) × 100Equation (1): Manufacturing yield (%) = (Weight of manufactured high softening point pitch / Weight of input raw material) × 100
한편, 상기 원료로 사용되는 석유계 잔사유는 본 기술분야에서 사용되는 것이라면 특별히 제한이 없으나, 예를 들어, 상기 석유계 잔사유는, 열분해 연료유 (Pyrolysis Fuel Oil, PFO), 나프타분해 잔사유 (Naphtha Cracking Bottom Oil, NCB), 에틸렌 잔사유 (Ethylene Bottom Oil, EBO), FCC-DO (Fluid Catalytic Cracking-Decant Oil), RFCC-DO (Residue Fluid Catalytic Cracking-Decant Oil), 및 방향족 추출물 (Aromatic Extract, AE)으로 구성된 군에서 선택되는 1종 이상을 포함할 수 있다. Meanwhile, the petroleum residue used as the raw material is not particularly limited as long as it is used in the present technical field, but for example, the petroleum residue is pyrolysis fuel oil (PFO), naphtha cracking residue oil. (Naphtha Cracking Bottom Oil, NCB), Ethylene Bottom Oil (EBO), FCC-DO (Fluid Catalytic Cracking-Decant Oil), RFCC-DO (Residue Fluid Catalytic Cracking-Decant Oil), and aromatic extract (Aromatic It may include one or more types selected from the group consisting of Extract, AE).
또한, 상기 석유계 잔사유를 수소화처리된(hydrotreated)된 것을 원료로서 사용할 수 있으므로, 상기 석유계 잔사유를 포함하는 원료에는, 석유계 잔사유 및 수소화처리된 석유계 잔사유도 포함될 수 있다.In addition, since the hydrotreated petroleum residue can be used as a raw material, the raw material containing the petroleum residue may also include petroleum residue and hydrotreated petroleum residue.
산화 열처리 단계(S1)의 공정 온도는 산화 열처리 단계에서의 반응물의 온도로서, 바람직하게는 250~400℃일 수 있고, 300~400℃일 수 있고, 300~350℃일 수 있다. 산화 열처리 공정의 반응물의 온도가 250℃ 미만인 경우, 상기 석유계 잔사유의 분자량이 충분히 증가하지 않아, 최종 산물인 고연화점 피치의 수율이 저하되는 문제가 발생할 수 있다. 또한, 산화 열처리 공정의 반응물의 온도가 400℃ 초과인 경우, 상기 산화 열처리 공정의 반응물 내의 퀴놀린 불용분의 함량이 급격하게 증가되어, 코킹(coking) 현상이 발생될 수 있다. 또한, 상기 석유계 잔사유를 고온 조건 또는 산화 반응 조건에서 열처리하여, 방향족 화합물들의 과도한 중합 반응이 진행되는 경우, 상기 석유계 잔사유가 불용성 물질로 전환될 수도 있다.The process temperature of the oxidation heat treatment step (S1) is the temperature of the reactant in the oxidation heat treatment step, and is preferably 250 to 400°C, 300 to 400°C, or 300 to 350°C. If the temperature of the reactants in the oxidation heat treatment process is less than 250°C, the molecular weight of the petroleum residue may not increase sufficiently, which may result in a decrease in the yield of the final product, high softening point pitch. In addition, when the temperature of the reactant of the oxidation heat treatment process exceeds 400°C, the content of quinoline insoluble matter in the reactant of the oxidation heat treatment process may rapidly increase, resulting in a coking phenomenon. In addition, when the petroleum residue is heat-treated under high temperature conditions or oxidation reaction conditions, and excessive polymerization of aromatic compounds occurs, the petroleum residue may be converted into an insoluble material.
산화 열처리 단계(S1)의 공정 시간은 바람직하게는 1~20 시간일 수 있고, 5~20 시간일 수 있고, 10~15 시간일 수 있으나, 이에 반드시 한정되는 것은 아니다. 산화 열처리 단계의 공정 시간이 1시간 미만인 경우, 산화 반응이 충분히 일어나지 않을 수 있다. 또한, 산화 열처리 단계의 공정 수행 시간이 20 시간을 초과하는 경우, 과도한 중합반응을 유발하여, 최종 산물인 고연화점 피치의 물성이 변질될 수 있다. 특히, 과도하게 산화 반응이 진행될 경우, 제조된 고연화점 피치의 산소 함량이 높을 수 있다. 이에 따라, 이후 이차전지 음극재의 원료로 사용될 때 이차전지의 성능이 저하될 수 있다. The process time of the oxidation heat treatment step (S1) may preferably be 1 to 20 hours, 5 to 20 hours, or 10 to 15 hours, but is not necessarily limited thereto. If the process time of the oxidation heat treatment step is less than 1 hour, the oxidation reaction may not sufficiently occur. In addition, if the process performance time of the oxidation heat treatment step exceeds 20 hours, excessive polymerization may occur and the physical properties of the final product, high softening point pitch, may be deteriorated. In particular, if the oxidation reaction proceeds excessively, the oxygen content of the produced high softening point pitch may be high. Accordingly, the performance of the secondary battery may deteriorate when it is later used as a raw material for a secondary battery negative electrode material.
산화 열처리 단계(S1)에서, 상기 산화성 기체의 장입 유량은, 바람직하게는 상기 석유계 잔사유 1 kg 대비 0.01~2 L/min일 수 있고, 0.3~2 L/min일 수 있고, 0.5~2 L/min일 수 있고, 0.3~1 L/min일 수 있다. 상기 석유계 잔사유 1 kg 대비 상기 산화성 기체의 유량이 0.01 L/min를 미만일 경우, 가교반응이 충분히 일어나지 않아 제품의 수율 및 품질을 저하시킬 수 있다. 반면, 상기 석유계 잔사유 1 kg 대비 상기 산화성 기체의 유량이 2 L/min를 초과할 경우, 주입되는 산화성 기체 양이 과도하여, 중질성분인 톨루엔 불용분의 함량이 급격하게 증가하고, 퀴놀린 불용분(QI)의 함량도 증가되는 문제가 발생할 수 있다.In the oxidation heat treatment step (S1), the charging flow rate of the oxidizing gas may preferably be 0.01 to 2 L/min, 0.3 to 2 L/min, and 0.5 to 2 L/min relative to 1 kg of petroleum residue oil. It may be L/min, and may be 0.3 to 1 L/min. If the flow rate of the oxidizing gas is less than 0.01 L/min relative to 1 kg of petroleum residue oil, the crosslinking reaction may not sufficiently occur, which may reduce the yield and quality of the product. On the other hand, when the flow rate of the oxidizing gas exceeds 2 L/min relative to 1 kg of petroleum residue, the amount of oxidizing gas injected is excessive, and the content of toluene-insoluble matter, which is a heavy component, rapidly increases, and quinoline-insoluble matter A problem may arise in which the content of QI increases.
산화 열처리 단계(S1)에서, 상기 산화성 기체는, 공기, 산소 및 오존으로 구성된 군에서 선택되는 1종 이상을 포함할 수 있고, 예를 들어, 상기 산화성 기체는 대기 중의 공기를 바로 사용할 수 있다. 또한, 상기 산화성 기체에 불활성 기체를 희석하여 사용할 수 있으므로, 상기 산화성 기체는 희석용 불활성 기체를 더 포함할 수 있다. 상기 희석용 불활성 기체는 질소 및 아르곤으로 구성된 군에서 선택되는 1종 이상을 포함할 수 있다. In the oxidation heat treatment step (S1), the oxidizing gas may include one or more types selected from the group consisting of air, oxygen, and ozone. For example, the oxidizing gas may directly use air in the atmosphere. In addition, since the oxidizing gas can be used by diluting an inert gas, the oxidizing gas may further include an inert gas for dilution. The inert gas for dilution may include one or more types selected from the group consisting of nitrogen and argon.
일반적으로, 최종 산물인 고연화점 피치의 연화점을 증가시키기 위해, 고압 조건 하에서 촉매를 사용할 수 있고, 고연화점 피치 내의 퀴놀린 불용분(QI) 함량을 감소시키기 위해, 산화성 기체와 함께 퍼옥사이드(peroixide)계 화합물을 혼입하여 사용해 왔다. Generally, in order to increase the softening point of the final product, high softening point pitch, a catalyst can be used under high pressure conditions, and in order to reduce the quinoline insoluble content (QI) content in the high softening point pitch, peroxide is used together with an oxidizing gas. System compounds have been mixed and used.
그러나, 고압 조건 하에서 촉매를 사용할 경우, 고가의 고압 용기가 필요할 뿐만 아니라 촉매를 제거하는 별도의 공정이 필요하므로, 고연화점 피치를 생산하는 비용이 증가할 수 있다. However, when using a catalyst under high pressure conditions, not only an expensive high pressure vessel is required but also a separate process to remove the catalyst is required, which may increase the cost of producing high softening point pitch.
또한, 산화성 기체에 퍼옥사이드계 화합물을 추가적으로 혼입할 경우, 퍼옥사이드계 화합물의 높은 반응성에 의해 제조 공정 중 폭발 위험이 있을 수 있고, 퍼옥사이드계 화합물의 비용, 위험물 관리 비용, 및 폐수 처리 비용이 증가할 수 있다. 이에 따라, 대규모의 고연화점 피치를 제조하기 위한 경제성이 저하될 수 있다.In addition, if peroxide-based compounds are additionally mixed into the oxidizing gas, there may be a risk of explosion during the manufacturing process due to the high reactivity of the peroxide-based compounds, and the cost of the peroxide-based compounds, hazardous material management costs, and wastewater treatment costs may increase. It can increase. Accordingly, the economic feasibility of manufacturing large-scale high softening point pitch may be reduced.
본 발명에 따르면, 상기 산화 열처리 공정에 의해 석유계 잔사유의 분자량이 증가될 수 있고, 최종 산물인 고연화점 피치의 수율이 향상될 수 있다. 특히, 상기 산화 열처리 공정에서 고압 조건이 요구되지 않을 수 있고, 촉매를 사용하지 않을 수 있어, 경제적이고 고품질의 석유계 고연화점 피치를 제조할 수 있다.According to the present invention, the molecular weight of petroleum residue can be increased by the oxidation heat treatment process, and the yield of high softening point pitch, which is the final product, can be improved. In particular, in the oxidation heat treatment process, high pressure conditions may not be required and a catalyst may not be used, so economical and high-quality petroleum-based high softening point pitch can be produced.
나아가, 본 발명에 따르면, 산화 열처리 공정이 수행되기 전 또는 산화 열처리 공정이 수행되는 동안, 상기 산화 반응기로 퍼옥사이드계 화합물을 사용하지 않을 수 있다. 이와 같이 퍼옥사이드계 화합물을 사용하지 않음에 따라, 제조 공정은 경제적일 수 있고, 제조 공정 중 폭발 위험이 방지될 수 있다는 이점이 존재한다.Furthermore, according to the present invention, a peroxide-based compound may not be used as the oxidation reactor before or while the oxidation heat treatment process is performed. By not using peroxide-based compounds, the manufacturing process can be economical and the risk of explosion during the manufacturing process can be prevented.
한편, 상기 산화 열처리된 석유계 잔사유는 산화 열처리 단계(S1)에 의해 석유계 피치로 제조될 수 있다. 따라서, 본 명세서에서 '석유계 피치'는 상기 산화 열처리 단계(S1)에 의해 산화 열처리된 석유계 잔사유를 의미할 수 있다.Meanwhile, the oxidation heat-treated petroleum residue can be produced into petroleum pitch through the oxidation heat treatment step (S1). Therefore, in this specification, 'petroleum-based pitch' may refer to petroleum-based residue oil subjected to oxidation heat treatment in the oxidation heat treatment step (S1).
< 감압 열처리 단계(S2) >< Reduced pressure heat treatment step (S2) >
상기 산화 열처리 단계(S1)의 결과물인 석유계 피치를 감압 조건에서 가열하는 감압 열처리 단계(S2)를 수행할 수 있다. 상기 감압 열처리 공정은 감압 열처리 장치 내에서 수행될 수 있다. A reduced pressure heat treatment step (S2) may be performed in which the petroleum pitch resulting from the oxidation heat treatment step (S1) is heated under reduced pressure conditions. The reduced pressure heat treatment process may be performed in a reduced pressure heat treatment apparatus.
감압 열처리 단계(S2)가 수행되는 감압 열처리 장치는, 초기 반응물의 연화점 상승 속도를 제어하기 위해 반응물의 샘플링 장치, 반응기의 오프 가스(Off Gas)로 유출되는 오일의 유출량을 조절하는 장치, 반응기의 내부 압력을 조절하는 장치를 포함할 수 있다.The reduced pressure heat treatment device in which the reduced pressure heat treatment step (S2) is performed includes a sampling device for the reactants to control the rate of increase in softening point of the initial reactants, a device for controlling the amount of oil flowing out of the off gas of the reactor, and a device for controlling the amount of oil flowing out of the reactor. It may include a device for regulating internal pressure.
감압 열처리 단계(S2)에 의해, 상기 석유계 피치의 중질 유분(heavy oil)이 제거될 수 있고, 연화점이 증가될 수 있으며, 톨루엔 불용분의 함량이 증가되어 피치의 탄화 수율이 증가될 수 있다. By the reduced pressure heat treatment step (S2), the heavy oil of the petroleum pitch can be removed, the softening point can be increased, and the content of toluene insoluble content can be increased to increase the carbonization yield of the pitch. .
만일, 본 발명과 달리, 상기 석유계 피치에 대하여 감압 열처리 단계가 아닌, 상압 열처리 단계 또는 가압 열처리 단계를 수행할 경우, 중질 유분(heavy oil)의 제거가 어려울 수 있고, 피치의 연화점의 증가되지 않아 문제점이 발생할 수 있다.If, unlike the present invention, the petroleum-based pitch is subjected to an atmospheric pressure heat treatment step or a pressure heat treatment step rather than a reduced pressure heat treatment step, removal of heavy oil may be difficult, and the softening point of the pitch may not increase. This may cause problems.
감압 열처리 단계(S2)의 공정 압력은, 바람직하게는 1~300 torr일 수 있고, 1~100 torr일 수 있고, 1~200 torr일 수 있고, 50~250 torr일 수 있고, 80~100 torr일 수 있고, 80~150 torr일 수 있으나, 이에 반드시 한정되는 것은 아니다. The process pressure of the reduced pressure heat treatment step (S2) is preferably 1 to 300 torr, 1 to 100 torr, 1 to 200 torr, 50 to 250 torr, and 80 to 100 torr. It may be 80 to 150 torr, but it is not necessarily limited thereto.
감압 열처리 단계(S2)의 공정 열처리 온도는, 바람직하게는 300~430℃일 수 있고, 200~400℃일 수 있고, 300~350℃일 수 있다. 상기 감압 열처리 공정의 열처리 온도가 300℃ 미만인 경우, 중질 유분(heavy oil)의 제거가 어려울 수 있고, 톨루엔 불용분의 생성이 저하되어 고품질의 고연화점 피치의 제조가 어려울 수 있다. 또한, 피치 내의 중질 유분이 충분히 제거되지 않아 석유계 피치의 연화점을 증가시키는데 한계가 있을 수 있다. 상기 감압 열처리 공정의 열처리 온도가 430℃ 초과인 경우, 상기 석유계 피치의 코킹 현상이 발생하여 코크스가 형성될 수 있고, 퀴놀린 불용분(QI)의 함량이 급격하게 증가되는 문제점이 있을 수 있다. The process heat treatment temperature of the reduced pressure heat treatment step (S2) may preferably be 300 to 430°C, 200 to 400°C, or 300 to 350°C. If 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 matter may be reduced, making it difficult to manufacture high-quality, high softening point pitch. In addition, there may be a limit to increasing the softening point of petroleum-based pitch because the heavy oil in the pitch is not sufficiently removed. If the heat treatment temperature of the reduced pressure heat treatment process is higher than 430°C, coking of the petroleum pitch may occur and coke may be formed, and the content of quinoline insoluble matter (QI) may rapidly increase.
감압 열처리 단계(S2)의 공정 시간은, 바람직하게는 1~20시간일 수 있고, 4~20시간일 수 있고, 5~15시간일 수 있고, 5~12시간일 수 있다. 상기 감압 열처리 공정의 수행 시간이 1시간 미만인 경우, 중질 유분이 충분하게 제거되지 않을 수 있어, 고연화점의 피치를 제조하기 어려울 수 있다. 또한, 열중합 반응 시간의 부족으로 톨루엔 불용분이 충분하게 생성되지 않을 수 있고, 탄화 수율이 낮은 저품질의 고연화점 피치가 제조될 수 있다. 상기 감압 열처리 공정의 수행 시간이 20시간을 초과하는 경우, 과도한 중합반응이 진행되어 톨루엔 불용분이 과도하게 생성될 수 있고, 공정 시간의 증가로 인해 공정의 운전 비용 및 제품의 제조 비용이 증가할 수 있다.The process time of the reduced pressure heat treatment step (S2) is preferably 1 to 20 hours, 4 to 20 hours, 5 to 15 hours, or 5 to 12 hours. If the reduced pressure heat treatment process is performed for less than 1 hour, heavy oil may not be sufficiently removed, making it difficult to manufacture pitch with a high softening point. In addition, due to insufficient thermal polymerization reaction time, toluene insoluble matter may not be sufficiently generated, and low-quality, high softening point pitch with low carbonization yield may be produced. If the performance time of the reduced pressure heat treatment process exceeds 20 hours, excessive polymerization may proceed and excessive toluene insoluble matter may be generated, and the operation cost of the process and the manufacturing cost of the product may increase due to the increase in process time. there is.
감압 열처리 단계(S2)에서, 불활성 기체 또는 스팀(steam)을 혼입할 수 있고, 상기 불활성 기체는 질소 및 아르곤으로 구성된 군에서 선택되는 1종 이상을 포함할 수 있으며, 이로써 상기 석유계 피치의 중질 유분이 더욱 효과적으로 제거될 수 있다. 특히, 불활성 기체 또는 스팀을 가열하여 장입할 경우, 중질 유분이 더욱 효과적으로 제거될 수 있다.In the reduced pressure heat treatment step (S2), an inert gas or steam may be mixed, and the inert gas may include at least one selected from the group consisting of nitrogen and argon, thereby reducing the heavy weight of the petroleum pitch. Oil can be removed more effectively. In particular, when inert gas or steam is heated and charged, heavy oil can be removed more effectively.
예를 들어, 상기 불활성 기체 또는 스팀의 유량은 상기 석유계 피치 1 kg 대비 0.01~2.0 L/min일 수 있으나, 이에 한정되는 것은 아니다. For example, the flow rate of the inert gas or steam may be 0.01 to 2.0 L/min relative to 1 kg of petroleum pitch, but is not limited thereto.
본 발명의 감압 열처리 단계(S2)에서는 산화성 기체를 장입하지 않는 것을 특징으로 한다. 만일, 본 발명과는 다르게, 감압 열처리 단계(S2)에서 산화성 기체를 장입할 경우, 고온에서의 산화 반응에 의해 퀴놀린 불용분이 급격하게 형성되는 문제점이 있다.The reduced pressure heat treatment step (S2) of the present invention is characterized in that no oxidizing gas is charged. If, unlike the present invention, an oxidizing gas is charged in the reduced pressure heat treatment step (S2), there is a problem in that quinoline insoluble matter is rapidly formed due to an oxidation reaction at high temperature.
< 고연화점 피치 ><High softening point pitch>
본 발명에 따른 석유계 고연화점 피치의 제조방법으로 제조된 석유계 고연화점 피치의 연화점은, 예를 들어 150~300℃일 수 있고, 바람직하게는 200~300℃인 것을 목적으로 한다.The softening point of the petroleum-based high softening point pitch produced by the method for producing the petroleum-based high softening point pitch according to the present invention may be, for example, 150 to 300°C, and is preferably 200 to 300°C.
본 발명에 따른 석유계 고연화점 피치의 제조방법으로 제조된 석유계 고연화점 피치에 포함된 퀴놀린 불용분(QI)의 함량은, 예를 들어 1% 이하일 수 있고, 바람직하게는 0.001~1%인 것을 목적으로 하여, 퀴놀린 불용성 물질의 생성이 억제될 수 있다.The content of quinoline insoluble content (QI) contained in the petroleum-based high softening point pitch produced by the method for producing the petroleum-based high softening point pitch according to the present invention may be, for example, 1% or less, and preferably 0.001 to 1%. For this purpose, the production of quinoline insoluble substances can be suppressed.
이와 같이, 본 발명에 따르면 산화성 기체의 방울 크기나 분산을 조절함으로써 산화 열처리 단계를 보다 효율적으로 수행할 수 있다. 또한, 산화 열처리 단계를 수행하는 장치를 감압 열처리 단계에 적용하게 되면, 감압 열처리 단계에서 유분을 제거하기 위해 투입되는 불활성 기체의 방울 크기도 조절할 수 있고, 이로써 최종제품인 고연화점 피치의 연화점을 효과적으로 증가시키고, 퀴놀린 불용성 물질의 생성을 억제 등을 시킨 고품질의 석유계 고연화점 피치를 높은 수율로 제조할 수 있다.As such, according to the present invention, the oxidation heat treatment step can be performed more efficiently by controlling the droplet size or dispersion of the oxidizing gas. In addition, when a device that performs the oxidation heat treatment step is applied to the reduced pressure heat treatment step, the droplet size of the inert gas introduced to remove oil in the reduced pressure heat treatment step can be adjusted, thereby effectively increasing the softening point of the final product, high softening point pitch. It is possible to produce high-quality petroleum-based high softening point pitch with high yield by suppressing the formation of quinoline insoluble substances.
본 발명의 석유계 고연화점 피치는 탄소재 또는 흑연재의 원료, 탄소재 또는 흑연재의 전구체 물질로 사용될 수 있다. 예를 들어, 석유계 고연화점 피치에 대하여 탄화 공정 및 흑연화 공정을 통해 탄소 섬유의 전구체 물질로 사용할 수 있다. The petroleum-based high softening point pitch of the present invention can be used as a raw material for carbon materials or graphite materials, or as a precursor material for carbon materials or graphite materials. For example, petroleum-based high softening point pitch can be used as a precursor material for carbon fiber through a carbonization process and a graphitization process.
일 실시예로, 본 발명의 석유계 고연화점 피치는 음극재(예컨대, 천연 흑연 음극재, 인조 흑연 음극재 등)의 바인더 물질 또는 코팅 물질로 사용될 수 있다. In one embodiment, the petroleum-based high softening point pitch of the present invention can be used as a binder material or coating material for anode materials (e.g., natural graphite anode materials, artificial graphite anode materials, etc.).
일 실시예로, 석유계 고연화점 피치에 탄화 공정을 수행하여 탄소계 음극재 물질로 사용될 수 있고, 탄화 공정 및 흑연화 공정을 통해 탄소 섬유의 전구체 물질로 사용될 수 있다. In one embodiment, the petroleum-based high softening point pitch can be used as a carbon-based anode material by performing a carbonization process, and it can be used as a precursor material for carbon fiber through a carbonization process and a graphitization process.
일 실시예로, 본 발명에 따른 석유계 고연화점 피치의 제조방법으로 제조된 석유계 고연화점 피치를 이차전지 음극재의 원료로 사용할 경우, 제작된 이차전지의 성능을 향상시킬 수 있다.As an example, when petroleum-based high softening point pitch manufactured by the method for manufacturing petroleum-based high softening point pitch according to the present invention is used as a raw material for a secondary battery anode material, the performance of the produced secondary battery can be improved.
이하에서는, 본 발명을 실시예에 의해 더욱 상세하게 설명한다. 그러나, 하기의 실시예는 본 발명을 예시하는 것일 뿐, 본 발명의 내용이 하기 실시예에 한정되는 것은 아니다.Below, the present invention will be explained in more detail by way of examples. However, the following examples only illustrate the present invention, and the content of the present invention is not limited to the following examples.
실시예 1Example 1
석유계 잔사유로 열분해연료유(PFO)를 원료로 하여, 산화 열처리 장치에서 산화 열처리 단계를 수행하였다. Using pyrolysis fuel oil (PFO) as a petroleum residue as a raw material, an oxidation heat treatment step was performed in an oxidation heat treatment device.
구체적으로, 산화 열처리 장치에서 직경(D1)이 220 mm인 산화 반응기에 석유계 잔사유로 열분해연료유(PFO)를 넣고, 산화성 기체로는 공기를 사용하여 석유계 잔사유 1kg 대비 유량을 1.0 L/min으로 장입하여 산화 열처리 반응을 실시하였다. Specifically, in the oxidation heat treatment device, pyrolysis fuel oil (PFO) as petroleum residue is placed in an oxidation reactor with a diameter (D1) of 220 mm, and air is used as the oxidizing gas, and the flow rate is 1.0 L compared to 1 kg of petroleum residue. The oxidation heat treatment reaction was performed by charging at a rate of /min.
이 때, 산화성 기체를 장입하는 유관의 직경(D2)은 1/8 inch였으므로, 산화 반응기 대비 유관의 직경의 비(D1/D2)는 69이었고, 유관의 개수는 4개였다. 산화 열처리 단계의 반응물의 온도는 300℃였고, 산화 열처리 공정은 10시간 동안 수행하였다.At this time, the diameter (D2) of the oil pipe for charging the oxidizing gas was 1/8 inch, so the ratio of the diameter of the oil pipe to the oxidation reactor (D1/D2) was 69, and the number of oil pipes was 4. The temperature of the reactant in the oxidation heat treatment step was 300°C, and the oxidation heat treatment process was performed for 10 hours.
이후, 200 torr의 압력으로 감압하였고, 400℃에서 10시간 동안 감압 열처리 단계를 수행하여 석유계 고연화점 피치를 제조하였다. Afterwards, the pressure was reduced to 200 torr, and a reduced pressure heat treatment step was performed at 400°C for 10 hours to prepare a petroleum-based high softening point pitch.
제조된 석유계 고연화점 피치의 연화점은 242℃이었고, 퀴놀린 불용성 물질의 함량은 0.08% 이었으며, 본 발명의 식 (1)에 따라 계산된 제조 수율은 28% 이었다.The softening point of the produced petroleum-based high softening point pitch was 242°C, the content of quinoline insoluble substances was 0.08%, and the production yield calculated according to equation (1) of the present invention was 28%.
실시예 2Example 2
석유계 잔사유로 열분해연료유(PFO)를 원료로 하여, 산화 열처리 장치에서 산화 열처리 단계를 수행하였다. Using pyrolysis fuel oil (PFO) as a petroleum residue as a raw material, an oxidation heat treatment step was performed in an oxidation heat treatment device.
구체적으로, 산화 열처리 장치에서 직경(D1)이 300 mm인 산화 반응기에 석유계 잔사유로 열분해연료유(PFO)를 넣고, 산화성 기체로는 공기를 사용하여 석유계 잔사유 1kg 대비 유량을 0.5 L/min으로 장입하여 산화 열처리 반응을 실시하였다. Specifically, in the oxidation heat treatment device, pyrolysis fuel oil (PFO) as petroleum residue is placed in an oxidation reactor with a diameter (D1) of 300 mm, and air is used as the oxidizing gas, and the flow rate is 0.5 L compared to 1 kg of petroleum residue. The oxidation heat treatment reaction was performed by charging at a rate of /min.
이 때, 산화성 기체를 장입하는 유관의 직경(D2)은 1/4 inch였으므로, 산화 반응기 대비 유관의 직경의 비(D1/D2)는 47이었고, 유관의 개수는 8개였다. 산화 열처리 단계의 반응물의 온도는 320℃였고, 산화 열처리 공정은 8시간 동안 수행하였다.At this time, the diameter (D2) of the oil pipe for charging the oxidizing gas was 1/4 inch, so the ratio of the diameter of the oil pipe to the oxidation reactor (D1/D2) was 47, and the number of oil pipes was 8. The temperature of the reactant in the oxidation heat treatment step was 320°C, and the oxidation heat treatment process was performed for 8 hours.
이후, 150 torr의 압력으로 감압하며, 350℃에서 12시간 동안 감압 열처리하여 석유계 고연화점 피치를 제조하였다. Thereafter, the pressure was reduced to 150 torr, and a reduced-pressure heat treatment was performed at 350°C for 12 hours to prepare a petroleum-based high softening point pitch.
제조된 석유계 고연화점 피치의 연화점은 245℃이었고, 퀴놀린 불용성 물질의 함량은 0.04% 이었으며, 본 발명의 식 (1)에 따라 계산된 제조 수율은 30% 이었다.The softening point of the produced petroleum-based high softening point pitch was 245°C, the content of quinoline insoluble substances was 0.04%, and the production yield calculated according to equation (1) of the present invention was 30%.
실시예 3Example 3
석유계 잔사유로 열분해연료유(PFO)를 원료로 하여, 산화 열처리 장치에서 산화 열처리 단계를 수행하였다. Using pyrolysis fuel oil (PFO) as a petroleum residue as a raw material, an oxidation heat treatment step was performed in an oxidation heat treatment device.
구체적으로, 산화 열처리 장치에서 직경(D1)이 220 mm인 산화 반응기에 석유계 잔사유로 열분해연료유(PFO)를 넣고, 산화성 기체로는 공기를 사용하여 석유계 잔사유 1kg 대비 유량을 1.0 L/min으로 장입하여 산화 열처리 반응을 실시하였다. Specifically, in the oxidation heat treatment device, pyrolysis fuel oil (PFO) as petroleum residue is placed in an oxidation reactor with a diameter (D1) of 220 mm, and air is used as the oxidizing gas, and the flow rate is 1.0 L compared to 1 kg of petroleum residue. The oxidation heat treatment reaction was performed by charging at a rate of /min.
이 때, 산화성 기체를 장입하는 유관의 직경(D2)은 1/8 inch였으므로, 산화 반응기 대비 유관의 직경의 비(D1/D2)는 69이었고, 유관의 개수는 8개였다. 산화 열처리 단계의 반응물의 온도는 300℃였고, 산화 열처리 공정은 10시간 동안 수행하였다.At this time, the diameter (D2) of the oil pipe for charging the oxidizing gas was 1/8 inch, so the ratio of the diameter of the oil pipe to the oxidation reactor (D1/D2) was 69, and the number of oil pipes was 8. The temperature of the reactant in the oxidation heat treatment step was 300°C, and the oxidation heat treatment process was performed for 10 hours.
이후, 200 torr의 압력으로 감압하며, 400℃에서 10시간 동안 감압 열처리하여 석유계 고연화점 피치를 제조하였다. Afterwards, the pressure was reduced to 200 torr, and a reduced-pressure heat treatment was performed at 400°C for 10 hours to prepare a petroleum-based high softening point pitch.
제조된 석유계 고연화점 피치의 연화점은 255℃이었고, 퀴놀린 불용성 물질의 함량은 0.03% 이었으며, 본 발명의 식 (1)에 따라 계산된 제조 수율은 31% 이었다.The softening point of the produced petroleum-based high softening point pitch was 255°C, the content of quinoline insoluble substances was 0.03%, and the production yield calculated according to equation (1) of the present invention was 31%.
비교예 1Comparative Example 1
석유계 잔사유로 열분해연료유(PFO)를 원료로 하여, 산화 열처리 장치에서 산화 열처리 단계를 수행하였다. Using pyrolysis fuel oil (PFO) as a petroleum residue as a raw material, an oxidation heat treatment step was performed in an oxidation heat treatment device.
구체적으로, 산화 열처리 장치에서 직경(D1)이 220 mm인 산화 반응기에 석유계 잔사유로 열분해연료유(PFO)를 넣고, 산화성 기체로는 공기를 사용하여 석유계 잔사유 1kg 대비 유량을 1.0 L/min으로 장입하여 산화 열처리 반응을 실시하였다. Specifically, in the oxidation heat treatment device, pyrolysis fuel oil (PFO) as petroleum residue is placed in an oxidation reactor with a diameter (D1) of 220 mm, and air is used as the oxidizing gas, and the flow rate is 1.0 L compared to 1 kg of petroleum residue. The oxidation heat treatment reaction was performed by charging at a rate of /min.
이 때, 산화성 기체를 장입하는 유관의 직경(D2)은 1/4 inch였으므로, 산화 반응기 대비 유관의 직경의 비(D1/D2)는 35이었고, 유관의 개수는 4개였다. 산화 열처리 단계의 반응물의 온도는 300℃였고, 산화 열처리 공정은 10시간 동안 수행하였다.At this time, the diameter (D2) of the oil pipe for charging the oxidizing gas was 1/4 inch, so the ratio of the diameter of the oil pipe to the oxidation reactor (D1/D2) was 35, and the number of oil pipes was 4. The temperature of the reactant in the oxidation heat treatment step was 300°C, and the oxidation heat treatment process was performed for 10 hours.
이후, 200 torr의 압력으로 감압하며, 400℃에서 10시간 동안 감압 열처리하여 석유계 고연화점 피치를 제조하였다. Afterwards, the pressure was reduced to 200 torr, and a reduced-pressure heat treatment was performed at 400°C for 10 hours to prepare a petroleum-based high softening point pitch.
제조된 석유계 고연화점 피치의 연화점은 185℃이었고, 퀴놀린 불용성 물질의 함량은 0.05% 이었으며, 본 발명의 식 (1)에 따라 계산된 제조 수율은 18% 이었다.The softening point of the produced petroleum-based high softening point pitch was 185°C, the content of quinoline insoluble material was 0.05%, and the production yield calculated according to equation (1) of the present invention was 18%.
비교예 2Comparative Example 2
석유계 잔사유로 열분해연료유(PFO)를 원료로 하여, 산화 열처리 장치에서 산화 열처리 단계를 수행하였다. Using pyrolysis fuel oil (PFO) as a petroleum residue as a raw material, an oxidation heat treatment step was performed in an oxidation heat treatment device.
구체적으로, 산화 열처리 장치에서 직경(D1)이 220 mm인 산화 반응기에 석유계 잔사유로 열분해연료유(PFO)를 넣고, 산화성 기체로는 공기를 사용하여 석유계 잔사유 1kg 대비 유량을 1.0 L/min으로 장입하여 산화 열처리 반응을 실시하였다. Specifically, in the oxidation heat treatment device, pyrolysis fuel oil (PFO) as petroleum residue is placed in an oxidation reactor with a diameter (D1) of 220 mm, and air is used as the oxidizing gas, and the flow rate is 1.0 L compared to 1 kg of petroleum residue. The oxidation heat treatment reaction was performed by charging at a rate of /min.
이 때, 산화성 기체를 장입하는 유관의 직경(D2)은 1/16 inch였으므로, 산화 반응기 대비 유관의 직경의 비(D1/D2)는 139이었고, 유관의 개수는 4개였다. 산화 열처리 단계의 반응물의 온도는 300℃였고, 산화 열처리 공정은 10시간 동안 수행하였다.At this time, the diameter (D2) of the oil pipe for charging the oxidizing gas was 1/16 inch, so the ratio of the diameter of the oil pipe to the oxidation reactor (D1/D2) was 139, and the number of oil pipes was 4. The temperature of the reactant in the oxidation heat treatment step was 300°C, and the oxidation heat treatment process was performed for 10 hours.
이후, 200 torr의 압력으로 감압하며, 400℃에서 10시간 동안 감압 열처리하여 석유계 고연화점 피치를 제조하였다. Afterwards, the pressure was reduced to 200 torr, and a reduced-pressure heat treatment was performed at 400°C for 10 hours to prepare a petroleum-based high softening point pitch.
제조된 석유계 고연화점 피치의 연화점은 242℃이었고, 퀴놀린 불용성 물질의 함량은 1.5%이었으며, 본 발명의 식 (1)에 따라 계산된 제조 수율은 28% 이었다.The softening point of the produced petroleum-based high softening point pitch was 242°C, the content of quinoline insoluble material was 1.5%, and the production yield calculated according to equation (1) of the present invention was 28%.
상기 실시예 1~3 및 비교예 1~2에서의, 산화 반응기 직경(D1)/유관 직경(D2)의 비, 유관의 개수, 및 제조된 석유계 고연화점 피치의 물성을 하기 표 1에 나타내었다.In Examples 1 to 3 and Comparative Examples 1 to 2, the ratio of the oxidation reactor diameter (D1) / oil pipe diameter (D2), the number of oil pipes, and the physical properties of the produced petroleum-based high softening point pitch are shown in Table 1 below. It was.
실시예 1Example 1 실시예 2Example 2 실시예 3Example 3 비교예 1Comparative Example 1 비교예 2Comparative Example 2
산화 반응기 직경(D1)/
유관 직경(D2)의 비Oxidation reactor diameter (D1)/
Ratio of pipe diameter (D2) 		6969 4747 6969 3535 139139
유관 개수 (개)Number of related connections (units) 44 44 88 44 44
고연화점 피치의 연화점 (℃)Softening point of high softening point pitch (℃) 242242 245245 255255 185185 242242
고연화점 피치의
퀴놀린 불용분 함량 (%)High softening point pitch
Quinoline insoluble content (%) 		0.080.08 0.040.04 0.030.03 0.050.05 1.51.5
고연화점 피치의
제조 수율 (%)High softening point pitch
Manufacturing yield (%) 		2828 3030 3131 1818 2828
상기 표 1을 참조하면, 상기 실시예 1 내지 상기 실시예 3의 석유계 고연화점 피치는 200℃ 이상의 높은 연화점, 및 1% 이하의 낮은 퀴놀린 불용분 함량, 25% 이상의 높은 고연화점 피치 제조 수율을 가짐을 확인할 수 있었다.Referring to Table 1, the petroleum-based high softening point pitch of Examples 1 to 3 has a high softening point of 200 ℃ or more, a low quinoline insoluble content of 1% or less, and a high softening point pitch production yield of 25% or more. I was able to confirm that I had it.
반면에, 상기 비교예 1은 산화 반응기 직경(D1)/유관 직경(D2)의 비가 34인 점을 제외하고는 상기 실시예 1과 동일한 원료를 사용하고 동일한 산화 반응기에서 동일한 산화 열처리 및 감압 열처리 운전 조건으로 고연화점 피치를 제조하였다. 비교예 1에서 제조된 고연화점 피치의 연화점이 충분히 상승하지 못하였고, 제조 수율도 낮은 것을 확인할 수 있었다.On the other hand, Comparative Example 1 used the same raw materials as Example 1 except that the ratio of the oxidation reactor diameter (D1) / pipe diameter (D2) was 34, and the same oxidation heat treatment and reduced pressure heat treatment were performed in the same oxidation reactor. High softening point pitch was manufactured under these conditions. It was confirmed that the softening point of the high softening point pitch produced in Comparative Example 1 was not sufficiently increased, and the manufacturing yield was also low.
또한, 상기 비교예 2는 산화 반응기 직경(D1)/유관 직경(D2)의 비가 139인 점을 제외하고는 상기 실시예 1과 동일한 원료를 사용하고 동일한 산화 반응기에서 동일한 산화 열처리 및 감압 열처리 운전 조건으로 고연화점 피치를 제조하였다. 비교예 2에서 제조된 고연화점 피치의 연화점이 충분히 상승하였고, 제조 수율도 높았지만, 퀴놀린 불용분 함량이 높게 생성되었음을 확인할 수 있다.In addition, Comparative Example 2 used the same raw materials as Example 1 except that the ratio of the oxidation reactor diameter (D1) / pipe diameter (D2) was 139, and the same oxidation heat treatment and reduced pressure heat treatment operating conditions were used in the same oxidation reactor. High softening point pitch was manufactured. It can be seen that the softening point of the high softening point pitch prepared in Comparative Example 2 was sufficiently increased and the production yield was high, but a high content of quinoline insoluble matter was produced.
이상 본 명세서의 실시예 및 도면을 참조하여 더욱 상세하게 설명하였으나, 본 명세서는 반드시 이러한 실시예 및 도면에 국한되는 것은 아니며, 본 명세서의 기술사상을 벗어나지 않는 범위 내에서 다양하게 변형 실시될 수 있다. 따라서, 본 명세서에 개시된 실시예는 본 발명의 기술 사상을 한정하기 위한 것이 아니라 설명하기 위한 것이고, 이러한 실시예에 의하여 본 발명의 기술 사상의 범위가 한정되는 것은 아니다. 그러므로, 이상에서 기술한 실시예는 모든 면에서 예시적인 것이며 한정적이 아닌 것으로 이해해야만 한다. 본 명세서 및 본 발명의 보호 범위는 청구범위에 의하여 해석되어야 하며, 그와 동등한 범위 내에 있는 모든 기술 사상은 본 명세서 및 본 발명의 권리범위에 포함되는 것으로 해석되어야 할 것이다.Although this specification has been described in more detail with reference to the embodiments and drawings, the present specification is not necessarily limited to these embodiments and drawings, and various modifications may be made without departing from the technical spirit of the present specification. . Accordingly, the embodiments disclosed in this specification are not intended to limit the technical idea of the present invention, but rather to explain it, and the scope of the technical idea of the present invention is not limited by these examples. Therefore, the embodiments described above should be understood in all respects as illustrative and not restrictive. The scope of protection of this specification and the present invention should be interpreted in accordance with the claims, and all technical ideas within the equivalent scope should be construed as being included in the scope of rights of this specification and the present invention.

Claims (12)

  1. 석유계 고연화점 피치의 제조방법으로서, As a method for producing petroleum-based high softening point pitch,
    석유계 잔사유를 포함하는 원료에 산화성 기체를 장입하여 가열하는 산화 열처리 단계; 및An oxidation heat treatment step of charging an oxidizing gas to a raw material containing petroleum residue and heating it; and
    상기 산화 열처리 단계의 결과물을 감압 조건에서 가열하는 감압 열처리 단계;를 포함하고,A reduced pressure heat treatment step of heating the result of the oxidation heat treatment step under reduced pressure conditions,
    상기 산화 열처리 단계는, 하기 조건 (1)을 만족하는 산화 열처리 장치에서 수행되는 것인,The oxidation heat treatment step is performed in an oxidation heat treatment device that satisfies the following condition (1),
    석유계 고연화점 피치의 제조방법:Manufacturing method of petroleum-based high softening point pitch:
    조건 (1): 40 ≤ D1/D2 ≤ 100Condition (1): 40 ≤ D1/D2 ≤ 100
    상기 조건 (1)에서, D1은 산화 반응기의 직경이고, D2는 산화성 기체를 장입하는 유관의 직경임. In the above condition (1), D1 is the diameter of the oxidation reactor, and D2 is the diameter of the oil pipe for charging the oxidizing gas.
  2. 제1항에 있어서,According to paragraph 1,
    상기 고연화점 피치에 포함된 퀴놀린 불용분(QI) 물질의 함량은 0.001~1%인,The content of quinoline insoluble (QI) material contained in the high softening point pitch is 0.001 to 1%,
    석유계 고연화점 피치의 제조방법.Method for producing petroleum-based high softening point pitch.
  3. 제1항에 있어서,According to paragraph 1,
    하기 식 (1)에 따라 계산되는 고연화점 피치의 제조 수율이 20~50%를 만족하는,The manufacturing yield of high softening point pitch calculated according to the following equation (1) satisfies 20 to 50%,
    석유계 고연화점 피치의 제조방법.Method for producing petroleum-based high softening point pitch.
    식 (1) : 제조 수율(%) = (제조된 고연화점 피치의 중량 / 투입되는 원료의 중량) × 100Equation (1): Manufacturing yield (%) = (Weight of manufactured high softening point pitch / Weight of input raw material) × 100
  4. 제1항에 있어서,According to paragraph 1,
    상기 고연화점 피치는 연화점이 200~300℃인,The high softening point pitch has a softening point of 200 to 300 ° C.
    석유계 고연화점 피치의 제조방법.Method for producing petroleum-based high softening point pitch.
  5. 제1항에 있어서,According to paragraph 1,
    상기 석유계 잔사유는, 열분해 연료유 (Pyrolysis Fuel Oil, PFO), 나프타분해 잔사유 (Naphtha Cracking Bottom Oil, NCB), 에틸렌 잔사유 (Ethylene Bottom Oil, EBO), FCC-DO (Fluid Catalytic Cracking-Decant Oil), RFCC-DO (Residue Fluid Catalytic Cracking-Decant Oil) 및 방향족 추출물 (Aromatic Extract, AE)로 구성된 군에서 선택되는 1종 이상을 포함하는,The petroleum residue oil includes Pyrolysis Fuel Oil (PFO), Naphtha Cracking Bottom Oil (NCB), Ethylene Bottom Oil (EBO), and FCC-DO (Fluid Catalytic Cracking- Containing at least one selected from the group consisting of Decant Oil), RFCC-DO (Residue Fluid Catalytic Cracking-Decant Oil), and aromatic extract (AE),
    석유계 고연화점 피치의 제조방법.Method for producing petroleum-based high softening point pitch.
  6. 제1항에 있어서,According to paragraph 1,
    상기 석유계 잔사유를 포함하는 원료는, 수소화처리된(hydrotreated) 석유계 잔사유를 포함하는,The raw material containing the petroleum residue includes hydrotreated petroleum residue,
    석유계 고연화점 피치의 제조방법.Method for producing petroleum-based high softening point pitch.
  7. 제1항에 있어서,According to paragraph 1,
    상기 산화 열처리 단계의 공정 온도는 250~400℃이고,The process temperature of the oxidation heat treatment step is 250 to 400°C,
    상기 산화 열처리 단계의 공정 시간은 1~20시간이고,The process time of the oxidation heat treatment step is 1 to 20 hours,
    상기 산화성 기체의 장입 유량은 상기 석유계 잔사유 1 kg 대비 0.01~2 L/min인,The charging flow rate of the oxidizing gas is 0.01 to 2 L/min compared to 1 kg of petroleum residue oil,
    석유계 고연화점 피치의 제조방법.Method for producing petroleum-based high softening point pitch.
  8. 제1항에 있어서,According to paragraph 1,
    상기 산화성 기체는, 공기, 산소 및 오존으로 구성된 군에서 선택되는 1종 이상을 포함하는,The oxidizing gas includes at least one selected from the group consisting of air, oxygen, and ozone.
    석유계 고연화점 피치의 제조방법.Method for producing petroleum-based high softening point pitch.
  9. 제8항에 있어서,According to clause 8,
    상기 산화성 기체는 희석용 불활성 기체를 더 포함하며,The oxidizing gas further includes an inert gas for dilution,
    상기 희석용 불활성 기체는 질소 및 아르곤으로 구성된 군에서 선택되는 1종 이상을 포함하는,The inert gas for dilution includes at least one selected from the group consisting of nitrogen and argon,
    석유계 고연화점 피치의 제조방법.Method for producing petroleum-based high softening point pitch.
  10. 제1항에 있어서,According to paragraph 1,
    상기 감압 열처리 단계의 공정 압력은 1~300 torr이고,The process pressure of the reduced pressure heat treatment step is 1 to 300 torr,
    상기 감압 열처리 단계의 공정 열처리 온도는 300~430℃이고,The process heat treatment temperature of the reduced pressure heat treatment step is 300 to 430°C,
    상기 감압 열처리 단계의 공정 시간은 4~20시간인,The process time of the reduced pressure heat treatment step is 4 to 20 hours,
    석유계 고연화점 피치의 제조방법.Method for producing petroleum-based high softening point pitch.
  11. 제1항에 있어서,According to paragraph 1,
    상기 감압 열처리 단계 수행시 불활성 기체를 혼입하고,When performing the reduced pressure heat treatment step, an inert gas is mixed,
    상기 불활성 기체는 질소 및 아르곤으로 구성된 군에서 선택되는 1종 이상을 포함하는,The inert gas includes at least one selected from the group consisting of nitrogen and argon,
    석유계 고연화점 피치의 제조방법.Method for producing petroleum-based high softening point pitch.
  12. 제1항 내지 제11항 중 어느 한 항에 따른 석유계 고연화점 피치의 제조방법에 따라 제조되는 석유계 고연화점 피치.Petroleum-based high softening point pitch manufactured according to the method for producing the petroleum-based high softening point pitch according to any one of claims 1 to 11.
PCT/KR2023/010870 2022-08-11 2023-07-26 Method for producing petroleum-based high-softening point pitch WO2024034929A1 (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017524746A (en) * 2015-05-19 2017-08-31 ユソン テレコム カンパニー、リミテッド High softening point pitch manufacturing method and high softening point pitch manufactured by this method
KR20180040807A (en) * 2016-10-13 2018-04-23 인하대학교 산학협력단 Manufacturing method of high purity pitch from fluidized catalytic cracking decant oil
KR20180051078A (en) * 2016-11-08 2018-05-16 한국화학연구원 A method of preparing isotropic pitch having high-softening point and preparing of carbon fiber containing the pitch
KR20210012074A (en) * 2019-07-23 2021-02-03 오씨아이 주식회사 The manufacturing method for petroleum based high softning point pitch
KR20220105211A (en) * 2021-01-18 2022-07-27 오씨아이 주식회사 The manufacturing method for petroleum-based high softening point pitch

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017524746A (en) * 2015-05-19 2017-08-31 ユソン テレコム カンパニー、リミテッド High softening point pitch manufacturing method and high softening point pitch manufactured by this method
KR20180040807A (en) * 2016-10-13 2018-04-23 인하대학교 산학협력단 Manufacturing method of high purity pitch from fluidized catalytic cracking decant oil
KR20180051078A (en) * 2016-11-08 2018-05-16 한국화학연구원 A method of preparing isotropic pitch having high-softening point and preparing of carbon fiber containing the pitch
KR20210012074A (en) * 2019-07-23 2021-02-03 오씨아이 주식회사 The manufacturing method for petroleum based high softning point pitch
KR20220105211A (en) * 2021-01-18 2022-07-27 오씨아이 주식회사 The manufacturing method for petroleum-based high softening point pitch

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