Preparing method of blended binder pitch, and binder pitch prepared thereby

Abstract

The present invention relates to a preparing method of a blended binder pitch and, more specifically, to: a method and a blended binder pitch prepared thereby, the method using petroleum pitch, thereby enabling a blended binder pitch to be efficiently and economically prepared with high process controllability, the blended binder pitch being a product with physical properties most similar to those of commercially used coal tar binder pitch so as to replace same.

Description

Method for manufacturing mixed binder pitch and binder pitch manufactured thereby

[0001] The present invention relates to a method for manufacturing a mixed binder pitch, and more specifically, to a method for manufacturing a mixed binder pitch using petroleum pitch, which has properties most similar to that of a commercially used coal tar binder pitch, efficiently and economically with high process controllability, and a mixed binder pitch manufactured thereby.

[0002] Coal tar pitch derived from coal tar, which has a high carbonization yield and binding strength with coke, etc., is mostly used as a binder pitch with a softening point ("SP") of 130℃ or lower, used for various carbon electrodes, graphite molded bodies, refractory brick binders, etc. for aluminum smelting or steelmaking in electric furnaces in steel mills.

[0003] Coal tar pitch, which is required as a binder pitch, has characteristics such as a high coking value (CV), a certain level of quinoline insoluble (QI) and beta-resin content, high wettability for coke, appropriate viscosity, and long-term storage stability, so it is not easy to replace it with other raw materials.

[0004] Coal tar pitch, which has properties suitable as a binder due to its high aromaticity, has seen its production gradually decline recently due to environmental concerns such as carbon neutrality. For example, if steel mills switch to hydrogen reduction ironmaking, coke will no longer be needed for iron production, and the amount of coal tar produced as a byproduct of coke production will also gradually decrease. Furthermore, coal tar itself contains a high content of polycyclic aromatic hydrocarbons (PAHs), which are carcinogenic, and thus, numerous efforts have been made to replace them.

[0005] Petroleum pitch is being studied extensively as an alternative to coal tar pitch, and in fact, petroleum pitch is being used as a small substitute for coal tar pitch. However, petroleum pitch manufactured only from petroleum residue oil has lower aromaticity than coal tar pitch, and thus has problems such as low quinoline insolubles, beta-resin and carbonization yield, and wettability to coke, so its use as a binder through mixing with coke, etc. is limited.

[0006] Accordingly, blended pitch, which is made by mixing coal tar pitch and petroleum pitch, is being studied as an alternative to replace the coal tar that is becoming scarce. However, it requires complex equipment and manufacturing facilities, and thus the manufacturing cost is high, so only a very small number of cases have actually been applied to commercialization and mass production, and there are still limitations.

[0007] Specifically, as a result of reviewing the known technologies for manufacturing conventional mixed pitches, US 5746906 A ("Prior Patent Document 1") discloses a method for manufacturing a coal tar pitch having a softening point of 130 to 175°C and then mixing it with a petroleum-based pitch having a softening point of 75 to 85°C, thereby producing a binder pitch having properties such as a softening point, a quinoline insoluble content, and a carbonization yield that are suitable for the properties of a commercially available binder pitch. The method increases the softening point by excessively removing heavy oils in the coal tar pitch under high temperature and high vacuum and then increasing the softening point, thereby increasing the quinoline insoluble (QI) content and the carbonization yield (CV) of the coal tar pitch. By mixing the coal tar pitch manufactured in this way with a petroleum-based pitch having a low softening point (SP), quinoline insoluble (QI), and carbonization yield (CV), a pitch within a commercially usable softening point range is manufactured. Petroleum pitch has a low aromatic content, which results in low quinoline insolubles (QI) and carbonization yield (CV). To overcome this, the above-described manufacturing method is disclosed. However, in order to produce coal tar pitch with a softening point of 130 to 175°C, as in Prior Patent Document 1, a harsh and energy-intensive manufacturing process, such as high temperature and high vacuum, is required. In addition, the pitch manufactured in this way has a fatal problem in that its viscosity is high and the probability of coking increases, which increases the possibility of blocking the heater or pipes of the manufacturing equipment and halting production. In the case of the physical properties of the binder pitch manufactured by the method of Prior Patent Document 1, such as carbonization yield (CV) and quinoline insolubles (QI) can be supplemented by coal tar pitch with a high softening point, but there are limitations such as a high probability of excessive mesophase formation, which results in insufficient wettability for coke. In addition, since the softening point of petroleum pitch is low, decomposition occurs when stored at high temperatures, reducing long-term storage stability. In addition, when applied as an actual binder, a large amount of volatile components are emitted during the product production process, which may cause problems when manufacturing with carbon materials.

[0008] KR 10-1977572 B1 ("Prior Patent Document 2") discloses a method for increasing the production yield of pitch by mixing a certain amount of coal tar to solve the problem of too low pitch production yield when producing pitch using petroleum-based raw materials. In the case of the pitch manufactured by the above method, the coal tar content is mixed at a maximum of 25 parts by weight per 100 parts by weight of pitch for carbon material precursors. Therefore, the final manufactured pitch is manufactured to be more physically affected by the properties of the petroleum-based raw material contained in greater quantities. Accordingly, there is a limitation in that it is still difficult to satisfy the required properties such as quinoline insolubles (QI), beta-resin, carbonization yield, and wettability to coke. In addition, if the raw materials are simply mixed and heat-treated without any processing as in Prior Patent Document 2, the temperatures at which coal tar and the petroleum-based raw material become pitch are different, making it difficult to control the properties of the final manufactured pitch. Furthermore, the lack of any proposed treatment for byproducts like oil makes this method difficult to implement in practice. For example, when processing coal tar, each component is separated and refined based on boiling point. However, if coal tar is mixed with a petroleum-based raw material, which is a different raw material from coal tar, and then distilled, the resulting product contains other substances with the same boiling point, requiring a separate refining process. This significantly reduces process efficiency and economic feasibility.

[0009] US 4176043 A ("Prior Patent Document 3") discloses a method for manufacturing binder pitch by mixing petroleum-based raw materials and coal tar-based raw materials and then using air, a dehydrogenating agent such as chlorine or sulfur at a high temperature to increase the softening point. Although the manufacturing method of Prior Patent Document 3 is effective in increasing the softening point, the polymerization method using a dehydrogenating agent has the limitation that it does not help increase the carbonization yield compared to the method of increasing the carbonization yield by heat treatment of coal tar-based raw materials. In addition, since the polymerization conditions of petroleum-based raw materials and coal tar-based raw materials are different, the method of using a dehydrogenating agent after mixing has difficulties in controlling product quality. In addition, there is a problem that the softening point of any one of the mixed raw materials increases rapidly, which raises concerns about clogging of the piping of the manufacturing device or coking, and significantly reduces process efficiency and controllability.

[0010] Therefore, it is still necessary to develop a method for manufacturing binder pitch that can secure the properties required for a commercial product, such as an appropriate softening point and viscosity, a high carbon yield (CV), an appropriate quinoline insoluble (QI) content and beta-resin content, wettability to coke, content of heterogeneous elements such as nitrogen and sulfur, and mesophase content, while also having excellent process efficiency and controllability.

[0011] [List of Prior Patent Literature]

[0012] Prior patent document 1: US 5746906 A

[0013] Prior patent document 2: KR 10-1977572 B1

[0014] Prior patent document 3: US 4176043 A

[0015] The purpose of the present invention is to provide a method for producing a mixed binder pitch that can be used as a binder for carbon products and a binder pitch having excellent quality and storage stability produced by the method.

[0016] Specifically, the present invention relates to a method for manufacturing blended pitch, which can be used as a binder pitch by mixing petroleum-based pitch, as a substitute for coal tar pitch, which is currently used as a binder pitch but whose production volume is decreasing.

[0017] As described above, there are various problems such as low reproducibility of the process, low carbonization yield in terms of the quality of the manufactured binder pitch, quinoline insoluble matter, beta-resin content, and high mesophase content, resulting in low wettability to coke, which are limitations and problems of the existing mixed pitch manufacturing method.

[0018] Accordingly, in order to solve this problem, the present invention provides a method for manufacturing a mixed pitch as a binder pitch efficiently, economically, and with high controllability, which can satisfy the manufacturing process conditions required for mass production and commercialization and the desired physical properties of the manufactured mixed pitch, and at the same time, can maintain the quality even during transport and storage by ensuring long-term storage stability of the manufactured mixed pitch.

[0019] The purpose of the present invention is not limited to the aforementioned purposes, and other unmentioned purposes and advantages of the present invention can be understood through the following description and will be more clearly understood through the embodiments of the present invention. Furthermore, it will be readily apparent that the purposes and advantages of the present invention can be realized by the means and combinations thereof set forth in the claims.

[0020] In order to achieve the above purpose, according to the first aspect of the present invention,

[0021] (S1) A step of producing a residue oil bottom having a softening point of 30°C to 80°C by distilling a petroleum residue having an aromatic index (fa) of 0.6 or more and a sulfur content of 1.5 wt% or less;

[0022] (S2) A step of manufacturing an oxidized petroleum pitch having a softening point of 80°C to 130°C by oxidizing and heat-treating the residual oil of the S1 step;

[0023] (S3) A step of producing a medium-temperature coal tar pitch having a softening point of 60°C to 110°C by distilling coal tar;

[0024] (S4) a step of mixing the oxidized petroleum pitch of the S2 step and the medium-temperature coal tar pitch of the S3 step; and

[0025] (S5) a step of heat-treating the mixture of the above step S4 to obtain a mixed binder pitch;

[0026] The above mixed binder pitch has a softening point of 100°C to 130°C, a quinoline insoluble (QI) content of 4 wt% or more, a beta-resin content of 15 wt% or more, a carbonization yield (CV) of 52 wt% or more, a mesophase content of 2 vol% or less, a sulfur content of 1 wt% or less, and a wettability measurement factor (△P) for coke measured according to the following measurement method 1 of 10°C or less.

[0027] A method for manufacturing a mixed binder pitch can be provided.

[0028] [Measurement method 1] Place the mixed binder pitch on a calcined coke bed, and measure the contact angle while increasing the temperature from 20℃, and plot the y-axis with the contact angle (°) and the x-axis with the temperature (℃) to create a graph, and then set the temperature point on the x-axis where the tangent to the inflection point of the graph intersects as P1, and the temperature point where the contact angle (y) becomes 0 (°) as P2, and then calculate P2-P1 as △P (℃).

[0029] The above petroleum residue is at least one selected from pyrolysis fuel oil (PFO), naphtha cracking bottom oil (NCB), ethylene bottom oil (EBO), fluid catalytic cracking decant oil (FCC-DO), residue fluid catalytic cracking decant oil (RFCC-DO), and aromatic extract (AE), and the petroleum residue may or may not have been hydrogenated.

[0030] The above S1 step can produce residual oil batam by removing light oil and heavy oil by distillation in a continuous or batch distillation device under pressure conditions of 760 torr or less and temperature conditions of 250°C to 420°C.

[0031] The oxidation heat treatment of the above S2 step can be performed by mixing an oxidizing gas containing at least one of air, oxygen, and ozone into the residual oil.

[0032] The above oxidizing gas may be diluted with one or more inert gases selected from nitrogen and argon.

[0033] An oxidizing gas is mixed in a flow rate of 50 mL / min to 2.0 L / min for 1 kg of the above residual oil batam, and the oxidation heat treatment can be performed in a continuous or batch reactor at a temperature of 250°C to 400°C for a time of 1 hour to 15 hours.

[0034] In the above S3 step, the coal tar is a low-boiling-point substance including moisture and aromatic components (BTX) removed.

[0035] In the above S3 step, a reforming reaction is performed on coal tar from which the low-boiling-point material has been removed in a continuous or batch distillation unit under pressure conditions of 800 torr or less and temperature conditions of 250°C to 420°C while removing light oil and heavy oil, thereby producing a medium-temperature coal tar pitch.

[0036] In the above step S4, the medium-temperature coal tar pitch can be mixed in an amount of 50 to 90 wt% and the oxidized petroleum pitch can be mixed in an amount of 50 to 10 wt% based on a total weight of 100 wt% of the medium-temperature coal tar pitch and the oxidized petroleum pitch.

[0037] The heat treatment of the above S5 step can be performed by performing a reforming reaction by heat treatment for 3 hours or more and 15 hours or less in a continuous or batch heat treatment device under pressure conditions of 760 torr or less and temperature conditions of 280°C to 420°C.

[0038] In the heat treatment of the above S5 step, blowing of one or more of steam, nitrogen, and argon can be performed simultaneously to remove heavy oil.

[0039] The above-mentioned manufactured mixed binder pitch can exhibit long-term storage stability with a softening point change of 10°C or less compared to the storage time when stored for 15 days or more in a closed system at a temperature of 230°C.

[0040] According to a second aspect of the present invention, a mixed binder pitch manufactured by a method for manufacturing a mixed binder pitch according to the first aspect of the present invention can be provided.

[0041]

[0042] The present invention can provide a method for producing a mixed binder pitch mixed with petroleum pitch that can replace conventional coal tar binder pitch, and a mixed binder pitch produced thereby.

[0043] The mixed pitch manufactured by the method for manufacturing the binder pitch of the present invention is most similar to coal tar binder pitch in terms of softening point, quinoline insoluble (QI) content, beta-resin content, high carbonization yield, low mesophase content, wettability with coke, long-term storage stability, etc., and thus can exhibit excellent characteristics as a binder pitch.

[0044] In addition, the method for manufacturing a binder pitch of the present invention has almost no possibility of causing process manufacturing problems such as excessive coking or pipe clogging commercially, and has excellent process controllability as the manufacturing process does not cause abnormal operation, and can present a method for manufacturing a mixed pitch that is more efficient and economical than the conventional method.

[0045] In addition to the effects described above, specific effects of the present invention are described below while explaining specific details for carrying out the invention.

[0046] FIG. 1 is a flowchart schematically illustrating a method for manufacturing a binder pitch according to one embodiment of the present invention.

[0047] Figure 2 schematically illustrates a method for measuring a contact angle (θ(°)) in the present invention.

[0048] Figure 3 is an example graph illustrating a method for confirming the wettability of a pitch in the present invention.

[0049] The aforementioned purposes, features, and advantages are described in detail below, so that those skilled in the art can easily practice the technical concepts of the present invention. In describing the present invention, detailed descriptions of known technologies related to the present invention will be omitted if they are deemed to unnecessarily obscure the gist of the present invention. The terms described below are terms that were described in consideration of their functions and actions in the present invention, and the meaning of each term should be interpreted based on the contents throughout this specification.

[0050] In this specification, when a component is referred to as being on another component, it means that it can be formed directly on the other component, or a third component may be interposed between them. Furthermore, in the drawings, the thicknesses of the components are exaggerated for the sake of clarity. Parts designated by the same reference numerals throughout the specification represent the same components.

[0051] The terminology used herein is for the purpose of describing embodiments and is not intended to limit the present invention. In this specification, singular forms also include plural forms, unless specifically stated otherwise. The terms "comprises," "includes," and the like, used herein, do not exclude the presence or addition of one or more other components.

[0052] In this specification, quinoline insolubles (QI) refer to solid particles that are insoluble in quinoline solvents. The measurement method for quinoline insolubles is based on ASTM D2318.

[0053] In this specification, toluene insoluble (TI) refers to solid particles that are insoluble in toluene solvent. The measurement method for toluene insoluble is based on the ISO 6376 method.

[0054] In this specification, β-resin means the remaining substance after subtracting the amount of quinoline insoluble from the amount of toluene insoluble (TI).

[0055] In this specification, carbon yield refers to 'Coking Value (CV)', and the method for measuring carbon yield is based on the ASTM D4715 method.

[0056] In this specification, the aromaticity index refers to Aromaticity (fa) and is measured according to the Brown-Ladner method.

[0057] In this specification, mesophase refers to an optically anisotropic liquid crystal carbon phase, measured according to the ASTM D4616 method.

[0058] In this specification, residue oil bottom refers to a residual oil raw material having a softening point of 30°C or higher, obtained by further removing heavy oil and middle oil from residual oil that is almost in the form of oil.

[0059] In this specification, wettability measurement refers to Light Metal, 2002, p. 525, and if the wettability measurement factor (△P) measured according to the following measurement method 1 is 10℃ or lower, the wettability is judged to be excellent.

[0060] [Measurement method 1] Place the mixed binder pitch on a calcined coke bed, and measure the contact angle while increasing the temperature from 20℃, and plot the y-axis with the contact angle (°) and the x-axis with the temperature (℃) to create a graph. Then, the temperature point on the x-axis where the tangent to the inflection point of the graph intersects is set as P1, and the temperature point where the contact angle (y) becomes 0 (°) is set as P2, and then P2-P1 is calculated as △P.

[0061] The present invention will be described in more detail with reference to FIGS. 2 and 3. As shown in FIG. 2, the pitch to be measured is placed on a calcined coke bed and the contact angle (°) is measured. The contact angle is measured while gradually increasing the temperature from 20°C, and the y-axis is plotted with the contact angle (°) and the x-axis with the temperature (°C), and this is represented in a graph as shown in FIG. 3.

[0062] P1 in Fig. 3 refers to the point where the tangent to the inflection point of the curve in the graph intersects the x-axis, and P2 refers to the temperature at which the pitch completely passes through the calcined coke bed (the temperature when the contact angle becomes 0°).

[0063] The calcined coke bed is a type of plate-shaped product manufactured using general petroleum coke or petroleum coke, and since the contact angle of the calcined coke bed itself is 0°, the pitch completely passing through the calcined coke bed means that no pitch remains on the calcined coke bed and is absorbed, and thus the contact angle is measured as 0°. The measured P2-P1 is defined as ΔP, and when ΔP is 10°C or less, the wettability for coke is judged to be appropriate, and therefore ΔP is used as a factor for judging the wettability for coke.

[0064] The “long-term storage stability” described in this specification is determined by checking the change in physical properties such as softening point when the pitch is stored in an autoclave container at 230℃, atmospheric pressure, and stored for 3 weeks.

[0065] Carbon products in which the binder of this specification is used include, but are not limited to, various carbon electrodes, graphite molded bodies, refractory bricks, etc. for aluminum smelting, steelmaking in electric furnaces at steel mills, etc.

[0066] The general properties of coal tar pitch, a binder pitch for aluminum smelters commercially produced in this technical field, are as shown in Table 1 below.

[0067] Item Content Softening Point 100℃ to 130℃ Quinoline Insoluble ≥ 4.0 wt% β-resin ≥ 15.0 wt% Coking Value ≥ 52.0 wt% Mesophase ≤ 2.0 vol% Wettability (ΔP) ≤ 10℃ Sulfur Content ≤ 1.0 wt%

[0068]

[0069] Hereinafter, the present invention will be described in detail.

[0070] Referring to FIG. 1, according to one aspect of the present invention, a method for manufacturing a mixed binder pitch including the following steps (S1) to (S5) can be provided.

[0071] (S1) A step of producing a residue oil bottom having a softening point of 30°C to 80°C by distilling a petroleum residue having an aromatic index (fa) of 0.6 or more and a sulfur content of 1.5 wt% or less;

[0072] (S2) A step of manufacturing an oxidized petroleum pitch having a softening point of 80°C to 130°C by oxidizing and heat-treating the residual oil of the S1 step;

[0073] (S3) A step of producing a medium-temperature coal tar pitch having a softening point of 60°C to 110°C by distilling coal tar;

[0074] (S4) a step of mixing the oxidized petroleum pitch of the S2 step and the medium-temperature coal tar pitch of the S3 step; and

[0075] (S5) A step of heat-treating the mixture of step S4 to obtain a mixed binder pitch.

[0076] The mixed binder pitch manufactured according to one aspect of the present invention can satisfy all of the following characteristics: a softening point of 100°C to 130°C, a quinoline insoluble (QI) content of 4 wt% or more, a beta-resin content of 15 wt% or more, a carbonization yield (CV) of 52 wt% or more, a mesophase content of 2 vol% or less, a sulfur content of 1 wt% or less, and a wettability measurement factor (△P) for coke measured according to the following measurement method 1 of 10°C or less.

[0077] According to one embodiment of the present invention, the manufactured mixed binder pitch can exhibit long-term storage stability in which the softening point change is 10°C or less compared to the storage time when stored for 15 days or more in a closed system at a temperature of 230°C.

[0078] Because the chemical and physical properties of coal tar and petroleum residues produced under different process conditions vary, careful consideration must be given to the selection of raw materials for use as binders. To produce the binder pitch targeted by the present invention, the selection and processing of the petroleum residues used as raw materials are crucial.

[0079] From this point of view, according to one embodiment of the present invention, the petroleum residue may be at least one selected from pyrolysis fuel oil (PFO), naphtha cracking bottom oil (NCB), ethylene bottom oil (EBO), fluid catalytic cracking decant oil (FCC-DO), residue fluid catalytic cracking decant oil (RFCC-DO), and aromatic extract (AE), and the petroleum residue may or may not have been hydrogenated.

[0080] In addition, it is important to select the petroleum residue as a raw material having an aromatic index (fa) of 0.6 or more and a sulfur content of 1.5 wt% or less. If the aromatic index of the petroleum residue raw material is less than 0.6, thermal polymerization does not occur well, making it difficult to form pitch, which may reduce the yield. In addition, if the sulfur content of the petroleum residue raw material exceeds 1.5 wt%, the sulfur component of the raw material remains in the final binder pitch, which may lower the quality of the binder pitch, and may cause environmental pollution and adversely affect workers and the manufacturing environment during the manufacturing process.

[0081] According to one embodiment of the present invention, the step S1 may be to remove light oil and heavy oil by distillation in a continuous or batch distillation unit under pressure conditions of 760 torr or less and temperature conditions of 250°C to 420°C to produce residual oil batam having a softening point of 30°C to 80°C. If the softening point of the produced residual oil batam is lower than 30°C, a longer reaction time is required in the subsequent process, which reduces the efficiency of the process, and if the softening point is higher than 80°C, there is a problem in that an excessive amount of oil is removed, which lowers the final yield. In addition, if the temperature condition of the distillation is lower than 250°C, oil removal may not be performed well, and if it is higher than 420°C, coking may occur, which may cause serious problems in the process.

[0082] According to one embodiment of the present invention, the oxidation heat treatment in step S2 may be performed by mixing an oxidizing gas including at least one of air, oxygen, and ozone into the residual oil bath.

[0083] For example, the oxidizing gas can be either air directly, among the types described above, or air diluted with one or more inert gases, such as nitrogen or argon. Another example is selecting oxygen as the oxidizing gas and diluting it with nitrogen to adjust the oxygen concentration. However, this is not limited to these examples, and can be appropriately modified and applied depending on the production conditions and equipment.

[0084] According to one embodiment of the present invention, the oxidation heat treatment of the S2 step may be performed in a continuous or batch reactor at a temperature of 250°C to 400°C for a period of 1 hour to 15 hours, and may be performed by mixing an oxidizing gas at a flow rate of 50 mL / min to 2.0 L / min per 1 kg of residual oil.

[0085] In the mixed binder pitch manufacturing method of the present invention, the purpose of performing the oxidation heat treatment is to increase the molecular weight of the residual oil batam, thereby raising the softening point and increasing the manufacturing yield. If the oxidation heat treatment reaction temperature condition is less than 250℃, the molecular weight of the residual oil batam does not increase sufficiently, so the rate of increase in the softening point is slow and the yield does not increase, so the purpose of the oxidation heat treatment cannot be achieved. On the other hand, if the oxidation heat treatment temperature exceeds 400℃, an exothermic reaction may occur and a coking phenomenon may also occur, so there is a risk in process operation, and there are problems that rapid changes in physical properties may occur, which also lowers the quality of the product.

[0086] If the oxidation heat treatment reaction time is less than 1 hour, the reaction time is too short and the reaction does not occur sufficiently. If it exceeds 15 hours, excessive polymerization may occur, causing the properties of the resulting pitch to deviate from the required specifications. In addition, the process time is prolonged, making it uneconomical. Within the above time range, the reaction time can be appropriately adjusted considering process conditions, throughput during the process, etc.

[0087] If the flow rate of the oxidizing gas injected during the oxidation heat treatment reaction is less than 50 mL / min per 1 kg of petroleum residue, the reaction rate is too slow, so the softening point increase rate is too slow. If it exceeds 2.0 L / min, the amount of the injected oxidizing gas component is too excessive, so a rapid reaction occurs, making it difficult to maintain consistency in the quality of the manufactured product, and there is a high possibility that problems may occur in the process, making it unsuitable.

[0088] According to one embodiment of the present invention, in the step S3, the coal tar is used in which low-boiling-point substances including moisture and aromatic components (BTX) have been removed.

[0089] In this way, coal tar from which low-boiling-point substances have been removed is distilled and reformed in a continuous or batch distillation device under pressure conditions of 800 torr or less and temperature conditions of 250°C to 420°C while removing light and heavy oils such as indene oil, naphthalene, methylnaphthalene, absorption oil, and creosote, thereby producing a medium-temperature coal tar pitch having a softening point of 60°C to 110°C.

[0090] According to one embodiment of the present invention, in the S4 step, the medium-temperature coal tar pitch may be mixed in an amount of 50 to 90 wt% and the oxidized petroleum pitch may be mixed in an amount of 50 to 10 wt% based on a total weight of 100 wt% of the medium-temperature coal tar pitch and the oxidized petroleum pitch.

[0091] When the blended content of oxidized petroleum pitch exceeds 50 wt%, the amount of petroleum pitch, which is hot in terms of the properties required for binder pitch, increases, resulting in a significant deterioration in the properties of the final product. In addition, when the blended content of oxidized petroleum pitch is less than 10 wt%, the properties of the resulting binder pitch become close to coal tar pitch, but this does not satisfy the purpose of the present invention to replace coal tar pitch, and when considering the raw material and process costs, there is a limitation in that the process efficiency and economic feasibility are significantly reduced.

[0092] According to one embodiment of the present invention, when mixing the two different materials (medium temperature coal tar pitch and oxidized petroleum pitch), it is suitable to mix them in a liquid state, and considering the softening point of each material, it is appropriate to mix them in a temperature range of 200°C to 420°C, and for example, it is more preferable to mix them in a temperature of 250°C to 380°C.

[0093] According to one embodiment of the present invention, the heat treatment in step S5 is for manufacturing the final binder pitch through a reforming reaction of the two mixed pitches, and specifically, the reforming reaction may be performed by heat treating for 3 hours or more and 15 hours or less in a continuous or batch heat treatment device under pressure conditions of 760 torr or less and temperature conditions of 280°C to 420°C.

[0094] The reason why the S5 stage heat treatment of the present invention is performed under pressure conditions of 760 torr or less is to raise the softening point while removing the heavy oil content remaining in the pitch after the oxidation heat treatment reaction in the case of oxidized petroleum pitch, and at the same time, to induce a polymerization reaction to increase the beta-resin content and increase the carbonization yield. In addition, for the case of medium-temperature coal tar pitch, the purpose is to remove heavy oil content such as creosote contained therein, raise the softening point, and increase the beta-resin content and carbonization yield.

[0095] If the reaction is carried out under pressurized conditions, it is difficult to remove heavy oil, so it is appropriate to carry out the reaction under conditions of, for example, 760 torr or less, 400 torr or less is more appropriate, and 200 torr or less is even more appropriate.

[0096] The temperature condition of the S5 step heat treatment of the present invention is suitably in the range of 280°C to 420°C. Within the above temperature condition range, a chemical reaction occurs between the heterogeneous materials of the medium-temperature coal tar pitch and the oxidized petroleum pitch, thereby increasing the carbonization yield and beta-resin content, and ensuring long-term storage stability. At temperatures below 280°C, it is difficult to remove heavy oil components, and the reactivity between the two heterogeneous materials is minimal, making it difficult to achieve the above-described effects. In addition, at temperatures exceeding 420°C, the reactivity is too high, so the reaction rate increases sharply, resulting in rapid formation of mesophase, which may adversely affect the properties of the binder pitch being manufactured. In addition, a coking reaction may occur, forming coke, which may cause problems in the final product quality and the manufacturing process. Therefore, the temperature condition for the heat treatment in the S5 stage is appropriately 280°C to 420°C, and a temperature range of 320°C to 380°C is more appropriate.

[0097] If the reaction time of the above S5 heat treatment is less than 3 hours, it is too short and sufficient reaction does not occur, making it difficult to manufacture high-quality binder pitch. If it exceeds 15 hours, excessive reaction occurs or the process time increases, reducing economic feasibility and efficiency. Therefore, the reaction time of the S5 heat treatment is appropriately 3 hours to 15 hours, and for example, 5 hours to 10 hours is even more appropriate, but is not necessarily limited thereto and may be appropriately changed depending on the process conditions, the amount of raw material to be processed, etc.

[0098] According to one embodiment of the present invention, if necessary, by blowing in at least one of steam, nitrogen and argon in the heat treatment of step S5, the heavy oil content can be easily removed, and the heat treatment reforming reaction can also be performed simultaneously.

[0099] Hereinafter, the present invention will be described in more detail by way of examples. However, the following examples are merely illustrative of the present invention, and the scope of the present invention is not limited to the following examples.

[0100] Example 1

[0101] Using FCC-DO with an aromatic index of 0.73 and a sulfur content of 0.62 wt% as a raw material, light and heavy oils were removed through batch vacuum distillation at 380°C and 150 torr to produce residual oil batam with a softening point of 55.3°C. From coal tar, from which low-boiling-point substances such as moisture and aromatic components (BTX) were removed, medium-temperature coal tar pitch with a softening point of 95°C was produced through batch distillation at 350°C and 700 torr.

[0102] By introducing 0.8 liter / min of air into the reactor based on lkg of residual oil having a softening point of 55.3°C, an oxidation heat treatment reaction was performed at a temperature of 350°C for 10 hours to produce oxidized petroleum pitch having a softening point of 108.2°C.

[0103] The above-mentioned medium-temperature coal tar pitch and oxidized petroleum pitch were mixed at a weight ratio of medium-temperature coal tar pitch: oxidized petroleum pitch = 70:30 at a temperature of 300°C. Then, heat treatment was performed at a pressure of 700 torr and a temperature of 380°C for 10 hours to produce a blended binder pitch having a softening point of 114.1°C, a QI content of 6.1 wt%, a beta-resin content of 25 wt%, a carbonization yield (CV) of 56 wt%, a mesophase content of 0.02 vol%, a wettability ΔP of 4.8°C, and a sulfur content of 0.53 wt%.

[0104] When the above mixed binder pitch was stored in a closed autoclave at a temperature of 230°C for 20 days, the softening point increased by 1.8°C and finally changed to 115.9°C.

[0105] Example 2

[0106] Using the FCC-DO used in Example 1 as a raw material, light and heavy oils were removed through batch vacuum distillation under the conditions of 370°C and 100 torr to produce residual oil batam having a softening point of 49.8°C. In addition, using the coal tar used in Example 1, medium-temperature coal tar pitch having a softening point of 87.2°C was produced under the conditions of 350°C and 770 torr. 0.5 liter / min of air was introduced into the reactor per 1 kg of residual oil batam having a softening point of 49.8°C, and an oxidation heat treatment reaction was performed at a temperature of 360°C for 8 hours to produce oxidized petroleum pitch having a softening point of 115.3°C.

[0107] The above-mentioned medium-temperature coal tar pitch and oxidized petroleum pitch were mixed at a weight ratio of medium-temperature coal tar pitch: oxidized petroleum pitch = 75:25 at a temperature of 320°C. Then, heat treatment was performed at a pressure of 650 torr and a temperature of 360°C for 12 hours to produce a blended binder pitch having a softening point of 118.1°C, a QI content of 6.8 wt%, a beta-resin content of 27 wt%, a carbonization yield (CV) of 57.5 wt%, a mesophase content of 0.01 vol%, a wettability ΔP of 4.3°C, and a sulfur content of 0.47 wt%.

[0108] When the above mixed binder pitch was stored in a closed autoclave at a temperature of 230°C for 20 days, the softening point increased by 1.6°C and finally changed to 119.7°C.

[0109] Example 3

[0110] Using pyrolysis fuel oil (PFO) with an aromatic index of 0.78 and a sulfur content of 0.1 wt% as a raw material, light and heavy oils were removed through a continuous distillation process under the conditions of 320℃ and 750 torr to produce residual batam with a softening point of 44.2℃. Coal tar from which low-boiling-point substances such as moisture and aromatic components (BTX) were removed was subjected to continuous distillation under the conditions of 355℃ and 250 torr to produce medium-temperature coal tar pitch with a softening point of 82℃. 0.3 L / min of air was introduced into the reactor per lkg of residual batam with a softening point of 44.2℃, and an oxidation heat treatment reaction was performed at a temperature of 300℃ for 3 hours to produce oxidized petroleum pitch with a softening point of 102.5℃.

[0111] The above-mentioned medium-temperature coal tar pitch and oxidized petroleum pitch were mixed at a temperature of 310°C in a weight ratio of medium-temperature coal tar pitch: oxidized petroleum pitch = 85:15 (total content of medium-temperature coal tar pitch and oxidized petroleum pitch was 100 wt). Then, a heat treatment was performed at a pressure of 760 torr and a temperature of 370°C for 8 hours to produce a blended binder pitch having a softening point of 124.2°C, a QI content of 7.1 wt%, a beta-resin content of 22 wt%, a carbonization yield (CV) of 58.1 wt%, a mesophase content of 0.01 vol%, a wettability factor ΔP of 5.3°C, and a sulfur content of 0.37 wt%.

[0112] When the above mixed binder pitch was stored in a closed autoclave at a temperature of 230°C for 20 days, the softening point increased by 3.8°C and finally changed to 128°C, indicating excellent long-term storage stability.

[0113] Comparative Example 1

[0114] Using FCC-DO with an aromatic index of 0.58 and a sulfur content of 3.83 wt% as a raw material, residual oil batam with a softening point of 51.6°C was produced under the same conditions as in Example 1. Thereafter, an experiment was conducted under the same conditions as in Example 1 to produce oxidized petroleum pitch with a softening point of 106.4°C.

[0115] This was mixed with the medium-temperature coal tar pitch of Example 1 in the same ratio as in Example 1, and then a heat treatment reaction was performed to manufacture a mixed binder pitch having a softening point of 107.1°C, a QI content of 5.7 wt%, a beta-resin content of 17 wt%, a carbonization yield (CV) of 51 wt%, a mesophase content of 0.02 vol%, a wettability factor ΔP of 7.4°C, and a sulfur content of 2.88 wt%.

[0116] When the above mixed binder pitch was stored in a closed autoclave at a temperature of 230°C for 20 days, the softening point increased by 6.2°C and finally changed to 113.3°C.

[0117] As can be seen from the above results, if a raw material having an aromatic index and sulfur content exceeding the standards of the present invention is used, the softening point, carbonization yield, sulfur content, etc. of the binder pitch manufactured will deviate from the intended standards, making it unsuitable as a binder pitch required commercially.

[0118] Comparative Example 2

[0119] The experiment was conducted in the same manner as in Example 2 using the FCC-DO used in Example 1 as a raw material, but the mixing ratio was reversed to Example 2, with a medium-temperature coal tar pitch: oxidized petroleum pitch = 25:75 (weight ratio). Then, after performing heat treatment in the same manner as in Example 2, a mixed binder pitch having a softening point of 113.4°C, a QI content of 2.5 wt%, a beta-resin content of 13.1 wt%, a carbonization yield (CV) of 49.2 wt%, a mesophase content of 0.01 vol%, a wettability factor ΔP of 10.2°C, and a sulfur content of 0.58 wt% was manufactured.

[0120] When the above mixed binder pitch was stored in a closed autoclave at a temperature of 230°C for 20 days, the softening point increased by 12.3°C and finally changed to 125.7°C.

[0121] As can be seen from the above results, if mixing is performed at a ratio outside the mixing ratio specified in the present invention and a heat treatment reaction is performed, a binder pitch having poor QI content, carbonization yield, wettability, and long-term storage properties is produced, which is not suitable as a binder pitch required commercially.

[0122] Comparative Example 3

[0123] Using the same raw materials as in Example 2, an oxidized petroleum pitch having a softening point of 115.3°C was manufactured in the same manner, and at the same time, a medium-temperature coal tar pitch having a softening point of 108.5°C was manufactured under conditions of 375°C and 730 torr, which is different from Example 2.

[0124] The above-mentioned oxidized petroleum pitch and the medium-temperature coal tar pitch of Example 1 were mixed in the same ratio as in Example 1, but unlike Example 2, no heat treatment reaction was performed.

[0125] As a result, a mixed binder pitch having a softening point of 110.2°C, a QI content of 4.7 wt%, a beta-resin content of 12.6 wt%, a carbonization yield (CV) of 50.7 wt%, a mesophase content of 0.01 vol%, a wettability factor ΔP of 6.6°C, and a sulfur content of 0.57 wt% was manufactured.

[0126] When the above mixed binder pitch was stored in a closed autoclave at a temperature of 230°C for 20 days, the softening point increased by 14.1°C and finally changed to 124.3°C.

[0127] As can be seen from the above results, when the heat treatment reaction specified in the present invention is not performed, the mutual reaction between the oxidized petroleum pitch and the medium-temperature coal tar pitch does not occur, so the beta-resin content and carbonization yield fall below the target standard, and the stability of the produced pitch is poor, so that the softening point changes significantly even when stored for a long period of time, which is not suitable as a binder pitch required for commercial purposes.

[0128] Comparative Example 4

[0129] Using the same raw materials as Example 1, and proceeding in the same manner, medium-temperature coal tar pitch: oxidized petroleum pitch were mixed in a weight ratio of 70:30. Then, after heat treatment at a pressure of 700 torr and a temperature of 250°C for 10 hours, a mixed binder pitch having a softening point of 103.7°C, a QI content of 3.2 wt%, a beta-resin content of 14.7 wt%, a carbonization yield (CV) of 50.4 wt%, a mesophase content of 0.01 vol%, a wettability factor ΔP of 3.2°C, and a sulfur content of 0.52 wt% was manufactured.

[0130] When the above mixed binder pitch was stored in a closed autoclave at a temperature of 230°C for 20 days, the softening point increased by 11.3°C and finally changed to 115°C.

[0131] As can be seen from the above results, when the heat treatment reaction is performed at a temperature lower than the heat treatment reaction temperature range specified in the present invention, the mutual reaction between the oxidized petroleum pitch and the medium-temperature coal tar pitch does not occur, so the softening point increase is insufficient, the beta-resin content and the carbonization yield fall below the standards targeted in the present invention, and the stability of the produced pitch is poor, so that the softening point changes significantly even when stored for a long time, which is not suitable as a binder pitch required commercially.

[0132] Comparative Example 5

[0133] The same method as in Comparative Example 4 was used, but the medium-temperature coal tar pitch: oxidized petroleum pitch was mixed at a weight ratio of 70:30. Then, when the reaction was performed at a pressure of 700 torr and a temperature of 440°C, coking was observed after 3 hours of reaction, and the reaction was stopped.

[0134] As can be seen from the above results, when the heat treatment reaction is performed at a temperature higher than the heat treatment reaction temperature range suggested in the present invention, excessive mesophase formation and coking are observed due to rapid reactivity, making this a method that is not suitable for commercial use.

[0135] Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Softening point ( o C) 114.1118.1124.2107.1113.4110.2103.7 Not measurable QI content (wt%) 6.16.87.15.72.54.73.2 Not measurable β-resin content (wt%) 2527221713.112.614.7 Not measurable Carbon yield (wt%) 5657.558.15149.250.750.4 - Mesophase (vol%) 0.020.010.010.020.010.010.010.01 Not measurable Wettability ( o C)4.84.35.37.410.26.63.2-Sulfur content (wt%)0.530.470.372.880.580.570.52-Change in softening point after long-term storage ( o C)1.81.63.86.212.314.111.3-

[0136] ※ In Table 2 above, “-” indicates that it was not measured.

[0137]

[0138] Although the present 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 implemented without departing from the technical spirit of the present specification. Therefore, the embodiments disclosed in the present specification are not intended to limit the technical spirit of the present invention, but to explain it, and the scope of the technical spirit of the present invention is not limited by these embodiments. Therefore, it should be understood that the embodiments described above are illustrative in all aspects and not restrictive. The protection scope of the present specification and the present invention should be interpreted by the claims, and all technical ideas within a scope equivalent thereto should be interpreted as being included in the scope of rights of the present specification and the present invention.

Claims

1. (S1) A step of producing a residue oil bottom having a softening point of 30°C to 80°C by distilling a petroleum residue having an aromatic index (fa) of 0.6 or more and a sulfur content of 1.5 wt% or less; (S2) A step of manufacturing an oxidized petroleum pitch having a softening point of 80°C to 130°C by performing an oxidation heat treatment on the residual oil of the step S1; (S3) A step of distilling coal tar to produce a medium-temperature coal tar pitch having a softening point of 60°C to 110°C; (S4) a step of mixing the oxidized petroleum pitch of the S2 step and the medium temperature coal tar pitch of the S3 step; and (S5) a step of heat-treating the mixture of step S4 to obtain a mixed binder pitch; A method for producing a mixed binder pitch, wherein the mixed binder pitch has a softening point of 100°C to 130°C, a quinoline insoluble (QI) content of 4 wt% or more, a beta-resin content of 15 wt% or more, a carbonization yield (CV) of 52 wt% or more, a mesophase content of 2 vol% or less, a sulfur content of 1 wt% or less, and a wettability measurement factor (△P) for coke measured according to the following measurement method 1 of 10°C or less. [Measurement Method 1] Place the mixed binder pitch on a calcined coke bed, and measure the contact angle while increasing the temperature from 20℃, plot the y-axis with the contact angle (°) and the x-axis with the temperature (℃) to create a graph, and then set the temperature point on the x-axis where the tangent to the inflection point of the graph intersects as P1, and the temperature point where the contact angle (y) becomes 0 (°) as P2, and then calculate P2-P1 as △P (℃).

2. In paragraph 1, The above petroleum residual oil is at least one selected from pyrolysis fuel oil (PFO), 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 (AE). A method for producing a mixed binder pitch, wherein the above petroleum residue is hydrogenated or not.

3. In paragraph 1, The above step S1 is a method for producing a mixed binder pitch, wherein light oil and heavy oil are removed by distillation in a continuous or batch distillation unit under pressure conditions of 760 torr or less and temperature conditions of 250°C to 420°C to produce residual oil batam.

4. In paragraph 1, A method for manufacturing a mixed binder pitch, wherein the oxidation heat treatment in the above step S2 is performed while mixing an oxidizing gas containing at least one of air, oxygen, and ozone into the residual oil batam.

5. In paragraph 4, A method for manufacturing a mixed binder pitch, wherein the above-mentioned oxidizing gas is diluted with at least one inert gas selected from nitrogen and argon.

6. In paragraph 4, An oxidizing gas is mixed at a flow rate of 50 mL / min to 2.0 L / min for 1 kg of the above residual oil, A method for manufacturing a mixed binder pitch, wherein the above oxidation heat treatment is performed in a continuous or batch reactor at a temperature of 250°C to 400°C for 1 hour to 15 hours.

7. In paragraph 1, In the above step S3, the coal tar is free of low boiling point substances including moisture and aromatic components (BTX). The above S3 step is a method for producing a mixed binder pitch, wherein the low-boiling-point material is removed from the coal tar, and a reforming reaction is performed in a continuous or batch distillation unit under pressure conditions of 800 torr or less and temperature conditions of 250°C to 420°C while removing light oil and heavy oil, to produce a medium-temperature coal tar pitch.

8. In paragraph 1, A method for producing a mixed binder pitch, wherein, in the step S4 above, the medium-temperature coal tar pitch is mixed in an amount of 50 to 90 wt% and the oxidized petroleum pitch is mixed in an amount of 50 to 10 wt% based on a total weight of 100 wt% of the medium-temperature coal tar pitch and the oxidized petroleum pitch.

9. In paragraph 1, A method for manufacturing a mixed binder pitch, wherein the heat treatment in the above step S5 is performed by heat treating for a period of 3 hours or more and 15 hours or less in a continuous or batch heat treatment device under pressure conditions of 760 torr or less and temperature conditions of 280°C to 420°C to perform a reforming reaction.

10. In paragraph 1, A method for manufacturing a mixed binder pitch, wherein, in the heat treatment of the above step S5, blowing is simultaneously performed to remove heavy oil components, at least one of steam, nitrogen and argon.

11. In paragraph 1, A method for manufacturing a mixed binder pitch, wherein the above-mentioned manufactured mixed binder pitch exhibits long-term storage stability in which a change in softening point is 10°C or less compared to the time of storage when stored for 15 days or longer in a closed system under temperature conditions of 230°C.

12. A mixed binder pitch manufactured by a method for manufacturing a mixed binder pitch according to any one of claims 1 to 11.

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