Preparation method of petroleum-based high-softening-point asphalt

Abstract

The preparation method of the petroleum-based high-softening-point asphalt disclosed by the invention can comprise the following steps of: preparing a mixed raw material, namely mixing an asphaltene extract into petroleum-based residual oil; an oxidation heat treatment step for introducing an oxidizing gas into the mixed raw material and heating the mixed raw material; and a reduced pressure heat treatment step of heating the product of the oxidation heat treatment step under reduced pressure conditions. The asphaltene extract may contain 30-100 wt% of an asphaltene component when the total weight of the extract is 100 wt%, and the softening point of the high softening point pitch may be 150-300 DEG C.

Description

Technical Field

[0001] The invention relates to a method for preparing petroleum-based high-softening-point asphalt and the high-softening-point asphalt prepared by the method. Background Art

[0002] High softening point asphalt is used as a raw material or precursor for various carbon materials and graphite materials such as carbon fiber, activated carbon, and secondary battery negative electrode materials. In order to prepare high softening point asphalt, there is generally known a method of using coal-based or petroleum-based materials as raw materials through an oxidation process and a heat treatment process.

[0003] It is known that when high softening point asphalt is used as a raw material for secondary battery negative electrode materials, the less quinoline insoluble substances, inorganic impurities such as metals, or heteroatoms such as nitrogen and sulfur contained in the high softening point asphalt, the better the effect of improving battery capacity, life characteristics, and output power characteristics. Petroleum-based raw materials do not actually contain quinoline insoluble substances, so compared with high softening point asphalt prepared using coal-based materials as raw materials, high softening point asphalt prepared using petroleum-based materials as raw materials has the advantage of relatively less quinoline insoluble substances.

[0004] However, in the case of preparing high softening point asphalt using petroleum-based substances as raw materials, the coking value of the prepared high softening point asphalt is lower than the coking value of high softening point asphalt prepared using coal-based substances as raw materials. Therefore, the product quality is unfavorable and there is a problem of low carbonization yield when using high softening point asphalt as raw material.

[0005] In order to improve the carbonization yield of petroleum-based high softening point asphalt, the previous technology for preparing high softening point asphalt using petroleum-based raw materials proposed the use of peroxide compounds (KR2014-0090062A) or halogen compounds (KR1997-0036066A, KR2000-0026341A, KR2015-0069372A). When using the above method to prepare high softening point asphalt, explosive or corrosive chemicals are used in the preparation process, so there are problems of increased process operating costs and increased safety risks.

[0006] The present inventors have thus confirmed that petroleum-based high softening point asphalt can be produced in an economical, efficient and safe manner by controlling the physical properties of petroleum-based raw materials and adjusting the operating conditions in the production process, thereby completing the present invention. Summary of the invention

[0007] Technical issues

[0008] The object of the present invention is to provide a method for preparing a high-quality petroleum-based high softening point asphalt having increased yield and coking value by using a mixed feedstock comprising petroleum-based residual oil and asphaltene extract.

[0009] The object of the present invention is to provide a method for economically and safely preparing high-quality petroleum-based high-softening point asphalt.

[0010] The purpose of the present invention is not limited to the purpose mentioned above, and other purposes and advantages of the present invention not mentioned can be understood through the following description, and will be more clearly understood through the embodiments of the present invention. Moreover, it is obvious that the purposes and advantages of the present invention can be achieved by the means and combinations thereof shown in the scope of the invention claims.

[0011] Technical Solution

[0012] In order to achieve the above object, according to the present invention, a method for preparing a petroleum-based high softening point asphalt can be provided, comprising: a step of preparing a mixed raw material, mixing an asphaltene extract in a petroleum-based residual oil; an oxidative heat treatment step, charging an oxidizing gas into the mixed raw material for heating; and a reduced pressure heat treatment step, heating the product of the oxidative heat treatment step under reduced pressure. When the total weight of the asphaltene extract is 100 weight percent (wt%), the asphaltene extract contains 30 to 100 weight percent of asphaltene components, and the softening point of the high softening point asphalt is 150 to 300°C.

[0013] The high softening point asphalt may have a softening point of 200 to 300°C.

[0014] Relative to the mixed raw material, the preparation yield of the high softening point asphalt can be 30-50%, and the coking value of the high softening point asphalt can be 65-85 weight percent.

[0015] When the total weight of the asphaltene extract is 100 weight percent, the nitrogen (N) component and the sulfur (S) component in the asphaltene extract may be less than 0.2 weight percent, respectively.

[0016] The mixing ratio of the petroleum-based residual oil to the asphaltene extract may be 90 weight percent:10 weight percent to 60 weight percent:40 weight percent.

[0017] The petroleum-based residual oil may include one or more selected from the group consisting of pyrolysis fuel oil (PFO), naphtha cracking bottom oil (NCB), ethylene tar (EBO), fluid catalytic cracking-decant oil (FCC-DO), residue fluid catalytic cracking-decant oil (RFCC-DO) and aromatic extract (AE).

[0018] The petroleum-based residual oil may include hydro-treated petroleum-based residual oil.

[0019] The process temperature of the oxidation heat treatment step can be 250-400° C., the process time of the oxidation heat treatment step can be 1-20 hours, and the charging flow rate of the oxidizing gas can be 0.01-2 L / min relative to 1 kg of the petroleum-based residual oil.

[0020] The oxidizing gas may include one or more selected from the group consisting of air, oxygen, and ozone.

[0021] The oxidizing gas may further include an inert gas for dilution, and the inert gas for dilution may include one or more selected from the group consisting of nitrogen gas and argon gas.

[0022] The process pressure of the reduced pressure heat treatment step may be 1 to 300 torr, the process heat treatment temperature of the reduced pressure heat treatment step may be 300 to 430° C., and the process time of the reduced pressure heat treatment step may be 4 to 20 hours.

[0023] In the reduced pressure heat treatment step, an inert gas or steam may be mixed, and the inert gas may include one or more selected from the group consisting of nitrogen and argon.

[0024] After the step of preparing a mixed raw material by mixing the asphaltene extract with the petroleum-based residual oil and before the step of oxidative heat treatment of heating the mixed raw material by injecting an oxidizing gas into the mixed raw material, a step of removing low-boiling substances with a boiling point of 300° C. or less may be included.

[0025] The step of removing the low boiling point substances can be performed by distilling the mixed raw material at a temperature of 250 to 400°C.

[0026] According to still another embodiment of the present invention, a petroleum-based high softening point asphalt prepared according to the method for preparing a petroleum-based high softening point asphalt according to one embodiment of the present invention may be provided.

[0027] According to another embodiment of the present invention, a negative electrode material for a secondary battery including a petroleum-based high softening point asphalt prepared according to the method for preparing a petroleum-based high softening point asphalt according to one embodiment of the present invention may be provided.

[0028] Effects of the Invention

[0029] The preparation method of the petroleum-based high softening point asphalt of the present invention can use a mixed raw material of mixed asphaltene extracts in petroleum-based residual oil to prepare a petroleum-based high softening point asphalt that simultaneously improves the preparation yield and coking value, thereby preparing a petroleum-based high softening point asphalt with high quality and high carbonization yield.

[0030] The preparation method of the petroleum-based high softening point asphalt of the present invention does not use peroxide compounds or halogen compounds, does not have explosion hazards in the preparation process, and can reduce the discharge of environmental pollutants. Therefore, high-quality petroleum-based high softening point asphalt can be prepared safely and economically.

[0031] When a negative electrode material for a secondary battery comprising the petroleum-based high softening point pitch prepared by the method for preparing the petroleum-based high softening point pitch of the present invention is used, the capacity, life and charge and discharge efficiency of the secondary battery can be improved.

[0032] The specific effects of the present invention will be described together with the above-mentioned effects in the following detailed description of the invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 It is a sequence diagram for illustrating a method for preparing a petroleum-based high softening point asphalt according to an example of the present invention.

[0034] Figure 2 The present invention is a simplified process diagram for illustrating a method for preparing a petroleum-based high softening point asphalt according to an example of the present invention. DETAILED DESCRIPTION

[0035] The above-mentioned purposes, features and advantages will be described in detail in the following content, and ordinary technicians in the technical field to which the present invention belongs can easily implement the technical ideas of the present invention. In the process of describing the present invention, if the detailed description of the known technology related to the present invention is judged to be likely to unnecessarily confuse the gist of the present invention, its detailed description will be omitted. The terms described below are terms recorded after considering the functions and effects in the present invention, and the meaning of each term should be interpreted based on the overall content of this specification.

[0036] In this specification, when it is mentioned that a certain structural element is located on other structural elements, it means that it can be directly formed on other structural elements or a third structural element can be interposed between them. In addition, in the drawings, the thickness of the structural elements may be exaggerated for the effective description of the technical content. In the entire specification, parts represented by the same reference numerals represent the same structural elements.

[0037] In various embodiments of the present specification, the terms "first", "second", "third", etc. are used to describe various structural elements, but these structural elements are not limited by these terms. These terms are only used to distinguish a certain structural element from other structural elements.

[0038] The terms used in this specification are used to illustrate the embodiments, rather than to limit the present invention. In this specification, unless otherwise specified, a sentence in the singular includes the plural form. The descriptions such as "comprising" and "containing" used in this specification do not exclude the existence of the mentioned structural element or the addition of one or more other structural elements.

[0039] In this specification, the content (weight percentage) of elements is based on the measurement using the "Flash Elemental Analyzer CHNO / S" equipment of Thermo Fisher.

[0040] Hereinafter, the present invention will be described in detail.

[0041] According to one embodiment of the present invention, a method for preparing petroleum-based high softening point asphalt can be provided.

[0042] Reference Figure 1 and Figure 2 The method for preparing a petroleum-based high softening point asphalt according to an embodiment of the present invention may include: a step S1 of preparing a mixed raw material, mixing an asphaltene extract with a petroleum-based residual oil; an oxidative heat treatment step S2, injecting an oxidizing gas into the mixed raw material for heating; and a reduced pressure heat treatment step S3, heating the product of the oxidative heat treatment step under reduced pressure conditions.

[0043] Step of preparing a mixed raw material by mixing an asphaltene extract with petroleum-based residual oil (Step S1)

[0044] In the process of preparing petroleum-based asphalt, as described later, the petroleum-based residual oil is subjected to an oxidative heat treatment step S2. The oxidative heat treatment step is a step that can introduce oxygen functional groups, and induces polymerization between structural components while removing low-molecular fat chains of the asphalt. This can increase the preparation yield according to the conditions of the oxidative heat treatment step, but is limited in improving the coking value of the generated high softening point asphalt.

[0045] In the present invention, in order to improve the coking value of petroleum-based asphalt, it is necessary to induce the polymerization of aromatic compounds and remove aliphatic compounds. In order to solve this technical problem, a preparation method is derived that can simultaneously improve the preparation yield and coking value of high softening point asphalt prepared using petroleum-based raw materials.

[0046] Specifically, the softening point of the high softening point asphalt targeted in the present invention can be 150-300° C., preferably, 200-300° C. Moreover, when the high softening point asphalt prepared in the present invention is converted to a percentage based on the weight basis of the high softening point asphalt prepared relative to the weight of the total raw materials calculated by the following formula (1), preferably, the preparation yield is 30% or more, preferably, 30%-50%, and at the same time, preferably, the coking value is 65 weight percent or more, preferably, 65-85 weight percent.

[0047] Formula (1): Preparation yield (%) = (weight of prepared high softening point asphalt / weight of raw materials added) × 100

[0048] As a result of numerous studies, the inventors of the present invention have focused on the fact that in order to prepare a high softening point asphalt having the excellent physical properties as described above, the production yield and the coking value can be simultaneously improved by increasing the amount of heavy aromatic compounds present in the petroleum-based residual oil used as a raw material for preparing the high softening point asphalt, thereby completing the method for preparing the high softening point asphalt of the present invention by mixing an asphalt extract having an asphalt component in petroleum-based residual oil to use as a mixed raw material.

[0049] On the other hand, in petroleum-based raw materials, asphaltene components exist in a variety of mixtures, among which asphaltene components are known to be contained in large quantities mainly in heavy crude oil as substances with large molecular weights. Generally, asphaltene is insoluble in low molecular weight alkane solvents, but is soluble in low molecular weight aromatic hydrocarbon solvents such as benzene or toluene or polar organic solvents.

[0050] When the total weight of the extract is 100 weight percent, for example, preferably, the asphaltene extract of the present invention may contain 30 to 100 weight percent of asphaltene components, for example, preferably, may contain 50 to 100 weight percent of asphaltene components, for example, preferably, may contain 50 to 90 weight percent of asphaltene components.

[0051] Furthermore, in the process of preparing the petroleum-based high softening point asphalt of the present invention, the less nitrogen and sulfur components in the mixed asphaltene extract, the better, preferably, each of which is less than 0.2 weight percent. If the nitrogen or sulfur component is greater than 0.2 weight percent, when the petroleum-based high softening point asphalt is used as a negative electrode material for a battery, there is a problem of reducing battery characteristics due to the generation of nitrogen or sulfur compounds.

[0052] The raw material for extracting the asphaltene component is not particularly limited, and one or more raw materials selected from oil sand bitumen, heavy oil, vacuum distillation residue oil, solvent deasphalting (SDA) residue oil, cracked fuel oil and fluid catalytic cracking clarified oil may be used.

[0053] Asphaltene components can be extracted from petroleum-based raw materials by a dissolution extraction method using a soluble organic solvent or a precipitation method using an insoluble organic solvent, but are not limited thereto. Specific examples of the dissolution extraction method include a method of separating the asphaltene components by dissolving the asphaltene components in a solvent such as benzene, toluene, propane, butane, and pentane. Specific examples of the precipitation method include a method of separating the asphaltene components by precipitating the asphaltene components using a solvent such as n-heptane (e.g., a solvent deasphalting method (SDA, Solvent De-Asphalting)).

[0054] For example, the extracted asphaltene extract is a high boiling point mixture, and it is impossible to extract only a single specific component. The extracted component will vary depending on the solvent used.

[0055] Preferably, the asphaltene component of the present invention is a substance that is insoluble in n-heptane solvent but soluble in toluene solvent, but is not limited thereto.

[0056] According to the present invention, in the process of preparing petroleum-based high softening point asphalt, the preparation yield of high softening point asphalt can be increased by more than 30% by mixing asphaltene extract into petroleum-based residual oil, and high-performance high softening point asphalt with a coking value of more than 65 weight percent can be prepared.

[0057] According to the present invention, in the process of preparing petroleum-based high softening point asphalt, for example, preferably, the mixing ratio of the asphaltene extract mixed in the petroleum-based raw material is 90 weight percent:10 weight percent to 60 weight percent:40 weight percent. If the mixing ratio exceeds 60 weight percent:40 weight percent, problems may occur during the transfer and stirring of the raw materials due to the excessively high viscosity of the mixed raw materials.

[0058] In order to prepare the mixed raw material of the present invention, the method of mixing the petroleum-based residual oil and the asphaltene extract is not particularly limited, and a mechanical mixing method can be used. Specifically, a mixer or a stirrer can be used.

[0059] In the present invention, in order to prepare asphalt, the petroleum-based residual oil used as a raw material is not particularly limited as long as it is used in the technical field to which the present invention belongs. For example, the petroleum-based residual oil may include one or more selected from the group consisting of cracking fuel oil, naphtha cracking bottom oil, ethylene tar, fluidized catalytic cracking clarified oil, heavy oil catalytic cracking clarified oil and aromatic extracts.

[0060] Furthermore, the petroleum-based residual oil may be a hydrotreated petroleum-based residual oil as a raw material. The raw material containing the petroleum-based residual oil may further contain petroleum-based residual oil and hydrotreated petroleum-based residual oil.

[0061] Oxidation heat treatment step S2

[0062] The process temperature of the oxidative heat treatment step S2 is the temperature of the reactants in the oxidative heat treatment step, preferably, it can be 250-400°C, can be 300-400°C, can be 300-350°C. If the temperature of the reactants in the oxidative heat treatment process is less than 250°C, the molecular weight of the petroleum-based residual oil will not increase sufficiently, resulting in a problem of reduced yield of high softening point asphalt as the final product. In addition, if the reactants in the oxidative heat treatment process are greater than 400°C, coking will occur due to a sharp increase in the content of quinoline insolubles in the reactants in the oxidative heat treatment process. In addition, if the petroleum-based residual oil is heat-treated under high temperature conditions or oxidation reaction conditions and an excessive polymerization reaction of aromatic compounds occurs, the petroleum-based residual oil will be converted into insoluble substances.

[0063] Preferably, the process time of the oxidative heat treatment step S2 can be 1 to 20 hours, can be 5 to 20 hours, can be 10 to 15 hours, but is not limited thereto. If the process time of the oxidative heat treatment step is less than 1 hour, it will be difficult for the oxidation reaction to fully occur. In addition, if the process time of the oxidative heat treatment step is greater than 20 hours, the physical properties of the high softening point asphalt as the final product will be deteriorated due to inducing excessive polymerization reaction. In particular, if the oxidation reaction is excessively carried out, the oxygen content of the prepared high softening point asphalt will be increased. This will reduce the performance of the secondary battery when it is subsequently used as a raw material for the negative electrode material of a secondary battery.

[0064] In the oxidative heat treatment step S2, preselectively, the charging flow rate of the oxidizing gas can be 0.01 to 2 L / min, 0.3 to 2 L / min, 0.5 to 2 L / min, or 0.3 to 1 L / min relative to 1 kg of the petroleum-based residual oil. If the flow rate of the oxidizing gas is less than 0.01 L / min relative to 1 kg of the petroleum-based residual oil, the yield and quality of the product will be reduced due to insufficient cross-linking reaction. On the other hand, if the flow rate of the oxidizing gas is greater than 2 L / min relative to 1 kg of the petroleum-based residual oil, the excessive amount of the oxidizing gas will cause a sharp increase in the content of toluene-insoluble components as heavy components and an increase in the content of quinoline-insoluble matter (QI).

[0065] In the oxidation heat treatment step S2, the oxidizing gas may include one or more selected from the group consisting of air, oxygen and ozone. For example, the oxidizing gas may directly use air in the atmosphere. In addition, the oxidizing gas may be diluted with an inert gas for use. Therefore, the oxidizing gas may also include an inert gas for dilution. The inert gas for dilution may include one or more selected from the group consisting of nitrogen and argon.

[0066] Generally, in order to increase the softening point of high-softening-point asphalt as the final product, a catalyst can be used under high pressure conditions, and in order to reduce the quinoline insoluble (QI) content in the high-softening-point asphalt, a peroxide (peroixide) compound can be mixed with an oxidizing gas for use.

[0067] However, if the catalyst is used under high pressure conditions, not only expensive high pressure vessels are required, but also an additional process for removing the catalyst is required, which increases the cost of producing high softening point asphalt.

[0068] Furthermore, if peroxide compounds are added to the oxidizing gas, there will be an explosion hazard during the preparation process due to the high reactivity of peroxide compounds, which will increase the cost of peroxide compounds, the cost of hazardous materials management and the cost of wastewater treatment. Therefore, the economic efficiency of large-scale production of high softening point asphalt will be reduced.

[0069] According to the present invention, the molecular weight of petroleum-based residual oil can be increased by the oxidation heat treatment process, thereby improving the yield of high softening point asphalt as the final product. In particular, the oxidation heat treatment process does not require high pressure conditions and does not use a catalyst, and can produce economical and high-quality petroleum-based high softening point asphalt.

[0070] Furthermore, according to the present invention, before or during the oxidation heat treatment process, peroxide compounds may not be used as the oxidation reactor. Not using the peroxide compounds has the advantage of making the preparation process economical and preventing explosion hazards in the preparation process.

[0071] On the other hand, the oxidative heat-treated petroleum-based residual oil can be prepared into petroleum-based asphalt through the oxidative heat treatment step S2. Therefore, the "petroleum-based asphalt" in this specification can refer to the petroleum-based residual oil oxidatively heat-treated through the oxidative heat treatment step S2.

[0072] Reduced pressure heat treatment step S3

[0073] A reduced pressure heat treatment step S3 of heating the petroleum-based asphalt, which is a product of the oxidative heat treatment step S2, under reduced pressure may be performed. The reduced pressure heat treatment step may be performed in a reduced pressure heat treatment device.

[0074] In order to control the softening point rising rate of the initial reactants, the reduced pressure heat treatment device for performing the reduced pressure heat treatment step S3 may include a sampling device for the reactants, a device for adjusting the outflow of oil flowing out in the form of waste gas (Off Gas) of the reactor, and a device for adjusting the internal pressure of the reactor.

[0075] The heavy oil of the petroleum-based asphalt can be removed by the reduced pressure heat treatment step S3, the softening point can be increased, and the content of toluene-insoluble components can be increased, thereby increasing the carbonization yield of the asphalt.

[0076] If the petroleum-based asphalt is subjected to a normal pressure heat treatment step or a pressure heat treatment step instead of a reduced pressure heat treatment step unlike the present invention, it will be difficult to remove the heavy oil and the softening point of the asphalt will not be increased.

[0077] Preferably, the process pressure of the reduced pressure heat treatment step S3 can be 1 to 300 Torr, 1 to 100 Torr, 1 to 200 Torr, 50 to 250 Torr, 80 to 100 Torr, or 80 to 150 Torr, but is not limited thereto.

[0078] Preferably, the heat treatment temperature of the reduced pressure heat treatment step S3 can be 300-430°C, can be 200-400°C, or can be 300-350°C. If the heat treatment temperature of the reduced pressure heat treatment process is less than 300°C, it will be difficult to remove the heavy oil, and it will be difficult to prepare high-quality high-softening point asphalt due to the reduced generation of toluene insolubles. In addition, there will be limitations in increasing the softening point of petroleum-based asphalt due to insufficient removal of the heavy oil in the asphalt. If the heat treatment temperature of the reduced pressure heat treatment process is greater than 430°C, coke will be formed due to the coking phenomenon of the petroleum-based asphalt, and there will be a problem of a sharp increase in the content of quinoline insolubles (QI).

[0079] Preferably, the process time of the reduced pressure heat treatment step S3 can be 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 carried out for less than 1 hour, the heavy oil cannot be fully removed, making it difficult to prepare asphalt with a high softening point. In addition, due to insufficient time for the thermal polymerization reaction, toluene insolubles cannot be fully generated, thereby preparing low-quality high softening point asphalt with a low carbonization yield. If the reduced pressure heat treatment process is carried out for more than 20 hours, toluene insolubles will be excessively generated due to excessive polymerization reaction, and the operating cost of the process and the preparation cost of the product will increase due to the increase in process time.

[0080] In the reduced pressure heat treatment step S3, an inert gas or steam may be mixed, and the inert gas may include one or more selected from the group consisting of nitrogen and argon, thereby more effectively removing the heavy oil from the petroleum-based asphalt. In particular, when the inert gas or steam is heated and then charged, the heavy oil can be more effectively removed.

[0081] 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 the petroleum-based asphalt, but is not limited thereto.

[0082] The reduced pressure heat treatment step S3 of the present invention is characterized in that no oxidizing gas is charged. If an oxidizing gas is charged in the reduced pressure heat treatment step S3 unlike the present invention, there is a problem that quinoline insolubles are rapidly formed due to the oxidation reaction at high temperature.

[0083] Low boiling point material removal step

[0084] The method for preparing petroleum-based high softening point asphalt of the present invention may further include a step of removing low-boiling point substances with a boiling point below 300°C after step S1 of mixing asphaltene extract with the petroleum-based residual oil to prepare a mixed raw material and before step S2 of oxidative heat treatment of injecting oxidizing gas into the mixed raw material for heating.

[0085] The raw material of petroleum-based residual oil is a mixture of various substances with boiling points ranging from low to high. The distribution of boiling points of each company's products is different. The low-boiling point substances contained in petroleum-based residual oil have not been clearly identified, such as benzene, toluene, xylene, styrene, indene, naphthalene, methylnaphthalene, biphenyl, fluorene, etc.

[0086] If high softening point asphalt is prepared when the raw materials contain low-boiling point substances, more process time will be required for preparation with high softening point, and the problem of low yield and relatively low softening point asphalt being prepared in the same preparation time will occur.

[0087] Therefore, in order to increase the preparation yield of high softening point asphalt and achieve a high softening point, it is preferred to remove low boiling point substances.

[0088] Specifically, the low boiling point substance in the present invention may refer to a substance having a boiling point of 300° C. or less when 70% is distilled on a distillation curve measured according to ASTM D86.

[0089] The method for removing the low boiling point substance is not limited. Preferably, distillation can be used. The process temperature of the distillation can be 250 to 400° C., but is not limited thereto and can be adjusted appropriately.

[0090] High softening point asphalt

[0091] Preferably, the softening point of the petroleum-based high softening point asphalt prepared by the method for preparing the petroleum-based high softening point asphalt of the present invention may be 150 to 300°C, more preferably, may be 200 to 300°C.

[0092] Preferably, relative to the total weight of the mixed raw materials, the weight preparation yield (percentage) of the petroleum-based high softening point asphalt can be 30% to 50%, and the coking value of the high softening point asphalt can be 65 to 85 weight percent.

[0093] As described above, the petroleum-based high softening point asphalt prepared by the method for preparing the petroleum-based high softening point asphalt of the present invention has a high softening point and can also significantly increase the preparation yield and coking value.

[0094] The coking value of pitch is a physical property that affects the yield of conversion into carbon materials when the pitch is carbonized, and is comprehensively affected by the molecular weight, aromatization index, molecular structure, etc. of the pitch. The coking value of the high softening point pitch of the present invention can be 50 weight percent or more, can be 65 weight percent or more, and preferably has a range of 65 weight percent to 85% relative to the total weight of the petroleum-based high softening point pitch. If the coking value of the high softening point pitch is less than 65 weight percent, more volatile substances are produced when the high softening point pitch is carbonized and the yield of conversion into carbon materials is low, so there is a problem that it cannot be used as a raw material for carbon materials. On the other hand, if the coking value of the high softening point pitch is greater than 85 weight percent, the high softening point pitch contains almost no volatile substances, but will be composed of aromatized hydrocarbons with large molecular weight, which will make it difficult to process the high softening point pitch or difficult to evenly coat it on the negative electrode material of the secondary battery.

[0095] 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 a precursor of carbon materials or graphite materials. When used as a raw material for various carbon materials and graphite materials, it can be used as an excellent precursor with a high carbonization yield. For example, the petroleum-based high softening point pitch can be used as a precursor of carbon fibers through a carbonization process and a graphitization process. In addition, the activated carbon prepared using the petroleum-based high softening point pitch of the present invention can have excellent specific surface area and mechanical strength.

[0096] Specifically, the petroleum-based high softening point asphalt of the present invention can be used as a binder or coating material for negative electrode materials (e.g., natural graphite negative electrode materials, artificial graphite negative electrode materials, etc.). As a specific embodiment, the petroleum-based high softening point asphalt can be used as a carbon-based negative electrode material by carbonizing it, and can be used as a precursor of carbon fiber by carbonizing and graphitizing it.

[0097] As described above, when the petroleum-based high softening point pitch prepared by the method for preparing the petroleum-based high softening point pitch of the present invention is used as a raw material for a negative electrode material of a secondary battery, the performance of the prepared secondary battery can be improved.

[0098] Embodiments of the invention

[0099] The present invention will be described in more detail below by way of examples. However, the following examples are only for illustrating the present invention, and the content of the present invention is not limited to the following examples.

[0100] Example 1

[0101] (1) The cracked fuel oil was dissolved by a toluene solvent to obtain an asphaltene extract. The asphaltene extract had an asphaltene content of 75 weight percent, a nitrogen content of 0.02 weight percent, and a sulfur content of 0.05 weight percent.

[0102] (2) Pyrolysis fuel oil as petroleum-based residual oil and the asphaltene extract prepared in (1) are mixed in a ratio of 80 weight percent:20 weight percent, and then mixed at room temperature for 30 minutes using a mechanical mixer to prepare a mixed raw material.

[0103] (3) After the mixed raw material is placed in an oxidation reactor, an oxidative heat treatment reaction is carried out. Air is used as an oxidizing gas and is charged at a flow rate of 0.4 L / min relative to 1 kg of the mixed raw material. The temperature of the reactants in the oxidative heat treatment step is 300°C and the reaction time is 10 hours.

[0104] (4) Then, the pressure was reduced to 100 Torr or less, and a reduced-pressure heat treatment was performed at 400° C. for 10 hours to prepare a petroleum-based high-softening-point asphalt.

[0105] The petroleum-based high-softening-point asphalt prepared in Example 1 has a softening point of 242° C., a preparation yield of 34%, and a coking value of 65 weight percent.

[0106] Example 2

[0107] The same method as in Example 1 was used except that in (2) of Example 1, the cracked fuel oil and the asphaltene extract were mixed in a ratio of 70 weight percent:30 weight percent.

[0108] The softening point of the petroleum-based high-softening-point asphalt prepared in Example 2 is 245° C., the preparation yield is 39%, and the coking value is 69 weight percent.

[0109] Example 3

[0110] The same method as in Example 1 was used except that in (2) of Example 1, the cracked fuel oil and the asphaltene extract were mixed in a ratio of 60 weight percent:40 weight percent.

[0111] The softening point of the petroleum-based high-softening-point asphalt prepared in Example 3 is 244° C., the preparation yield is 43%, and the coking value is 71 weight percent.

[0112] Comparative Example 1

[0113] The same procedure as in Example 1 was followed except that (1) and (2) of Example 1 were not performed and only cracked fuel oil, which is a petroleum-based residue, was used in place of the mixed feedstock in (3).

[0114] The softening point of the petroleum-based high-softening-point asphalt prepared in Comparative Example 1 is 243° C., the preparation yield is 25%, and the coking value is 60 weight percent.

[0115] The preparation conditions and measurement values ​​of the high softening point asphalt in Examples 1 to 3 and Comparative Example 1 are shown in Table 1 below.

[0116] Table 1

[0117]

[0118] Referring to Table 1, it can be confirmed that the petroleum-based high softening point asphalt of Examples 1 to 3 has a high softening point of more than 200°C, a high high softening point asphalt preparation yield of more than 30% and a high coking value of more than 65 weight percent.

[0119] In contrast, the comparative example 1 uses a raw material without mixing asphaltene extract in petroleum-based residual oil, and prepares high softening point asphalt in the same oxidation reactor under the same oxidation heat treatment and reduced pressure heat treatment conditions. It can be seen that although the prepared high softening point asphalt has a high softening point, the preparation yield and coking value are lower than those of Examples 1 to 3.

[0120] The above is described in more detail with reference to the embodiments and drawings of this specification, but this specification is not limited to the embodiments and drawings, and various modifications can be implemented without departing from the technical ideas of this specification. Therefore, the embodiments disclosed in this specification are not intended to limit the technical ideas of the present invention, but are used to illustrate the present invention, and the scope of the technical ideas of the present invention is not limited to these embodiments. Therefore, no matter from which aspect, the embodiments described above should be interpreted as examples rather than limitations. The protection scope of this specification and the present invention should be interpreted in accordance with the protection scope of the invention claims, and all technical ideas within the same scope should be interpreted as included in the scope of rights of this specification and the present invention.

Claims

1. A method for preparing petroleum-based high softening point asphalt, characterized in that: include: a step of preparing a blended feedstock by blending the asphaltene extract in a petroleum-based residual oil; an oxidative heat treatment step, wherein an oxidizing gas is introduced into the mixed raw material to heat the mixed raw material; and a reduced pressure heat treatment step of heating the product of the oxidative heat treatment step under reduced pressure, When the total weight of the asphaltene extract is 100 weight percent, the asphaltene extract contains 30 to 100 weight percent of asphaltene components. The high softening point asphalt has a softening point of 150-300°C.

2. The method for preparing petroleum-based high softening point asphalt according to claim 1, characterized in that: The preparation yield of the high softening point asphalt is 30 to 50% relative to the mixed raw material.

3. The method for preparing petroleum-based high softening point asphalt according to claim 1, characterized in that: The coking value of the high softening point asphalt is 65 to 85 weight percent.

4. The method for preparing petroleum-based high softening point asphalt according to claim 1, characterized in that: When the total weight of the asphaltene extract is 100 weight percent, the nitrogen content and the sulfur content in the asphaltene extract are respectively less than 0.2 weight percent.

5. The method for preparing petroleum-based high softening point asphalt according to claim 1, characterized in that: The mixing ratio of the petroleum-based residual oil to the asphaltene extract is 90 weight percent:10 weight percent to 60 weight percent:40 weight percent.

6. The method for preparing petroleum-based high softening point asphalt according to claim 1, characterized in that: The high softening point asphalt has a softening point of 200 to 300°C.

7. The method for preparing petroleum-based high softening point asphalt according to claim 1, characterized in that: The petroleum-based residual oil includes at least one selected from the group consisting of cracked fuel oil, naphtha cracked bottom oil, ethylene tar, fluidized catalytic cracking clarified oil, heavy oil catalytic cracking clarified oil and aromatic extracts.

8. The method for preparing petroleum-based high softening point asphalt according to claim 1, characterized in that: The petroleum-based residual oil comprises hydrogenated petroleum-based residual oil.

9. The method for preparing petroleum-based high softening point asphalt according to claim 1, characterized in that: The process temperature of the oxidation heat treatment step is 250-400°C. The process time of the oxidation heat treatment step is 1 to 20 hours. The injection flow rate of the oxidizing gas is 0.01 to 2 L / min relative to 1 kg of the petroleum-based residual oil.

10. The method for preparing petroleum-based high softening point asphalt according to claim 1, characterized in that: The oxidizing gas includes one or more selected from the group consisting of air, oxygen, and ozone.

11. The method for preparing petroleum-based high softening point asphalt according to claim 1, characterized in that: The oxidizing gas further includes an inert gas for dilution. The dilution inert gas includes at least one selected from the group consisting of nitrogen gas and argon gas.

12. The method for preparing petroleum-based high softening point asphalt according to claim 1, characterized in that: The process pressure of the reduced pressure heat treatment step is 1 to 300 Torr, The heat treatment temperature of the reduced pressure heat treatment step is 300-430°C. The process time of the reduced pressure heat treatment step is 4 to 20 hours.

13. The method for preparing petroleum-based high softening point asphalt according to claim 1, characterized in that: In the reduced pressure heat treatment step, an inert gas or steam is mixed in. The inert gas includes at least one selected from the group consisting of nitrogen gas and argon gas.

14. The method for preparing petroleum-based high softening point asphalt according to claim 1, characterized in that: After the step of preparing a mixed raw material by mixing the asphaltene extract with the petroleum-based residual oil and before the step of oxidative heat treatment of heating the mixed raw material by injecting an oxidizing gas, the method further includes a step of removing low-boiling substances having a boiling point of less than 300°C.

15. The method for preparing petroleum-based high softening point asphalt according to claim 14, characterized in that: The step of removing the low boiling point substances is performed by distilling the mixed raw material at a temperature of 250 to 400°C.

16. A petroleum-based high softening point asphalt, characterized in that: Prepared by the method for preparing petroleum-based high softening point asphalt according to any one of claims 1 to 15.

17. A negative electrode material for a secondary battery, characterized in that: A petroleum-based high softening point asphalt prepared by the method for preparing a petroleum-based high softening point asphalt according to any one of claims 1 to 15.

Images