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

Abstract

The method for preparing the petroleum-based high-softening-point pitch according to the present invention is characterized by comprising: an oxidation heat treatment step in which an oxidizing gas is introduced into a raw material containing a petroleum-based residual oil to heat the raw material; and a reduced-pressure heat treatment step for heating the product of the oxidation heat treatment step under reduced-pressure conditions, the oxidation heat treatment step being performed in an oxidation heat treatment device satisfying the following condition (1). Condition (1): 40 < = D1 / D2 < = 100 (In said condition (1), D1 is the diameter of the oxidation reactor, and D2 is the diameter of the flow tube into which the oxidizing gas is introduced).

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] In order to improve the preparation yield of high softening point asphalt, the previous technology of preparing high softening point asphalt using petroleum-based raw materials or coal-based raw materials (for example, KR1997-0036066A, KR2000-0026341A, KR2014-0090062A, JP1995-194966A, etc.) is a method using dangerous substances such as halogen compounds and peroxide compounds, which has the problem of difficulty in achieving economical and safe processes or the high softening point asphalt prepared has a high content of quinoline insolubles.

[0005] Furthermore, in the preparation process of high softening point asphalt, a method for effectively performing an oxidation process in order to suppress the formation of quinoline-insoluble substances, a method for effectively increasing the softening point of high softening point asphalt, a method for increasing the preparation yield of high softening point asphalt, etc. have not yet been disclosed, and therefore there is a need to develop these methods. Summary of the invention

[0006] Technical issues

[0007] The object of the present invention is to provide a method for preparing a petroleum-based high softening point asphalt with a high softening point using a raw material containing petroleum-based residual oil, while significantly reducing the content of quinoline insoluble matter and preparing a petroleum-based high softening point asphalt with an improved yield.

[0008] Another object of the present invention is to provide a method for economically and safely preparing high-quality petroleum-based high-softening point asphalt.

[0009] 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.

[0010] Technical Solution

[0011] In order to achieve the above-mentioned purpose, according to the present invention, there can be provided a method for preparing a petroleum-based high softening point asphalt, comprising: an oxidative heat treatment step, in which an oxidizing gas is introduced into a raw material containing petroleum-based residual oil for heating; and a reduced pressure heat treatment step, in which the product of the oxidative heat treatment step is heated under reduced pressure conditions, wherein the oxidative heat treatment step is carried out in an oxidative heat treatment device that satisfies the following condition (1).

[0012] Condition (1): 40 ≤ D1 / D2 ≤ 100

[0013] In the condition (1), D1 is the diameter of the oxidation reactor, and D2 is the diameter of the flow pipe filled with oxidizing gas.

[0014] Effects of the Invention

[0015] The preparation method of the petroleum-based high softening point asphalt of the present invention can effectively carry out the heat treatment step, and is easy to increase the softening point of the asphalt in the heat treatment step. At the same time, it can reduce the quinoline insoluble substances formed in the preparation process, and has the advantage of being able to prepare high-quality petroleum-based high softening point asphalt with high preparation yield.

[0016] Furthermore, 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 low quinoline insoluble content. When a negative electrode material for a secondary battery containing the high softening point asphalt is used, the capacity, life and charge and discharge efficiency of the secondary battery can be improved.

[0017] 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

[0018] 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.

[0019] 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.

[0020] Best Mode for Carrying Out the Invention

[0021] 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.

[0022] 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.

[0023] 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.

[0024] 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.

[0025] If there is no other explanation, "%" in this specification shall be interpreted as "weight percentage".

[0026] Hereinafter, the present invention will be described in detail.

[0027] One embodiment of the present invention provides a method for preparing petroleum-based high softening point asphalt.

[0028] 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: an oxidative heat treatment step S1, in which an oxidizing gas is introduced into a raw material containing petroleum-based residual oil for heating; and a reduced pressure heat treatment step S2, in which a product of the oxidative heat treatment step is heated under reduced pressure conditions.

[0029] Oxidation heat treatment step S1

[0030] The oxidation heat treatment step in the method for preparing high softening point asphalt can be carried out by charging an oxidizing gas into a raw material containing petroleum-based residual oil and heating it. As described in detail below, the oxidation heat treatment step of the present invention does not use substances that cause process hazards such as peroxide compounds, and focuses on reducing the content of quinoline insolubles by adjusting the size and dispersion of the bubbles of the oxidizing gas, thereby achieving the desired high softening point range of the asphalt, and at the same time, the preparation yield of the high softening point asphalt can be improved, thereby completing the present invention.

[0031] Specifically, the inventors have confirmed the following problems as a result of numerous studies: the larger the size of the bubbles of the oxidizing gas introduced into the raw material containing petroleum-based residual oil, the slower the oxidation reaction rate; the shorter the residence time in the raw material solution containing petroleum-based residual oil as the raw material at a high reaction temperature; and the problem that if the bubble size of the oxidizing gas is too small, the oxidation reactivity will increase, resulting in an increase in quinoline insolubles.

[0032] Furthermore, in the reduced pressure heat treatment step described in detail below, in order to increase the softening point of the high-softening point asphalt, high-boiling point substances should also be effectively removed, and a method of introducing an inert gas is generally used. In this case, the larger the surface area of ​​the inert gas, that is, the smaller the size of the bubbles, the smoother the increase in the softening point. On the other hand, there is a disadvantage that the pressure of the flow tube increases, and further, if the surface area is too large, there is a problem that the softening point is difficult to increase.

[0033] As a solution to the above-mentioned problem, the present invention proposes a method for controlling the bubble size of the oxidizing gas charged in the oxidation heat treatment step. That is, the bubble size of the oxidizing gas is controlled by adjusting the ratio of the diameters of the "reactor" and the "oxidizing gas charging flow pipe" of the oxidation heat treatment device for performing the oxidation heat treatment step, thereby achieving the object of the present invention. This can be embodied by the following condition (1) regarding the oxidation heat treatment device.

[0034] Condition (1): 40 ≤ D1 / D2 ≤ 100

[0035] In the condition (1), D1 is the diameter of the oxidation reactor, and D2 is the diameter of the flow pipe filled with oxidizing gas.

[0036] In this way, the bubble size and dispersibility of the oxidizing gas can be adjusted by the ratio of the diameter (D1) of the oxidation reactor and the diameter (D2) of the flow tube filled with the oxidizing gas. Specifically, the larger the bubble size of the oxidizing gas, the slower the oxidation reaction rate and the shorter the residence time in the solution phase. In addition, if the bubble size of the oxidizing gas is too small, the quinoline insoluble matter will increase due to the increased oxidation reactivity. From the perspective of achieving the purpose of the present invention by solving the above problems, D1 / D2 can be adjusted. For example, D1 / D2 can be 40 to 100, 40 to 80, or 45 to 70. Since the bubble size of the oxidizing gas is related to the area of ​​the flow tube, if the value of D1 / D2 is less than 40, there will be problems that occur when the bubble size of the oxidizing gas is too small, and if it is greater than 100, there will be problems that occur when the bubble size of the oxidizing gas is too large.

[0037] In the oxidation heat treatment device, the number of flow tubes filled with oxidizing gas is not limited, for example, it can be single or multiple, and the number of flow tubes can be adjusted in consideration of the flow rate. For example, the more the number of flow tubes, the higher the dispersion of the oxidizing gas, but if the number of flow tubes is increased when the flow rate is small, the problem of no flow in some flow tubes will occur. From this point of view, the number of flow tubes is not particularly limited, for example, the number of flow tubes can be multiple, can be 1 to 20, can be 1 to 10, but is not limited thereto.

[0038] 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 can be, for example, 150 to 300°C, preferably, 200 to 300°C is targeted.

[0039] The content of quinoline insoluble matter (QI) contained in 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, for example, 1% or less, preferably, 0.001% to 1% is targeted.

[0040] According to the method for preparing petroleum-based high softening point asphalt of the present invention, the preparation yield of high softening point asphalt can be improved. Specifically, it can be prepared at a high preparation yield of, for example, 20% to 50%, for example, 30% to 50%, while showing a softening point of 200 to 300°C. The present invention does not contain halogen compounds used in the past as additives, which is meaningful in that petroleum-based high softening point asphalt can be prepared at a high yield. On the other hand, the preparation yield of high softening point asphalt is calculated according to the following formula (1).

[0041] Formula (1): Preparation yield (%) = (weight of prepared high softening point asphalt / weight of raw materials added) × 100

[0042] On the other hand, the petroleum-based residual oil that can be 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 can 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 clarified oil (FCC-DO, Fluid Catalytic Cracking-Decant Oil), heavy oil catalytic cracking clarified oil (RFCC-DO, Residue Fluid Catalytic Cracking-Decant Oil) and aromatic extract (AE).

[0043] Furthermore, the petroleum-based residual oil that has been hydrotreated may be used as a raw material. Therefore, the raw material containing the petroleum-based residual oil may include petroleum-based residual oil and hydrotreated petroleum-based residual oil.

[0044] The process temperature of the oxidative heat treatment step S1 is the temperature of the reactants in the oxidative heat treatment step, preferably, it can be 250-400°C, it can be 300-400°C, it 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 is not sufficiently increased, and the yield of the high softening point asphalt as the final product is reduced. In addition, if the temperature of the reactants in the oxidative heat treatment process is greater than 400°C, coking will occur due to the sharp increase in the content of quinoline insolubles in the reactants of the oxidative heat treatment process. In addition, if the petroleum-based residual oil is heat-treated under high temperature conditions or oxidation reaction conditions, resulting in excessive polymerization of aromatic compounds, the petroleum-based residual oil will also be converted into insoluble substances.

[0045] Preferably, the process time of the oxidative heat treatment step S1 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.

[0046] In the oxidative heat treatment step S1, 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 insolubles as a heavy component and an increase in the content of quinoline insolubles (QI).

[0047] In the oxidation heat treatment step S1, 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.

[0048] 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.

[0049] 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.

[0050] 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.

[0051] 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.

[0052] 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.

[0053] 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 S1. 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 S1.

[0054] Reduced pressure heat treatment step S2

[0055] A reduced pressure heat treatment step S2 may be performed to heat the petroleum-based asphalt, which is a product of the oxidative heat treatment step S1, under reduced pressure. The reduced pressure heat treatment step may be performed in a reduced pressure heat treatment device.

[0056] 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 S2 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.

[0057] The heavy oil of the petroleum-based asphalt can be removed by the reduced pressure heat treatment step S2, the softening point can be increased, and the content of toluene insoluble matter can be increased, thereby increasing the carbonization yield of the asphalt.

[0058] 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 increase.

[0059] Preferably, the process pressure of the reduced pressure heat treatment step S2 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.

[0060] Preferably, the heat treatment temperature of the reduced pressure heat treatment step S2 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).

[0061] Preferably, the process time of the reduced pressure heat treatment step S2 can be 1 to 20 hours, can be 4 to 20 hours, can be 5 to 15 hours, can be 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, and it will be 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, and low-quality high-softening point asphalt with a low carbonization yield will be prepared. 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.

[0062] In the reduced pressure heat treatment step S2, 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.

[0063] 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.

[0064] The reduced pressure heat treatment step S2 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 S2 unlike the present invention, there is a problem that quinoline insolubles are rapidly formed due to the oxidation reaction at high temperature.

[0065] High softening point asphalt

[0066] For example, 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 can be 150 to 300°C, preferably, 200 to 300°C is targeted.

[0067] For example, the content of quinoline insoluble matter (QI) contained in the petroleum-based high softening point asphalt prepared by the method for preparing petroleum-based high softening point asphalt of the present invention can be less than 1%, preferably, with 0.001% to 1% as the target, which can inhibit the generation of quinoline insoluble matter.

[0068] Thus, according to the present invention, the oxidation heat treatment step can be more effectively performed by adjusting the bubble size or dispersion of the oxidizing gas. Furthermore, if a device for performing the oxidation heat treatment step is used in the reduced pressure heat treatment step, the bubble size of the inactive gas introduced in the reduced pressure heat treatment step to remove the oil content can also be adjusted, thereby effectively increasing the softening point of the high softening point asphalt as the final product, thereby being able to prepare high-quality petroleum-based high softening point asphalt with suppressed production of quinoline-insoluble substances at a high yield.

[0069] The petroleum-based high softening point pitch of the present invention can be used as a raw material of carbon material or graphite material, or a precursor of carbon material or graphite material. For example, the petroleum-based high softening point pitch can be used as a precursor of carbon fiber through a carbonization process and a graphitization process.

[0070] As one embodiment, the petroleum-based high softening point pitch of the present invention can be used as a binder material or a coating material for negative electrode materials (eg, natural graphite negative electrode materials, artificial graphite negative electrode materials, etc.).

[0071] As an embodiment, petroleum-based high softening point asphalt can be used as a carbon-based negative electrode material by subjecting it to a carbonization process, and can be used as a precursor of carbon fibers by subjecting it to a carbonization process and a graphitization process.

[0072] As an embodiment, when the petroleum-based high softening point asphalt prepared by the method for preparing the petroleum-based high softening point asphalt 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. DETAILED DESCRIPTION

[0073] 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.

[0074] Example 1

[0075] As petroleum-based residual oil, pyrolysis fuel oil is used as a raw material to carry out an oxidative heat treatment step in an oxidative heat treatment device.

[0076] Specifically, in an oxidation heat treatment device, pyrolysis fuel oil is placed as petroleum-based residual oil in an oxidation reactor with a diameter D1 of 220 mm, and air is used as an oxidizing gas. Air is charged at a flow rate of 1.0 L / min relative to 1 kg of pyrolysis fuel oil to carry out an oxidative heat treatment reaction.

[0077] In this case, the diameter D2 of the flow tube filled with oxidizing gas is 1 / 8 inch, so the ratio of the diameter of the oxidation reactor to the flow tube (D1 / D2) is 69, and the number of the flow tubes is 4. The temperature of the reactants in the oxidation heat treatment step is 300° C., and the oxidation heat treatment process is carried out for 10 hours.

[0078] Then, the pressure was reduced to 200 Torr, and a reduced pressure heat treatment step was performed at a temperature of 400° C. for 10 hours to prepare a petroleum-based high softening point asphalt.

[0079] The softening point of the prepared petroleum-based high-softening-point asphalt is 242° C., the content of quinoline-insoluble matter is 0.08%, and the preparation yield calculated according to formula (1) of the present invention is 28%.

[0080] Example 2

[0081] As petroleum-based residual oil, pyrolysis fuel oil is used as a raw material to carry out an oxidative heat treatment step in an oxidative heat treatment device.

[0082] Specifically, in an oxidation heat treatment device, pyrolysis fuel oil is placed as petroleum-based residual oil in an oxidation reactor with a diameter D1 of 300 mm, and air is used as an oxidizing gas. Air is charged at a flow rate of 0.5 L / min relative to 1 kg of pyrolysis fuel oil to carry out an oxidative heat treatment reaction.

[0083] In this case, the diameter D2 of the flow tube filled with oxidizing gas is 1 / 4 inch, so the ratio of the diameter of the oxidation reactor to the flow tube (D1 / D2) is 47, and the number of the flow tubes is 8. The temperature of the reactants in the oxidative heat treatment step is 320°C, and the oxidative heat treatment process is carried out for 8 hours.

[0084] Then, the pressure was reduced to 150 Torr, and a reduced-pressure heat treatment was performed at 350° C. for 12 hours to prepare a petroleum-based high-softening-point asphalt.

[0085] The softening point of the prepared petroleum-based high-softening-point asphalt is 245° C., the content of quinoline-insoluble matter is 0.04%, and the preparation yield calculated according to formula (1) of the present invention is 30%.

[0086] Example 3

[0087] As petroleum-based residual oil, pyrolysis fuel oil is used as a raw material to carry out an oxidative heat treatment step in an oxidative heat treatment device.

[0088] Specifically, in an oxidation heat treatment device, pyrolysis fuel oil is placed as petroleum-based residual oil in an oxidation reactor with a diameter D1 of 220 mm, and air is used as an oxidizing gas. Air is charged at a flow rate of 1.0 L / min relative to 1 kg of pyrolysis fuel oil to carry out an oxidative heat treatment reaction.

[0089] In this case, the diameter D2 of the flow tube filled with oxidizing gas is 1 / 8 inch, so the ratio of the diameter of the oxidation reactor to the flow tube (D1 / D2) is 69, and the number of the flow tubes is 8. The temperature of the reactants in the oxidation heat treatment step is 300°C, and the oxidation heat treatment process is carried out for 10 hours.

[0090] Then, the pressure was reduced to 200 Torr, and a reduced-pressure heat treatment was performed at 400° C. for 10 hours to prepare a petroleum-based high-softening-point asphalt.

[0091] The softening point of the prepared petroleum-based high-softening-point asphalt is 255° C., the content of quinoline-insoluble matter is 0.03%, and the preparation yield calculated according to formula (1) of the present invention is 31%.

[0092] Comparative Example 1

[0093] As petroleum-based residual oil, pyrolysis fuel oil is used as a raw material to carry out an oxidative heat treatment step in an oxidative heat treatment device.

[0094] Specifically, in an oxidation heat treatment device, pyrolysis fuel oil is placed as petroleum-based residual oil in an oxidation reactor with a diameter D1 of 220 mm, and air is used as an oxidizing gas. Air is charged at a flow rate of 1.0 L / min relative to 1 kg of pyrolysis fuel oil to carry out an oxidative heat treatment reaction.

[0095] In this case, the diameter D2 of the flow tube filled with oxidizing gas was 1 / 4 inch, the ratio of the diameter of the oxidation reactor to the flow tube (D1 / D2) was 35, and the number of the flow tubes was 4. The temperature of the reactants in the oxidative heat treatment step was 300°C, and the oxidative heat treatment process was carried out for 10 hours.

[0096] Then, the pressure was reduced to 200 Torr, and a reduced-pressure heat treatment was performed at 400° C. for 10 hours to prepare a petroleum-based high-softening-point asphalt.

[0097] The softening point of the prepared petroleum-based high-softening-point asphalt is 185° C., the content of quinoline-insoluble matter is 0.05%, and the preparation yield calculated according to formula (1) of the present invention is 18%.

[0098] Comparative Example 2

[0099] As petroleum-based residual oil, pyrolysis fuel oil is used as a raw material to carry out an oxidative heat treatment step in an oxidative heat treatment device.

[0100] Specifically, in an oxidation heat treatment device, pyrolysis fuel oil is placed as petroleum-based residual oil in an oxidation reactor with a diameter D1 of 220 mm, and air is used as an oxidizing gas. Air is charged at a flow rate of 1.0 L / min relative to 1 kg of pyrolysis fuel oil to carry out an oxidative heat treatment reaction.

[0101] In this case, the diameter D2 of the flow tube filled with oxidizing gas was 1 / 16 inch, the ratio of the diameter of the oxidation reactor to the flow tube (D1 / D2) was 139, and the number of the flow tubes was 4. The temperature of the reactants in the oxidation heat treatment step was 300°C, and the oxidation heat treatment process was carried out for 10 hours.

[0102] Then, the pressure was reduced to 200 Torr, and a reduced-pressure heat treatment was performed at 400° C. for 10 hours to prepare a petroleum-based high-softening-point asphalt.

[0103] The softening point of the prepared petroleum-based high-softening-point asphalt is 242° C., the content of quinoline-insoluble matter is 1.5%, and the preparation yield calculated according to formula (1) of the present invention is 28%.

[0104] The ratio of the oxidation reactor diameter D1 / flow tube diameter D2, the number of flow tubes and the physical properties of the prepared petroleum-based high softening point asphalt in Examples 1 to 3 and Comparative Examples 1 to 2 are shown in Table 1 below.

[0105] Table 1

[0106]

[0107] 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 low quinoline insoluble content of less than 1%, and a high high softening point asphalt preparation yield of more than 25%.

[0108] In contrast, the high softening point asphalt was prepared in Comparative Example 1 using the same raw materials as in Example 1, in the same oxidation reactor, under the same oxidation heat treatment and reduced pressure heat treatment operating conditions, except that the ratio of the oxidation reactor diameter D1 / flow tube diameter D2 was 34. It can be confirmed that the softening point of the high softening point asphalt prepared in Comparative Example 1 was not sufficiently increased, and the preparation yield was also low.

[0109] In addition, except that the ratio of oxidation reactor diameter D1 / flow tube diameter D2 is 139, the high softening point asphalt is prepared in the same oxidation reactor and under the same oxidation heat treatment and reduced pressure heat treatment operating conditions using the same raw materials as in Example 1 in Comparative Example 2. It can be confirmed that the softening point of the high softening point asphalt prepared in Comparative Example 2 is sufficiently increased, and the preparation yield is also high, but the content of the generated quinoline insoluble matter is high.

[0110] 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: an oxidative heat treatment step of heating the feedstock containing petroleum-based residual oil by injecting an oxidizing gas; and a reduced pressure heat treatment step of heating the product of the oxidative heat treatment step under reduced pressure, The oxidation heat treatment step is carried out in an oxidation heat treatment device that satisfies the following condition (1): Condition (1): 40 ≤ D1 / D2 ≤ 100 In the condition (1), D1 is the diameter of the oxidation reactor, and D2 is the diameter of the flow pipe filled with oxidizing gas.

2. The method for preparing petroleum-based high softening point asphalt according to claim 1, characterized in that: The content of quinoline insoluble matter in the high softening point asphalt is 0.001% to 1%.

3. The method for preparing petroleum-based high softening point asphalt according to claim 1, characterized in that: The yield of high softening point asphalt calculated by the following formula (1) satisfies 20-50%, Formula (1): Preparation yield (%) = (weight of prepared high softening point asphalt / weight of input raw materials) × 100.

4. 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.

5. 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 thermal cracking fuel oil, naphtha cracking bottom oil, ethylene tar, fluidized catalytic cracking clarified oil, heavy oil catalytic cracking clarified oil and aromatic extracts.

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

7. 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.

8. 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.

9. The method for preparing petroleum-based high softening point asphalt according to claim 8, 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.

10. 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.

11. 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 is mixed in. The inert gas includes at least one selected from the group consisting of nitrogen gas and argon gas.

12. 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 11.

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