Preparation method of coal-based palaeo-malon resin-based high-softening-point pitch

Abstract

The application discloses a preparation method of coal-based ancient malon resin-based high-softening-point pitch, which comprises the following steps: mixing ancient malon-indene resin and refined medium-temperature pitch, and then performing air oxidation to obtain coal-based ancient malon resin-based high-softening-point pitch with uniform components and a high coking value; when the coal-based ancient malon resin-based high-softening-point pitch is used for coating of a negative material of a lithium ion battery, the capacity of the lithium ion battery can be improved; when the coal-based ancient malon resin-based high-softening-point pitch is used as a refractory binder pitch, the strength and oxidation resistance of the refractory material can be improved.

Description

Technical Field

[0001] This invention belongs to the field of coal chemical technology and relates to a method for preparing high softening point asphalt, specifically a method for preparing coal-based coumarone resin-based high softening point asphalt. Background Technology

[0002] High softening point asphalt refers to asphalt with a softening point above 100℃, especially above 120℃. High softening point asphalt has a wide range of applications due to its excellent high-temperature resistance. Currently, among domestic manufacturers researching high softening point asphalt, the main manufacturers of coal-based asphalt are Jining and Zhanjiang, where two manufacturers are piloting small quantities of coal-based coated asphalt. The main manufacturers of oil-based asphalt are Liaoyang Xinde and Dalian Huaqiang.

[0003] Currently, there is relatively little research in China on high softening point asphalt, and the main focus is on modified asphalt with a softening point of around 110℃. For example, Baowu Carbon Materials uses a flash distillation method to produce high-temperature asphalt containing high levels of quinoline insolubles. Mixing this high-temperature asphalt with soft asphalt yields modified asphalt with a reasonable composition. After air oxidation, high softening point asphalt is obtained. This high softening point asphalt can be used to prepare low-thermal-conductivity foamed carbon through low-pressure self-foaming technology. Anshan Thermal Energy Research Institute Co., Ltd. of China Steel Group uses coal tar refined soft asphalt as raw material and employs both vacuum distillation and air oxidation methods to produce high softening point asphalt with a softening point higher than 240℃. Comparing the oxides and carbides produced after spinning the asphalt, carbon fibers produced by vacuum distillation have an uneven surface and lower strength; while carbon fibers produced by vacuum distillation followed by air oxidation have a smooth surface and higher strength. The main type of coal-based tar pitch imported from abroad is high softening point coal-based tar pitch from Rüdeger in Germany. Currently, a small portion is used for coating negative electrode materials, but its rate performance and capacity in lithium batteries are relatively poor. Most of it is used as a mixed binder for magnesium-carbon bricks, but due to its high price, some manufacturers are reluctant to accept it. Summary of the Invention

[0004] To address the aforementioned deficiencies in the existing technology, the purpose of this invention is to provide a method for preparing coal-based coumarone resin-based high softening point pitch. The method involves mixing coumarone-indene resin and refined medium-temperature pitch, followed by air oxidation to obtain a coal-based coumarone resin-based high softening point pitch with uniform composition and high coking value. This coal-based coumarone resin-based high softening point pitch can improve the capacity of lithium-ion batteries when used for coating lithium-ion battery anode materials. Furthermore, when used as a binder pitch for refractory materials, it can improve the strength and oxidation resistance of refractory materials.

[0005] To achieve the above objectives, the present invention adopts the following technical solution:

[0006] This invention provides a method for preparing coal-based coumarone resin-based high softening point pitch, comprising the following steps:

[0007] S1, coal-based coumarone-indene resin is added to refined medium-temperature asphalt to form coal-based coumarone resin-based mixed asphalt with a softening point of 70-90℃.

[0008] S2, the coal-based coumarone resin-based mixed asphalt is subjected to air oxidation in a nitrogen-adjusted atmosphere to obtain coal-based coumarone resin-based high softening point asphalt.

[0009] Preferably, in step S1, the amount of coal-based coumarone-indene resin added to the coal-based coumarone resin-based mixed bitumen is 70-90 wt%; and the amount of refined medium-temperature bitumen added is 10-20 wt%.

[0010] Preferably, in step S1, the softening point of the coal-based coumarone-indene resin is 80–120°C.

[0011] Preferably, in step S1, the refined medium-temperature asphalt is obtained by purification using a disc centrifuge.

[0012] Preferably, in step S1, the content of quinoline insolubles in the refined medium-temperature asphalt is ≤0.2wt%, and the softening point of the refined medium-temperature asphalt is 65-90℃.

[0013] Preferably, in step S2, the amount of nitrogen used in the nitrogen-adjusted atmosphere is 0.33–0.7 Nm³. 3 / kg, air consumption is 0.33~0.7Nm 3 / kg.

[0014] Preferably, in step S2, the temperature during the air oxidation process is 270–350°C.

[0015] Preferably, the softening point of the coal-based coumarone resin-based high softening point pitch is 180–290°C; the coking value is 75–85%.

[0016] The method for preparing coal-based coumarone resin-based high softening point pitch provided by this invention has the following beneficial effects:

[0017] 1. The preparation method of coal-based coumarone resin-based high softening point pitch of the present invention involves mixing coumarone-indene resin and refined medium-temperature pitch, followed by air oxidation to obtain coal-based coumarone resin-based high softening point pitch with uniform composition and high coking value; this coal-based coumarone resin-based high softening point pitch can improve the capacity of lithium-ion batteries when used for coating lithium-ion battery anode materials, and can improve the strength and oxidation resistance of refractory materials when used as a binder pitch for refractory materials;

[0018] 2. The preparation method of coal-based coumarone resin-based high softening point pitch of the present invention makes it easier to mix the coal-based coumarone-indene resin and coal-based refined medium-temperature pitch evenly, with some components complementing each other and the component distribution being narrower.

[0019] 3. The coal-based coumarone resin-based high softening point pitch of the present invention has a more uniform component distribution as seen from the thermogravimetric analysis. When used for coating lithium-ion battery anode materials, the anode materials will have a higher bulk density, thereby increasing the capacity of lithium-ion batteries. When the coal-based coumarone resin-based high softening point pitch is used as a binder pitch for refractory materials, it can improve the strength and oxidation resistance of refractory materials. Attached Figure Description

[0020] Other features, objects, and advantages of the present invention will become more apparent from the following detailed description of non-limiting embodiments with reference to the accompanying drawings:

[0021] Figure 1 This is a schematic flowchart of the preparation method of coal-based coumarone resin-based high softening point bitumen in this invention.

[0022] Figure 2 This is the structural formula of the coumarone-indene resin in this invention. Detailed Implementation

[0023] To better understand the above-mentioned technical solutions of the present invention, the technical solutions of the present invention will be further described below in conjunction with embodiments.

[0024] Combination Figure 1 As shown, the present invention provides a method for preparing coal-based coumarone resin-based high softening point bitumen, comprising the following steps:

[0025] S1, coal-based coumarone-indene resin is added to refined medium-temperature pitch to form a coal-based coumarone resin-based mixed pitch with a softening point of 70–90℃. The coal-based coumarone-indene resin has a softening point of 80–120℃ and a molecular weight of 600–850 m / z, and its structural formula is as follows: Figure 2 As shown. Refined medium-temperature asphalt was obtained by purification using a disc centrifuge. The content of quinoline-insoluble matter in this refined medium-temperature asphalt was ≤0.2wt%, and its softening point was 65–90℃. In the coal-based coumarone resin-based mixed asphalt, the addition amount of coal-based coumarone-indene resin was 70–90wt%; the addition amount of refined medium-temperature asphalt was 10–20wt%.

[0026] S2, the coal-based coumarone resin-based mixed asphalt is subjected to air oxidation in a nitrogen-adjusted atmosphere to obtain coal-based coumarone resin-based high softening point asphalt. Specifically, in the nitrogen-adjusted atmosphere, the nitrogen dosage is 0.33–0.7 Nm³. 3 / kg, air consumption is 0.33~0.7Nm 3 / kg. During air oxidation, the temperature was controlled at 270–350℃. The final prepared coal-based coumarone resin-based high softening point pitch had a softening point of 180–290℃ and a coking value of 75–85%.

[0027] The coal-based coumarone resin-based high softening point pitch prepared above can be used as a binder pitch for refractory materials, a coating pitch, and a spinning pitch. When used for coating lithium-ion battery anode materials, the anode materials will have a higher bulk density, thereby increasing the capacity of the lithium-ion battery. When used as a binder pitch for refractory materials, this coal-based coumarone resin-based high softening point pitch can improve the strength and oxidation resistance of refractory materials.

[0028] The preparation method of coal-based coumarone resin-based high softening point pitch of the present invention will be further described below with specific examples.

[0029] Example 1

[0030] The preparation method of coal-series coumarone resin-based high softening point pitch in this embodiment is as follows:

[0031] A coal-based coumarone-indene resin with a softening point of 90℃ was used. This resin was added to a centrifuge with a softening point of 75℃ to obtain refined medium-temperature pitch, resulting in a coal-based coumarone resin-based mixed pitch with a softening point of 81℃. The coal-based coumarone resin-based mixed pitch contained 85 wt% coal-based coumarone-indene resin and 15 wt% refined medium-temperature pitch. The refined medium-temperature pitch contained 0.15 wt% quinoline-insoluble matter. Then, the coal-based coumarone resin-based mixed pitch was oxidized in air at 325℃ under a nitrogen-adjusted atmosphere to obtain a coal-based coumarone resin-based high-softening-point pitch with a softening point of 262℃. The nitrogen dosage in the nitrogen-adjusted atmosphere was 0.33–0.7 Nm³. 3 / kg, air consumption is 0.33~0.7Nm 3 / kg.

[0032] The coking value of the coal-based coumarone resin-based high softening point pitch prepared above is 79%, and it can be used as coating pitch.

[0033] Example 2

[0034] The preparation method of coal-series coumarone resin-based high softening point pitch in this embodiment is as follows:

[0035] A coal-based coumarone-indene resin with a softening point of 90℃ was used. This resin was added to a centrifuge with a softening point of 75℃ to obtain refined medium-temperature pitch, resulting in a coal-based coumarone resin-based mixed pitch with a softening point of 86℃. The coal-based coumarone resin-based mixed pitch contained 90 wt% coal-based coumarone-indene resin and 10 wt% refined medium-temperature pitch. The refined medium-temperature pitch contained 0.15 wt% quinoline-insoluble matter. Then, the coal-based coumarone resin-based mixed pitch was oxidized in air at 325℃ under a nitrogen-adjusted atmosphere to obtain a coal-based coumarone resin-based high softening point pitch with a softening point of 282℃. The nitrogen dosage in the nitrogen-adjusted atmosphere was 0.33–0.7 Nm³. 3 / kg, air consumption is 0.33~0.7Nm 3 / kg.

[0036] The coking value of the coal-based coumarone resin-based high softening point pitch prepared above is 84%, which can be used as spinning pitch.

[0037] Example 3

[0038] The preparation method of coal-series coumarone resin-based high softening point pitch in this embodiment is as follows:

[0039] A coal-based coumarone-indene resin with a softening point of 90℃ was added to a centrifuge with a softening point of 75℃ to obtain refined medium-temperature pitch, resulting in a coal-based coumarone resin-based mixed pitch with a softening point of 78℃. The coal-based coumarone resin-based mixed pitch contained 70 wt% coal-based coumarone-indene resin and 30 wt% refined medium-temperature pitch; the refined medium-temperature pitch contained 0.15 wt% quinoline-insoluble matter. Then, the coal-based coumarone resin-based mixed pitch was oxidized in air at 325℃ under a nitrogen-adjusted atmosphere to obtain a coal-based coumarone resin-based high softening point pitch with a softening point of 220℃. The nitrogen dosage in the nitrogen-adjusted atmosphere was 0.33–0.7 Nm³. 3 / kg, air consumption is 0.33~0.7Nm 3 / kg.

[0040] The coal-based coumarone resin-based high softening point pitch prepared above has a coking value of 77% and can be used as a binder pitch for refractory materials.

[0041] Those skilled in the art should recognize that the above embodiments are merely illustrative of the present invention and are not intended to limit the present invention. Any variations or modifications to the above embodiments that are within the spirit and essence of the present invention will fall within the scope of the claims of the present invention.

Claims

1. A method for preparing coal-series coumarone resin-based high softening point pitch, characterized in that, Includes the following steps: S1, coal-based coumarone-indene resin is added to refined medium-temperature asphalt to form coal-based coumarone resin-based mixed asphalt with a softening point of 70-90℃; The softening point of the coal-based coumarone-indene resin is 80–120℃, and the molecular weight is 600–850 m / z. The content of quinoline insoluble matter in the refined medium-temperature asphalt is ≤0.2wt%, and the softening point of the refined medium-temperature asphalt is 65~90℃; In the coal-based coumarone resin-based mixed bitumen, the amount of coal-based coumarone-indene resin added is 70-90 wt%; the amount of refined medium-temperature bitumen added is 10-20 wt%. S2, the coal-based coumarone resin-based mixed asphalt is subjected to air oxidation in a nitrogen-adjusted atmosphere to obtain coal-based coumarone resin-based high softening point asphalt. In the nitrogen-adjusted atmosphere, the nitrogen consumption is 0.33–0.7 Nm³. 3 / kg, air consumption is 0.33~0.7Nm 3 / kg; The softening point of the coal-series coumarone resin-based high softening point pitch is 180–290℃, and the coking value is 75–85%.

2. The method for preparing coal-series coumarone resin-based high softening point pitch according to claim 1, characterized in that, In step S1, the refined medium-temperature asphalt is obtained by purification using a disc centrifuge.

3. The method for preparing coal-series coumarone resin-based high softening point pitch according to claim 1, characterized in that, In step S2, the temperature during the air oxidation process is 270–350°C.

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