Method for preparing a resin carbon material from a tar coupling component
By utilizing the properties of aromatic tar and coal tar through extraction pretreatment, distillation cutting, and catalytic cross-linking condensation reaction, high-quality multifunctional resin carbon materials are prepared, solving the problem of the ineffective utilization of aromatic tar and realizing the preparation of low-cost, high-quality resin carbon materials.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- LIAONING UNIVERSITY OF PETROLEUM AND CHEMICAL TECHNOLOGY
- Filing Date
- 2024-05-21
- Publication Date
- 2026-05-15
AI Technical Summary
Existing technologies struggle to effectively utilize aromatic tar, especially styrene tar and ethylene tar, to prepare high-quality, multifunctional resin carbon materials, leading to resource waste and increased costs.
Multifunctional resin carbon materials are prepared by extraction pretreatment, distillation and separation, and catalytic cross-linking condensation reaction, combined with oxygen-containing compounds in coal tar as cross-linking agents and modifiers. High-quality resin carbon materials are prepared by utilizing the purity of ethylene tar and styrene tar and combining the characteristics of oxygen-containing compounds in coal tar.
This approach enables the efficient utilization of aromatic tar resources, reduces the cost of preparing multifunctional resin carbon materials, expands the sources of raw materials, and improves product quality.
Smart Images
Figure CN118419904B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to a method for preparing resin carbon materials, and more particularly to a method for preparing resin carbon materials using tar-coupled components. Background Technology
[0002] Aromatic tar includes ethylene tar, styrene tar, and coal tar. These tars are characterized by high content of gum and asphaltenes, and high viscosity, severely limiting their deep processing and utilization as fuel energy, resulting in relatively low prices. Styrene tar and coal tar are hazardous wastes, prohibited from direct sale, and require hazardous waste treatment by companies with environmental qualifications. Ethylene tar is mostly sold as fuel oil by enterprises. With increasingly stringent environmental requirements and improved laws and regulations, styrene tar and coal tar were included in the latest "National Hazardous Waste List" in 2016, requiring legal qualifications for disposal, thus increasing enterprise costs. Therefore, adopting reasonable treatment methods for aromatic tar, especially styrene tar and coal tar, to transform waste into valuable resources and improve economic efficiency is of great significance.
[0003] Multifunctional resin carbon materials mainly refer to low-carbon materials, such as phenolic resins, medium-carbon materials, such as coumarone resins, and high-carbon resin materials, such as spinnable pitch carbon materials and graphite coating materials for lithium-ion battery anodes. Phenolic resins possess excellent mechanical and heat resistance properties and are widely used in industries such as diamond products and grinding wheel manufacturing. They exhibit strong adhesion, good chemical stability, high heat resistance, low shrinkage during hardening, and dimensional stability of the finished products. Spinnable pitch carbon materials are high-performance pitch materials with advantages such as good plasticity, flexibility, elasticity, and fracture resistance. They can be used as raw material pitch for high-performance pitch-based carbon fibers, needle coke for ultra-high power electrodes, mesophase carbon microspheres, high thermal conductivity foamed carbon, and ultra-high specific surface area activated carbon. Coated pitch, as a surface modifier for graphite materials, modifies defects such as pores, grooves, and cracks in graphite, improving the electrochemical reversible capacity and cycle performance of the material. Coated pitch has advantages such as good electrical insulation, heat resistance, and light resistance, and the coating material improves the performance of the anode.
[0004] Currently, the conventional raw material for multifunctional resin carbon materials in my country is the heavy component of ethylene tar. There are few reports on the preparation of carbon materials from the light component of ethylene tar and styrene tar. The light component of coal tar (170–230℃ fraction) contains a large amount of oxygen-containing compounds, making it an excellent crosslinking agent for crosslinking condensation reactions. The middle fraction of coal tar (230–350℃ fraction) is an excellent modifier for carbon material preparation, improving indicators such as quinoline insoluble content, wettability, and viscosity. The pitch component of coal tar can be used to prepare carbon materials, but its high impurity content results in lower quality carbon materials. After solvent extraction pretreatment, it can be used as a pitch raw material for high-carbon resins. Fully utilizing the coupled raw materials of styrene tar and the light component of ethylene tar, and using the oxygen-containing compound fraction and middle fraction of coal tar as condensation crosslinking agents and modifiers for catalytic crosslinking polymerization to produce high-quality, low-cost novel resin carbon materials is of great significance. Summary of the Invention
[0005] The embodiments of the present invention provide a method for preparing resin carbon materials from tar-coupled components, and provide a novel method for preparing carbon materials from ethylene tar light components and styrene tar.
[0006] To achieve the above objectives, the embodiments of the present invention adopt the following technical solutions:
[0007] A method for preparing resin carbon materials from tar-coupled components includes the following steps: pre-treatment of the tar-coupled components by extraction; separation of the extracted components by distillation to obtain light aromatic tar-coupled components and heavy aromatic tar-coupled components; and catalytic cross-linking and condensation reactions of the light aromatic tar-coupled components and heavy aromatic tar-coupled components, followed by deep vacuum separation to obtain multifunctional resin carbon materials.
[0008] Furthermore, the distillation cutting adopts a distillation cutting device, and the solvent used for the extraction pretreatment comes from the 150-170℃ distillate oil distilled by the distillation cutting device.
[0009] Furthermore, the catalysts used in the catalytic crosslinking condensation reaction include a mixture of petroleum alkylbenzene sulfonic acid and organic aldehydes.
[0010] Furthermore, the multifunctional resin carbon material includes at least one of low-carbon resin, medium-carbon resin, and high-carbon resin.
[0011] Furthermore, the tar coupling components include coal tar, styrene tar, and ethylene tar, with the ratio of coal tar, styrene tar, and ethylene tar being 1–3:2–4:3–7.
[0012] Furthermore, the apparatus used for the catalytic crosslinking condensation reaction includes a light component catalytic condensation apparatus and a heavy component catalytic condensation apparatus; wherein, the coal tar distillation fraction at 170–230°C directly enters the light component catalytic condensation apparatus to participate in the reaction, and the coal tar distillation fraction at 230–350°C directly enters the heavy component catalytic condensation apparatus to participate in the reaction.
[0013] Furthermore, the light aromatic tar coupling component is a light tar fraction with a temperature range of 170–350°C, and the heavy aromatic tar coupling component is a heavy tar fraction with a temperature range greater than 350°C.
[0014] Furthermore, the conditions for distillation and separation are a temperature of 280–350°C and a pressure of 0.1 MPa.
[0015] Furthermore, the catalytic cross-linking condensation reaction conditions for the light aromatic tar coupled components are a temperature of 300–350℃ and a time of 5–10 h; the catalytic cross-linking condensation reaction conditions for the heavy aromatic tar coupled components are a temperature of 350–420℃ and a time of 5–10 h.
[0016] Furthermore, the deep decompression separation conditions are a temperature of 350–420℃ and a pressure of -0.095–-0.1 MPa.
[0017] The method for preparing resin carbon materials using tar coupling components provided in this invention fully utilizes the advantages of ethylene tar and styrene tar, which contain almost no sulfur, nitrogen, or other heteroatoms, and the characteristics of coal tar, which is rich in oxygen-containing organic matter. Based on the formation process of high-carbon resin materials, a condensation method is formulated to achieve the purpose of preparing high-quality multifunctional resin carbon materials. The oxygen-containing heteroatom compounds in coal tar are fully utilized, promoting the cross-linking reaction of styrene tar and the light components of ethylene tar, greatly reducing the raw material cost for preparing resin carbon materials, and expanding the source of raw materials for multifunctional resin carbon materials. Attached Figure Description
[0018] Figure 1 This is a process route diagram for preparing resin carbon materials from tar-coupled components, provided in an embodiment of the present invention. Detailed Implementation
[0019] The embodiments of the present invention will now be described in detail with reference to the accompanying drawings.
[0020] The terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of this invention, unless otherwise stated, "a plurality of" means two or more.
[0021] Example 1: As Figure 1As shown, the tar coupling components are used as raw materials, wherein the ratio of coal tar:styrene tar:ethylene tar is 1:2:7. The coal tar fraction above 350℃ is mixed with styrene tar and ethylene tar in a certain proportion and then enters the extraction pretreatment unit to remove ash and magnetic impurities. The purified tar coupling components are then distilled and separated to obtain a light aromatic tar coupling component below 280℃ and a heavy aromatic tar coupling component above 280℃. The light aromatic tar coupling component is mixed with the coal tar fraction below 230℃ and undergoes catalytic cross-linking condensation under the action of a catalyst. The reaction was carried out with a catalyst amount of 1% of the weight of the light aromatic tar coupling component, at 300℃ for 5 hours. The heavy aromatic tar coupling component was mixed with the 230-350℃ fraction of coal tar and subjected to a catalytic cross-linking condensation reaction under the action of a catalyst, with a catalyst amount of 1% of the weight of the heavy aromatic tar coupling component, at 350℃ for 5 hours. After the reaction, the two materials entered a deep vacuum separation unit to obtain aromatic solvent oil, low-carbon resin, medium-carbon resin and high-carbon resin. The properties of the products are shown in Tables 1 to 4.
[0022] Example 2: The tar coupling component was used as the raw material, wherein the ratio of coal tar:styrene tar:ethylene tar was 1:2:7. The coal tar >350℃ fraction was mixed with styrene tar and ethylene tar in a certain proportion and then fed into an extraction pretreatment unit to remove ash and magnetic impurities. The purified tar coupling component was then distilled and separated to obtain a <300℃ light aromatic tar coupling component and a >300℃ heavy aromatic tar coupling component. The light aromatic tar coupling component was mixed with the coal tar <230℃ fraction and catalytically crosslinked under the action of a catalyst. The condensation reaction was carried out at 320℃ for 5 hours, with the catalyst amount being 1% of the weight of the light aromatic tar coupling component. The heavy aromatic tar coupling component was mixed with the 230-350℃ fraction of coal tar and subjected to a catalytic cross-linking condensation reaction under the action of a catalyst, with the catalyst amount being 1% of the weight of the heavy aromatic tar coupling component. The reaction conditions were 360℃ for 5 hours. After the reaction, the two materials entered a deep vacuum separation unit to obtain aromatic solvent oil, low-carbon resin, medium-carbon resin and high-carbon resin. The properties of the products are shown in Tables 1 to 4.
[0023] Example 3: A tar-coupled component was used as the raw material, wherein the ratio of coal tar:styrene tar:ethylene tar was 2:3:5. The coal tar fraction >350℃ was mixed with the styrene tar and ethylene tar in a specific ratio and then fed into an extraction pretreatment unit to remove ash and magnetic impurities. The purified tar-coupled component was then distilled and separated to obtain a <300℃ light aromatic tar-coupled component and a >300℃ heavy aromatic tar-coupled component. The light aromatic tar-coupled component was mixed with the coal tar fraction <230℃ and subjected to catalytic crosslinking condensation under the action of a catalyst. The reaction was carried out with a catalyst amount of 1.5% of the weight of the light aromatic tar coupling component, at 330℃ for 7 hours. The heavy aromatic tar coupling component was mixed with the 230-350℃ fraction of coal tar and subjected to a catalytic cross-linking condensation reaction under the action of a catalyst, with a catalyst amount of 1.5% of the weight of the heavy aromatic tar coupling component, at 380℃ for 7 hours. After the reaction, the two materials entered a deep vacuum separation unit to obtain aromatic solvent oil, low-carbon resin, medium-carbon resin and high-carbon resin. The properties of the products are shown in Tables 1 to 4.
[0024] Example 4: Using tar-coupled components as raw materials, wherein the ratio of coal tar:styrene tar:ethylene tar is 2:3:5, the coal tar >350℃ fraction is mixed with styrene tar and ethylene tar in a certain proportion and then fed into an extraction pretreatment unit to remove ash and magnetic impurities. The purified tar-coupled components are then distilled and separated to obtain a <330℃ light aromatic tar-coupled component and a >330℃ heavy aromatic tar-coupled component. The light aromatic tar-coupled component is mixed with the coal tar <230℃ fraction and subjected to catalytic cross-linking under the action of a catalyst. The condensation reaction was carried out at 3% of the weight of the light aromatic tar coupling component, with a reaction temperature of 330℃ and a reaction time of 7 hours. The heavy aromatic tar coupling component was mixed with the 230-350℃ fraction of coal tar and carried out a catalytic cross-linking condensation reaction under the action of a catalyst, with a catalyst amount of 3% of the weight of the heavy aromatic tar coupling component, with a reaction temperature of 400℃ and a reaction time of 6 hours. After the reaction, the two materials entered a deep vacuum separation unit to obtain aromatic solvent oil, low-carbon resin, medium-carbon resin and high-carbon resin. The properties of the products are shown in Tables 1 to 4.
[0025] Example 5: Using tar-coupled components as raw materials, wherein the ratio of coal tar:styrene tar:ethylene tar is 3:4:3, the coal tar >350℃ fraction is mixed with styrene tar and ethylene tar in a certain proportion and then fed into an extraction pretreatment unit to remove ash and magnetic impurities. The purified tar-coupled components are then distilled and separated to obtain a <350℃ light aromatic tar-coupled component and a >350℃ heavy aromatic tar-coupled component. The light aromatic tar-coupled component is mixed with the coal tar <230℃ fraction and subjected to catalytic cross-linking under the action of a catalyst. The condensation reaction was carried out at 350°C for 5 hours, with the catalyst amount being 5% of the weight of the light aromatic tar coupling component. The heavy aromatic tar coupling component was mixed with the coal tar fraction at 230-350°C and subjected to a catalytic cross-linking condensation reaction under the action of a catalyst, with the catalyst amount being 5% of the weight of the heavy aromatic tar coupling component. The reaction conditions were 420°C for 5 hours. After the reaction, the two materials entered a deep vacuum separation unit to obtain aromatic solvent oil, low-carbon resin, medium-carbon resin and high-carbon resin. The properties of the products are shown in Tables 1 to 4.
[0026] Table 1. Parameters of light aromatic oils in Examples 1-5
[0027]
[0028]
[0029] Among them, the initial boiling point (IBP) and the final boiling point (FBP) are specified.
[0030] Table 2 Parameters of low-carbon resins in Examples 1-5
[0031] project Softening point / °C Coking value / % Quinoline insoluble matter / % Ash content / % Example 1 40 41.25 0.01 0.01 Example 2 46 42.34 0.01 0.01 Example 3 50 44.46 0.01 0.01 Example 4 61 46.33 0.01 0.01 Example 5 68 48.46 0.01 0.01
[0032] Table 3. Parameters of medium carbon resin in Examples 1-5
[0033] project Softening point / °C Coking value / % Quinoline insoluble matter / % Ash content / % Example 1 90 51.36 0.02 0.02 Example 2 118 53.21 0.02 0.02 Example 3 132 55.12 0.03 0.03 Example 4 149 57.92 0.04 0.03 Example 5 151 60.21 0.05 0.03
[0034] Table 4. Parameters of high-carbon resins in Examples 1-5
[0035] project Softening point / °C Coking value / % Quinoline insoluble matter / % Ash content / % Example 1 185 61.21 0.14 0.04 Example 2 206 63.35 0.18 0.04 Example 3 244 68.25 0.32 0.05 Example 4 265 73.33 0.45 0.05 Example 5 280 80.45 0.75 0.05
[0036] In summary, the method for preparing resin carbon materials using tar coupling components provided in this invention fully utilizes the advantages of ethylene tar and styrene tar being almost free of sulfur, nitrogen, and other heteroatoms, and the characteristics of coal tar being rich in oxygen-containing organic matter. Based on the formation process of high-carbon resin materials, a condensation method is formulated to achieve the purpose of preparing high-quality multifunctional resin carbon materials. The oxygen-containing heteroatom compounds in coal tar are fully utilized, promoting the cross-linking reaction of styrene tar and the light components of ethylene tar, greatly reducing the raw material cost for preparing resin carbon materials, and expanding the source of raw materials for multifunctional resin carbon materials.
[0037] In the description of this specification, specific features, structures, materials, or characteristics may be combined in any suitable manner in one or more embodiments or examples.
[0038] The above are merely specific embodiments of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention should be included within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.
Claims
1. A method for preparing resin carbon materials using tar-coupled components, characterized in that, Includes the following steps: The tar coupling components include coal tar, styrene tar and ethylene tar. The coal tar >350℃ fraction is mixed with styrene tar and ethylene tar in a certain proportion and then subjected to extraction pretreatment. The extracted components are then distilled and separated to obtain light aromatic tar coupling components and heavy aromatic tar coupling components. After undergoing catalytic crosslinking and condensation reactions, light aromatic hydrocarbon tar coupled components and heavy aromatic hydrocarbon tar coupled components are separated by deep vacuum separation to obtain multifunctional resin carbon materials. The apparatus used for the catalytic crosslinking condensation reaction includes a light component catalytic condensation apparatus and a heavy component catalytic condensation apparatus; wherein, the coal tar distillation fraction at 170~230℃ directly enters the light component catalytic condensation apparatus to participate in the reaction, and the coal tar distillation fraction at 230~350℃ directly enters the heavy component catalytic condensation apparatus to participate in the reaction.
2. The method for preparing resin carbon materials according to claim 1, characterized in that, The distillation cutting process uses a distillation cutting device, and the solvent used for the extraction pretreatment comes from the 150~170℃ distillate oil distilled by the distillation cutting device.
3. The method for preparing resin carbon materials according to claim 1, characterized in that, The catalysts used in catalytic crosslinking condensation reactions include mixtures of petroleum alkylbenzene sulfonic acid and organic aldehydes.
4. The method for preparing resin carbon materials according to claim 1, characterized in that, Multifunctional resin carbon materials include at least one of low-carbon resin, medium-carbon resin and high-carbon resin.
5. The method for preparing resin carbon materials according to claim 1, characterized in that, The ratio of coal tar, styrene tar and ethylene tar is 1~3:2~4:3~7.
6. The method for preparing resin carbon materials according to claim 1, characterized in that, The light aromatic tar coupling component is light tar fraction with a temperature range of 170~350℃, and the heavy aromatic tar coupling component is heavy tar fraction with a temperature range greater than 350℃.
7. The method for preparing resin carbon materials according to claim 1, characterized in that, The conditions for distillation and separation are a temperature of 280~350℃ and a pressure of 0.1MPa.
8. The method for preparing resin carbon materials according to claim 1, characterized in that, The catalytic cross-linking condensation reaction conditions for light aromatic tar coupled components are 300~350℃ and 5~10h; the catalytic cross-linking condensation reaction conditions for heavy aromatic tar coupled components are 350~420℃ and 5~10h.
9. The method for preparing resin carbon materials according to claim 1, characterized in that, The deep pressure reduction separation conditions are a temperature of 350~420℃ and a pressure of -0.095~-0.1MPa.