Process device for co-production of pitch-based hard carbon and porous carbon

Abstract

The utility model discloses a process device for co-producing asphalt-based hard carbon and porous carbon, which comprises a raw material bin, a first-stage non-melting device, a second-stage non-melting device and a non-melting asphalt powder bin which are connected in sequence, and the non-melting asphalt powder bin is respectively connected with a carbonization device and a first-stage activation device. The carbonization device, the grading device I and the product A bin are sequentially connected, the primary activation device is respectively connected with the secondary activation device and the grading device II, the grading device II is connected with the product B bin, and the secondary activation device, the grading device III and the product C bin are sequentially connected. According to the utility model, asphalt is used as a raw material, the cost is low, the added value of products is high, hard carbon and porous carbon production processes required in the energy storage field are effectively combined, and the hard carbon material can be co-produced while the porous carbon is produced, so that the processes are flexible, adjustable, continuous, stable and reliable, the products have good quality consistency, and the product types and product indexes are flexible and adjustable; the market change can be timely adapted.

Description

Technical Field

[0001] This utility model relates to the field of asphalt production technology, and in particular to a process apparatus for co-producing asphalt-based hard carbon and porous carbon. Background Technology

[0002] With the accelerated global energy structure transformation, the pursuit of high specific energy in new energy batteries (including lithium-ion batteries, solid-state batteries, and sodium-ion batteries) has driven the development of next-generation energy storage materials technology and market demand. These include porous carbon core frameworks for silicon-carbon anode materials produced by chemical vapor deposition (CVD) and hard carbon materials for sodium-ion batteries. The raw materials for preparing these materials mainly include biomass, coal-based materials, asphalt and asphalt coke, and polymer materials. Porous carbon or hard carbon materials prepared from different raw materials each have their own advantages, but they are currently in the early stages of industrialization. There are still gaps between the current state and market demand in terms of product performance, precise control of product structure, and quality consistency.

[0003] Asphalt-based raw materials have stable sources and supply, and good product consistency. Their ash and impurity content is low, generally not exceeding 0.5%, making them advantageous for producing high-purity porous carbon or hard carbon materials for electrode production. Furthermore, asphalt-based substances are mainly composed of C and H elements with fewer heteroatom chemical groups, exhibiting high chemical tunability. Their structure can be developed and designed using various methods as needed, making them more industrially viable for adapting to diverse energy storage material requirements in the future. The preparation of pitch-based hard carbon and porous carbon typically requires cross-linking modification of pitch to alter the inherent properties of its soft carbon precursor. Common methods include pre-oxidation treatment or chemical modification using oxidants such as concentrated nitric acid, concentrated sulfuric acid, and hydrogen peroxide to introduce a series of functional groups containing ethers, anhydrides, sulfur, and nitrogen, thereby altering the molecular rearrangement process during pitch carbonization and obtaining a disordered carbon structure. However, these methods are technically challenging, lack precise control over the modification process, and cannot guarantee the consistency of product structure and performance. Furthermore, the use of oxidants such as concentrated nitric acid and concentrated sulfuric acid presents environmental governance issues. Currently, the modified processes used in the industry, like materials prepared from other raw materials, still lag behind market demands in terms of product performance and precise control of product structure. The process control is too simplistic, making it impossible to adjust product structure, performance, and product types in a timely manner according to market needs, thus limiting their application in the next-generation energy storage field. Utility Model Content

[0004] To address the aforementioned shortcomings, this invention provides a process apparatus for co-producing pitch-based hard carbon and porous carbon. It can simultaneously produce porous carbon materials while producing hard carbon, and can precisely control the structure and types of hard carbon and porous carbon products according to market demand, while ensuring good product quality consistency.

[0005] To solve the above-mentioned technical problems, the technical solution of this utility model is: a process device for co-producing pitch-based hard carbon and porous carbon, comprising a raw material silo, a primary non-melting device, a secondary non-melting device, and a non-melting pitch powder silo connected in sequence. The non-melting pitch powder silo is connected to a carbonization device and a primary activation device. The carbonization device, a grading device I, and a product A silo are connected in sequence. The primary activation device is connected to the secondary activation device and a grading device II. The grading device II is connected to a product B silo. The secondary activation device, a grading device III, and a product C silo are connected in sequence. The primary and secondary non-melting devices are both connected to an oxidizing gas source and an inert gas source. The primary and secondary activation devices are both connected to an activation gas source and an inert gas source. A gas crossover line connects the primary and secondary activation devices. The activation gas source is connected to the inert gas source.

[0006] A process for co-producing pitch-based hard carbon and porous carbon includes the following steps: the raw material is carbonized and graded after being infusible to obtain hard carbon, and activated and graded to obtain porous carbon; the raw pitch undergoes a first-stage and a second-stage infusible process to obtain infusible pitch suitable for porous carbon or hard carbon; the infusible pitch is then activated in a first-stage and a second-stage stepwise process to obtain porous carbon, and the concentration and type of activation gas can be arbitrarily adjusted as needed.

[0007] Furthermore, the method includes the following steps:

[0008] Step 1: Raw material non-melting treatment; The raw material asphalt powder is transported from the raw material silo to the primary non-melting device, where a certain concentration of oxidizing gas is introduced at a lower temperature to carry out the primary non-melting operation; After the reaction is completed, it is transported to the secondary non-melting device, where a certain concentration of oxidizing gas is introduced at a certain temperature to carry out the secondary non-melting operation, resulting in non-melting asphalt powder, which is then transported to the non-melting asphalt powder silo.

[0009] Step 2, Hard Carbon Production Process: The non-melting asphalt powder is transported to the carbonization device, where it undergoes carbonization under inert gas protection, and then transported to the grading device I. After grading, it is transported to the product silo to obtain product A hard carbon.

[0010] Step 3: Porous carbon production process; Unmelted asphalt powder is transported to the primary activation device, where a certain concentration of activation gas is introduced at a certain temperature. After primary activation, the material is classified by the grading device II and then sent to the product B silo to obtain product B porous carbon; The material after primary activation is then activated by the secondary activation device, where a certain concentration of activation gas is introduced at a certain temperature, and then transported to the grading device III for further classification and sent to the product C silo to obtain product C porous carbon.

[0011] Further, in step one, the raw material is any one or a mixture of two or more of the following: coal tar pitch, medium-low temperature coal tar pitch, petroleum pitch, ethylene tar pitch, and catalytic residue pitch, with a softening point of 180℃-350℃; or a modified pitch of the above-mentioned pitches, and the particle size D... 50 2-30um, D 90 ≤100um.

[0012] Furthermore, the modified asphalt is any one or a mixture of two or more of oxidized asphalt, polymer-modified asphalt, and heteroatom-doped asphalt.

[0013] Furthermore, in step one, the non-melting temperature of the raw material non-melting treatment process is 250-330℃ for the first stage and 330-450℃ for the second stage.

[0014] Furthermore, in step one, the oxidizing gas in the raw material non-melting treatment process is any one or a mixture of two or more of the following: air, oxygen, and ozone; the concentration of the oxidizing gas is adjusted by mixing it with any proportion of the inert gas nitrogen or argon.

[0015] Furthermore, in step two, the carbonization temperature in the hard carbon production process is 600-1800℃.

[0016] Furthermore, in step three, the activation gas in the primary activation device of the porous carbon production process is a mixture of CO2, nitrogen, argon, or any two or more of them with water vapor, and the water vapor accounts for 50-100% of the volume percentage of the activation gas; the activation gas in the secondary activation device of the porous carbon production process is a mixture of water vapor, nitrogen, argon, or any two or more of them with CO2, and the CO2 accounts for 50-100% of the volume percentage of the activation gas.

[0017] Furthermore, in step three, the activation temperature of the primary and secondary activation devices in the porous carbon production process is 600-1300℃.

[0018] This invention utilizes asphalt as a raw material, resulting in low cost and high added value. It allows for flexible and adjustable processes, continuous and stable operation, and flexible adjustment of product types and specifications, enabling timely adaptation to market changes and reducing market risks for enterprises. This invention effectively combines the production processes of hard carbon and porous carbon required in the energy storage field, overcoming the shortcomings of asphalt-based raw materials, such as difficulty in forming hard carbon structures after carbonization, and the difficulty in creating pores and controlling the structure during the preparation of porous carbon. This enhances its applicability in the next-generation energy storage field. Attached Figure Description

[0019] To more clearly illustrate the technical solutions in this utility model or related technologies, the drawings used in the description of the embodiments or related technologies will be briefly introduced below. Obviously, the drawings described below are some embodiments of this utility model. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0020] Figure 1 This is a production process route diagram for this utility model.

[0021] The components are: 1. Raw material silo; 2. Primary non-melting device; 3. Secondary non-melting device; 4. Non-melting asphalt powder silo; 5. Carbonization device; 6. Grading device I; 7. Product A silo; 8. Primary activation device; 9. Secondary activation device; 10. Grading device II; 11. Product B silo; 12. Grading device III; 13. Product C silo. Detailed Implementation

[0022] The following will be combined with the appendix Figure 1 The technical solution of this utility model has been clearly and completely described. Obviously, the described embodiments are only some, not all, of the embodiments of this utility model. Based on the embodiments of this utility model, all other embodiments obtained by those skilled in the art without creative effort are within the protection scope of this utility model.

[0023] The present invention is described in detail below through specific embodiments, but this does not limit the scope of protection of the present invention. Unless otherwise specified, the experimental methods used in the present invention are all conventional methods, and the experimental equipment, materials, reagents, etc. used can all be obtained commercially.

[0024] In the description of this utility model, it should be noted that the terms "vertical," "horizontal," "inner," and "outer," etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings. They are used only for the convenience of describing this utility model and simplifying the description, and do not indicate or imply that the device or component referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limitations on this utility model. Furthermore, the terms "first," "second," and "third" are used only for distinction and should not be construed as indicating or implying relative importance.

[0025] Furthermore, the technical features involved in the different embodiments of this utility model described below can be combined with each other as long as they do not conflict with each other.

[0026] A process apparatus for co-producing pitch-based hard carbon and porous carbon includes a raw material silo 1, a primary non-melting device 2, a secondary non-melting device 3, and a non-melting pitch powder silo 4 connected in sequence. The non-melting pitch powder silo 4 is connected to a carbonization device 5 and a primary activation device 8. The carbonization device 5, a grading device I 6, and a product A silo 7 are connected in sequence. The primary activation device 8 is connected to a secondary activation device 9 and a grading device II 10. The grading device II 10 is connected to a product B silo 11. The secondary activation device 9, a grading device III 12, and a product C silo 13 are connected in sequence. The primary non-melting device 2 and the secondary non-melting device 3 are both connected to an oxidizing gas source and an inert gas source. The primary activation device 8 and the secondary activation device 9 are both connected to an activation gas source and an inert gas source. A gas crossover line connects the primary activation device 8 and the secondary activation device 9. The activation gas source is connected to the inert gas source.

[0027] A process for co-producing pitch-based hard carbon and porous carbon includes the following steps: after the raw material is infusible, it undergoes carbonization and classification to obtain hard carbon, and after activation and classification, it obtains porous carbon. The raw material pitch undergoes a primary and secondary infusible process to obtain infusible pitch, achieving precise control over the infusible process for different types of pitch raw materials, thus obtaining infusible pitch suitable for porous carbon or hard carbon. The infusible pitch is then further activated in a primary and secondary stepwise manner to obtain porous carbon. The concentration and type of activation gas can be arbitrarily adjusted as needed to achieve precise control over the pore structure of the porous carbon and meet different application requirements.

[0028] The specific procedures are as follows:

[0029] Step 1: Raw Material Non-Melting Treatment. Raw material asphalt powder is transported from raw material silo 1 to the primary non-melting device 2, where a certain concentration of oxidizing gas is introduced at a lower temperature for primary non-melting. After the reaction, it is transported to the secondary non-melting device 3, where a certain concentration of oxidizing gas is introduced at a certain temperature for secondary non-melting, resulting in non-melting asphalt powder, which is then transported to the non-melting asphalt powder silo 4. The concentration of the oxidizing gas is adjusted by mixing it with an inert gas.

[0030] The raw material is any one or a mixture of two or more of the following: coal tar pitch, medium-low temperature coal tar pitch, petroleum pitch, ethylene tar pitch, and catalytic residue pitch, with a softening point of 180℃-350℃; or a modified pitch of the above-mentioned pitches, and the particle size D is [missing information]. 50 2-30um, D 90 ≤100um.

[0031] Modified asphalt is any one or a mixture of two or more of oxidized asphalt, polymer-modified asphalt, and heteroatom-doped asphalt. The polymer used in modified asphalt can be phenolic resin, epoxy resin, polyacrylonitrile, or other high-molecular-weight organic resins; heteroatom doping can be done by nitrogen, oxygen, sulfur, phosphorus, boron, and their compounds.

[0032] The non-melting temperature of the raw material non-melting treatment process is 250-330℃ for the first stage and 330-450℃ for the second stage.

[0033] The oxidizing gas in the non-melting raw material treatment process is any one or a mixture of two or more of the following: air, oxygen, and ozone; the concentration of the oxidizing gas is adjusted by mixing it with inert gases such as nitrogen or argon in any proportion.

[0034] The equipment used for primary and secondary non-melting processes can be fluidized beds, converters, roller kilns, or box furnaces, and the types and concentrations of oxidizing gases used can be the same or different.

[0035] Step 2, Hard Carbon Production Process. The non-melting asphalt powder is conveyed to the carbonization unit 5, where it undergoes carbonization under inert gas protection. After carbonization, it is conveyed to the grading unit I 6, and after grading, it is conveyed to the product A silo 7 to obtain product A hard carbon.

[0036] The carbonization temperature in the hard charcoal production process is 600-1800℃.

[0037] Carbonization equipment can be fluidized bed, converter, roller kiln or box furnace.

[0038] Step 3: Porous Carbon Production Process. Unmelted asphalt powder is conveyed to the primary activation unit 8, where a specific concentration of activation gas is introduced at a certain temperature. After primary activation, the material is classified by the grading unit II 10 and then sent to product B silo 11 to obtain product B porous carbon. The material after primary activation can then be further activated by the secondary activation unit 9, where a specific concentration of activation gas is introduced at a certain temperature. After further classification by the grading unit III 12, it is sent to product C silo 13 to obtain product C porous carbon.

[0039] In the primary activation unit of the porous carbon production process, the activation gas is a mixture of CO2, nitrogen, argon, or any two or more of them with water vapor, and the water vapor accounts for 50-100% of the volume percentage of the activation gas; in the secondary activation unit of the porous carbon production process, the activation gas is a mixture of CO2, or any two or more of them with water vapor, nitrogen, argon, or any two or more of them, and the CO2 accounts for 50-100% of the volume percentage of the activation gas.

[0040] The activation temperature of the primary and secondary activation devices in the porous carbon production process is 600-1300℃.

[0041] The devices used for primary and secondary activation can be fluidized beds, converters, roller kilns, or box furnaces.

[0042] Using the process method of this utility model, following the specific steps described above, 12 batches of asphalt raw materials were selected. The asphalt indicators for each batch of raw materials are shown in Table 1. The process parameters for the non-melting treatment of the raw materials are shown in Table 2. The process parameters for the hard carbon production process are shown in Table 3. The process parameters for the porous carbon production process are shown in Table 4. The performance indicators of the hard carbon product used in sodium-ion batteries are shown in Table 5. The performance indicators of the porous carbon are shown in Table 6. The porous carbon product produced using the process method of this utility model can be used in fields such as supercapacitors, silicon-carbon anodes, environmental remediation, or catalyst carriers. The hard carbon product can be used in energy storage battery fields such as lithium-ion batteries and sodium-ion batteries.

[0043] Table 1. Asphalt Indicators for Each Batch of Raw Materials

[0044]

[0045] Table 2 Non-melting treatment process parameters

[0046]

[0047] Table 3 Process parameters for hard carbon production

[0048] batch number Carbonization temperature / °C Carbonization device 1 1050 fluidized bed 2 1200 converter 3 1450 converter 4 950 Roller kiln 5 1600 Box furnace 6 1100 fluidized bed 7 800 converter 8 1200 fluidized bed 9 1550 Box furnace 10 1350 Roller kiln 11 900 converter 12 1180 fluidized bed

[0049] Table 4 Activation Treatment Process Parameters

[0050]

[0051] Table 5 Performance Indicators of Hard Carbon Products

[0052]

[0053] Table 6 Performance Indicators of Porous Carbon Products

[0054]

[0055] The embodiments described above are merely preferred embodiments of this utility model, and not all feasible embodiments of this utility model. For those skilled in the art, any obvious modifications made without departing from the principles and spirit of this utility model should be considered to be included within the scope of protection of the claims of this utility model. Although this utility model has been described above with reference to embodiments, various modifications can be made and components can be replaced with equivalents without departing from the scope of this utility model. In particular, as long as there is no technical conflict, the features in the embodiments disclosed in this utility model can be combined with each other in any way. The lack of an exhaustive description of these combinations in this specification is merely for the sake of brevity and resource conservation. Therefore, this utility model is not limited to the specific embodiments disclosed herein, but includes all technical solutions falling within the scope of the claims.

Claims

1. A process apparatus for co-producing pitch-based hard carbon and porous carbon, characterized in that, It includes a raw material silo, a primary non-melting device, a secondary non-melting device, and a non-melting asphalt powder silo connected in sequence. The non-melting asphalt powder silo is connected to the carbonization device and the primary activation device. The carbonization device, the grading device I, and the product A silo are connected in sequence. The primary activation device is connected to the secondary activation device and the grading device II. The grading device II is connected to the product B silo. The secondary activation device, the grading device III, and the product C silo are connected in sequence.

2. The process apparatus for co-producing pitch-based hard carbon and porous carbon according to claim 1, characterized in that, Both the primary non-melting device and the secondary non-melting device are connected to an oxidizing gas source and an inert gas source.

3. The process apparatus for co-producing pitch-based hard carbon and porous carbon according to claim 1, characterized in that, Both the primary activation device and the secondary activation device are connected to the activation gas source and the inert gas source.

4. The process apparatus for co-producing pitch-based hard carbon and porous carbon according to claim 1, characterized in that, A gas cross-line connects the primary activation device and the secondary activation device, and the activation gas source is connected to the inert gas source.

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