Preparation system and method of porous electrode carbon

Abstract

The invention provides a preparation system and method of porous electrode carbon. The system mainly comprises a two-section temperature-variable carbonization fluidized bed and an activation fluidized bed. According to the method, small-particle-size polymer particles are softened in the carbonization process and bonded with a large number of heat carrier particles to form composite particles, so that self bonding and excessive growth are avoided, and controllable carbonization is achieved in the two-section temperature-changing carbonization fluidized bed; and introducing the composite particles into an activation fluidized bed, carrying out high-temperature activation, and removing the heat carrier to obtain the porous carbon electrode carbon particles. According to the method, adhesion of polymer particles during carbonization is avoided, the problem of instability of superfine particle fluidization operation is solved, the links of grinding and heating and cooling are reduced, and the method has the advantages of being low in cost and capable of being continuously operated.

Description

Technical Field

[0001] The present application relates to the technical field of electrochemical energy storage electrode materials, and in particular, to a system and method for preparing porous electrode carbon. Background Art

[0002] Devices based on clean electrochemical energy storage mechanisms, such as various secondary batteries, supercapacitors, lithium-ion capacitors or their hybrid devices, are important electrical energy storage systems and have made great progress in recent years. The positive electrode materials of supercapacitors and lithium-ion capacitors are porous activated carbon with large specific surface area. Secondary batteries such as lithium-ion negative electrode materials (silicon-carbon negative electrode) also use porous activated carbon with large specific surface area as a fixed carrier of silicon particles, which accounts for about 50% of the weight of the silicon-carbon negative electrode.

[0003] This porous activated carbon is mainly composed of biomass or organic polymers as precursors, and is composed of carbonization (dehydrogenation, deoxidation or other elements at high temperature) and activation (pore formation) steps. However, the current activation method is relatively mature, but there are few reports on carbonization. In actual operation, some precursor particles will become soft and sticky at high temperatures, forming particularly large sticky agglomerates, and the particle size and density are not very controllable. Not only that, there is also a wall sticking phenomenon, which is particularly difficult to operate in engineering. The huge carbonized agglomerates or particles finally generated have to be ground into small particles and then activated. The strength of the agglomerates after carbonization is particularly large, so a large amount of mechanical energy is required.

[0004] It can be seen that the existing process has problems such as uncontrollable particle size, easy formation of huge carbonized agglomerates, wall adhesion, poor particle fluidity and high energy consumption. Therefore, it is urgent to propose a preparation system and method for porous electrode carbon that is easy to operate, can be smoothly carbonized and activated, and is energy-saving. Summary of the invention

[0005] To solve the above problems, the present application provides a system and method for preparing porous electrode carbon, which bonds polymer particles and small-size heat carrier particles to form a composite carbonized material, which can achieve smooth carbonization and activation and avoid the formation of huge carbonized agglomerates or particles, making the particle size more controllable. The heat carrier particles can be removed by cooling in the final step, omitting multiple cooling, grinding and other operation steps, thereby achieving the effect of easy control of engineering operations and reduced energy consumption.

[0006] In a first aspect, the present application provides a system for preparing porous electrode carbon, comprising a carbonization fluidized bed, an activation fluidized bed and a heat carrier removal reactor connected in series in sequence; A porous distribution plate is arranged in the reaction zone of the carbonization fluidized bed, and the porous distribution plate divides the reaction zone into a first reaction zone and a second reaction zone. The first reaction zone is provided with a fluidizing gas inlet and a composite carbonization material outlet, and the second reaction zone is provided with a mixed raw material inlet and a fluidized tail gas outlet; An overflow pipe is arranged outside the carbonization fluidized bed, one end of the overflow pipe is connected to the first reaction zone, and the other end of the overflow pipe is connected to the second reaction zone; The bottom of the activated fluidized bed is provided with an activated gas inlet and an activated material outlet; the top of the activated fluidized bed is provided with a composite carbonized material inlet and an activated tail gas outlet; The heat carrier removal reactor is filled with acid or water.

[0007] Optionally, the first reaction zone is provided with a first temperature control device, and the first temperature control device is used to control the operating temperature of the first reaction zone to be 500°C-950°C.

[0008] Optionally, the second reaction zone is provided with a second temperature control device, and the second temperature control device is used to control the operating temperature of the second reaction zone to 200°C-400°C.

[0009] Optionally, the activated fluidized bed is provided with a third temperature control device, and the third temperature control device is used to control the operating temperature of the activated fluidized bed reaction zone to 850°C-1050°C.

[0010] In a second aspect, the present application provides a method for preparing porous electrode carbon, which is applicable to the system for preparing porous electrode carbon of the first aspect, and comprises: The temperature of the first reaction zone of the carbonized fluidized bed is controlled to be 500°C-950°C, and the temperature of the second reaction zone is controlled to be 200°C-400°C; The fluidizing gas is fed into the first reaction zone through the fluidizing gas inlet, and the mixed raw material of the polymer particles and the heat carrier particles is fed into the second reaction zone through the mixed raw material inlet. Under the action of the fluidizing gas, the polymer particles and the heat carrier particles are compounded and carbonized in the first reaction zone and the second reaction zone to form a composite carbonized material; The temperature of the reaction zone of the activated fluidized bed is controlled to be 850°C-1050°C, and the composite carbonized material enters the activated fluidized bed through the composite carbonized material outlet and the composite carbonized material inlet in sequence, and reacts with the activated gas to form an activated material; The activated material is introduced into a heat carrier removal reactor containing acid or water, and the heat carrier particles in the activated material are removed by the acid or water, and finally a porous electrode carbon product is obtained; Wherein, the polymer particles include at least one of epoxy resin, phenolic resin, urea-formaldehyde resin, unsaturated resin and polycarbonate resin; the diameter of the polymer particles is 5 μm-16 μm; The heat carrier particles include at least one of magnesium oxide, sodium chloride, potassium chloride, calcium chloride, calcium oxide, sodium silicate, calcium carbonate, sodium carbonate and magnesium carbonate; and the diameter of the heat carrier particles is 60 μm-200 μm.

[0011] Optionally, under the action of the fluidizing gas, the polymer particles and the heat carrier particles are compounded and carbonized in the first reaction zone and the second reaction zone, including: Under the action of the fluidizing gas, the polymer particles melt and soften in the second reaction zone, and bond and solidify with the heat carrier particles to form composite particles; The composite particles move downward to the first reaction zone through the porous distribution plate and the overflow pipe under the action of gravity, and are carbonized to obtain the composite carbonized material.

[0012] Optionally, the mass ratio of the polymer particles to the heat carrier particles is 1:(1-3).

[0013] Optionally, the fluidizing gas includes at least one of CO, H2, Ar, He, CO2 and CH4.

[0014] Optionally, the activation gas includes at least one of CO2 and H2O.

[0015] In a third aspect, the present application provides a porous electrode carbon prepared by the preparation method described in the second aspect, wherein the specific surface area of ​​the porous electrode carbon is 1600 m 2 / g-2800 m 2 / g.

[0016] In summary, the present application includes at least one of the following beneficial technical effects: 1. The present application provides a system for preparing porous electrode carbon. The system realizes continuous production from composite carbonized materials to porous electrode carbon by setting up a carbonization fluidized bed, an activation fluidized bed and a heat carrier removal reactor in series. The continuous process helps to maintain the integrity and stability of the material and improve the specific surface area and electrochemical properties of the porous electrode carbon. Specifically, by setting a porous distribution plate, the carbonization fluidized bed is divided into two temperature-varying reaction zones, so that the temperature of the carbonization process is more controllable. Specifically, the first reaction zone is used for compounding and preliminary carbonization, and the second reaction zone is used for more in-depth carbonization, which helps to form a uniform, dense, and moderately granular carbonization structure.

[0017] 2. In the preparation method of porous electrode carbon provided in the present application, polymer particles and heat carrier particles are directly used to form composite particles, which solves the problem that small-size particles cannot be fluidized, avoids the formation of large particle agglomerates, reduces the grinding process of large particles, omits the temperature increase and decrease operation steps, reduces the number of preparation equipment by about 30%, reduces equipment investment by 25%-30%, and makes small particles easier to carbonize and activate, reduces the amount of fluidizing gas and activation gas by 50%, and can increase the production capacity per unit time by 3 times-10 times; this method connects carbonization and activation, effectively utilizes the thermal energy of carbonized materials, shortens the preparation time by 80%-90%, and reduces the activation energy consumption by 60%-70%. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings required for use in the description of the embodiments of the present application will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative labor.

[0019] Figure 1 A structural diagram of a porous electrode carbon preparation system proposed in an embodiment of the present application is shown; Figure 2 A flow chart of a method for preparing porous electrode carbon proposed in an embodiment of the present application is shown.

[0020] Description of reference numerals: 1. Carbonized fluidized bed; 11. porous distribution plate; 111. first reaction zone; 1111. fluidizing gas inlet; 1112. composite carbonization material outlet; 112. second reaction zone; 1121. mixed raw material inlet; 1122. fluidizing tail gas outlet; 12. overflow pipe; 2. Activated fluidized bed; 21. Activated gas inlet; 22. Activated material outlet; 23. Composite carbonization material inlet; 24. Activated tail gas outlet; 3. Heat carrier removal reactor. DETAILED DESCRIPTION

[0021] The following will be combined with the drawings in the embodiments of the present application to clearly and completely describe the technical solutions in the embodiments of the present application. Obviously, the described embodiments are part of the embodiments of the present application, not all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of this application.

[0022] In the drawings, the size of the constituent elements, the thickness of the layer or the area may be exaggerated for the sake of clarity. Therefore, any implementation of the present disclosure is not necessarily limited to the size shown in the drawings, and the shapes and sizes of the components in the drawings do not reflect the true proportions. In addition, the drawings schematically show ideal examples, and any implementation of the present disclosure is not limited to the shapes or values ​​shown in the drawings.

[0023] In the related art, porous carbon is mainly composed of biomass or organic polymers as precursors, which are composed of carbonization and activation steps. In the carbonization process, some precursor particles will become soft and sticky at high temperatures, forming particularly large sticky agglomerates, and the particle size and density are not well controlled. At the same time, there is also a wall sticking phenomenon, which is particularly difficult to operate in engineering. In addition, the huge carbonized agglomerates or particles finally generated have to be ground into small particles and then activated. The strength of the agglomerates after carbonization is particularly large, so a large amount of mechanical energy is required.

[0024] In addition, since the flow characteristics of extremely small particles are not good and it is not easy to process them by engineering, the carbonized material after cooling and grinding is still large particles. After heating and activation, the activated material still needs to go through the steps of cooling and grinding before it can be used as electrode carbon (its common particle size is 5-7μm).

[0025] It can be seen that there are multiple steps of grinding operations and multiple heating and cooling processes in this process. In addition, in the final grinding process, the specific surface area and pore volume of the material are greatly lost, resulting in the disconnection between the final product quality control and the operation control of the activation link. These problems have become common problems in electrode carbon in several industries and have not been well solved for a long time.

[0026] In view of the shortcomings of the prior art, the embodiments of the present application provide a technology that utilizes a heat carrier medium to assist in carbonization. By bonding with small-size polymer particles to form composite particles, not only can carbonization and activation be carried out smoothly and continuously, but also the problem of poor fluidity of small particles is overcome, and multiple cooling and grinding steps in the carbonization and activation process are avoided. Only in the last step is cooling and removing the heat carrier medium, thereby achieving the effect of easy control of engineering operation and low energy consumption.

[0027] See also Figure 1 , Figure 1 The structure diagram of a porous electrode carbon preparation system proposed in the embodiment of the present application is shown, which specifically includes: A carbonization fluidized bed 1, an activation fluidized bed 2 and a heat carrier removal reactor 3 are connected in series in sequence; A porous distribution plate 11 is provided in the reaction zone of the carbonization fluidized bed 1. The porous distribution plate 11 divides the reaction zone into a first reaction zone 111 and a second reaction zone 112. The first reaction zone 111 is provided with a fluidizing gas inlet 1111 and a composite carbonization material outlet 1112. The second reaction zone 112 is provided with a mixed raw material inlet 1121 and a fluidized tail gas outlet 1122. An overflow pipe 12 is disposed outside the carbonization fluidized bed 1, one end of the overflow pipe 12 is connected to the first reaction zone 111, and the other end is connected to the second reaction zone 112; An activation gas inlet 21 and an activation material outlet 22 are provided at the bottom of the activation fluidized bed 2; a composite carbonization material inlet 23 and an activation tail gas outlet 24 are provided above the activation fluidized bed 2; The heat carrier removal reactor 3 is filled with acid or water.

[0028] The porous electrode carbon preparation system realizes continuous and efficient processing of raw materials, improves the quality and performance of the final product, and reduces environmental pollution and energy consumption.

[0029] Among them, by setting up a carbonization fluidized bed 1, and using a porous distribution plate 11 to divide its interior into two temperature-variable reaction zones, temperature control of the continuous carbonization process of the raw material is achieved, wherein fluidizing gas is introduced into the first reaction zone 111 to suspend the raw material particles and keep them evenly distributed, and the second reaction zone 112 receives the preliminarily carbonized material and then conducts further carbonization reaction; by setting up a composite carbonization material outlet 1112, the carbonized material can be timely discharged, making the carbonization process more controllable; by setting up an overflow pipe 12, it is helpful to maintain the material balance during the reaction process, and the preliminarily carbonized material is returned to the first reaction zone 111 for further carbonization treatment.

[0030] By setting up an activation fluidized bed 2, the carbonized material is activated to improve the pore structure and electrochemical performance of the material. The activated material is discharged through the activation material outlet 22 to provide high-quality raw materials for subsequent electrode preparation.

[0031] By setting up a heat carrier removal device, the heat carrier particles attached to the mixed material are removed to obtain a porous activated carbon product. In addition, other impurities on the material can also be removed by acid or water, which helps to improve the purity of the porous activated carbon product.

[0032] In some embodiments, the porous distribution plate 11 includes: any one of a flat porous distribution plate, a conical porous distribution plate, a folded shell porous distribution plate, a porous ceramic distribution plate and a metal porous plate, and the type of the porous distribution plate 11 is not specifically limited in the embodiments of the present application. The material of the porous distribution plate 11 includes: one of stainless steel, titanium alloy, zirconium oxide, aluminum oxide, silicon oxide or other composite materials, and the material of the porous distribution plate 11 is not specifically limited in the embodiments of the present application.

[0033] In some embodiments, the heat carrier removal reactor 3 may be a stirrer, and the specific type is not specifically limited in the embodiments of the present application.

[0034] In some embodiments, the first reaction zone 111 is provided with a first temperature control device, and the first temperature control device is used to control the operating temperature of the first reaction zone 111 to be 500° C.-950° C.

[0035] In some embodiments, the second reaction zone 112 is provided with a second temperature control device, and the second temperature control device is used to control the operating temperature of the second reaction zone 112 to be 200° C.-400° C.

[0036] In specific implementation, by setting the first temperature control device and the second temperature control device, the temperature of the first reaction zone 111 and the second reaction zone 112 can be more accurately controlled to ensure the balance and continuous progress of the carbonization reaction, thereby improving the output and efficiency. Among them, the working temperature range of the first reaction zone 111 is relatively wide, which can adapt to different types of biomass raw materials for carbonization, making the system more flexible and adaptable.

[0037] In some embodiments, the activated fluidized bed 2 is provided with a third temperature control device, which is used to control the operating temperature of the reaction zone of the activated fluidized bed 2 to be 850° C.-1050° C. By providing the third temperature control device, it is beneficial to accurately control the temperature of the activated fluidized bed 2, optimize the activation process, and make the reaction more efficient and stable.

[0038] The present application also provides a method for preparing porous electrode carbon, see Figure 2 , Figure 2 The flowchart of a method for preparing porous electrode carbon provided in an embodiment of the present application is shown, and the specific steps include: S1: Control the temperature of the first reaction zone of the carbonization fluidized bed to be 500°C-950°C, and the temperature of the second reaction zone to be 200°C-400°C; S2: Fluidizing gas is fed into the first reaction zone through the fluidizing gas inlet, and a mixed raw material of polymer particles and heat carrier particles is fed into the second reaction zone through the mixed raw material inlet. Under the action of the fluidizing gas, the polymer particles and the heat carrier particles are compounded and carbonized in the first reaction zone and the second reaction zone to form a composite carbonized material; S3: Controlling the temperature of the reaction zone of the activated fluidized bed to be 850°C-1050°C, the composite carbonized material sequentially enters the activated fluidized bed through the composite carbonized material outlet and the composite carbonized material inlet, and reacts with the activated gas to form an activated material; S4: introducing the activated material into a heat carrier removal reactor filled with acid or water, and removing the heat carrier particles in the activated material by the acid or water, and finally obtaining a porous electrode carbon product; The polymer particles include at least one of epoxy resin, phenolic resin, urea-formaldehyde resin, unsaturated resin and polycarbonate resin; the diameter of the polymer particles is 5 μm-16 μm; The heat carrier particles include at least one of magnesium oxide, sodium chloride, potassium chloride, calcium chloride, calcium oxide, sodium silicate, calcium carbonate, sodium carbonate and magnesium carbonate; and the diameter of the heat carrier particles is 60 μm-200 μm.

[0039] In specific implementation, by optimizing the carbonization and activation processes, and effectively removing the heat carrier, the final porous electrode carbon product has a higher specific surface area, a larger pore volume and a more uniform particle size distribution.

[0040] The embodiment of the present application introduces heat carrier particles to disperse the polymer particles, making it difficult for the polymer particles to form large particles or agglomerate at high temperatures, thus solving the problem that small-size particles cannot be fluidized. The carbonization and activation are connected to effectively utilize the heat energy of the carbonized material, reduce multiple temperature rise and fall and grinding operations, reduce mechanical energy consumption, simplify the preparation process, shorten the preparation cycle, and improve preparation efficiency.

[0041] By controlling the temperature of the first reaction zone of the carbonization fluidized bed to 500°C-950°C and the temperature of the second reaction zone to 200°C-400°C, the carbonization process under two temperature gradients is realized, which avoids the rapid softening and adhesion of polymer particles (precursor particles) at high temperatures, and reduces the occurrence of sticky agglomeration and wall adhesion. By introducing the fluidizing gas, the polymer particles and the heat carrier particles can be fully mixed and evenly heated in the first reaction zone and the second reaction zone to promote the carbonization reaction. The fluidizing gas can also play a role in stirring and dispersing, which helps to form a composite carbonized material with uniform particles and stable structure.

[0042] The activation process is fully carried out by controlling the reaction zone temperature of the activated fluidized bed to 850°C-1050°C. High temperature activation helps to form more pore structures, thereby increasing the specific surface area and pore volume of the porous electrode carbon.

[0043] By arranging the composite carbonized material to enter the activated fluidized bed through the composite carbonized material outlet and the composite carbonized material inlet in sequence, continuous treatment of the carbonization and activation processes is achieved, thereby improving the preparation efficiency.

[0044] Finally, the activated material is introduced into a heat carrier removal reactor filled with acid or water, and the heat carrier particles are removed by the action of the acid or water, thereby avoiding the influence of the heat carrier particles on the product quality.

[0045] In specific implementation, the polymer particles can form a stable carbon structure during the carbonization process, so that the final product has better mechanical strength and chemical stability; the heat carrier particles interact with the polymer particles during the reaction process to promote the formation of small-particle composite carbonized materials.

[0046] The diameter of the polymer particles is 5 μm-16 μm, so that the polymer particles can be fully dispersed between the heat carrier particles, which is beneficial to the heat transfer and reaction uniformity during the carbonization process. At the same time, the smaller particle size can also increase the contact area between the polymer particles and the heat carrier particles, promoting the composite effect between the two.

[0047] The diameter of the heat carrier particles is 60 μm-200 μm, which enables the heat carrier particles to maintain good fluidity and dispersion during the reaction, which is conducive to the transfer of heat and the uniform formation of composite carbonized materials. The larger particle size can also provide sufficient space to accommodate the volume change of the polymer particles during the carbonization process.

[0048] In some embodiments, the acid contained in the heat carrier removal reactor may be at least one of sulfuric acid, phosphoric acid, hydrochloric acid, and nitric acid.

[0049] In some embodiments, under the action of the fluidizing gas, the polymer particles and the heat carrier particles are compounded and carbonized in the first reaction zone and the second reaction zone, including: Under the action of the fluidizing gas, the polymer particles melt and soften in the second reaction zone, and bond and solidify with the heat carrier particles to form composite particles; The composite particles move downward to the first reaction zone through the porous distribution plate and the overflow pipe under the action of gravity, and are carbonized to obtain a composite carbonized material.

[0050] In specific implementation, under the action of the fluidizing gas, the polymer particles can be evenly heated and melted and softened in the second reaction zone, and the heat provided by the heat carrier particles promotes the bonding and solidification between the polymer particles and the heat carrier particles, forming structurally stable composite particles; solving the problem that the polymer particles quickly soften and stick together to form large sticky agglomerates at high temperatures; and under the stirring and dispersing action of the fluidizing gas, further preventing the occurrence of wall sticking.

[0051] Under the action of gravity, the composite particles move downward to the first reaction zone for further carbonization treatment, so that the composite particles can be heated more evenly during the carbonization process, avoiding the problem of local overheating or incomplete carbonization. The porous distribution plate and overflow pipe are provided to help adjust the movement speed and residence time of the composite particles and further optimize the carbonization process.

[0052] In some embodiments, the mass ratio of polymer particles to heat carrier particles is 1:(1-3).

[0053] In specific implementation, the mass ratio of polymer particles to heat carrier particles is 1:1, 1:1.5, 1:2, 1:2.5 or 1:3. By limiting the mass ratio between polymer particles and heat carrier particles, heat can be more efficiently transferred from the heat carrier particles to the polymer particles, so that the polymer particles are quickly melted and softened in the second reaction zone, reducing energy consumption. By accurately controlling the mass ratio of polymer particles to heat carrier particles, it is also beneficial to achieve effective utilization of resources and reduce unnecessary waste.

[0054] In some embodiments, the fluidizing gas includes at least one of CO, H2, Ar, He, CO2, and CH4.

[0055] The fluidizing gas has a certain reducing property and can participate in the carbonization reaction to promote the carbonization of polymer particles.

[0056] In some embodiments, the activation gas includes at least one of CO 2 and H 2 O.

[0057] CO2 and H2O undergo redox reactions with the composite carbonized material at high temperatures, creating pores in the composite carbonized material to form a porous structure. These pore structures help increase the surface area of ​​the electrode, provide more active sites, and promote the adsorption and reaction of electrolyte ions.

[0058] In some embodiments, the present application provides a porous electrode carbon prepared by the above preparation method, and the specific surface area of ​​the porous electrode carbon is 1600 m 2 / g-2800 m 2 / g, which can provide more active sites for the ions in the electrolyte to adsorb and react, and can also carry more charges to increase the rate of electrochemical reactions.

[0059] In order to enable those skilled in the art to understand the present application more clearly, a system and method for preparing a porous electrode carbon of the present application are now described in detail through the following examples.

[0060] Example Example 1 1. Fluidizing gas (N2) is introduced into the first reaction zone of the carbonization fluidized bed through the fluidizing gas inlet, and the temperature of the first reaction zone is controlled to be 750 ℃-780 ℃. The gas passes through the porous distribution plate and enters the second reaction zone, and the temperature of the second reaction zone is controlled to be 250 ℃-350 ℃; 2. Mix polymer particles (90% phenolic resin and 10% urea-formaldehyde resin, particle size 6 μm-12 μm) and heat carrier particles (sodium chloride, particle size 60 μm-120 μm) in a ratio of 1:1, and introduce the obtained mixed raw material into the second reaction zone in the carbonization fluidized bed through the mixed raw material inlet. The mixed raw material is suspended by the fluidizing gas to form a uniformly mixed state; 3. Under the action of the fluidizing gas, the polymer particles melt and soften rapidly in the second reaction zone, bond with the heat carrier particles, and solidify after 3 minutes to form composite particles. A large amount of organic gas generated during the carbonization process moves upward with the fluidizing gas and is discharged from the carbonization fluidized bed through the fluidizing tail gas outlet; 4. The composite particles in the second reaction zone continue to increase, and move downward through the porous distribution plate and the overflow pipe under the action of gravity to reach the first reaction zone, and continue to carbonize for 5 hours to form a composite carbonized material; 5. The composite carbonized material is discharged from the carbonization fluidized bed through the composite carbonized material outlet, and then enters the activation fluidized bed through the composite carbonized material inlet. The activation gas (CO2) is introduced into the activation fluidized bed from the activation gas inlet to contact the composite carbonized material, and activated at 1000°C for 0.5 hours to form an activated material; 6. The activated material is discharged from the activated fluidized bed through the activated material outlet, and the activated tail gas is discharged from the activated fluidized bed through the activated tail gas outlet; 7. The activated material is introduced into a heat carrier removal reactor filled with water to remove the heat carrier particles and obtain a specific surface area of ​​2000 m 2 / g of porous electrode carbon product.

[0061] Example 2 1. Fluidizing gas (50% H2, 50% CO2) is introduced into the first reaction zone of the carbonization fluidized bed through the fluidizing gas inlet, and the temperature of the first reaction zone is controlled to be 930°C-950°C. The gas passes through the porous distribution plate and enters the second reaction zone, and the temperature of the second reaction zone is controlled to be 350°C-400°C; 2. Mix polymer particles (10% phenolic resin and 90% epoxy resin, particle size 5μm-12μm) and heat carrier particles (magnesium oxide, particle size 100μm-200μm) in a ratio of 1:3, and introduce the obtained mixed raw material into the second reaction zone in the carbonization fluidized bed through the mixed raw material inlet. The mixed raw material is suspended by the fluidizing gas to form a uniformly mixed state; 3. Under the action of the fluidizing gas, the polymer particles melt and soften rapidly in the second reaction zone, bond with the heat carrier particles, and solidify after 3 minutes to form composite particles. A large amount of organic gas generated during the carbonization process moves upward with the fluidizing gas and is discharged from the carbonization fluidized bed through the fluidizing tail gas outlet; 4. The composite particles in the second reaction zone continue to increase, and move downward through the porous distribution plate and the overflow pipe under the action of gravity to reach the first reaction zone, and continue to carbonize for 0.5 hours to form a composite carbonized material; 5. The composite carbonized material is discharged from the carbonization fluidized bed through the composite carbonization material outlet, and then enters the activation fluidized bed through the composite carbonization material inlet. The activation gas (90% CO2, 10% H2O) is introduced into the activation fluidized bed from the activation gas inlet to contact with the composite carbonized material and activated at 850°C for 6 hours. 6. The activated material is discharged from the activated fluidized bed through the activated material outlet, and the activated tail gas is discharged from the activated fluidized bed through the activated tail gas outlet; 7. The activated material is introduced into a heat carrier removal reactor containing acid (hydrochloric acid) to remove the heat carrier particles and obtain a specific surface area of ​​2400 m 2 / g of porous electrode carbon product.

[0062] Example 3 1. Fluidizing gas (10% CO2, 90% Ar) is introduced into the first reaction zone of the carbonization fluidized bed through the fluidizing gas inlet, and the temperature of the first reaction zone is controlled to be 500°C-750°C. The gas passes through the porous distribution plate and enters the second reaction zone, and the temperature of the second reaction zone is controlled to be 200°C-400°C; 2. Mix polymer particles (90% phenolic resin and 10% urea-formaldehyde resin, particle size 5μm-15μm) and heat carrier particles (90% calcium carbonate, 10% magnesium carbonate, particle size 80μm-150μm) in a ratio of 1:2, and introduce the obtained mixed raw material into the second reaction zone in the carbonization fluidized bed through the mixed raw material inlet. The mixed raw material is suspended by the fluidizing gas to form a uniformly mixed state; 3. Under the action of the fluidizing gas, the polymer particles melt and soften rapidly in the second reaction zone, bond with the heat carrier particles, and solidify after 1.3 minutes to form composite particles. A large amount of organic gas generated during the carbonization process moves upward with the fluidizing gas and is discharged from the carbonization fluidized bed through the fluidizing tail gas outlet; 4. The composite particles in the second reaction zone continue to increase, and move downward through the porous distribution plate and the overflow pipe under the action of gravity to reach the first reaction zone, and continue to carbonize for 4 hours to form a composite carbonized material; 5. The composite carbonized material is discharged from the carbonization fluidized bed through the composite carbonization material outlet, and then enters the activation fluidized bed through the composite carbonization material inlet. The activation gas (H2O) is introduced into the activation fluidized bed from the activation gas inlet to contact with the composite carbonized material and activated at 950°C for 4 hours. 6. The activated material is discharged from the activated fluidized bed through the activated material outlet, and the activated tail gas is discharged from the activated fluidized bed through the activated tail gas outlet; 7. The activated material is introduced into a heat carrier removal reactor containing acid (hydrochloric acid) to remove the heat carrier particles and obtain a specific surface area of ​​1800 m 2 / g of porous electrode carbon product.

[0063] Example 4 1. Fluidizing gas (20% He, 80% CO) is introduced into the first reaction zone of the carbonization fluidized bed through the fluidizing gas inlet, and the temperature of the first reaction zone is controlled to be 500°C-600°C. The gas passes through the porous distribution plate and enters the second reaction zone, and the temperature of the second reaction zone is controlled to be 200°C-250°C. 2. Mix polymer particles (30% urea-formaldehyde resin and 70% polycarbonate resin, particle size 6μm-12μm) and heat carrier particles (50% magnesium oxide, 50% calcium oxide, particle size 60μm-200μm) in a ratio of 1:3, and introduce the obtained mixed raw material into the second reaction zone in the carbonization fluidized bed through the mixed raw material inlet. The mixed raw material is suspended by the fluidizing gas to form a uniformly mixed state; 3. Under the action of the fluidizing gas, the polymer particles melt and soften rapidly in the second reaction zone, bond with the heat carrier particles, and solidify after 3 minutes to form composite particles. A large amount of organic gas generated during the carbonization process moves upward with the fluidizing gas and is discharged from the carbonization fluidized bed through the fluidizing tail gas outlet; 4. The composite particles in the second reaction zone continue to increase, and move downward through the porous distribution plate and the overflow pipe under the action of gravity to reach the first reaction zone, and continue to carbonize for 8 hours to form a composite carbonized material; 5. The composite carbonized material is discharged from the carbonization fluidized bed through the composite carbonization material outlet, and then enters the activation fluidized bed through the composite carbonization material inlet. The activation gas (CO2) is introduced into the activation fluidized bed from the activation gas inlet to contact with the composite carbonized material and activated at 1020°C for 3 hours; 6. The activated material is discharged from the activated fluidized bed through the activated material outlet, and the activated tail gas is discharged from the activated fluidized bed through the activated tail gas outlet; 7. The activated material is introduced into a heat carrier removal reactor containing acid (sulfuric acid) to remove the heat carrier particles and obtain a specific surface area of ​​2800 m 2 / g of porous electrode carbon product.

[0064] Example 5 1. Fluidizing gas (50% CH4, 50% CO2) is introduced into the first reaction zone of the carbonization fluidized bed through the fluidizing gas inlet, and the temperature of the first reaction zone is controlled to be 750-780°C. The gas passes through the porous distribution plate and enters the second reaction zone, and the temperature of the second reaction zone is controlled to be 240-250°C. 2. Mix polymer particles (50% phenolic resin and 10% urea-formaldehyde resin, particle size 5μm-16μm) and heat carrier particles (potassium chloride, particle size 90μm-130μm) in a ratio of 2:3, and introduce the obtained mixed raw material into the second reaction zone in the carbonization fluidized bed through the mixed raw material inlet, so that the mixed raw material is suspended by the fluidizing gas to form a uniformly mixed state; 3. Under the action of the fluidizing gas, the polymer particles melt and soften rapidly in the second reaction zone, bond with the heat carrier particles, and solidify after 0.3 minutes to form composite particles. A large amount of organic gas generated during the carbonization process moves upward with the fluidizing gas and is discharged from the carbonization fluidized bed through the fluidizing tail gas outlet; 4. The composite particles in the second reaction zone continue to increase, and move downward through the porous distribution plate and the overflow pipe under the action of gravity to reach the first reaction zone, and continue to carbonize for 3 hours to form a composite carbonized material; 5. The composite carbonized material is discharged from the carbonization fluidized bed through the composite carbonization material outlet, and then enters the activation fluidized bed through the composite carbonization material inlet. The activation gas (40% CO2, 60% water vapor) is introduced into the activation fluidized bed from the activation gas inlet to contact with the composite carbonized material and activated at 1050 °C for 0.2 hours; 6. The activated material is discharged from the activated fluidized bed through the activated material outlet, and the activated tail gas is discharged from the activated fluidized bed through the activated tail gas outlet; 7. The activated material is introduced into a heat carrier removal reactor containing acid (nitric acid) to remove the heat carrier particles and obtain a specific surface area of ​​1600 m 2 / g of porous electrode carbon product.

[0065] Example 6 1. Fluidizing gas (Ar) is introduced into the first reaction zone of the carbonization fluidized bed through the fluidizing gas inlet, and the temperature of the first reaction zone is controlled to be 870°C-920°C. The gas passes through the porous distribution plate and enters the second reaction zone, and the temperature of the second reaction zone is controlled to be 280°C-320°C; 2. Mix polymer particles (10% phenolic resin, 80% unsaturated resin and 10% urea-formaldehyde resin, particle size 8μm-16μm) and heat carrier particles (magnesium oxide, particle size 100μm-200μm) at a ratio of 1:1.6, and introduce the obtained mixed raw material into the second reaction zone in the carbonization fluidized bed through the mixed raw material inlet. The mixed raw material is suspended by the fluidizing gas to form a uniformly mixed state; 3. Under the action of the fluidizing gas, the polymer particles melt and soften rapidly in the second reaction zone, bond with the heat carrier particles, and solidify after 3 minutes to form composite particles. A large amount of organic gas generated during the carbonization process moves upward with the fluidizing gas and is discharged from the carbonization fluidized bed through the fluidizing tail gas outlet; 4. The composite particles in the second reaction zone continue to increase, and move downward through the porous distribution plate and the overflow pipe under the action of gravity to reach the first reaction zone, and continue to carbonize for 5 hours to form a composite carbonized material; 5. The composite carbonized material is discharged from the carbonization fluidized bed through the composite carbonized material outlet, and then enters the activation fluidized bed through the composite carbonized material inlet. The activation gas (H2O) is passed into the activation fluidized bed from the activation gas inlet to contact with the composite carbonized material, and activated at 1000°C for 1 hour; 6. The activated material is discharged from the activated fluidized bed through the activated material outlet, and the activated tail gas is discharged from the activated fluidized bed through the activated tail gas outlet; 7. The activated material is introduced into a heat carrier removal reactor filled with acid (50% sulfuric acid + 50% nitric acid) to remove the heat carrier particles and obtain a specific surface area of ​​2250 m 2 / g of porous electrode carbon product.

[0066] In summary, the present application provides a system and method for preparing porous electrode carbon, which mainly includes a two-stage variable temperature carbonization fluidized bed and an activated fluidized bed. The method is that small-sized polymer particles soften during the carbonization process, and bond with a large number of heat carrier particles to form composite particles, thereby avoiding self-adhesion and excessive growth with a high probability, and controllably carbonizing in a two-stage variable temperature carbonization fluidized bed; then the composite particles are passed into the activated fluidized bed for high-temperature activation, and after removing the heat carrier, porous carbon electrode carbon particles are obtained. This method avoids the adhesion of polymer particles during carbonization, solves the instability problem of ultrafine particle fluidization operation, and reduces the grinding and temperature rise and fall steps, and has the advantages of low cost and continuous operation.

[0067] The various embodiments in this specification are described in a progressive manner, and each embodiment focuses on the differences from other embodiments. The same or similar parts between the various embodiments can be referenced to each other.

[0068] Although the preferred embodiments of the present application have been described, those skilled in the art may make additional changes and modifications to these embodiments once they have learned the basic creative concept. Therefore, the appended claims are intended to be interpreted as including the preferred embodiments and all changes and modifications that fall within the scope of the embodiments of the present application.

[0069] Finally, it should be noted that, in this article, relational terms such as first and second, etc. are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the terms "include", "comprise" or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article or terminal device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or terminal device. In the absence of further restrictions, the elements defined by the sentence "including one..." do not exclude the existence of other identical elements in the process, method, article or terminal device including the elements.

[0070] The above is a detailed introduction to the system and method for preparing a porous electrode carbon provided by the present application. Specific examples are used in this article to illustrate the principles and implementation methods of the present application. The description of the above embodiments is only used to help understand the method of the present application and its core idea; at the same time, for general technicians in this field, according to the ideas of the present application, there will be changes in the specific implementation methods and application scopes. In summary, the content of this specification should not be understood as a limitation on the present application.

Claims

1. A system for preparing porous electrode carbon, characterized in that: It comprises a carbonization fluidized bed, an activation fluidized bed and a heat carrier removal reactor which are connected in series in sequence; A porous distribution plate is arranged in the reaction zone of the carbonization fluidized bed, and the porous distribution plate divides the reaction zone into a first reaction zone and a second reaction zone. The first reaction zone is provided with a fluidizing gas inlet and a composite carbonization material outlet, and the second reaction zone is provided with a mixed raw material inlet and a fluidized tail gas outlet; An overflow pipe is arranged outside the carbonization fluidized bed, one end of the overflow pipe is connected to the first reaction zone, and the other end of the overflow pipe is connected to the second reaction zone; The bottom of the activated fluidized bed is provided with an activated gas inlet and an activated material outlet; the top of the activated fluidized bed is provided with a composite carbonized material inlet and an activated tail gas outlet; The heat carrier removal reactor is filled with acid or water.

2. The system for preparing porous electrode carbon according to claim 1, characterized in that: The first reaction zone is provided with a first temperature control device, and the first temperature control device is used to control the working temperature of the first reaction zone to be 500°C-950°C.

3. The system for preparing porous electrode carbon according to claim 1, characterized in that: The second reaction zone is provided with a second temperature control device, and the second temperature control device is used to control the operating temperature of the second reaction zone to 200°C-400°C.

4. The system for preparing porous electrode carbon according to claim 1, characterized in that: The activated fluidized bed is provided with a third temperature control device, and the third temperature control device is used to control the operating temperature of the activated fluidized bed reaction zone to be 850°C-1050°C.

5. A method for preparing porous electrode carbon, characterized in that: The method is applicable to the preparation system of the porous electrode carbon according to any one of claims 1 to 4, and the method comprises: The temperature of the first reaction zone of the carbonized fluidized bed is controlled to be 500°C-950°C, and the temperature of the second reaction zone is controlled to be 200°C-400°C; The fluidizing gas is fed into the first reaction zone through the fluidizing gas inlet, and the mixed raw material of the polymer particles and the heat carrier particles is fed into the second reaction zone through the mixed raw material inlet. Under the action of the fluidizing gas, the polymer particles and the heat carrier particles are compounded and carbonized in the first reaction zone and the second reaction zone to form a composite carbonized material; The temperature of the reaction zone of the activated fluidized bed is controlled to be 850°C-1050°C, and the composite carbonized material enters the activated fluidized bed through the composite carbonized material outlet and the composite carbonized material inlet in sequence, and reacts with the activated gas to form an activated material; The activated material is introduced into a heat carrier removal reactor containing acid or water, and the heat carrier particles in the activated material are removed by the acid or water, and finally a porous electrode carbon product is obtained; Wherein, the polymer particles include at least one of epoxy resin, phenolic resin, urea-formaldehyde resin, unsaturated resin and polycarbonate resin; the diameter of the polymer particles is 5 μm-16 μm; The heat carrier particles include at least one of magnesium oxide, sodium chloride, potassium chloride, calcium chloride, calcium oxide, sodium silicate, calcium carbonate, sodium carbonate and magnesium carbonate; and the diameter of the heat carrier particles is 60 μm-200 μm.

6. The method for preparing porous electrode carbon according to claim 5, characterized in that: Under the action of the fluidizing gas, the polymer particles and the heat carrier particles are compounded and carbonized in the first reaction zone and the second reaction zone, including: Under the action of the fluidizing gas, the polymer particles melt and soften in the second reaction zone, and bond and solidify with the heat carrier particles to form composite particles; The composite particles move downward to the first reaction zone through the porous distribution plate and the overflow pipe under the action of gravity, and are carbonized to obtain the composite carbonized material.

7. The method for preparing porous electrode carbon according to claim 5, characterized in that: The mass ratio of the polymer particles to the heat carrier particles is 1:(1-3).

8. The method for preparing porous electrode carbon according to claim 5, characterized in that: The fluidizing gas includes at least one of CO, H2, Ar, He, CO2 and CH4.

9. The method for preparing porous electrode carbon according to claim 5, characterized in that: The activation gas includes at least one of CO2 and H2O.

10. A porous electrode carbon obtained by the method for preparing porous electrode carbon according to any one of claims 5 to 9, characterized in that: The specific surface area of ​​the porous electrode carbon is 1600 m 2 / g-2800 m 2 / g.

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