A system and method for converting catalytic diesel into porous carbon

Abstract

The present invention provides a system and method for converting catalytic diesel into porous carbon, belonging to the technical fields of chemical manufacturing equipment and carbon materials. The method is applicable to a fluidized bed system in which a carbonization fluidized bed and an activation fluidized bed are connected in series. It includes: directly spraying the preheated catalytic diesel or spraying it through the inlet of the catalytic diesel for the carbonization fluidized bed under the carrier of an inert gas. The catalytic diesel cracks at high temperature to obtain carbon particles; introducing a fluidizing gas through the fluidizing gas inlet at the bottom of the carbonization fluidized bed to keep the carbon particles in a fluidized state, and the carbon particles exit the carbonization fluidized bed through the carbon particle outlet of the carbonization fluidized bed and enter the activation fluidized bed through a series connection pipeline; and introducing an activation gas through the activation gas inlet at the bottom of the activation fluidized bed to form pores in the carbon particles in a fluidized state, thereby forming porous carbon. The present invention uses catalytic diesel as a raw material and matches a corresponding system to achieve the goals of reasonable energy utilization, large-scale, continuous, and low-cost production of porous carbon.

Description

Technical Field

[0001] The present invention relates to the technical fields of chemical manufacturing equipment and carbon materials, and particularly to a system and method for converting catalytic diesel into porous carbon. Background Art

[0002] Porous carbon is a material with a wide range of uses. It can be used for adsorption, energy storage, and catalyst carriers, and can also form composite materials with other substances, such as loading metals to form catalysts; or depositing silicon to form silicon-carbon anode materials.

[0003] The raw materials for producing porous carbon are also very extensive, such as various biomass raw materials, including plant fruit shells, seed coats, stems, or wood; as well as coal, tar, asphalt, etc. However, although the market for applications such as electrochemical energy storage has increased sharply, there are dual requirements for high-quality porous carbon and low-cost manufacturing. For example, coconut shells are mainly used to prepare high-end electrode carbon for supercapacitors. However, the supply of coconut shells is limited and cannot meet the greater demand for electrode carbon in the market. The output of petroleum coke, coal, asphalt, etc. is huge and the price is relatively low, but due to the various impurities it contains, it is difficult to meet the purity requirements of electrochemical energy storage for electrode carbon products after being prepared into porous carbon. Chemicals such as furan resin, phenolic resin, polyacrylonitrile fiber, etc. can be used for the manufacture of high-quality porous carbon, but their raw material costs are relatively high. At the same time, biomass is affected by various regional minerals, with different types and contents of impurities, which brings great inconvenience to subsequent purification, resulting in high manufacturing costs and quality control costs. The low product consistency has always been criticized.

[0004] In addition, when preparing porous carbon from various raw materials, carbonization and activation processes are required, and the yield based on the raw materials is not high. For example, most biomass is carbohydrates, and a large amount of carbon, hydrogen, and oxygen elements escape in the form of CO2, H2O, and CO during the carbonization process. During the activation process, when using water and CO2 or KOH, NaOH and other media, the carbon element is turned into CO and CO2 and escapes. Relatively speaking, the final yield of porous carbon from biomass raw materials is much lower than that of raw materials such as asphalt.

[0005] In addition, when using petroleum coke to prepare carbon materials, a batch production method is often adopted, and the device is switched from room temperature to 500°C within 30 - 48 hours. This causes excessive thermal expansion and contraction of the material of the metal reactor, often resulting in weld cracking, barrel wall deformation, high maintenance costs, and safety hazards.

[0006] Therefore, considering raw material costs, stable supply of raw materials, product yield, product purity, etc., there are still many challenges in preparing high-purity high-end porous carbon. Summary of the Invention

[0007] In view of the above problems existing in the prior art, the present invention provides a system and method for converting catalytic diesel into porous carbon. The present invention proposes to use catalytic diesel as a raw material with a high carbon content, large production volume, uniform quality, and few impurities, and match it with corresponding devices for the preparation of porous carbon to achieve the goals of reasonable energy utilization, large-scale, continuous, and low-cost manufacturing, so as to provide high-quality porous carbon materials for more application fields.

[0008] The specific invention content is as follows:

[0009] In the first aspect, the present invention provides a method for converting catalytic diesel into porous carbon. The method is applicable to a fluidized bed system in which a carbonization fluidized bed and an activation fluidized bed are connected in series, and includes:

[0010] Preparing carbon particles from catalytic diesel: controlling the temperature in the carbonization fluidized bed to be 900 - 1200 °C and the pressure to be 0.1 - 0.7 MPa, and directly spraying the preheated catalytic diesel or spraying it through the raw material catalytic diesel inlet of the carbonization fluidized bed under the entrainment of an inert gas. The catalytic diesel cracks at high temperature to obtain carbon particles;

[0011] Transferring carbon particles: introducing a fluidizing gas through the fluidizing gas inlet at the bottom of the carbonization fluidized bed to make the carbon particles in a fluidized state inside the carbonization fluidized bed, and discharging the carbon particles from the carbon particle outlet of the carbonization fluidized bed and entering the activation fluidized bed through a series-connected pipeline;

[0012] Preparing porous carbon: controlling the temperature in the activation fluidized bed to be 800 - 950 °C and the pressure to be 0.1 - 1.0 MPa, and introducing an activation gas through the activation gas inlet at the bottom of the activation fluidized bed to make the carbon particles form pores for 2 - 10 h in a fluidized state to form porous carbon.

[0013] Optionally, after introducing the fluidizing gas through the fluidizing gas inlet at the bottom of the carbonization fluidized bed, the fluidizing gas is mixed with the gas generated during the cracking process and discharged through the gas outlet at the top of the carbonization fluidized bed, and used as a first heat exchange medium for preheating the catalytic diesel.

[0014] Optionally, after the first heat exchange medium is used to preheat the catalytic diesel, the method includes:

[0015] Separating the gas generated during the cracking process from the fluidizing gas, and using the fluidizing gas for recycling.

[0016] Optionally, after introducing the activation gas through the activation gas inlet at the bottom of the activation fluidized bed, the activation gas is mixed with the gas generated during the pore-forming process and discharged through the gas outlet at the top of the activation fluidized bed, and used as a second heat exchange medium for preheating the fluidizing gas or the activation gas.

[0017] Optionally, if the pressure of the carbonization fluidized bed is lower than that of the activation fluidized bed, during the process of transferring the carbon particles, the method further includes: adjusting the pressure to make the pressure of the carbonization fluidized bed higher than that of the activation fluidized bed, and the pressure difference is 0.05 - 0.2 MPa.

[0018] Optionally, after the transfer of the carbon particles is completed, the method further includes: disconnecting the series pipeline.

[0019] Optionally, the temperature of the preheated catalytic diesel is 350 - 550 °C.

[0020] Optionally, the inert gas is one or a combination of more of N2, Ar, CO, and CH4;

[0021] The fluidizing gas is one or a combination of more of N2, Ar, CO, and CH4;

[0022] The activation gas is water vapor or CO2.

[0023] Optionally, the porous carbon is microporous carbon or mesoporous carbon;

[0024] The specific surface area of the microporous carbon is 1000 - 3000 m 2 / g; the micropore volume is 5 - 10 times that of the mesopore volume;

[0025] The specific surface area of the mesoporous carbon is 1000 - 3000 m 2 / g; the mesopore volume is 0.3 - 5 times that of the micropore volume.

[0026] In a second aspect, the present invention provides a system for converting catalytic diesel into porous carbon, the system is used to perform the method for converting catalytic diesel into porous carbon described in the first aspect above, the system includes a carbonization fluidized bed and an activation fluidized bed connected in series, and the volume of the carbonization fluidized bed is 2 - 4 times that of the activation fluidized bed;

[0027] The carbonization fluidized bed is used to pyrolyze catalytic diesel to generate carbon particles at high temperature;

[0028] The activation fluidized bed is used to activate the carbon particles into porous carbon at high temperature.

[0029] Compared with the prior art, the present invention has the following advantages:

[0030] The present invention provides a method for converting catalytic diesel into porous carbon. The method is applicable to a fluidized bed system in which a carbonization fluidized bed and an activation fluidized bed are connected in series, and includes: preparing carbon particles from catalytic diesel: controlling the temperature in the carbonization fluidized bed to be 900 - 1200 °C and the pressure to be 0.1 - 0.7 MPa, and directly spraying the preheated catalytic diesel or spraying it through the raw material catalytic diesel inlet 5 of the carbonization fluidized bed under the carrier of an inert gas. The catalytic diesel cracks at high temperature to obtain carbon particles; transferring the carbon particles: introducing a fluidizing gas through the fluidizing gas inlet at the bottom of the carbonization fluidized bed to make the carbon particles in a fluidized state inside the carbonization fluidized bed, and discharging the carbon particles from the carbon particle outlet of the carbonization fluidized bed and entering the activation fluidized bed through a series pipeline; preparing porous carbon: controlling the temperature in the activation fluidized bed to be 800 - 950 °C and the pressure to be 0.1 - 1.0 MPa, and introducing an activation gas through the activation gas inlet at the bottom of the activation fluidized bed to make the carbon particles form pores for 2 - 10 h in a fluidized state to form porous carbon. The present invention uses catalytic diesel as a carbon source and matches a corresponding preparation system to achieve the goal of mass production, high yield, continuous production, and low-cost manufacturing of porous carbon. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for use in the description of the embodiments or the prior art. Obviously, the following drawings are only some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on these drawings.

[0032] Figure 1 The flowchart of the method for converting catalytic diesel into porous carbon provided by the embodiment of the present invention is shown;

[0033] Figure 2 The schematic structural diagram of the system for converting catalytic diesel into porous carbon provided by the embodiment of the present invention is shown.

[0034] DESCRIPTION OF THE REFERENCE NUMERALS:

[0035] Among them, 1 - carbonization fluidized bed; 2 - activation fluidized bed; 3 - fluidizing gas inlet; 4 - tail gas outlet; 5 - catalytic diesel inlet; 6 - carbon particle outlet; 7 - carbon particle inlet; 8 - activation gas inlet; 9 - tail gas outlet; 10 - porous carbon product outlet. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0036] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. The following description of at least one exemplary embodiment is actually only illustrative and in no way limits the present invention and its application or use. Based on the embodiments of the present invention, any product identical or similar to the present invention obtained by anyone under the inspiration of the present invention or by combining the features of the present invention with those of other prior arts falls within the protection scope of the present invention. In addition, all other embodiments obtained by those of ordinary skill in the art without creative efforts belong to the protection scope of the present invention.

[0037] If the specific experimental steps or conditions are not specified in the embodiments, the operations or conditions of the conventional experimental steps described in the prior art in this field can be followed. The reagents and other instruments used without indicating the manufacturer can be obtained as conventional reagent products through commercial purchase. In addition, the accompanying drawings are only schematic diagrams of the embodiments of the present invention and are not necessarily drawn to scale. The same reference numerals in the drawings represent the same or similar parts, and thus the repeated description of them will be omitted. Some of the block diagrams shown in the drawings are functional entities and do not necessarily correspond to physically or logically independent entities.

[0038] For technologies, methods, and devices known to those of ordinary skill in the relevant field, detailed discussions may not be made, but in appropriate cases, the said technologies, methods, and devices should be regarded as part of the specification of the present invention.

[0039] In the description of the present invention, it should be understood that using terms such as "first" and "second" to limit components is only for the convenience of differentiating the corresponding components. Without further statement, the above terms have no special meaning and thus cannot be construed as limiting the protection scope of the present invention.

[0040] In addition, the technical features involved in different embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0041] From the perspectives of reducing raw material costs, increasing product yield and purity, the present invention makes a comprehensive consideration and proposes to use catalytic diesel as the carbon source and match the corresponding devices to achieve the goal of mass production, high yield, continuous production, and low-cost manufacturing of porous carbon. The specific implementation content is as follows:

[0042] In the first aspect, the present invention provides a method for converting catalytic diesel into porous carbon, and the method is applicable to a fluidized bed system in which a carbonization fluidized bed and an activation fluidized bed are connected in series. Figure 1 The flowchart of the method for converting catalytic diesel into porous carbon provided by the embodiment of the present invention is shown, as Figure 1As shown, it includes:

[0043] S1. Preparation of carbon particles from catalytic diesel: Control the temperature in the carbonization fluidized bed to be 900 - 1200 °C and the pressure to be 0.1 - 0.7 MPa. Directly spray the preheated catalytic diesel or spray it through the raw material catalytic diesel inlet 5 of the carbonization fluidized bed under the carrier of inert gas. The catalytic diesel cracks at high temperature to obtain carbon particles.

[0044] S2. Transfer of carbon particles: Pass fluidizing gas through the fluidizing gas inlet at the bottom of the carbonization fluidized bed to make the carbon particles in a fluidized state inside the carbonization fluidized bed, and the carbon particles exit the carbonization fluidized bed through the carbon particle outlet of the carbonization fluidized bed and enter the activation fluidized bed through a series of pipes.

[0045] S3. Preparation of porous carbon: Control the temperature in the activation fluidized bed to be 800 - 950 °C and the pressure to be 0.1 - 1.0 MPa. Pass activation gas through the activation gas inlet at the bottom of the activation fluidized bed to make the carbon particles form pores for 2 - 10 h in a fluidized state to form porous carbon.

[0046] In specific implementation, before proposing the method scheme design for preparing porous carbon using catalytic diesel as a carbon source, the present invention conducted a large number of comparative studies and found that compared with using tar and asphalt as carbon sources to prepare carbon materials, catalytic diesel is a liquid with higher viscosity, better fluidity, easier to heat and vaporize, and the coking probability at the nozzle is reduced; the reaction preheating structure and internal coke cleaning structure can be simplified, effectively reducing the equipment cost by 3% - 10%. Although the carbon content of catalytic diesel is slightly lower than that of asphalt and it is relatively difficult to carbonize, it also makes the proportion of gas generated during the carbonization process larger and the diameter of carbon particles smaller, which is not only beneficial to maintaining the fluidization state in the reactor but also conducive to the direct application of subsequent small-particle electrode materials, effectively reducing the cost of the crushing link by 20% - 50%. The fluidization operation reduces the process management cost by 30% - 50%.

[0047] In addition, compared with biomass, coal, asphalt, and tar, catalytic diesel has fewer impurities and a comparable price. When preparing high-purity porous carbon, the subsequent purification cost is reduced by 50% - 80%; while the price of catalytic diesel is much lower than that of phenolic resin, furan resin, etc., and the carbon yield is comparable or slightly higher, making the cost of preparing high-purity porous carbon decrease by 50% - 80%. The carbon yield of catalytic diesel is much higher than that of biomass raw materials. Since both carbonization and activation are endothermic reactions at high temperature, the total energy consumption of carbonization and activation is reduced by 30% - 50%.

[0048] The above method is applicable to Figure 2 the schematic structural diagram of the system for converting catalytic diesel into porous carbon provided by the embodiment of the present invention shown, as Figure 2As shown in the figure, the system includes a carbonization fluidized bed and an activation fluidized bed connected in series. The volume of the carbonization fluidized bed is 2 to 4 times that of the activation fluidized bed. The carbonization fluidized bed is used to crack catalytic diesel to generate carbon particles at high temperature. The activation fluidized bed is used to activate the carbon particles into porous carbon at high temperature. The carbonization fluidized bed 1 and the activation fluidized bed 2 are connected in series, and the carbonization fluidized bed 1 has a large volume and can store heat. When the activation fluidized bed 2 discharges materials in batches, the high-temperature carbon particles can be conveniently transferred into the activation fluidized bed 2. In this way, the temperature of the activation fluidized bed 2 hardly drops, which not only saves the time and energy consumption of activation heating, but also reduces the influence of temperature changes on the reactor material and welding deformation, etc. The reactor maintenance cost is saved by 20% - 30%, the energy consumption is saved by 30% - 40%, and the production intensity is increased by 50% - 80%.

[0049] Refer to Figure 2 The embodiments of the present invention will be explained in detail. In the embodiments of the present invention, two series-connected fluidized beds are used to separately carry out the carbon particle preparation and the pore formation process on the surface of the carbon particles, namely the carbonization fluidized bed 1 and the activation fluidized bed 2. The preparation method is as follows: The preheated catalytic diesel is sprayed into the carbonization fluidized bed 1 from the upper raw material inlet 5, and under pressurized and high-temperature conditions (900 - 1200 °C, pressure 0.1 - 0.7 MPa), thermal cracking occurs to generate carbon particles, methane, and hydrogen. The catalytic diesel can be directly sprayed in, or it can be sprayed in under the carrier of an inert gas after being mixed with the inert gas. The inert gas is selected from one or a combination of more of N2, Ar, CO, and CH4.

[0050] Furthermore, the fluidizing gas is introduced into the fluidizing gas inlet 3 at the bottom of the carbonization fluidized bed 1 to make the generated carbon particles in a suspended state. The fluidizing gas is selected from one or a combination of more of N2, Ar, CO, and CH4. The carbon particles in the fluidized state leave the carbonization fluidized bed through the carbon particle outlet 6 of the carbonization fluidized bed 1 and enter the activation fluidized bed through the series pipeline. The activation gas inlet 8 at the bottom of the activation fluidized bed 2 is provided with an activation medium (steam or CO2 gas). After the carbon particles enter the activation fluidized bed 2, under the action of the activation medium (steam or CO2) for 2 - 10 h, porous carbon is generated and discharged from the porous carbon product outlet 10 to complete the collection. Using this system for the conversion of catalytic diesel - porous carbon can achieve the rational utilization of energy and the goal of mass production, continuous production, and low-cost manufacturing of porous carbon, in order to provide high-quality porous carbon materials for more application fields.

[0051] In some embodiments, after introducing fluidizing gas through the fluidizing gas inlet 3 at the bottom of the carbonization fluidized bed 1, the fluidizing gas is mixed with the gas generated during the cracking process (mainly composed of methane and hydrogen), and discharged through the tail body outlet 4 at the top of the carbonization fluidized bed 1. As the first heat exchange medium, it can be used to preheat catalytic diesel to make the temperature of the catalytic diesel reach the preheating temperature of 350 - 550 °C. This reduces the additional consumption of energy and realizes the reasonable distribution and secondary utilization of heat during the preparation process. Further, after the first heat exchange medium is used to preheat the catalytic diesel, after separating the gas generated during the cracking process from the fluidizing gas, the fluidizing gas can be used for recycling. This reduces the additional use of sulfide gas and realizes the reasonable distribution and secondary utilization of materials during the preparation process.

[0052] Optionally, after introducing activation gas through the activation gas inlet 8 at the bottom of the activation fluidized bed 2, the activation gas is mixed with the gas generated during the pore-forming process and discharged through the tail body outlet 9 at the top of the activation fluidized bed 2. As the second heat exchange medium, it can be used to preheat the fluidizing gas or the activation gas. This reduces the additional consumption of energy and realizes the reasonable distribution and secondary utilization of heat during the preparation process.

[0053] In some embodiments, the pressures of the carbonization fluidized bed 1 and the activation fluidized bed 2 in the embodiments of the present invention are independently controlled and adjusted by a pressure control device. Generally, the pressure for carbonization in the carbonization fluidized bed 1 is lower than the pressure for activation in the activation fluidized bed 2. Therefore, during the transfer of the carbon particles generated in the carbonization fluidized bed 1 to the activation fluidized bed 2, it is necessary to adjust the pressures of the carbonization fluidized bed 1 and the activation fluidized bed 2 so that the pressure of the carbonization fluidized bed 1 is higher than that of the activation fluidized bed 2, and the pressure difference is 0.05 - 0.2 MPa, so that the carbon particles in the fluidized state can smoothly enter the activation fluidized bed 2. Further, after the transfer of the carbon particles is completed, the series pipeline used for transferring the carbon particles is disconnected. While providing a stable pressure and temperature environment for the carbon particle activation process, the carbonization fluidized bed 1 can carry out the preparation of the second batch of carbon particles. The independent control of the operating pressures of the carbonization fluidized bed 1 and the activation fluidized bed 2 makes the activation process more flexible, obtaining qualified products in a short time, increasing the production intensity by 20% - 35%, and greatly improving the equipment utilization rate and the yield of porous carbon.

[0054] In some embodiments, the porous carbon obtained by controlling the activation temperature, pressure, corresponding time, and the switching of the activation medium in the embodiments of the present invention is microporous carbon or mesoporous carbon; among them, the specific surface area of the microporous carbon is 1000 - 3000 m 2 / g; the micropore volume is 5 - 10 times that of the mesopore volume; the specific surface area of the mesoporous carbon is 1000 - 3000 m 2 / g; the mesopore volume is 0.3 - 5 times that of the micropore volume. The obtained porous carbon can be directly used as an adsorption material, energy storage material or catalytic material, or can be used for depositing other materials to form composite materials (such as catalytic materials or silicon-carbon anode materials, etc.).

[0055] To enable those skilled in the art to understand the present invention more clearly, the following examples are now used to detail a system and method for converting catalytic diesel into porous carbon according to the present invention.

[0056] Example 1

[0057] Connect the carbonization fluidized bed 1 and the activation fluidized bed 2 in sequence to form an integral body. The volume of the carbonization fluidized bed 1 is 2 times that of the activation fluidized bed.

[0058] Inject the preheated diesel (preheated to 350 °C) into the carbonization fluidized bed 1 through the catalytic diesel inlet 5, and crack it at a high temperature (900 °C) to generate carbon particles and hydrogen. Control the pressure to be 0.3 MPa. The carbon particles sink to the bottom of the carbonization fluidized bed 1 under the action of gravity.

[0059] Introduce the fluidizing gas (N2) from the fluidizing gas inlet 3 of the carbonization fluidized bed 1 to make the carbon particles in a fluidized state and accumulate a large amount of heat. Control the pressure of the carbonization fluidized bed 1 to be 0.15 MPa higher than that of the activation fluidized bed 2. Send the high-temperature carbon particles out from the carbon particle outlet 6, and then send them into the activation fluidized bed 2 through the carbon particle inlet 7, and then close the pipeline between the carbon particle outlet 6 and the carbon particle inlet 7.

[0060] The gas generated by cracking and the fluidizing gas are discharged from the carbonization fluidized bed 1 through the tail gas outlet 4 together. This high-temperature gas can be used for preheating the catalytic diesel. After heat exchange, the fluidizing gas is separated and recycled.

[0061] Introduce the activation gas (H2O) from the activation gas inlet 8 of the activation fluidized bed 2 to make the carbon particles form pores in a fluidized state (pressure is 1.0 MPa, temperature is 950 °C, time is 2 hours) to form porous carbon (microporous carbon, specific surface area 1000 m 2 / g, the micropore volume is 5 times that of the mesopore volume).

[0062] The gas generated by pore formation and the activation gas are discharged from the activation fluidized bed 2 through the tail gas outlet 9 together. This high-temperature gas can be used for preheating the fluidizing gas or the activation gas.

[0063] Remove the porous carbon from the porous carbon product outlet 10 of the activation fluidized bed 2. After heat recovery utilization, it is cooled and packaged for use as a product. This product can be used as an adsorption material, energy storage material and catalyst carrier.

[0064] Example 2

[0065] Connect the carbonization fluidized bed 1 and the activation fluidized bed 2 in sequence to form an integral whole. The volume of the carbonization fluidized bed 1 is three times that of the activation fluidized bed.

[0066] Inject the preheated diesel oil (preheated to 450 °C) into the carbonization fluidized bed 1 through the catalytic diesel oil inlet 5 under the carrier of nitrogen, and crack it at a high temperature (1200 °C). Control the pressure to be 0.5 MPa to generate carbon particles and hydrogen. The carbon particles sink to the bottom of the carbonization fluidized bed 1 under the action of gravity.

[0067] Introduce the fluidizing gas (Ar) through the fluidizing gas inlet 3 of the carbonization fluidized bed 1 to make the carbon particles in a fluidized state and accumulate a large amount of heat. Control the pressure of the carbonization fluidized bed 1 to be 0.18 MPa higher than that of the activation fluidized bed 2. Send the high-temperature carbon particles out from the carbon particle outlet 6 and then send them into the activation fluidized bed 2 through the carbon particle inlet 7. Then close the pipeline between the carbon particle outlet 6 and the carbon particle inlet 7. The cracked gas and the fluidizing gas are discharged from the carbonization fluidized bed 1 together through the tail gas outlet 4. This high-temperature gas can be used for preheating the catalytic diesel oil. After heat exchange, the fluidizing gas is separated and recycled.

[0068] Introduce the activation gas (50% H2O, 50% CO2) through the activation gas inlet 8 of the activation fluidized bed 2 to make the carbon particles form pores in a fluidized state (pressure is 0.3 MPa, temperature is 920 °C, time is 8 hours) to form porous carbon (mesoporous carbon, specific surface area 3000 m 2 / g, the mesoporous pore volume is twice that of the microporous pore volume). The gas generated during pore formation and the activation gas are discharged from the activation fluidized bed 2 together through the tail gas outlet 9. This high-temperature gas can be used for preheating the fluidizing gas or the activation gas.

[0069] Remove the porous carbon from the activation fluidized bed 2 through the porous carbon product outlet 10. After using the waste heat, cool and package it for use as a product. This product can be used as an adsorption material, an energy storage material, a catalytic material and a catalyst support, and as a material for depositing silicon.

[0070] Example 3

[0071] Connect the carbonization fluidized bed 1 and the activation fluidized bed 2 in sequence to form an integral whole. The volume of the carbonization fluidized bed 1 is 2.5 times that of the activation fluidized bed.

[0072] Inject the preheated diesel oil (preheated to 500 °C) into the carbonization fluidized bed 1 through the catalytic diesel oil inlet 5 under the carrier of CH4. Crack it at a high temperature (1000 °C). Control the pressure to be 0.6 MPa to generate carbon particles and hydrogen. The carbon particles sink to the bottom of the carbonization fluidized bed 1 under the action of gravity.

[0073] Introduce fluidizing gas (CH4) through the fluidizing gas inlet 3 of the carbonization fluidized bed 1 to fluidize the carbon particles and accumulate a large amount of heat. Control the pressure of the carbonization fluidized bed 1 to be 0.13 MPa higher than that of the activation fluidized bed 2. Send the high-temperature carbon particles out from the carbon particle outlet 6 and then feed them into the activation fluidized bed 2 through the carbon particle inlet 7. Then close the pipeline between the carbon particle outlet 6 and the carbon particle inlet 7. The gas generated by pyrolysis and the fluidizing gas are discharged from the carbonization fluidized bed 1 through the tail gas outlet 4 together. This high-temperature gas can be used for preheating catalytic diesel. After heat exchange, the fluidizing gas is separated and recycled.

[0074] Introduce activation gas (H2O) through the activation gas inlet 8 of the activation fluidized bed 2 to form pores in the carbon particles under fluidized state (pressure is 0.5 MPa, temperature is 900 °C, time is 1 hour), and then introduce CO2 to react for 1 hour at the same temperature under a pressure of 0.2 MPa to form porous carbon (mesoporous carbon, specific surface area is 1800 m 2 / g, and the mesoporous pore volume is twice that of the microporous pore volume). The gas generated during pore formation and the activation gas are discharged from the activation fluidized bed 2 through the tail gas outlet 9 together. This high-temperature gas can be used for preheating the fluidizing gas or the activation gas.

[0075] Remove the porous carbon from the porous carbon product outlet 10 of the activation fluidized bed 2. After utilizing the waste heat, it is cooled and packaged for use as a product. This product can be used as an adsorption material, an energy storage material, a catalytic material and a catalyst support, and a material for depositing silicon.

[0076] Example 4

[0077] Connect the carbonization fluidized bed 1 and the activation fluidized bed 2 in sequence to form an integral whole. The volume of the carbonization fluidized bed 1 is 2.5 times that of the activation fluidized bed.

[0078] Inject the preheated diesel (preheated to 550 °C) into the carbonization fluidized bed 1 through the catalytic diesel inlet 5 under the carrier of CH4. Pyrolyze at a high temperature (1050 °C), control the pressure to be 0.25 MPa, and generate carbon particles and hydrogen. The carbon particles sink to the bottom of the carbonization fluidized bed 1 under the action of gravity.

[0079] Introduce fluidizing gas (CH4) through the fluidizing gas inlet 3 of the carbonization fluidized bed 1 to fluidize the carbon particles and accumulate a large amount of heat. Control the pressure of the carbonization fluidized bed 1 to be 0.1 MPa higher than that of the activation fluidized bed 2. Send the high-temperature carbon particles out from the carbon particle outlet 6 and then feed them into the activation fluidized bed 2 through the carbon particle inlet 7. Then close the pipeline between the carbon particle outlet 6 and the carbon particle inlet 7. The gas generated by pyrolysis and the fluidizing gas are discharged from the carbonization fluidized bed 1 through the tail gas outlet 4 together. This high-temperature gas can be used for preheating catalytic diesel. After heat exchange, the fluidizing gas is separated and recycled.

[0080] Activating gas (H2O) is introduced through the activating gas inlet 8 of the activation fluidized bed 2 to form pores in the carbon particles under the fluidized state (pressure: 0.1 MPa, temperature: 800 °C, time: 6 hours). Then, CO2 is introduced and reacted at a pressure of 0.5 MPa and 920 °C for 4 hours to form porous carbon (mesoporous carbon, specific surface area: 3000 m 2 / g, mesopore volume is 0.3 times that of the micropore volume). The gas generated during pore formation and the activating gas are discharged from the tail gas outlet 9 of the activation fluidized bed 2 together. This high-temperature gas can be used for preheating the fluidizing gas or the activating gas.

[0081] The porous carbon is removed from the activation fluidized bed 2 through the porous carbon product outlet 10. After heat recovery, it is cooled and packaged for use as a product. This product can be used as an adsorption material, energy storage material, catalytic material and catalyst support, and material for depositing silicon.

[0082] Example 5

[0083] The carbonization fluidized bed 1 and the activation fluidized bed 2 are connected in sequence to form an integral unit. The volume of the carbonization fluidized bed 1 is 4 times that of the activation fluidized bed.

[0084] The preheated diesel (preheated to 500 °C) is sprayed into the carbonization fluidized bed 1 through the catalytic diesel inlet 5 under the carrier of 50% N2 and 50% CO gas and cracked at a high temperature (1050 °C). The pressure is controlled at 0.1 MPa to generate carbon particles and hydrogen. The carbon particles sink to the bottom of the fluidized bed 1 under the action of gravity.

[0085] Fluidizing gas (50% N2 and 50% CO) is introduced through the fluidizing gas inlet 3 of the carbonization fluidized bed 1 to keep the carbon particles in a fluidized state and accumulate a large amount of heat. The pressure of the carbonization fluidized bed 1 is controlled to be 0.15 MPa higher than that of the activation fluidized bed 2. The high-temperature carbon particles are sent out from the carbon particle outlet 6 and then fed into the activation fluidized bed 2 through the carbon particle inlet 7, and then the pipeline between the carbon particle outlet 6 and the carbon particle inlet 7 is closed. The gas generated by cracking and the fluidizing gas are discharged from the tail gas outlet 4 of the carbonization fluidized bed 1 together. This high-temperature gas can be used for preheating the catalytic diesel. After heat exchange, the fluidizing gas is separated and recycled.

[0086] Activating gas (CO2) is introduced through the activating gas inlet 8 of the activation fluidized bed 2 to form pores in the carbon particles under the fluidized state (pressure: 0.8 MPa, temperature: 850 °C, time: 1 hour). Then, 50% H2O and 50% CO2 are introduced and reacted at a pressure of 0.5 MPa and 800 °C for 2 hours to form porous carbon (mesoporous carbon, specific surface area: 1000 m 2 / g, mesopore volume is 2 times that of the micropore volume). The gas generated during pore formation and the activating gas are discharged from the tail gas outlet 9 or the activation fluidized bed 2 together. This high-temperature gas can be used for preheating the fluidizing gas or the activating gas.

[0087] The porous carbon is removed from the activated fluidized bed 2 through the porous carbon product outlet 10. After the waste heat is utilized, it is cooled and packaged for use as a product. This product can be used as an adsorption material, an energy storage material, a catalytic material and a catalyst carrier, and a material for depositing silicon.

[0088] Example 6

[0089] The carbonization fluidized bed 1 and the activated fluidized bed 2 are connected in sequence to form an integral unit. The volume of the carbonization fluidized bed 1 is 2.5 times that of the activated fluidized bed.

[0090] The preheated diesel oil (preheated to 400 °C) is sprayed into the carbonization fluidized bed 1 through the catalytic diesel inlet 5 under the carrier of 90% N2 and 10% Ar gas. It is cracked at a high temperature (1200 °C), and the pressure is controlled at 0.3 MPa to generate carbon particles and hydrogen. The carbon particles sink to the bottom of the fluidized bed 1 under the action of gravity.

[0091] The fluidizing gas (90% N2 and 10% Ar) is introduced through the fluidizing gas inlet 3 of the carbonization fluidized bed 1 to keep the carbon particles in a fluidized state and accumulate a large amount of heat. The pressure of the carbonization fluidized bed 1 is controlled to be 0.1 MPa higher than that of the activated fluidized bed 2. The high-temperature carbon particles are sent out from the carbon particle outlet 6 and then fed into the activated fluidized bed 2 through the carbon particle inlet 7, and then the pipeline between the carbon particle outlet 6 and the carbon particle inlet 7 is closed. The gas generated by cracking and the fluidizing gas are discharged from the tail gas outlet 4 of the carbonization fluidized bed 1 together. This high-temperature gas can be used for preheating the catalytic diesel oil. After heat exchange, the fluidizing gas is separated and recycled.

[0092] The activating gas (80% H2O, 20% CO2) is introduced through the activating gas inlet 8 of the activated fluidized bed 2 to form pores in the carbon particles in a fluidized state (pressure 0.1 MPa, temperature 900 °C, time 3 hours), and then react at a pressure of 0.4 MPa and 850 °C for 4 hours to form porous carbon (mesoporous carbon, specific surface area 2200 m 2 / g, the mesoporous pore volume is 5 times that of the microporous pore volume). The gas generated by pore formation and the activating gas are discharged from the tail gas outlet 9 of the activated fluidized bed 2 together. This high-temperature gas can be used for preheating the fluidizing gas or the activating gas.

[0093] The porous carbon is removed from the activated fluidized bed 2 through the porous carbon product outlet 10. After the waste heat is utilized, it is cooled and packaged for use as a product. This product can be used as an adsorption material, an energy storage material, a catalytic material and a catalyst carrier, and a material for depositing silicon.

[0094] Example 7

[0095] The carbonization fluidized bed 1 and the activated fluidized bed 2 are connected in sequence to form an integral unit. The volume of the carbonization fluidized bed 1 is 3 times that of the activated fluidized bed.

[0096] Preheated diesel oil (preheated to 400 °C) is injected into the carbonization fluidized bed 1 through the catalytic diesel inlet 5 under the carrier of 50% N2 and 50% Ar gas. It cracks at a high temperature (900 °C), and the pressure is controlled at 0.7 MPa to generate carbon particles and hydrogen. The carbon particles sink to the bottom of the fluidized bed 1 under the action of gravity.

[0097] Fluidizing gas (50% N2 and 50% Ar) is introduced into the carbonization fluidized bed 1 through the fluidizing gas inlet 3, so that the carbon particles are in a fluidized state and accumulate a large amount of heat. The pressure of the carbonization fluidized bed 1 is controlled to be 0.05 MPa higher than that of the activation fluidized bed 2. The high-temperature carbon particles are sent out from the carbon particle outlet 6 and then sent into the activation fluidized bed 2 through the carbon particle inlet 7, and then the pipeline between the carbon particle outlet 6 and the carbon particle inlet 7 is closed. The gas generated by cracking and the fluidizing gas are discharged from the carbonization fluidized bed 1 together from the tail gas outlet 4. This high-temperature gas can be used for preheating catalytic diesel oil. After heat exchange, the fluidizing gas is separated and recycled.

[0098] Activation gas (10% H2O, 90% CO2) is introduced into the activation fluidized bed 2 through the activation gas inlet 8, so that the carbon particles are pore-formed in a fluidized state (pressure is 0.3 MPa, temperature is 900 °C, time is 6 hours) to form porous carbon (microporous carbon, specific surface area 3000 m 2 / g, the micropore volume is 10 times that of the mesopore volume). The gas generated by pore formation and the activation gas are discharged from the activation fluidized bed 2 together from the tail gas outlet 9. This high-temperature gas can be used for preheating the fluidizing gas or the activation gas.

[0099] The porous carbon is removed from the activation fluidized bed 2 through the porous carbon product outlet 10. After waste heat utilization, it is cooled and packaged for use as a product.

[0100] In the description of this specification, the description referring to terms such as "one embodiment", "some embodiments", "example", "specific example", or "some examples" means that the specific features, structures, materials, or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic expressions of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials, or characteristics described can be combined in a suitable manner in any one or more embodiments or examples. In addition, those skilled in the art can combine and combine the different embodiments or examples described in this specification.

[0101] For the method embodiments, for the sake of simplicity of description, they are all expressed as a series of combinations of actions. However, those skilled in the art should be aware that the present invention is not limited by the described order of actions, because according to the present invention, certain steps can be performed in other orders or simultaneously. Secondly, those skilled in the art should also be aware that the embodiments described in the specification are all preferred embodiments, and the actions and components involved are not necessarily essential to the present invention.

[0102] The above has introduced in detail a system and method for converting catalytic diesel into porous carbon provided by the present invention. Specific examples are used herein to elaborate on the principle and implementation manner of the present invention. The description of the above embodiments is only used to help understand the method and its core idea of the present invention; at the same time, for those of ordinary skill in the art, according to the idea of the present invention, there will be changes in the specific implementation manner and application scope. In summary, the content of this specification should not be construed as a limitation to the present invention.

Claims

1. A method for converting catalytic diesel into porous carbon, characterized in that, The method is applicable to a fluidized bed system in which a carbonization fluidized bed and an activation fluidized bed are connected in series, and includes: Preparing carbon particles from catalytic diesel: controlling the temperature in the carbonization fluidized bed to be 900 - 1200 °C and the pressure to be 0.1 - 0.7 MPa, and directly spraying the preheated catalytic diesel or spraying it through the raw material inlet of the carbonization fluidized bed under the carrier of an inert gas. The catalytic diesel cracks at high temperature to obtain carbon particles; Transferring carbon particles: introducing a fluidizing gas through the fluidizing gas inlet at the bottom of the carbonization fluidized bed to make the carbon particles in a fluidized state inside the carbonization fluidized bed, and discharging the carbon particles from the carbon particle outlet of the carbonization fluidized bed and entering the activation fluidized bed through a series pipeline; Preparing porous carbon: controlling the temperature in the activation fluidized bed to be 800 - 950 °C and the pressure to be 0.1 - 1.0 MPa, and introducing an activation gas through the activation gas inlet at the bottom of the activation fluidized bed to make the carbon particles form pores for 2 - 10 h in a fluidized state to form porous carbon; After introducing the fluidizing gas through the fluidizing gas inlet at the bottom of the carbonization fluidized bed, the fluidizing gas is mixed with the gas generated during the cracking process and discharged through the gas outlet at the top of the carbonization fluidized bed, and is used as the first heat exchange medium for preheating the catalytic diesel; After the first heat exchange medium preheats the catalytic diesel, the gas generated during the cracking process is separated from the fluidizing gas, and the fluidizing gas is used for recycling; After introducing the activation gas through the activation gas inlet at the bottom of the activation fluidized bed, the activation gas is mixed with the gas generated during the pore formation process and discharged through the gas outlet at the top of the activation fluidized bed, and is used as the second heat exchange medium for preheating the fluidizing gas or the activation gas; The volume of the carbonization fluidized bed is 2 - 4 times the volume of the activation fluidized bed.

2. The method for converting catalytic diesel into porous carbon according to claim 1, characterized in that, If the pressure of the carbonization fluidized bed is lower than the pressure of the activation fluidized bed, during the process of transferring carbon particles, the method further includes: adjusting the pressure to make the pressure of the carbonization fluidized bed higher than the pressure of the activation fluidized bed, and the pressure difference is 0.05 - 0.2 MPa.

3. The method for converting catalytic diesel into porous carbon according to claim 1, characterized in that, After the transfer of carbon particles is completed, the method further includes: disconnecting the series pipeline.

4. The method for converting catalytic diesel into porous carbon according to claim 1, characterized in that, The temperature of the preheated catalytic diesel is 350 - 550 °C.

5. The method for converting catalytic diesel into porous carbon according to claim 1, characterized in that, The inert gas is composed of one or more of N2, Ar, CO, and CH4; The fluidizing gas is composed of one or more of N2, Ar, CO, and CH4; The activation gas is water vapor or CO2.

6. The method for converting catalytic diesel into porous carbon according to claim 1, characterized in that, The porous carbon is microporous carbon or mesoporous carbon; The specific surface area of the microporous carbon is 1000 - 3000 m 2 / g; the micropore volume is 5 - 10 times that of the mesopore volume; The specific surface area of the mesoporous carbon is 1000 - 3000 m 2 / g; the mesopore volume is 0.3 - 5 times that of the micropore volume.

7. A system for converting catalytic diesel into porous carbon, characterized in that, The system is used to perform the method for converting catalytic diesel into porous carbon according to any one of claims 1 - 6. The system includes a carbonization fluidized bed and an activation fluidized bed connected in series; The carbonization fluidized bed is used to crack catalytic diesel to generate carbon particles at high temperature; The activation fluidized bed is used to activate the carbon particles into porous carbon at high temperature.

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