Carbon material, and method and system for producing the same

Abstract

The application discloses a kind of carbon materials and its preparation method and system, the preparation method includes S1, prepares carbon material particle;S2, carbon material particle and 0.5~10L / min of H2 are preheated;S3, after preheating, the doped material and H2 are sent into gas-solid fluidized bed reactor and are reacted, after gas-solid separation, solid cooling, low-sulfur carbon material, i.e., desulfurized carbon is obtained.The carbon material obtained by the application has low sulfur content, does not need additional desulfurization treatment when applied to other industries, and has high stability.

Description

Technical Field

[0001] This invention belongs to the fields of metallurgy, materials and chemical engineering, and relates to a carbon material and its preparation method and system. Background Technology

[0002] Carbon materials, as an important class of high-performance carbon-based materials, have wide applications in lithium-ion battery anodes, supercapacitors, conductive composite materials, and catalyst supports. Their performance is highly dependent on their microstructure and impurity content, with residual sulfur being one of the key factors affecting material quality. Sulfur in carbon materials typically exists as organic sulfides (such as thiophene and sulfides) or inorganic sulfur (such as sulfates). During high-temperature processing or electrochemical applications, sulfur-containing gases are easily released, leading to decreased conductivity, impaired structural stability, and potentially causing equipment corrosion and environmental pollution. Therefore, developing efficient and low-energy-consumption desulfurization processes is one of the core technological challenges in improving the performance of carbon materials.

[0003] Traditional desulfurization processes mainly include high-temperature calcination, chemical acid washing, and oxidation. High-temperature calcination is typically carried out at temperatures above 1200℃ in an inert atmosphere, removing sulfur through thermal decomposition. However, it suffers from high energy consumption, long reaction times, and a tendency to damage the graphitized structure of materials. Furthermore, it is inefficient at removing some thermally stable sulfides (such as sulfates). Chemical acid washing uses strong acids (such as nitric acid and hydrochloric acid) to remove sulfur impurities. While it can achieve high desulfurization rates at low temperatures, it consumes large amounts of acid, incurs high wastewater treatment costs, and easily introduces metal ion contamination, affecting material purity. Oxidation uses oxidants such as ozone and hydrogen peroxide to convert sulfur into soluble sulfates, which are then removed by water washing. However, the process is complex, oxidants are expensive, and there is a risk of over-oxidizing the carbon skeleton, leading to deterioration of specific surface area and pore structure. All of these methods share common problems such as poor environmental performance, demanding process conditions, or material performance degradation.

[0004] In recent years, hydrogen reduction (HRP) has attracted attention as a green desulfurization technology. Its principle involves the reduction reaction of hydrogen with sulfur-containing components at high temperatures to generate gaseous hydrogen sulfide (H2S), which is then desorbed. This method offers advantages such as high reaction selectivity and no waste liquid discharge. Currently, HRP desulfurization is mostly carried out in fixed-bed or moving-bed reactors, which suffers from high energy consumption, uneven local temperature distribution, and fluctuating sulfur removal rates (60%-85%). Furthermore, when processing high-sulfur feedstocks (sulfur content > 5 wt%), the concentrated exothermic reaction can easily lead to bed sintering, and the complex temperature control system restricts large-scale application. In contrast, fluidized-bed reactors, due to their high gas-solid contact efficiency and good heat transfer uniformity, are widely used in coal gasification and petroleum catalytic cracking. However, applying them to HRP desulfurization of carbon materials still faces multiple technical bottlenecks. For example, Chinese patent application CN117757498A discloses a method and system for preparing calcined petroleum coke using a delayed coking process. The method includes the following steps: rapidly heating residual oil to 600-800℃, introducing a reducing gas for desulfurization (the reducing gas flow rate is 5-15 L / h); subsequently sending it to a calcining unit for high-temperature reaction, and cooling to obtain calcined petroleum coke and an oil-gas mixture; the oil-gas mixture is then fractionated to obtain gasoline, diesel, and wax oil. This approach may have the following problems: the carbon material has low density and narrow particle size distribution, making it prone to bubble formation at conventional fluidized gas flow rates, leading to insufficient gas-solid contact. Summary of the Invention

[0005] The purpose of this invention is to provide a carbon material and its preparation method and system, so as to obtain high-quality carbon material with low sulfur content in a green, environmentally friendly, low-cost and high-efficiency manner.

[0006] To achieve the above-mentioned technical objectives, the technical solution of the present invention is as follows:

[0007] A method for preparing a carbon material includes the following steps:

[0008] S1. Prepare carbon material granules;

[0009] S2. Preheat the carbon material particles with 0.5-10 L / min of H2;

[0010] S3. The preheated dopant material and H2 are fed into a gas-solid fluidized bed reactor for reaction. After the reaction is completed, the gas and solid are separated and the solid is cooled to obtain low-sulfur carbon material, i.e., desulfurized carbon.

[0011] Existing carbon material desulfurization technologies generally suffer from problems such as difficulty in simultaneously achieving desulfurization efficiency and maintaining material structure, high energy consumption, and poor process continuity. Developing a highly efficient preparation method that can adapt to high-sulfur raw materials, achieve deep desulfurization (sulfur content <0.5wt%) under mild conditions, and simultaneously maintain the material's pore structure and mechanical strength has become a pressing technical challenge in this field. Based on this, this invention proposes a green preparation system for low-sulfur carbon materials, using a fluidized bed reactor as the core reactor and hydrogen as the reducing agent. By optimizing the fluidized gas flow rate, gas-solid separation is immediately performed after the gas-solid fluidized bed reactor reaction, thus constructing a green preparation system for low-sulfur carbon materials.

[0012] In a preferred embodiment of the present invention, the mass flow rate of the dopant in S2 is 0.5 to 10 t / h, and the volumetric flow rate of H2 is 1 to 4.5 L / min; preferably, the mass flow rate of the dopant is 0.5 to 2 t / h, and the volumetric flow rate of H2 is 1 to 2 L / min.

[0013] More preferably, the mass flow rate of the dopant material is 0.5 to 0.8 t / h.

[0014] Gas flow rate is a key parameter for controlling the fluidization state of materials. A hydrogen volumetric flow rate of 0.5–4.5 L / min is recommended. Within this range, gas-solid mass transfer efficiency and reaction kinetics requirements can be balanced, avoiding fluidization failure and side reactions. Higher gas flow rates can improve the fluidization effect of materials, but excessively high flow rates may cause materials to be carried away by the gas flow. Hydrogen reacts with sulfur-containing compounds to produce hydrogen sulfide gas, which is then recycled in the tail gas treatment unit.

[0015] In a preferred embodiment of the present invention, the carbon material in S1 is selected from one or more of petroleum coke, pitch coke, metallurgical coke or coal; preferably petroleum coke or coal; more preferably low-sulfur petroleum coke or coal, wherein the initial sulfur content in the low-sulfur petroleum coke is ≤10%.

[0016] The process of this invention has a good desulfurization effect on low-sulfur petroleum coke or coal.

[0017] In a preferred embodiment of the present invention, the particle size D90 of the carbon material particles in S1 is 1μm to 100μm; preferably 1μm to 50μm.

[0018] The particles with a diameter D90 = 100 μm should account for 80% to 90% of the total mass of the spare particles.

[0019] The particles are crushed to a D90 of 100 μm to allow them to exhibit free-flow dynamics under the influence of airflow during subsequent processing, facilitating full contact and reaction with the reducing gas hydrogen and enhancing mass transfer. Particles larger than 100 μm are less conducive to complete reaction. In the desulfurization of carbon materials, catalysts primarily improve desulfurization efficiency by adsorbing and activating sulfides such as thiophene sulfur, promoting the breaking of sulfur chemical bonds, and converting sulfur into easily removable substances such as hydrogen sulfide. Furthermore, a suitable catalyst's selective reaction mechanism can avoid damaging other components of the carbon material, ensuring that the material's performance remains unaffected.

[0020] In a preferred embodiment of the present invention, the carbon material particles in S1 are doped with a catalyst, which is one or more of Co-Mo-Ni-W, Pt / Al2O3, Ni2Mo3N / γ-Al2O3, Mo / TiO2, MoS2 / ZrO2, CoMo / C, SBA-15, MCM-14, KIT molecular sieve, etc., and the doping ratio is 1‰ to 1%; preferably SBA-15, with a doping ratio of 0.5% to 3%.

[0021] The Chinese patent application with publication number CN117757498A may have the following problems: hydrogen reduction kinetics are significantly affected by the catalyst, and existing supported catalysts (such as Fe / γ-Al2O3) are prone to pulverization and deactivation in the fluidized state due to particle collision, resulting in insufficient stability. This invention, by adjusting the type of catalyst, greatly reduces the desulfurization temperature and significantly reduces the energy consumption of the desulfurization process.

[0022] In a preferred embodiment of the present invention, the preheating temperature in S2 is 120-350°C; preferably 250-350°C.

[0023] Preheating at a certain temperature can reduce the heating residence time of the material in the reaction device, avoid additional energy consumption, and prevent the quality of carbon materials from being affected by large temperature fluctuations.

[0024] In a preferred embodiment of the present invention, the reaction temperature in S3 is 400-800°C and the reaction time is 30-50 minutes.

[0025] In a preferred embodiment of the present invention, the reaction temperature in S3 is 500-800°C and the reaction time is 50s-10min; preferably 700°C and the reaction time is 50s.

[0026] The physicochemical properties of carbon materials obtained by calcination time that is too short are generally low and do not meet the requirements for use; calcination time that is too long increases material loss and reduces yield.

[0027] This invention further reduces costs and improves efficiency through reaction kinetics regulation.

[0028] The present invention also discloses a low-sulfur carbon material prepared according to the preparation method described above, wherein the sulfur content of the carbon material is 0.1-1% and the particle stability is 70-90%.

[0029] The present invention also discloses a carbon material system, including a raw material pretreatment device. The outlets of the raw material pretreatment device and the catalyst storage device are connected to the inlet of the mixing device. The outlet of the mixing device is then connected in sequence to a preheating device, a gas-solid fluidized bed reactor, and a gas-solid separation device. The outlet of the gas storage device is connected to the inlet of the gas-solid fluidized bed reactor.

[0030] The Chinese patent application with publication number CN117757498A may have the following problem: if the H2S generated in the desulfurization reaction is not separated in time, a reverse reaction may occur, causing secondary sulfur pollution. This invention uses a gas-solid separation device to separate the reacted gas in a timely manner, thus avoiding secondary sulfur pollution.

[0031] The raw material pretreatment device includes a receiving hopper, the outlet of which is connected to the inlet of a bucket elevator, the outlet of the bucket elevator is connected to the inlet of a crusher, and the outlet of the crusher is connected to the inlet of a mixing device. It is mainly used to reduce the particle size of carbon materials and screen out materials that meet the particle size requirements.

[0032] The gas-solid separation device includes a cyclone separator, the slag outlet of which is connected to the feed inlet of the product collection device, and the gas outlet of which is connected to the gas inlet of the tail gas treatment device.

[0033] Catalyst storage device: It is used to store catalysts;

[0034] Gas storage device: It is used to store H2;

[0035] Preheating devices: These are divided into solid preheating devices and gas preheating devices, which are used to preheat and raise the temperature of pretreated materials and gases entering the reaction.

[0036] Gas-solid fluidized bed reactor: It is used to receive carbon materials and H2, providing a site for their reaction;

[0037] The gas-solid fluidized bed reactor is equipped with a heating and insulation component on its outer periphery: it is used to provide heat to the system so that the carbon materials and H2 can react fully;

[0038] Gas-solid separation unit: It is used to separate desulfurization carbon and tail gas;

[0039] Product collection device: It is used to collect solid products;

[0040] Exhaust gas treatment device: It is used to receive the exhaust gas after high-temperature reaction, treat the sulfur-containing gas, and separate the reducing gas for reuse.

[0041] A mixing device is used to mix the catalyst and the sieved material.

[0042] Preferably, the gas storage device is a liquid hydrogen storage tank.

[0043] Preferably, the preheating device is a preheating moving bed reactor; the gas preheating device is a heater.

[0044] Preferably, the system for preparing calcined petroleum coke further includes a gate valve and a gas flow regulating valve.

[0045] Preferably, the catalyst storage device is connected to the mixing device and the solid preheating reaction device by gate valves; the gas storage device is connected to the gas preheating device by a gas flow regulating valve.

[0046] Preferably, the cooling temperature of the solid after the high-temperature reaction is <60℃.

[0047] Preferably, the exhaust gas treatment device is a flue gas absorption tower.

[0048] The gas-solid fluidized bed includes one of the following: bubbling bed, turbulent bed, fast fluidized bed, circulating fluidized bed, riser reactor, and downflow reactor. Preferably, the gas-solid fluidized bed is a circulating fluidized bed.

[0049] Carbon materials are lifted to a crusher for crushing via an elevator, and then screened to obtain particles with a D90 of 100 μm. These particles are then fed into a mixing unit to be doped with a catalyst. After doping, the material is sent to a solid preheating unit for preheating to 120–350°C. Simultaneously, the H2 flow rate is controlled by adjusting a gas flow regulating valve and sent to a gas preheating unit for preheating. The reaction unit is then preheated to 400–800°C via a heating unit. The preheated doped material and H2 are then sent to the reaction unit to react for 30–50 seconds. After the reaction, the resulting gas-solid mixture is immediately sent to a gas-solid separation unit to separate the solid and gas. The resulting solid, after cooling, becomes desulfurized carbon. The tail gas is transported to a tail gas treatment unit for processing. The sulfur-containing gases are collected and treated to obtain chemical products. The separated hydrogen is returned to a hydrogen storage tank for reuse. Other carbon-containing combustible gases are transported via pipeline to the heating unit or a power plant for recycling, depending on the heating unit used.

[0050] The present invention will be further explained below:

[0051] This invention uses a fluidized bed reactor and H2 as a reducing agent to prepare high-quality, low-sulfur carbon materials. First, the carbon material is crushed and screened to improve the flowability of solid particles in the fluidized bed reactor, increasing its contact area with H2. Then, the dopant material and H2 are sent to a preheating device to be preheated to a specific temperature, reducing the heating time in the reaction device, avoiding additional energy consumption, and preventing the quality of the carbon material from being affected by large temperature fluctuations. Under an H2 atmosphere, high-temperature calcination of the dopant material in the reactor achieves efficient desulfurization. Hydrogen atoms, due to their strong affinity for sulfur atoms, can effectively remove sulfides from oil and gas, including sulfides, mercaptans, sulfones, and simple thiophenes, significantly improving desulfurization efficiency. Simultaneously, the hydrogen sulfide (H2S) gas generated in the desulfurization reaction further promotes the removal of sulfur from residual oil. The final carbon material has characteristics such as low sulfur content, high particle stability, and high conductivity, meeting the stringent requirements of subsequent applications.

[0052] The beneficial effects of this invention are as follows:

[0053] 1. The method for preparing low-sulfur carbon materials of the present invention involves desulfurizing the dopant material fed into the fluidized bed under an H2 atmosphere. A catalyst can be selectively added according to the product requirements. When the obtained carbon material is applied to other industries, no additional desulfurization treatment is required. The process is simple, highly flexible, and highly operable.

[0054] 2. Conventional high-temperature calcination desulfurization methods without catalysts require temperatures ≥1200℃; however, the desulfurization temperature of this invention is 400-800℃, and even without a catalyst, a desulfurization rate of over 95% can be achieved at 800℃ for 50 minutes. This significantly reduces the desulfurization temperature and energy consumption of the desulfurization process. Furthermore, this invention can directly produce carbon materials suitable for steelmaking, aluminum smelting, and battery anode applications.

[0055] 3. This invention innovatively optimizes the gas flow rate of H2, the particle size of carbon material, and the temperature, resulting in lower production costs, greater environmental friendliness, higher reduction efficiency, and lower reaction temperature, thus greatly improving production efficiency.

[0056] 4. In the method for preparing low-sulfur carbon materials of the present invention, the H2 obtained after treatment and separation of the tail gas generated in the desulfurization reaction can be returned to the hydrogen storage tank for secondary use in the desulfurization reaction. The separated carbon-containing combustible gas can be recycled for use in heating devices or sent to power plants, thereby improving resource utilization.

[0057] 5. The method for preparing calcined petroleum coke of the present invention has a desulfurization rate of ≥95%, and obtains carbon materials with low sulfur content and high particle stability, which have good application prospects.

[0058] 6. The system for preparing low-sulfur carbon materials of this invention can achieve a high degree of automation in production, realizing fully automated operation from raw material transportation, hydrogen mixing, reaction control to product collection. This significantly improves production efficiency, reduces manual intervention and operational errors, optimizes resource utilization, and lowers production costs. Simultaneously, the system possesses excellent scalability and flexibility, allowing adjustments to meet diverse product specifications and providing a reliable guarantee for the large-scale production of low-sulfur carbon materials. Attached Figure Description

[0059] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the accompanying drawings used in the description of the embodiments or the prior art will be briefly introduced below.

[0060] Figure 1 This is a diagram illustrating the hydrogen desulfurization mechanism under catalytic conditions.

[0061] Figure 2 This is a diagram of the production equipment for the carbon material of this invention;

[0062] Among them, 1-receiving hopper; 2-bucket elevator; 3-crusher; 4-mixing device; 5-preheating device; 6-gas storage device; 7-pressure reducing valve; 8-gas preheating device; 9-catalyst storage device; 10-gate valve; 11-screw feeder; 12-gas-solid fluidized bed reactor; 13-heating and insulation components; 14-air distribution plate; 15-cyclone separator; 16-desulfurization carbon storage tank; 17-flue gas absorption tower;

[0063] Figure 3 This is a flowchart illustrating the production process of the carbon material of this invention. Detailed Implementation

[0064] The following specific implementation examples further illustrate this point, but the present invention is not limited thereto. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

[0065] like Figure 2 As shown, a carbon material system includes:

[0066] The raw material pretreatment device and the catalyst storage device 9 are connected to the inlet of the mixing device 4. The outlet of the mixing device 4 is then connected in sequence to the preheating device 5, the gas-solid fluidized bed reactor 12, and the gas-solid separation device. The outlet of the gas storage device is connected to the inlet of the gas-solid fluidized bed reactor 12.

[0067] The raw material pretreatment device includes a receiving hopper 1, the outlet of the receiving hopper 1 is connected to the inlet of the bucket elevator 2, the outlet of the bucket elevator 2 is connected to the inlet of the crusher 3, and the outlet of the crusher 3 is connected to the inlet of the mixing device 4.

[0068] The gas-solid separation device includes a cyclone separator 15, the slag outlet of the cyclone separator 15 is connected to the feed inlet of the product collection device 16, and the air outlet of the cyclone separator 15 is connected to the air inlet of the tail gas treatment device 17.

[0069] Carbon materials are lifted to a crusher for crushing via an elevator, and then screened to obtain particles with a D90 of 100 μm. These particles are then fed into a mixing unit to be doped with a catalyst. After doping, the material is sent to a solid preheating unit for preheating to 120–350°C. Simultaneously, the H2 flow rate is controlled by adjusting a gas flow regulating valve and sent to a gas preheating unit for preheating. The reaction unit is then preheated to 400–800°C via a heating unit. The preheated doped material and H2 are then sent to the reaction unit to react for 30–50 seconds. After the reaction, the resulting gas-solid mixture is immediately sent to a gas-solid separation unit to separate the solid and gas. The resulting solid, after cooling, becomes desulfurized carbon. The tail gas is transported to a tail gas treatment unit for processing. The sulfur-containing gases are collected and treated to obtain chemical products. The separated hydrogen is returned to a hydrogen storage tank for reuse. Other carbon-containing combustible gases are transported via pipeline to the heating unit or a power plant for recycling, depending on the heating unit used.

[0070] Example 1

[0071] Such as process flow Figure 3 As shown, 10 kg of petroleum coke from a certain factory was taken, and its sulfur content was measured to be 8.6%. It was lifted to a crusher for crushing via an elevator, and then screened to obtain particles with a D90 = 100 μm. These particles were then fed into a mixing device and mixed with SBA-15 at a doping ratio of 5‰. After doping, the material was sent to a solid preheating device at a mass flow rate of 0.8 t / h to be preheated to 250℃. Simultaneously, the H2 flow rate was controlled at 1 L / min by adjusting the gas flow regulating valve and sent to a gas preheating device to be preheated to 250℃. The reaction device was then preheated to 700℃ using a heating device. The preheated doped material and H2 were then sent to the reaction device to react for 50 seconds. After the reaction, the resulting gas-solid mixture was immediately sent to a gas-solid separation device to separate the solid and gas. The solid was cooled to <60℃ and then removed to obtain desulfurized carbon. Testing showed a sulfur content of 0.88% and a particle stability of 80.23%.

[0072] Example 2

[0073] Such as process flow Figure 3As shown, 10 kg of petroleum coke from a certain factory was taken, and its sulfur content was measured to be 8.6%. It was lifted to a crusher for crushing via an elevator, and particles with a D90 = 1 μm were screened out by a screening device and fed into a mixing device to be doped with SBA-15 at a doping ratio of 5‰. After doping, the material was sent to a solid preheating device at a mass flow rate of 0.8 t / h to be preheated to 250℃. Simultaneously, the H2 flow rate was controlled at 1 L / min by adjusting the gas flow regulating valve and sent to a gas preheating device to be preheated to 250℃. The reaction device was preheated to 700℃ by a heating device, and then the preheated doped material and H2 were sent to the reaction device to react for 50 s. After the reaction, the resulting gas-solid mixture was immediately sent to a gas-solid separation device to separate the solid and gas. The solid was cooled to <60℃ and then removed to obtain desulfurized carbon. Testing showed that the sulfur content was 0.21% and the particle stability was 90.6%.

[0074] Comparative Example 1

[0075] Such as process flow Figure 3 As shown, 10 kg of petroleum coke from a certain factory was taken, and its sulfur content was measured to be 8.6%. It was lifted to a crusher for crushing via an elevator, and particles with a D90 = 1 cm were screened out by a screening device and fed into a mixing device to be mixed with SBA-15 at a doping ratio of 5‰. After doping, the material was sent to a solid preheating device at a mass flow rate of 0.8 t / h to be preheated to 250℃. Simultaneously, the H2 flow rate was controlled at 1 L / min by adjusting the gas flow regulating valve and sent to a gas preheating device to be preheated to 250℃. The reaction device was preheated to 700℃ by a heating device, and then the preheated doped material and H2 were sent to the reaction device to react for 50 s. After the reaction, the resulting gas-solid mixture was immediately sent to a gas-solid separation device to separate the solid and gas. The solid was cooled to <60℃ and then removed to obtain desulfurized carbon. Testing showed that the sulfur content was 3.8% and the particle stability was 60.8%.

[0076] Example 3

[0077] Such as process flow Figure 3As shown, 10 kg of petroleum coke from a certain factory was taken, and its sulfur content was measured to be 8.6%. It was lifted to a crusher for crushing, and then screened to obtain particles with a D90 = 100 μm. These particles were then fed to a solid preheating unit at a mass flow rate of 0.8 t / h to be preheated to 250℃. Simultaneously, the H2 flow rate was controlled at 1 L / min by adjusting the gas flow regulating valve and sent to a gas preheating unit to be preheated to 250℃. The reaction unit was then preheated to 700℃ by a heating device. The preheated dopant material and H2 were then fed back to the reaction unit for a reaction time of 50 seconds. After the reaction, the resulting gas-solid mixture was immediately sent to a gas-solid separation unit to separate the solid and gas. The solid was cooled to <60℃ and then removed to obtain desulfurized carbon. Testing showed a sulfur content of 0.92% and a particle stability of 80.15%.

[0078] Example 4

[0079] Such as process flow Figure 3 As shown, 10 kg of petroleum coke from a certain factory was taken, and its sulfur content was measured to be 8.6%. It was lifted to a crusher for crushing via an elevator, and then screened to obtain particles with a D90 = 100 μm. These particles were then fed into a mixing device and mixed with SBA-15 at a doping ratio of 1%. After doping, the material was sent to a solid preheating device at a mass flow rate of 0.8 t / h to be preheated to 250°C. Simultaneously, the H2 flow rate was controlled at 1 L / min by adjusting the gas flow regulating valve and sent to a gas preheating device to be preheated to 250°C. The reaction device was then preheated to 700°C via a heating device. The preheated doped material and H2 were then sent to the reaction device to react for 50 seconds. After the reaction, the resulting gas-solid mixture was immediately sent to a gas-solid separation device to separate the solid and gas. The solid was cooled to <60°C and then removed to obtain desulfurized carbon. Testing showed a sulfur content of 0.48% and a particle stability of 89.6%.

[0080] Comparative Example 2

[0081] Such as process flow Figure 3As shown, 10 kg of petroleum coke from a certain factory was taken, and its sulfur content was measured to be 8.6%. It was lifted to a crusher for crushing via an elevator, and then screened to obtain particles with a D90 = 100 μm. These particles were then fed into a mixing device and mixed with SBA-15 at a doping ratio of 5‰. After doping, the material was sent to a solid preheating device at a mass flow rate of 0.8 t / h to be preheated to 250℃. Simultaneously, the H2 flow rate was controlled at 5 L / min by adjusting the gas flow regulating valve and sent to a gas preheating device to be preheated to 250℃. The reaction device was then preheated to 700℃ using a heating device. The preheated doped material and H2 were then sent to the reaction device to react for 50 s. After the reaction, the resulting gas-solid mixture was immediately sent to a gas-solid separation device to separate the solid and gas. The solid was cooled to <60℃ and then removed to obtain desulfurized carbon. Testing showed a sulfur content of 1.06% and a particle stability of 78.6%.

[0082] Comparative Example 3

[0083] Such as process flow Figure 3 As shown, 10 kg of petroleum coke from a certain factory was taken, and its sulfur content was measured to be 8.6%. It was lifted to a crusher for crushing via an elevator, and then screened to obtain particles with a D90 = 100 μm. These particles were then fed into a mixing device and mixed with SBA-15 at a doping ratio of 5‰. After doping, the material was sent to a solid preheating device at a mass flow rate of 0.8 t / h to be preheated to 250℃. Simultaneously, the H2 flow rate was controlled at 0.5 L / min by adjusting the gas flow regulating valve and sent to a gas preheating device to be preheated to 250℃. The reaction device was then preheated to 700℃ using a heating device. The preheated doped material and H2 were then sent to the reaction device to react for 50 s. After the reaction, the resulting gas-solid mixture was immediately sent to a gas-solid separation device to separate the solid and gas. The solid was cooled to <60℃ and then removed to obtain desulfurized carbon. Testing showed a sulfur content of 1.24% and a particle stability of 78.2%.

[0084] Example 5

[0085] Such as process flow Figure 3As shown, 10 kg of petroleum coke from a certain factory was taken, and its sulfur content was measured to be 8.6%. It was lifted to a crusher for crushing via an elevator, and then screened to obtain particles with a D90 = 100 μm. These particles were then fed into a mixing device and mixed with SBA-15 at a doping ratio of 5‰. After doping, the material was sent to a solid preheating device at a mass flow rate of 0.8 t / h to be preheated to 250℃. Simultaneously, the H2 flow rate was controlled at 1 L / min by adjusting the gas flow regulating valve and sent to a gas preheating device to be preheated to 250℃. The reaction device was then preheated to 400℃ using a heating device. The preheated doped material and H2 were then sent to the reaction device to react for 50 seconds. After the reaction, the resulting gas-solid mixture was immediately sent to a gas-solid separation device to separate the solid and gas. The solid was cooled to <60℃ and then removed to obtain desulfurized carbon. Testing showed a sulfur content of 0.96% and a particle stability of 79.8%.

[0086] Example 6

[0087] Such as process flow Figure 3 As shown, 10 kg of petroleum coke from a certain factory was taken, and its sulfur content was measured to be 8.6%. It was lifted to a crusher for crushing via an elevator, and then screened by a screening device to obtain particles with a D90 = 100 μm. These particles were then fed into a mixing device and mixed with SBA-15 at a doping ratio of 5‰. After doping, the material was sent to a solid preheating device at a mass flow rate of 0.8 t / h to be preheated to 250℃. Simultaneously, the H2 flow rate was controlled at 1 L / min by adjusting the gas flow regulating valve and sent to a gas preheating device to be preheated to 250℃. The reaction device was then preheated to 800℃ by a heating device. The preheated doped material and H2 were then sent to the reaction device to react for 50 s. After the reaction, the resulting gas-solid mixture was immediately sent to a gas-solid separation device to separate the solid and gas. The solid was cooled to <60℃ and then removed to obtain desulfurized carbon. Testing showed that the sulfur content was 0.44% and the particle stability was 88.7%.

[0088] Comparative Example 4

[0089] Such as process flow Figure 3As shown, 10 kg of petroleum coke from a certain factory was taken, and its sulfur content was measured to be 8.6%. It was lifted to a crusher for crushing via an elevator, and then screened by a screening device to obtain particles with a D90 = 100 μm. These particles were then fed into a mixing device and mixed with SBA-15 at a doping ratio of 5‰. After doping, the material was sent to a solid preheating device at a mass flow rate of 0.8 t / h to be preheated to 250℃. Simultaneously, the H2 flow rate was controlled at 1 L / min by adjusting the gas flow regulating valve and sent to a gas preheating device to be preheated to 250℃. The reaction device was then preheated to 700℃ by a heating device. The preheated doped material and H2 were then sent to the reaction device to react for 30 seconds. After the reaction, the resulting gas-solid mixture was immediately sent to a gas-solid separation device to separate the solid and gas. The solid was cooled to <60℃ and then removed to obtain desulfurized carbon. Testing showed that the sulfur content was 1.8% and the particle stability was 76.8%.

[0090] Example 7

[0091] Such as process flow Figure 3 As shown, 10 kg of petroleum coke from a certain factory was taken, and its sulfur content was measured to be 8.6%. It was lifted to a crusher for crushing via an elevator, and then screened by a screening device to obtain particles with a D90 = 100 μm. These particles were then fed into a mixing device and mixed with SBA-15 at a doping ratio of 5‰. After doping, the material was sent to a solid preheating device at a mass flow rate of 0.8 t / h to be preheated to 250℃. Simultaneously, the H2 flow rate was controlled at 1 L / min by adjusting the gas flow regulating valve and sent to a gas preheating device to be preheated to 250℃. The reaction device was then preheated to 700℃ by a heating device. The preheated doped material and H2 were then sent to the reaction device to react for 50 min. After the reaction, the resulting gas-solid mixture was immediately sent to a gas-solid separation device to separate the solid and gas. The solid was cooled to <60℃ and then removed to obtain desulfurized carbon. Testing showed that the sulfur content was 0.38% and the particle stability was 88.4%.

[0092] Example 8

[0093] Such as process flow Figure 3As shown, 10 kg of coal from a certain factory was taken, and its sulfur content was measured to be 3.8%. It was then lifted to a crusher for crushing and screened to obtain particles with a D90 = 100 μm. These particles were then fed into a mixing device and mixed with SBA-15 at a doping ratio of 5‰. The doped material was then sent to a solid preheating device at a mass flow rate of 0.8 t / h to be preheated to 250℃. Simultaneously, the H2 flow rate was controlled at 1 L / min by adjusting the gas flow regulating valve and sent to a gas preheating device to be preheated to 250℃. The reaction device was then preheated to 700℃ by a heating device. The preheated doped material and H2 were then sent to the reaction device to react for 50 seconds. After the reaction, the resulting gas-solid mixture was immediately sent to a gas-solid separation device to separate the solid and gas. The solid was cooled to <60℃ and then removed to obtain desulfurized carbon. Testing showed a sulfur content of 0.16% and a particle stability of 89.8%.

[0094] Example 9

[0095] Such as process flow Figure 3 As shown, 10 kg of asphalt coke from a certain factory was taken, and its sulfur content was measured to be 7.8%. It was then lifted to a crusher for crushing via an elevator, and particles with a D90 = 100 μm were screened out by a screening device and fed into a mixing device to be mixed with SBA-15 at a doping ratio of 5‰. The doped material was then sent to a solid preheating device at a mass flow rate of 0.8 t / h to be preheated to 250℃. Simultaneously, the H2 flow rate was controlled at 1 L / min by adjusting the gas flow regulating valve and sent to a gas preheating device to be preheated to 250℃. The reaction device was then preheated to 700℃ by a heating device, and the preheated doped material and H2 were then sent to the reaction device to react for 50 s. After the reaction, the resulting gas-solid mixture was immediately sent to a gas-solid separation device to separate the solid and gas. The solid was cooled to <60℃ and then removed to obtain desulfurized carbon. Testing showed that the sulfur content was 0.82% and the particle stability was 80.3%.

[0096] Example 10

[0097] Such as process flow Figure 3As shown, 10 kg of petroleum coke from a certain factory was taken, and its sulfur content was measured to be 2.4%. It was lifted to a crusher for crushing via an elevator, and then screened by a screening device to obtain particles with a D90 = 100 μm. These particles were then fed into a mixing device and mixed with SBA-15 at a doping ratio of 5‰. After doping, the material was sent to a solid preheating device at a mass flow rate of 0.8 t / h to be preheated to 250℃. Simultaneously, the H2 flow rate was controlled at 1 L / min by adjusting the gas flow regulating valve and sent to a gas preheating device to be preheated to 250℃. The reaction device was then preheated to 700℃ by a heating device. The preheated doped material and H2 were then sent to the reaction device to react for 50 s. After the reaction, the resulting gas-solid mixture was immediately sent to a gas-solid separation device to separate the solid and gas. The solid was cooled to <60℃ and then removed to obtain desulfurized carbon. Testing showed that the sulfur content was 0.12% and the particle stability was 85.9%.

[0098] Table 1. Parameters of carbon materials in Examples 1-14

[0099]

[0100]

[0101] As shown in Table 1, Examples 1, 2, and Comparative Example 1 used particles with D90 values ​​of 100 μm, 1 μm, and 1 cm, respectively. The results indicate that smaller particle size leads to better desulfurization, but particle stability may decrease. For example, in Example 2, when D90 was 1 μm, the sulfur content decreased to 0.21%, while in Comparative Example 1, when D90 was 1 cm, the sulfur content reached as high as 3.8%. This is because smaller particles have a larger specific surface area, allowing for more thorough contact with hydrogen and more reactive sites, thus improving desulfurization efficiency. However, excessively small particle sizes may cause particle agglomeration during the reaction, affecting stability.

[0102] A comparison of Examples 1 and 4 shows that when the doping ratio increased from 5‰ to 1%, the sulfur content decreased from 0.88% to 0.48%, and the particle stability increased from 80.23% to 89.6%. Compared to Example 1, Example 3 did not include a catalyst. In Example 1, SBA-15, as a mesoporous material, provided more active sites, promoting the desulfurization reaction. Increasing the doping ratio further enhanced this effect, thereby improving desulfurization efficiency and particle stability.

[0103] Comparative Examples 2 and 3 used H2 flow rates of 5 L / min and 0.5 L / min, respectively. The results showed that both excessively high and low flow rates led to an increase in sulfur content. In Comparative Example 2, the sulfur content was 1.06% when the H2 flow rate was 5 L / min, while in Comparative Example 3, the sulfur content was 1.24% when the flow rate was 0.5 L / min. This indicates that the hydrogen flow rate needs to be controlled within a suitable range; too high a flow rate may lead to an overly vigorous reaction, while too low a flow rate will not provide sufficient hydrogen for the reaction, thus affecting the desulfurization effect.

[0104] Examples 5 and 6 were reacted at 400°C and 800°C, respectively, with sulfur contents of 0.96% and 0.44%. Increasing the temperature helps to improve the reaction rate and desulfurization efficiency, but excessively high temperatures may lead to an increase in side reactions and affect particle stability (the particle stability of Example 6 was 88.7%, slightly higher than the 80.23% of Example 1).

[0105] Comparative Example 4 and Example 7 were reacted at 30 s and 50 min, respectively, with sulfur contents of 1.8% and 0.38%. Extending the reaction time can improve the desulfurization effect, but excessively long time may increase energy consumption and the risk of side reactions, so efficiency and cost need to be considered comprehensively.

[0106] Examples 8 (coal), 9 (asphalt coke), and 10 (low-sulfur petroleum coke) show that the initial sulfur content and physicochemical properties of different raw materials have a significant impact on the desulfurization effect. For example, in Example 8, the initial sulfur content of the coal was 3.8%, and the sulfur content decreased to 0.16% after desulfurization, indicating that the process has a good desulfurization effect on coal.

[0107] In summary, the method and system of this invention can produce high-quality low-sulfur carbon materials with low sulfur content and high particle stability, providing a new path for the production of high-quality low-sulfur carbon materials.

Claims

1. A method for preparing a carbon material, characterized in that, Includes the following steps: S1. Prepare carbon material granules; The carbon material particles contain a catalyst, which is SBA-15, with a doping ratio of 5‰ to 1%; the carbon material is selected from one or more of petroleum coke, pitch coke, or coal. S2. Preheat the carbon material particles and H2; S3. The preheated dopant material and H2 are fed into a gas-solid fluidized bed reactor for reaction. After the reaction is completed, the gas and solid are separated and the solid is cooled to obtain low-sulfur carbon material, i.e., desulfurized carbon. The volumetric flow rate of H2 in S2 is 1~4.5 L / min; The particle size D90 of the carbon material particles in S1 is 1μm~100μm; The preheating temperature in S2 is 120~350 ℃; The reaction temperature in S3 is 500~700℃, and the reaction time is 50s~10min; the mass flow rate of the dopant material is 0.5~2t / h. The preparation method adopts a carbon material-based system, which includes a raw material pretreatment device. The outlets of the raw material pretreatment device and the catalyst storage device (9) are connected to the inlet of the mixing device (4). The outlet of the mixing device (4) is then connected in sequence to the preheating device (5), the gas-solid fluidized bed reactor (12), and the gas-solid separation device. The outlet of the gas storage device is connected to the inlet of the gas-solid fluidized bed reactor (12). The gas-solid separation device includes a cyclone separator, the slag outlet of the cyclone separator is connected to the feed inlet of the product collection device, and the gas outlet of the cyclone separator is connected to the gas inlet of the tail gas treatment device. After being processed by the exhaust gas treatment device, the separated hydrogen is returned to the hydrogen storage tank for reuse.

2. The method for preparing carbon materials according to claim 1, characterized in that, The H2 volumetric flow rate is 1~2 L / min.

3. The method for preparing carbon materials according to claim 1, characterized in that, The carbon material mentioned in S1 is selected from low-sulfur petroleum coke or coal, and the initial sulfur content in the low-sulfur petroleum coke is ≤10%.

4. The method for preparing carbon materials according to claim 1, characterized in that, The particle size D90 of the carbon material particles in S1 is 1μm~50μm.

5. The method for preparing carbon materials according to claim 1, characterized in that, The preheating temperature in S2 is 250~350 ℃.

6. A carbon material prepared by the method according to any one of claims 1-5, characterized in that, The sulfur content of the carbon material is 0.1-1%, and the particle stability is 70-90%.

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