Low-temperature alkali activation preparation method and device of petroleum coke-based porous carbon

Abstract

The invention discloses a low-temperature alkali activation preparation method and device of petroleum coke-based porous carbon, and belongs to the technical field of petroleum coke-based porous carbon. The preparation method comprises the following steps: S1, directional pretreatment, S2, directional compounding of a specific composite activator, S3, dynamic cooperative temperature control-negative pressure activation, and S4, targeted post-treatment, and through a series of innovative designs, the preparation efficiency of the petroleum coke-based porous carbon, the product quality and the controllability of the production process are remarkably improved; and a more reliable and efficient solution is provided for industrial production of petroleum coke-based porous carbon. All links are closely matched from the pretreatment process to the activation process and then to the post-treatment and intelligent control of matched devices, low-temperature efficient preparation, accurate control of reaction conditions and improvement of product quality are achieved, meanwhile, the intelligent monitoring and control functions are achieved, and the high-quality, low-cost and intelligent requirements of petroleum coke-based porous carbon preparation are comprehensively met. And the energy consumption and the production cost are reduced.

Description

Technical Field

[0001] This invention relates to the field of petroleum coke-based porous carbon technology, and more specifically, to a low-temperature alkali activation preparation method and apparatus for petroleum coke-based porous carbon. Background Technology

[0002] In the preparation of petroleum coke-based porous carbon, traditional methods have many drawbacks. Firstly, the activation temperature is high, typically requiring alkali activation reactions at 800℃ or even higher. This high temperature not only consumes a large amount of energy and increases production costs, but also places extremely high demands on the high-temperature resistance of the reaction equipment, leading to increased equipment maintenance costs.

[0003] On the other hand, traditional methods are not scientific enough in the selection and use of activators. A single activator is insufficient for precise control of the structure of petroleum coke, resulting in porous carbon that fails to meet increasingly diverse application requirements in terms of key performance indicators such as pore size distribution and specific surface area. Furthermore, traditional preparation processes lack precise control over reaction conditions; parameters such as heating rate and pressure are difficult to dynamically adjust according to the reaction progress, affecting the stability and consistency of product quality. In addition, post-processing is relatively crude. Traditional washing and drying methods cannot effectively remove impurities and may damage the structure of porous carbon, leading to a decline in its performance. During the drying process, the lack of precise control over factors such as temperature and gas atmosphere further affects product quality. Simultaneously, traditional preparation methods struggle to achieve comprehensive monitoring and intelligent control of the entire preparation process, making it difficult to promptly identify and resolve problems during production, which is detrimental to large-scale industrial production. Therefore, the existence of a low-temperature alkaline activation preparation method and apparatus for petroleum coke-based porous carbon is crucial. Summary of the Invention

[0004] The purpose of this invention is to provide a low-temperature alkali activation preparation method and apparatus for petroleum coke-based porous carbon, so as to solve the problems mentioned in the background art.

[0005] A method and apparatus for preparing petroleum coke-based porous carbon by low-temperature alkali activation, comprising the following steps:

[0006] S1. Directional pretreatment: Petroleum coke is pulverized and passed through a 250-mesh standard sieve to obtain petroleum coke powder with a particle size ≤61μm; then it is preheated at a constant temperature of 180℃ for 2.5h under a nitrogen atmosphere, during which nitrogen gas at a flow rate of 50mL / min is introduced simultaneously.

[0007] S2. Targeted compounding of the specific composite activator: The main activator, co-activator, and interface modifier are mixed uniformly at a mass ratio of 3.2:1:0.3 to obtain the specific composite activator; the main activator is KOH, the co-activator is a 1:1 mixture of ammonium chloride and ammonium carbonate, and the interface modifier is polyethylene glycol 400; the specific composite activator is mixed with the pretreated petroleum coke in S1 at a mass ratio of 2.2:1, and deionized water is added to adjust the material moisture content to 10%. Subsequently, a planetary ball mill is used for alternating "grinding-dispersion" treatment for 40 minutes, with a grinding speed of 350 r / min, a dispersion speed of 150 r / min, and an alternation cycle of 5 minutes.

[0008] S3. Dynamic Coordinated Temperature Control-Negative Pressure Activation: The material from S2 is placed in the reactor with the built-in spiral flow guide-temperature sensing linkage structure in S3. The dynamic negative pressure control system is activated, and the negative pressure is adjusted synchronously according to a three-stage heating process: The first stage heats up to 150℃ at a rate of 8℃ / min, while simultaneously adjusting the negative pressure to -0.03MPa and holding for 45min; the second stage heats up to 250℃ at a rate of 4℃ / min, while simultaneously adjusting the negative pressure to -0.035MPa and holding for 75min; the third stage heats up to 550℃ at a rate of 2.5℃ / min, while simultaneously adjusting the negative pressure to -0.04MPa and holding for 150min.

[0009] S4. Targeted post-treatment: The activated product in S3 is subjected to the following steps in sequence: ① First-stage washing with deionized water at room temperature three times, with a solid-liquid ratio of 1:10 each time, and a washing time of 20 min; ② Second-stage washing with 0.5 mol / L hydrochloric acid solution in a 50°C water bath twice, with a holding time of 30 min each time, and simultaneous application of 250W ultrasonic assistance; ③ Third-stage washing with deionized water in an 80°C water bath until the pH of the washing solution is 7.0±0.2, and stirring is maintained at 50 r / min during the washing process; After washing, a slurry with a mass concentration of 6% is prepared, dispersed by 40kHz pulsed ultrasonication for 25 min, and then subjected to gradient drying in an argon atmosphere: first drying at 80°C for 120 min, and then heating to 120°C for 240 min, with the temperature error controlled within ±3°C during the drying process.

[0010] Preferably, the number average molecular weight of polyethylene glycol 400 in S2 is 380-420, and the purity is ≥99.5%. The polyethylene glycol 400 is added in steps: first, 50% of the polyethylene glycol 400 is mixed evenly with the main activator, and then the co-activator and the remaining polyethylene glycol 400 are added. During the mixing process, the stirring rate is controlled at 200-250 r / min, and the stirring time is 15-20 min.

[0011] Preferably, the spiral flow guide-temperature sensing linkage structure in S3 includes 3-4 temperature sensors evenly distributed circumferentially along the inner wall of the reactor, a spiral flow guide vane set in the center, and a PLC controller; the detection end of the temperature sensor extends into the material 5-8cm, and the sampling frequency is 1 time / 30s; the PLC controller has a built-in temperature-speed correlation program, which controls the speed of the spiral flow guide vane to 150r / min when the temperature rises to 150℃; adjusts the speed to 220r / min when the temperature rises to 250℃; and adjusts the speed to 300r / min when the temperature rises to 550℃.

[0012] Preferably, the ultrasonic assistance during hydrochloric acid washing in S4 adopts a continuous ultrasonic mode, the ultrasonic probe is inserted into the slurry to a depth of 10-15cm, and the angle between the ultrasonic probe and the slurry surface is 30-45°; the ultrasonic power decreases linearly with washing time, and the attenuation rate is 1.67W / min; the constant temperature pickling tank is equipped with a jacketed insulation structure, and 50℃ constant temperature water is introduced into the jacket to maintain the temperature fluctuation of the pickling system ≤±2℃.

[0013] Preferably, in step S3, the nitrogen atmosphere in the reactor has a purity of ≥99.99%, and nitrogen is continuously introduced during the three-stage heating process at a flow rate of 30-40 mL / min. During the synergistic etching process of ammonia and KOH in step S3, the residence time of ammonia in the reactor is controlled to 20-30 min by adjusting the heating rate and negative pressure. During the gradient drying process in step S4, the argon flow rate is 60-80 mL / min, and during the heating stage, the argon flow rate increases linearly with the temperature increase, and the flow rate remains constant after the heating is completed.

[0014] It also includes a low-temperature alkali activation preparation device for petroleum coke-based porous carbon, comprising a base with four support legs fixedly mounted at the bottom, a sealing flange fixedly mounted at the top of the base, and a top cover fixedly connected to the sealing flange; a reaction liner fixedly mounted inside the base, the top of the reaction liner being sealed to the sealing flange; a discharge hole fixedly mounted at the bottom of the base, the top of the discharge hole penetrating the base and extending into the reaction liner; a temperature control chamber disposed between the interior of the base and the reaction liner; temperature control valves fixedly mounted on both sides of the discharge hole at the bottom of the base, the tops of the temperature control valves penetrating the base and fixedly connected to the temperature control chamber; and multiple pressure relief valves disposed on the exterior of the base. One end of the pressure relief valve passes through the base and is fixedly connected to the inside of the reaction vessel. A telescopic rod is fixedly installed on the top of the top cover. The bottom output end of the telescopic rod passes through the top cover and extends into the inside of the reaction vessel, and is fixedly connected to a stirring rod. The stirring rod moves up and down inside the reaction vessel, and multiple stirring blocks are fixedly sleeved on its outer side. A feed hole is fixedly installed on both sides of the telescopic rod on the top of the top cover. The bottom of the feed hole passes through the top cover and is connected to the inside of the reaction vessel. Multiple liquid inlets are fixedly installed on the top of the top cover. A water pipe is fixedly connected to the bottom of each of the multiple liquid inlets. The multiple water pipes pass through the top cover and extend into the bottom side of the inside of the reaction vessel. An intelligent monitoring and control system is installed inside the base.

[0015] Preferably, the intelligent monitoring and control system includes a PLC main controller, a multi-parameter sensing module, and a data acquisition module. The multi-parameter sensing module includes a temperature sensor distributed circumferentially along the inner wall of the reaction tank, a pressure transmitter embedded in the bottom of the reaction tank, and a pH sensor installed at the end of the water pipe. The temperature sensor has a sampling frequency of 1 time / 30s, a detection range of 0-600℃, and an accuracy of ±0.5℃. The pressure transmitter has a sampling range of -0.1MPa to 0MPa and an accuracy of ±0.001MPa. The pH sensor has a detection range of 0-14 and an accuracy of ±0.1. The data acquisition module is connected to the signals of each sensor and transmits the collected temperature, pressure, and pH data to the PLC main controller in real time.

[0016] Preferably, the intelligent monitoring and control system further includes a linkage execution module, which is signal-connected to the PLC main controller and drive-connected to the temperature control valve, telescopic rod, and pressure relief valve respectively. The PLC main controller has a built-in process parameter matching program. When the temperature sensor detects that the temperature in the first stage of S3 rises to 150°C, it automatically controls the opening of the temperature control valve to 40% and the speed of the telescopic rod driving the stirring rod to 150 r / min. When the temperature in the second stage rises to 250°C, the opening of the temperature control valve is adjusted to 60% and the stirring speed is adjusted to 220 r / min. When the temperature in the third stage rises to 550°C, the opening of the temperature control valve is adjusted to 80% and the stirring speed is adjusted to 300 r / min. When the pressure transmitter detects that the pressure deviates from the set value of the corresponding stage by ±0.002 MPa, it automatically adjusts the opening of the pressure relief valve for pressure compensation.

[0017] Preferably, the intelligent monitoring and control system further includes an anomaly warning module, which includes an audible and visual alarm and an emergency shut-off unit. The PLC main controller has a built-in threshold judgment program. When the temperature sensor detects that the temperature deviates from the set value of the corresponding stage in S3 by ±3℃, the pressure transmitter detects that the pressure deviates from the set value by ±0.005MPa, or the pH sensor detects that the pH of the washing liquid in S4 deviates from 7.0±0.5, the audible and visual alarm is immediately triggered. At the same time, the emergency shut-off unit automatically cuts off the power supply to the telescopic rod drive and the air / liquid inlet channel of the temperature control valve, and opens all pressure relief valves for emergency pressure relief.

[0018] Preferably, the intelligent monitoring and control system further includes a data storage and traceability module, which includes a solid-state drive and a data export interface. The solid-state drive stores temperature, pressure, and pH data collected by the multi-parameter sensing module, as well as the action parameters of the linkage execution module, in real time. The storage frequency is synchronized with the data acquisition frequency, and the storage duration is not less than 90 days. The data export interface adopts the USB 3.0 standard, supports data export in Excel or PDF format, and the exported data includes the acquisition timestamp and the corresponding process stage identifier.

[0019] Compared with the prior art, the advantages of this invention are:

[0020] Through a series of innovative designs, the preparation efficiency, product quality, and controllability of petroleum coke-based porous carbon have been significantly improved, providing a more reliable and efficient solution for the industrial production of petroleum coke-based porous carbon. From pretreatment to activation, post-treatment, and intelligent control of supporting equipment, each link works closely together to form a complete and efficient preparation system.

[0021] Overall, this preparation method and apparatus achieve low-temperature, high-efficiency preparation, precise control of reaction conditions, and improved product quality. It also features intelligent monitoring and control functions, comprehensively meeting the high-quality, low-cost, and intelligent requirements for the preparation of petroleum coke-based porous carbon. This not only reduces energy consumption and production costs but also improves the stability and consistency of product performance, providing strong support for the development of related industries.

[0022] First, the innovative design of the preparation method optimizes the entire preparation process. The directional pretreatment stage, through precise control of petroleum coke particle size and constant-temperature preheating, lays a solid foundation for subsequent reactions. The directional compounding of specific composite activators, employing a scientific ratio of main activator, co-activator, and interface modifier, combined with alternating "grinding-dispersion" treatment, ensures full contact between the activator and petroleum coke, facilitating precise control of the porous carbon structure. The dynamic synergistic temperature-negative-pressure activation process, through the synchronous adjustment of three-stage heating and negative pressure, and the stirring of materials by a spiral flow guide-temperature sensing linkage structure, effectively promotes the reaction and improves product quality. The targeted post-treatment stage, with multi-stage washing, ultrasonic assistance, and gradient drying, removes impurities while preserving the structure and properties of the porous carbon to the greatest extent possible.

[0023] Secondly, the rational structural design of the preparation device provides excellent hardware support for the preparation process. Sealing flanges and a top cover ensure the airtightness of the reaction vessel, while support legs guarantee the stability of the device. The design of the discharge port, temperature control valve, and pressure relief valve facilitates material discharge, temperature control, and pressure regulation. The feed port and liquid inlet facilitate the addition of materials and liquids, and the combination of the telescopic rod, stirring rod, and stirring block achieves effective mixing of the materials.

[0024] Furthermore, the intelligent monitoring and control system endows the device with intelligent monitoring and control capabilities. The multi-parameter sensing module collects key data such as temperature, pressure, and pH in real time, and the data acquisition module transmits the data to the PLC main controller. The linkage execution module, based on instructions from the PLC main controller, precisely controls the operation of equipment such as temperature control valves, telescopic rods, and pressure relief valves, ensuring the reaction proceeds according to preset process parameters. The anomaly early warning module promptly issues alarms and takes emergency measures when parameters deviate from set values, ensuring production safety. The data storage and traceability module records key data during the production process, facilitating quality traceability and process optimization. Attached Figure Description

[0025] Figure 1 This is a schematic diagram of the method flow structure of the present invention;

[0026] Figure 2 This is a schematic diagram of the overall structure of the device of the present invention;

[0027] Figure 3 This is a schematic diagram of the bottom structure of the device of the present invention;

[0028] Figure 4 This is a schematic cross-sectional view of the overall structure of the device of the present invention;

[0029] Figure 5 This is a schematic diagram of the internal structure of the device of the present invention;

[0030] Figure 6 This is a schematic diagram of the overall structure of the present invention.

[0031] The following are the labels in the diagram: 1. Base; 10. Support leg; 11. Sealing flange; 12. Temperature control valve; 13. Pressure relief valve; 14. Discharge hole; 15. Reaction tank; 2. Top cover; 20. Feed hole; 21. Liquid inlet; 22. Water pipe; 3. Telescopic rod; 30. Stirring rod; 31. Stirring block. Detailed Implementation

[0032] Example: Please refer to Figures 1-6 A method for preparing petroleum coke-based porous carbon by low-temperature alkali activation includes the following steps:

[0033] Step 1: Directional pretreatment. The petroleum coke is pulverized and passed through a 250-mesh standard sieve to obtain petroleum coke powder with a particle size ≤61μm. Then, it is preheated at a constant temperature of 180℃ for 2.5h under a nitrogen atmosphere, with nitrogen gas being introduced at a flow rate of 50mL / min simultaneously during the preheating process.

[0034] Step 2: Directional compounding of the specific composite activator. The main activator, co-activator, and interface modifier are mixed evenly at a mass ratio of 3.2:1:0.3 to obtain the specific composite activator. The main activator is KOH, the co-activator is a 1:1 mixture of ammonium chloride and ammonium carbonate, and the interface modifier is polyethylene glycol 400. The specific composite activator is mixed with the pretreated petroleum coke from Step 1 at a mass ratio of 2.2:1. Deionized water is added to adjust the moisture content of the material to 10%. Then, a planetary ball mill is used for alternating "grinding-dispersion" for 40 minutes. The grinding speed is 350 r / min, the dispersion speed is 150 r / min, and the alternation cycle is 5 minutes.

[0035] Step 3: Dynamic Coordinated Temperature Control - Negative Pressure Activation. Place the material from Step 2 into the reactor with the built-in spiral flow guide-temperature sensing linkage structure in Step 3. Turn on the dynamic negative pressure control system and adjust the negative pressure synchronously according to a three-stage heating process: The first stage heats up to 150℃ at a rate of 8℃ / min, while simultaneously adjusting the negative pressure to -0.03MPa and holding for 45min; the second stage heats up to 250℃ at a rate of 4℃ / min, while simultaneously adjusting the negative pressure to -0.035MPa and holding for 75min; the third stage heats up to 550℃ at a rate of 2.5℃ / min, while simultaneously adjusting the negative pressure to -0.04MPa and holding for 150min.

[0036] Step 4: Post-treatment with targeted solutions. The activated products from Step 3 are processed sequentially as follows: ① First-stage washing with deionized water at room temperature three times, with a solid-liquid ratio of 1:10 each time, for 20 minutes; ② Second-stage washing with 0.5 mol / L hydrochloric acid solution in a 50°C water bath twice, for 30 minutes each time, with simultaneous application of 250W ultrasonic assistance; ③ Third-stage washing with deionized water in an 80°C water bath until the pH of the washing solution is 7.0 ± 0.2, with stirring maintained at 50 r / min during the washing process; After washing, a slurry with a mass concentration of 6% is prepared, dispersed by 40 kHz pulsed ultrasonication for 25 minutes, and then subjected to gradient drying under an argon atmosphere: first dried at 80°C for 120 minutes, then heated to 120°C for 240 minutes, with the temperature error controlled within ±3°C during the drying process.

[0037] In this method, the petroleum coke is first pretreated in step one to control its particle size and preheat it, making its structure more conducive to subsequent reactions. In step two, a specific composite activator is prepared and thoroughly mixed with the petroleum coke to prepare for the activation reaction. In step three, the activation reaction is carried out in a specific reactor using a three-stage heating and negative pressure regulation process to promote the conversion of petroleum coke into porous carbon. In step four, the activated product undergoes multi-stage washing, ultrasonic dispersion, and gradient drying to obtain high-quality petroleum coke-based porous carbon. This method achieves low-temperature, high-efficiency preparation, improves product quality, and reduces energy consumption.

[0038] Specifically, in step two, the number average molecular weight of polyethylene glycol 400 is 380-420, and the purity is ≥99.5%. Polyethylene glycol 400 is added in steps: first, 50% of polyethylene glycol 400 is mixed evenly with the main activator, and then the co-activator and the remaining polyethylene glycol 400 are added. During the mixing process, the stirring speed is controlled at 200-250 r / min, and the stirring time is 15-20 min.

[0039] When using it, select polyethylene glycol 400 according to specific molecular weight and purity requirements, and add it in steps, along with specific stirring rates and times, so that polyethylene glycol 400 is fully mixed with the main and auxiliary activators, so as to better exert the interface regulation effect, optimize the interaction between the activator and petroleum coke, and improve product performance.

[0040] Specifically, the spiral flow guide-temperature sensing linkage structure in step three includes 3-4 temperature sensors evenly distributed circumferentially along the inner wall of the reactor, a centrally located spiral flow guide vane, and a PLC controller; the probe end of the temperature sensor extends 5-8 cm into the material, and the sampling frequency is 1 time / 30s; the PLC controller has a built-in temperature-speed correlation program, which controls the speed of the spiral flow guide vane to 150 r / min when the temperature rises to 150℃; adjusts the speed to 220 r / min when the temperature rises to 250℃; and adjusts the speed to 300 r / min when the temperature rises to 550℃.

[0041] During operation, a temperature sensor collects the material temperature in real time, and the PLC controller controls the rotation speed of the spiral guide vanes based on temperature changes. Different rotation speeds correspond to different temperature stages, ensuring more uniform heating of the material, promoting the reaction, and improving the stability and consistency of product quality.

[0042] Specifically, in step four, the ultrasonic assistance during hydrochloric acid washing adopts a continuous ultrasonic mode. The ultrasonic probe is inserted into the slurry to a depth of 10-15cm, and the angle between the ultrasonic probe and the slurry surface is 30-45°. The ultrasonic power decreases linearly with the washing time, and the attenuation rate is 1.67W / min. The constant temperature pickling tank is equipped with a jacketed insulation structure, and 50℃ constant temperature water is introduced into the jacket to maintain the temperature fluctuation of the pickling system ≤±2℃.

[0043] During use, the ultrasonic probe is inserted into the slurry at a specific depth and angle, employing continuous ultrasound with linear power attenuation. Combined with a sandwich insulation structure, it maintains stable temperature, effectively removes impurities, and avoids excessive damage to the porous carbon structure, thereby improving product purity and performance.

[0044] Specifically, in step three, the nitrogen atmosphere in the reactor has a purity of ≥99.99%, and nitrogen is continuously introduced during the three-stage heating process at a flow rate of 30-40 mL / min. During the synergistic etching process of ammonia and KOH in step three, the residence time of ammonia in the reactor is controlled to 20-30 min by adjusting the heating rate and negative pressure. During the gradient drying process in step four, the argon flow rate is 60-80 mL / min, and during the heating stage, the argon flow rate increases linearly with the temperature increase, and the flow rate is kept constant after the heating is completed.

[0045] In step three, high-purity nitrogen is continuously introduced to provide a stable environment for the reaction, while the residence time of ammonia is controlled to promote synergistic etching. In step four, during the gradient drying process, the flow rate of argon increases linearly during the heating phase to ensure drying efficiency, and then remains constant after heating to ensure stable product quality. By controlling the gas atmosphere and flow rate, reaction efficiency and product quality are improved.

[0046] It also includes a low-temperature alkali activation preparation device for petroleum coke-based porous carbon, comprising a base 1, four support legs 10 fixedly mounted at the bottom of the base 1, a sealing flange 11 fixedly mounted at the top of the base 1, and a top cover 2 fixedly connected to the sealing flange 11, a reaction liner 15 fixedly mounted inside the base 1, the top of the reaction liner 15 being sealed to the sealing flange 11, a discharge hole 14 fixedly mounted at the bottom of the base 1, the top of the discharge hole 14 penetrating the base 1 and extending into the reaction liner 15, a temperature control chamber being provided between the interior of the base 1 and the reaction liner 15, temperature control valves 12 fixedly mounted on both sides of the discharge hole 14 at the bottom of the base 1, the tops of the temperature control valves 12 penetrating the base 1 and fixedly connected to the temperature control chamber, and multiple pressure relief valves 13 being provided on the exterior of the base 1. One end of the pressure relief valve 13 passes through the base 1 and is fixedly connected to the inside of the reaction liner 15. A telescopic rod 3 is fixedly installed on the top of the top cover 2. The bottom output end of the telescopic rod 3 passes through the top cover 2 and extends into the inside of the reaction liner 15, and is fixedly connected to a stirring rod 30. The stirring rod 30 moves up and down inside the reaction liner 15, and multiple stirring blocks 31 are fixedly sleeved on its outer side. A feed hole 20 is fixedly installed on both sides of the telescopic rod 3 on the top of the top cover 2. The bottom of the feed hole 20 passes through the top cover 2 and is connected to the inside of the reaction liner 15. Multiple liquid inlets 21 are fixedly installed on the top of the top cover 2. A water pipe 22 is fixedly connected to the bottom of each liquid inlet 21. The multiple water pipes 22 pass through the top cover 2 and extend into the bottom side of the inside of the reaction liner 15. An intelligent monitoring and control system is installed inside the base 1.

[0047] During use, the reaction chamber is sealed by a stabilizing support leg device, a sealing flange, and a top cover. Materials enter the reaction chamber through the feed port and liquid inlet. A temperature control valve regulates the temperature of the temperature-controlled chamber, while a pressure relief valve regulates the internal pressure. A telescopic rod drives the stirring rod and stirring block to agitate the materials, providing hardware support for the preparation process and ensuring a smooth reaction.

[0048] Specifically, the intelligent monitoring and control system includes a PLC main controller, a multi-parameter sensing module, and a data acquisition module. The multi-parameter sensing module includes temperature sensors distributed circumferentially along the inner wall of the reaction tank 15, a pressure transmitter embedded in the bottom of the reaction tank 15, and a pH sensor installed at the end of the water pipe 22. The temperature sensor has a sampling frequency of 1 time / 30s, a detection range of 0-600℃, and an accuracy of ±0.5℃. The pressure transmitter has a sampling range of -0.1MPa to 0MPa and an accuracy of ±0.001MPa. The pH sensor has a detection range of 0-14 and an accuracy of ±0.1. The data acquisition module is connected to the signals of each sensor and transmits the collected temperature, pressure, and pH data to the PLC main controller in real time.

[0049] During use, temperature, pressure, and pH sensors collect corresponding parameters inside the reaction vessel in real time. The data acquisition module transmits these data to the PLC main controller, enabling real-time monitoring of key parameters in the reaction process and providing data support for precise control.

[0050] Specifically, the intelligent monitoring and control system also includes a linkage execution module, which is signal-connected to the PLC main controller and drive-connected to the temperature control valve 12, the telescopic rod 3, and the pressure relief valve 13, respectively. The PLC main controller has a built-in process parameter matching program. When the temperature sensor detects that the first stage temperature in S3 rises to 150℃, it automatically controls the opening of the temperature control valve 12 to 40%, and the telescopic rod 3 drives the stirring rod 30 to rotate at 150 r / min. When the second stage temperature is detected to rise to 250℃, the opening of the temperature control valve 12 is adjusted to 60%, and the stirring speed is adjusted to 220 r / min. When the third stage temperature is detected to rise to 550℃, the opening of the temperature control valve 12 is adjusted to 80%, and the stirring speed is adjusted to 300 r / min. When the pressure transmitter detects that the pressure deviates from the corresponding stage set value by ±0.002MPa, it automatically adjusts the opening of the pressure relief valve 13 for pressure compensation.

[0051] During use, the PLC main controller uses data from temperature and pressure sensors to precisely control the opening of the temperature control valve, the speed of the stirring rod, and the opening of the pressure relief valve through the linkage execution module, ensuring that the reaction proceeds according to the preset process parameters and improving the stability and consistency of product quality.

[0052] Specifically, the intelligent monitoring and control system also includes an anomaly warning module, which includes an audible and visual alarm and an emergency shut-off unit. The PLC main controller has a built-in threshold judgment program. When the temperature sensor detects that the temperature deviates from the set value of the corresponding stage in S3 by ±3℃, the pressure transmitter detects that the pressure deviates from the set value by ±0.005MPa, or the pH sensor detects that the pH of the washing liquid in S4 deviates from 7.0±0.5, the audible and visual alarm is immediately triggered. At the same time, the emergency shut-off unit automatically cuts off the power supply to the telescopic rod 3 and the air / liquid inlet channel of the temperature control valve 12, and opens all pressure relief valves 13 for emergency pressure relief.

[0053] When in use, if a key parameter deviates from the set threshold, the abnormal warning module will respond quickly, the audible and visual alarm will sound, and the emergency cut-off unit will take emergency measures to ensure production safety and avoid product quality problems or equipment damage caused by abnormal parameters.

[0054] Specifically, the intelligent monitoring and control system also includes a data storage and traceability module, which includes a solid-state drive and a data export interface. The solid-state drive stores temperature, pressure, and pH data collected by the multi-parameter sensing module, as well as the action parameters of the linkage execution module, in real time. The storage frequency is synchronized with the data acquisition frequency, and the storage duration is no less than 90 days. The data export interface adopts the USB 3.0 standard, supports data export in Excel or PDF format, and the exported data includes the acquisition timestamp and the corresponding process stage identifier.

[0055] When in use, solid-state drives store key production process data in real time. The data export interface allows for easy export of data in common formats, with timestamps and process stage identifiers, facilitating quality traceability and process optimization, and providing data support for production process improvement.

[0056] The foregoing has shown and described the basic principles, main features, and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely preferred examples and are not intended to limit the invention. Various changes and modifications can be made to the invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the present invention as claimed. The scope of protection of the present invention is defined by the appended claims and their equivalents.

Claims

1. A method for preparing petroleum coke-based porous carbon by low-temperature alkali activation, characterized in that, Includes the following steps: S1. Directional pretreatment: Petroleum coke is pulverized and passed through a 250-mesh standard sieve to obtain petroleum coke powder with a particle size ≤61μm; then it is preheated at a constant temperature of 180℃ for 2.5h under a nitrogen atmosphere, during which nitrogen gas at a flow rate of 50mL / min is introduced simultaneously. S2. Targeted compounding of the specific composite activator: The main activator, co-activator, and interface modifier are mixed uniformly at a mass ratio of 3.2:1:0.3 to obtain the specific composite activator; the main activator is KOH, the co-activator is a 1:1 mixture of ammonium chloride and ammonium carbonate, and the interface modifier is polyethylene glycol 400; the specific composite activator is mixed with the pretreated petroleum coke in S1 at a mass ratio of 2.2:1, and deionized water is added to adjust the material moisture content to 10%. Subsequently, a planetary ball mill is used for alternating "grinding-dispersion" treatment for 40 minutes, with a grinding speed of 350 r / min, a dispersion speed of 150 r / min, and an alternation cycle of 5 minutes. S3, Dynamic Coordinated Temperature Control-Negative Pressure Activation: Place the material from S2 into the reactor with the built-in spiral flow guide-temperature sensing linkage structure in S3, turn on the dynamic negative pressure control system, and adjust the negative pressure synchronously according to the three-stage heating process: In the first stage, heat up to 150℃ at a rate of 8℃ / min, and simultaneously adjust the negative pressure to -0.03MPa, and hold for 45min. In the second stage, the temperature is increased to 250℃ at a rate of 4℃ / min, while the negative pressure is adjusted to -0.035MPa and held for 75min. In the third stage, the temperature is increased to 550℃ at a rate of 2.5℃ / min, while the negative pressure is adjusted to -0.04MPa and held for 150min. S4. Targeted post-treatment: The activated product in S3 is subjected to the following steps in sequence: ① First-stage washing with deionized water at room temperature three times, with a solid-liquid ratio of 1:10 each time, and a washing time of 20 min; ② Second-stage washing with 0.5 mol / L hydrochloric acid solution in a 50°C water bath twice, with a holding time of 30 min each time, and simultaneous application of 250W ultrasonic assistance; ③ Third-stage washing with deionized water in an 80°C water bath until the pH of the washing solution is 7.0±0.2, and stirring is maintained at 50 r / min during the washing process; After washing, a slurry with a mass concentration of 6% is prepared, dispersed by 40kHz pulsed ultrasonication for 25 min, and then subjected to gradient drying in an argon atmosphere: first drying at 80°C for 120 min, and then heating to 120°C for 240 min, with the temperature error controlled within ±3°C during the drying process.

2. The method for preparing petroleum coke-based porous carbon by low-temperature alkali activation according to claim 1, characterized in that: The number average molecular weight of polyethylene glycol 400 in S2 is 380-420, and the purity is ≥99.5%. The polyethylene glycol 400 is added in steps. First, 50% of the polyethylene glycol 400 is mixed evenly with the main activator, and then the co-activator and the remaining polyethylene glycol 400 are added. During the mixing process, the stirring rate is controlled at 200-250 r / min, and the stirring time is 15-20 min.

3. The method for preparing petroleum coke-based porous carbon by low-temperature alkali activation according to claim 1, characterized in that: The spiral flow guide-temperature sensing linkage structure in S3 includes 3-4 temperature sensors evenly distributed circumferentially along the inner wall of the reactor, a spiral flow guide vane set in the center, and a PLC controller; the probe end of the temperature sensor extends into the material 5-8cm, and the sampling frequency is 1 time / 30s; the PLC controller has a built-in temperature-speed correlation program, which controls the speed of the spiral flow guide vane to 150r / min when the temperature rises to 150℃; adjusts the speed to 220r / min when the temperature rises to 250℃; and adjusts the speed to 300r / min when the temperature rises to 550℃.

4. The method for preparing petroleum coke-based porous carbon by low-temperature alkali activation according to claim 1, characterized in that: The ultrasonic assistance during the washing with hydrochloric acid solution in S4 adopts a continuous ultrasonic mode. The ultrasonic probe is inserted into the slurry to a depth of 10-15cm, and the angle between the ultrasonic probe and the slurry surface is 30-45°. The ultrasonic power decreases linearly with the washing time, and the attenuation rate is 1.67W / min. The constant temperature pickling tank is equipped with a jacketed insulation structure, and 50℃ constant temperature water is introduced into the jacket to maintain the temperature fluctuation of the pickling system ≤±2℃.

5. The method for preparing petroleum coke-based porous carbon by low-temperature alkali activation according to claim 1, characterized in that: In step S3, the nitrogen atmosphere in the reactor has a purity of ≥99.99%, and nitrogen is continuously introduced during the three-stage heating process at a flow rate of 30-40 mL / min. During the synergistic etching process of ammonia and KOH in step S3, the residence time of ammonia in the reactor is controlled to 20-30 min by adjusting the heating rate and negative pressure. During the gradient drying process in step S4, the argon flow rate is 60-80 mL / min, and during the heating stage, the argon flow rate increases linearly with the temperature increase, and the flow rate remains constant after the heating is completed.

6. A low-temperature alkali activation preparation apparatus for petroleum coke-based porous carbon, comprising the low-temperature alkali activation preparation method for petroleum coke-based porous carbon as described in claims 1-5, characterized in that: The system includes a base (1), four support legs (10) fixedly mounted on the bottom of the base (1), a sealing flange (11) fixedly mounted on the top of the base (1), and a top cover (2) fixedly connected to the sealing flange (11). A reaction liner (15) is fixedly mounted inside the base (1), and the top of the reaction liner (15) is sealed to the sealing flange (11). A discharge hole (14) is fixedly mounted on the bottom of the base (1), and the top of the discharge hole (14) penetrates the base (1) and extends into the reaction liner (15). A temperature control chamber is provided between the inside of the base (1) and the reaction liner (15). Temperature control valves (12) are fixedly mounted on both sides of the discharge hole (14) on the bottom of the base (1), and the top of the temperature control valves (12) penetrates the base (1) and is fixedly connected to the temperature control chamber. Multiple pressure relief valves (13) are provided on the outside of the base (1), and one end of the pressure relief valves (13) penetrates through the base (1). The base (1) is fixedly connected to the inside of the reaction liner (15). The top cover (2) is fixedly provided with a telescopic rod (3). The bottom output end of the telescopic rod (3) passes through the top cover (2) and extends into the inside of the reaction liner (15), and is fixedly connected with a stirring rod (30). The stirring rod (30) moves up and down inside the reaction liner (15), and multiple stirring blocks (31) are fixedly sleeved on the outside. The top cover (2) is fixedly provided with feed holes (20) on both sides of the telescopic rod (3). The bottom of the feed holes (20) passes through the top cover (2) and is connected to the inside of the reaction liner (15). The top cover (2) is fixedly provided with multiple liquid inlets (21). The bottom of the multiple liquid inlets (21) is fixedly connected with water pipes (22). The multiple water pipes (22) pass through the top cover (2) and extend into the bottom side of the inside of the reaction liner (15). The base (1) is provided with an intelligent monitoring and control system.

7. The low-temperature alkali activation preparation apparatus for petroleum coke-based porous carbon according to claim 6, characterized in that: The intelligent monitoring and control system includes a PLC main controller, a multi-parameter sensing module, and a data acquisition module. The multi-parameter sensing module includes a temperature sensor distributed circumferentially along the inner wall of the reaction tank (15), a pressure transmitter embedded in the bottom of the reaction tank (15), and a pH sensor installed at the end of the water pipe (22). The temperature sensor has a sampling frequency of 1 time / 30s, a detection range of 0-600℃, and an accuracy of ±0.5℃. The pressure transmitter has a sampling range of -0.1MPa to 0MPa and an accuracy of ±0.001MPa. The pH sensor has a detection range of 0-14 and an accuracy of ±0.

1. The data acquisition module is connected to the signals of each sensor and transmits the collected temperature, pressure, and pH data to the PLC main controller in real time.

8. The low-temperature alkali activation preparation apparatus for petroleum coke-based porous carbon according to claim 6, characterized in that: The intelligent monitoring and control system also includes a linkage execution module, which is connected to the PLC main controller and is driven by the temperature control valve (12), the telescopic rod (3), and the pressure relief valve (13). The PLC main controller has a built-in process parameter matching program. When the temperature sensor detects that the temperature in the first stage of S3 rises to 150°C, it automatically controls the opening of the temperature control valve (12) to 40% and the telescopic rod (3) drives the stirring rod (30) to rotate at 150 r / min. When the temperature in the second stage rises to 250°C, the opening of the temperature control valve (12) is adjusted to 60% and the stirring speed is adjusted to 220 r / min. When the temperature in the third stage rises to 550°C, the opening of the temperature control valve (12) is adjusted to 80% and the stirring speed is adjusted to 300 r / min. When the pressure transmitter detects that the pressure deviates from the corresponding stage setting value by ±0.002 MPa, it automatically adjusts the opening of the pressure relief valve (13) for pressure compensation.

9. The low-temperature alkali activation preparation apparatus for petroleum coke-based porous carbon according to claim 6, characterized in that: The intelligent monitoring and control system also includes an abnormal early warning module, which includes an audible and visual alarm and an emergency cut-off unit. The PLC main controller has a built-in threshold judgment program. When the temperature sensor detects that the temperature deviates from the set value of the corresponding stage in S3 by ±3℃, the pressure transmitter detects that the pressure deviates from the set value by ±0.005MPa, or the pH sensor detects that the pH of the washing liquid in S4 deviates from 7.0±0.5, the audible and visual alarm is immediately triggered. At the same time, the emergency cut-off unit automatically cuts off the power supply of the telescopic rod (3) and the air / liquid inlet of the temperature control valve (12), and opens all pressure relief valves (13) for emergency pressure relief.

10. The low-temperature alkali activation preparation apparatus for petroleum coke-based porous carbon according to claim 6, characterized in that: The intelligent monitoring and control system also includes a data storage and traceability module, which includes a solid-state drive and a data export interface. The solid-state drive stores temperature, pressure, and pH data collected by the multi-parameter sensing module, as well as the action parameters of the linkage execution module, in real time. The storage frequency is synchronized with the data acquisition frequency, and the storage duration is not less than 90 days. The data export interface adopts the USB 3.0 standard, supports data export in Excel or PDF format, and the exported data includes the acquisition timestamp and the corresponding process stage identifier.

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