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CN-121990572-A - Low-temperature alkali activation preparation method and device for petroleum coke-based porous carbon

CN121990572ACN 121990572 ACN121990572 ACN 121990572ACN-121990572-A

Abstract

The invention discloses a low-temperature alkali activation preparation method and a device for petroleum coke-based porous carbon, which belong to the technical field of petroleum coke-based porous carbon and comprise the following steps of S1, directional pretreatment, S2, directional compounding of specific compound activators, S3, dynamic collaborative temperature control-negative pressure activation, S4 and targeted aftertreatment, wherein the preparation efficiency, the product quality and the controllability of the production process of the petroleum coke-based porous carbon are obviously improved through a series of innovative designs, and a more reliable and efficient solution is provided for the industrial production of the petroleum coke-based porous carbon. From pretreatment to activation process, to aftertreatment and supporting device's intelligent control, each link closely cooperates, has realized the high-efficient preparation of low temperature, and accurate control reaction condition promotes product quality, possesses intelligent monitoring and control function simultaneously, has all-round high quality, low cost, the intelligent demand of having satisfied petroleum coke base porous carbon preparation. Not only reduces the energy consumption and the production cost.

Inventors

  • LI CHANGLI
  • WANG LI
  • YANG XIAOYUAN
  • QIN JINGRU
  • XU MENG
  • LI CHANGJIE

Assignees

  • 河南省大潮炭能科技有限公司

Dates

Publication Date
20260508
Application Date
20260228

Claims (10)

  1. 1. The low-temperature alkali activation preparation method of the petroleum coke-based porous carbon is characterized by comprising the following steps of: s1, directional pretreatment, namely crushing petroleum coke, passing through a 250-target standard sieve to obtain petroleum coke powder with the particle size less than or equal to 61 mu m, and preheating for 2.5 hours at the constant temperature of 180 ℃ in a nitrogen atmosphere, wherein nitrogen with the flow rate of 50mL/min is synchronously introduced in the preheating process; S2, directional compounding of a specific compound activator, namely uniformly mixing a main activator, a co-activator and an interface regulator according to a mass ratio of 3.2:1:0.3 to obtain the specific compound activator, wherein the main activator is KOH, the co-activator is a 1:1 compound of ammonium chloride and ammonium carbonate, the interface regulator is polyethylene glycol 400, mixing the specific compound activator and the pretreated petroleum coke in S1 according to a mass ratio of 2.2:1, adding deionized water to adjust the water content of the material to 10%, and then adopting a planetary ball mill to carry out 'grinding-dispersing' alternating treatment for 40min at a grinding rotating speed of 350r/min and a dispersing rotating speed of 150r/min at an alternating period of 5min; S3, dynamically and cooperatively controlling temperature and activating negative pressure, namely placing the materials in the S2 into a reaction kettle with a built-in spiral flow guiding and temperature sensing linkage structure in the S3, starting a dynamic negative pressure control system, and synchronously adjusting the negative pressure according to a three-stage heating process, wherein the first stage is used for heating to 150 ℃ at the speed of 8 ℃ per minute, synchronously adjusting the negative pressure to-0.03 MPa and preserving heat for 45min, the second stage is used for heating to 250 ℃ at the speed of 4 ℃ per minute, synchronously adjusting the negative pressure to-0.035 MPa and preserving heat for 75min, and the third stage is used for heating to 550 ℃ at the speed of 2.5 ℃ per minute, synchronously adjusting the negative pressure to-0.04 MPa and preserving heat for 150min; S4, carrying out targeted post-treatment, namely washing the activated product in S3 for 3 times at normal temperature by adopting ① first-stage deionized water, wherein the solid-to-liquid ratio is 1:10, the washing time is 20min, carrying out water bath washing for 2 times by adopting ② second-stage 0.5mol/L hydrochloric acid solution at 50 ℃, carrying out heat preservation for 30min each time, synchronously applying 250W ultrasonic assistance, carrying out water bath washing by adopting ③ third-stage deionized water at 80 ℃ until the pH value of the washing liquid is 7.0+/-0.2, keeping 50r/min stirring in the washing process, preparing slurry with the mass concentration of 6% after the washing is finished, adopting 40kHz pulse ultrasonic dispersion for 25min, then adopting gradient drying under argon atmosphere, drying for 120min before 80 ℃, and then heating to 120 ℃ and drying for 240min, wherein the temperature error in the drying process is controlled within +/-3 ℃.
  2. 2. The method for preparing the porous carbon based on petroleum coke by low-temperature alkali activation according to claim 1, wherein the polyethylene glycol 400 in the S2 has a number average molecular weight of 380-420 and a purity of 99.5% or more, the polyethylene glycol 400 is added step by step, 50% of the polyethylene glycol 400 is uniformly mixed with a main activator, then a co-activator and the rest polyethylene glycol 400 are added, and the stirring rate is controlled to be 200-250r/min and the stirring time is controlled to be 15-20min in the mixing process.
  3. 3. The low-temperature alkali activation preparation method of the petroleum coke-based porous carbon is characterized in that the spiral flow guiding-temperature sensing linkage structure in the step S3 comprises 3-4 temperature sensors uniformly distributed along the circumferential direction of the inner wall of a reaction kettle, spiral flow guiding blades and a PLC controller, wherein the detection end of each temperature sensor stretches into the material for 5-8cm, the acquisition frequency is 1 time/30S, a temperature-rotating speed correlation program is arranged in the PLC controller, when the temperature is increased to 150 ℃, the rotating speed of the spiral flow guiding blades is controlled to be 150r/min, when the temperature is increased to 250 ℃, the rotating speed is adjusted to be 220r/min, and when the temperature is increased to 550 ℃, the rotating speed is adjusted to be 300r/min.
  4. 4. The low-temperature alkali activation preparation method of the petroleum coke-based porous carbon is characterized in that a continuous ultrasonic mode is adopted in ultrasonic assistance during washing of a hydrochloric acid solution in the step S4, the depth of an ultrasonic probe inserted into slurry is 10-15cm, the included angle between the ultrasonic probe and the liquid level of the slurry is 30-45 degrees, ultrasonic power is linearly attenuated along with washing time, the attenuation rate is 1.67W/min, an interlayer heat-preserving structure is arranged in the constant-temperature pickling tank, 50 ℃ constant-temperature water is introduced into an interlayer, and the temperature fluctuation of the pickling system is maintained to be less than or equal to +/-2 ℃.
  5. 5. The low-temperature alkali activation preparation method of the petroleum coke-based porous carbon is characterized in that the purity of nitrogen atmosphere in a reaction kettle in the step S3 is more than or equal to 99.99%, nitrogen is continuously introduced in a three-stage heating process, the flow rate is 30-40mL/min, the residence time of ammonia in the reaction kettle is regulated and controlled to be 20-30min by controlling the heating rate and the negative pressure in the collaborative etching process of ammonia and KOH in the step S3, the flow rate of argon is 60-80mL/min in the gradient drying process in the step S4, and in the heating stage, the flow rate of argon is linearly increased along with the temperature rise, and the flow rate is kept constant after the temperature rise is completed.
  6. 6. A low-temperature alkali activation preparation device of petroleum coke-based porous carbon comprises a base (1) and is characterized in that four supporting legs (10) are fixedly arranged at the bottom of the base (1), a sealing flange (11) is fixedly arranged at the top of the base (1), a top cover (2) is fixedly connected with the sealing flange (11), a reaction liner (15) is fixedly arranged in the base (1), the top of the reaction liner (15) is in sealing connection with the sealing flange (11), a discharge hole (14) is fixedly arranged at the bottom of the base (1), the top of the discharge hole (14) penetrates through the base (1) and stretches into the reaction liner (15), a temperature control chamber is arranged between the inside of the base (1) and the reaction liner (15), temperature control valves (12) are fixedly arranged at two sides of the bottom of the discharge hole (14), the temperature control valves (12) penetrate through the base (1) and are fixedly connected with one ends of the base (13) which are fixedly connected with the inside of the base (1), the pressure release chamber (13), the utility model discloses a flexible control system for the reaction of gas-liquid separation, including top cap (2), telescopic link (3), top cap (2), bottom output runs through top cap (2) and stretch into inside reaction inner bag (15), and fixedly connected with puddler (30), whip (30) from top to bottom inside and outside fixed cover of reaction inner bag (15) are equipped with a plurality of stirring pieces (31), top cap (2) top is in telescopic link (3) both sides are all fixed and are provided with feed port (20), feed port (20) bottom runs through top cap (2) and with inside being linked together of reaction inner bag (15), top cap (2) top is fixed and is provided with a plurality of feed liquor holes (21), a plurality of equal fixedly connected with water pipe (22) in feed liquor hole (21) bottom, a plurality of water pipe (22) all run through top cap (2) and stretch into the inside bottom of reaction inner bag (15), base (1) inside is provided with intelligent monitoring control system.
  7. 7. The low-temperature alkali activation preparation device of petroleum coke-based porous carbon according to claim 6, wherein the intelligent monitoring control system comprises a PLC main controller, a multi-parameter sensing module and a data acquisition module, the multi-parameter sensing module comprises temperature sensors distributed circumferentially along the inner wall of the reaction liner (15), pressure transmitters embedded into the bottom of the reaction liner (15) and pH sensors arranged at the tail end of the water pipe (22), the acquisition frequency of the temperature sensors is 1 time/30 s, the acquisition range of the temperature sensors is 0-600 ℃, the precision is +/-0.5 ℃, the acquisition range of the pressure transmitters is-0.1 MPa to 0MPa, the precision is +/-0.001 MPa, the detection range of the pH sensors is 0-14, the precision is +/-0.1, and the data acquisition module is in signal connection with the sensors and transmits acquired temperature, pressure and pH data to the PLC main controller in real time.
  8. 8. The low-temperature alkali activation preparation device of petroleum coke-based porous carbon according to claim 6, wherein the intelligent monitoring control system further comprises a linkage execution module, the linkage execution module is in signal connection with a PLC main controller and is in driving connection with the temperature control valve (12), the telescopic rod (3) and the pressure relief valve (13) respectively, the PLC main controller is internally provided with a process parameter matching program, when a temperature sensor detects that the temperature of the first stage in the S3 is increased to 150 ℃, the opening degree of the temperature control valve (12) is automatically controlled to 40%, the telescopic rod (3) drives the stirring rod (30) to rotate at 150r/min, when the temperature of the second stage is detected to be increased to 250 ℃, the opening degree of the temperature control valve (12) is adjusted to 60%, the stirring rotation speed is adjusted to 220r/min, when the temperature of the third stage is detected to be increased to 550 ℃, the opening degree of the temperature control valve (12) is adjusted to 80%, the stirring rotation speed is adjusted to 300r/min, and when the pressure sensor detects that the pressure of the pressure sensor is deviated from a corresponding stage setting value of +/-0.002 MPa, the opening degree of the pressure transmitter is automatically adjusted to compensate the pressure.
  9. 9. The low-temperature alkali activation preparation device of petroleum coke-based porous carbon according to claim 6, wherein the intelligent monitoring control system further comprises an abnormality early warning module, the abnormality early warning module comprises an audible and visual alarm and an emergency cut-off unit, a threshold judgment program is built in a PLC main controller, when a temperature sensor detects that the temperature deviates from a set value of +/-3 ℃ in a corresponding stage in the S3, a pressure transmitter detects that the pressure deviates from the set value by +/-0.005 MPa, or a pH sensor detects that the pH of washing liquid in the S4 deviates from 7.0 +/-0.5, the audible and visual alarm is immediately triggered, and meanwhile, the emergency cut-off unit automatically cuts off a driving power supply of a telescopic rod (3) and an air inlet/liquid channel of a temperature control valve (12) and opens all pressure relief valves (13) for emergency pressure relief.
  10. 10. The low-temperature alkali activation preparation device of petroleum coke-based porous carbon according to claim 6, wherein the intelligent monitoring control system further comprises a data storage and tracing module, the data storage and tracing module comprises a solid state disk and a data export interface, the solid state disk stores temperature, pressure and pH data acquired by the multi-parameter sensing module in real time, and action parameters of the linkage execution module, the storage frequency is synchronous with the data acquisition frequency, the storage time is not less than 90 days, the data export interface adopts USB3.0 standard, data is exported in Excel or PDF format, and the exported data comprises an acquisition time stamp and a corresponding process stage identifier.

Description

Low-temperature alkali activation preparation method and device for petroleum coke-based porous carbon Technical Field The invention relates to the technical field of petroleum coke-based porous carbon, in particular to a low-temperature alkali activation preparation method and device of petroleum coke-based porous carbon. Background In the field of preparation of petroleum coke-based porous carbon, the traditional preparation method has a plurality of defects. On the one hand, the activation temperature is relatively high and it is generally necessary to carry out the alkali activation reaction at 800 ℃ or even higher. The high temperature not only consumes a large amount of energy and increases the production cost, but also has extremely high requirements on the high temperature resistance of the reaction equipment, and the equipment maintenance cost is also increased. On the other hand, conventional methods are not scientific in terms of the choice and use of the activator. The single activator is difficult to realize the accurate regulation and control of the petroleum coke structure, so that the prepared porous carbon is difficult to meet the increasingly diversified application requirements on key performance indexes such as pore size distribution, specific surface area and the like. In addition, the traditional preparation process lacks of accurate control on reaction conditions, parameters such as heating rate, pressure and the like are difficult to dynamically adjust according to the reaction process, stability and consistency of product quality are affected, and in addition, the post-treatment process is rough. Conventional washing and drying methods cannot remove impurities effectively and may damage the structure of the porous carbon, resulting in degradation of the performance thereof. In the drying process, the accurate control of factors such as temperature, gas atmosphere and the like is lacking, and the product quality is further influenced. Meanwhile, the traditional preparation method is difficult to realize comprehensive monitoring and intelligent control of the whole preparation process, the problems in the production process cannot be found and solved in time, and large-scale industrial production is not facilitated, so that the existence of the low-temperature alkali activation preparation method and device of the petroleum coke-based porous carbon is very important. Disclosure of Invention The invention aims to provide a low-temperature alkali activation preparation method and device for petroleum coke-based porous carbon, which are used for solving the problems in the background technology. A low-temperature alkali activation preparation method and a device for petroleum coke-based porous carbon comprise the following steps: s1, directional pretreatment, namely crushing petroleum coke, passing through a 250-target standard sieve to obtain petroleum coke powder with the particle size less than or equal to 61 mu m, and preheating for 2.5 hours at the constant temperature of 180 ℃ in a nitrogen atmosphere, wherein nitrogen with the flow rate of 50mL/min is synchronously introduced in the preheating process; S2, directional compounding of a specific compound activator, namely uniformly mixing a main activator, a co-activator and an interface regulator according to a mass ratio of 3.2:1:0.3 to obtain the specific compound activator, wherein the main activator is KOH, the co-activator is a 1:1 compound of ammonium chloride and ammonium carbonate, the interface regulator is polyethylene glycol 400, mixing the specific compound activator and the pretreated petroleum coke in S1 according to a mass ratio of 2.2:1, adding deionized water to adjust the water content of the material to 10%, and then adopting a planetary ball mill to carry out 'grinding-dispersing' alternating treatment for 40min at a grinding rotating speed of 350r/min and a dispersing rotating speed of 150r/min at an alternating period of 5min; S3, dynamically and cooperatively controlling temperature and activating negative pressure, namely placing the materials in the S2 into a reaction kettle with a built-in spiral flow guiding and temperature sensing linkage structure in the S3, starting a dynamic negative pressure control system, and synchronously adjusting the negative pressure according to a three-stage heating process, wherein the first stage is used for heating to 150 ℃ at the speed of 8 ℃ per minute, synchronously adjusting the negative pressure to-0.03 MPa and preserving heat for 45min, the second stage is used for heating to 250 ℃ at the speed of 4 ℃ per minute, synchronously adjusting the negative pressure to-0.035 MPa and preserving heat for 75min, and the third stage is used for heating to 550 ℃ at the speed of 2.5 ℃ per minute, synchronously adjusting the negative pressure to-0.04 MPa and preserving heat for 150min; S4, carrying out targeted post-treatment, namely washing the activated product in S3 for 3 times