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CN-122010114-A - Petroleum-based hierarchical porous carbon material and preparation method thereof

CN122010114ACN 122010114 ACN122010114 ACN 122010114ACN-122010114-A

Abstract

The invention relates to the technical field of carbon material preparation, and discloses a petroleum-based hierarchical porous carbon material and a preparation method thereof. Heavy oil with high aromatic hydrocarbon content such as catalytic cracking slurry oil is used as a raw material, thermal polycondensation reaction is carried out in inert atmosphere to generate intermediate phase microsphere precursors, oxidation fixation treatment is carried out in oxygen-containing atmosphere after crushing, and the intermediate phase microsphere precursors are mixed with an alkaline activator. Then, the product is subjected to high-temperature chemical activation treatment under an inert atmosphere, and then the product is further subjected to physical activation under the atmosphere of CO 2 and water vapor, and then the graded porous carbon material is obtained through acid washing, water washing and drying treatment. The porous carbon material obtained by the method has a hierarchical pore structure with cooperative micropores and mesopores, and forms a communicated three-dimensional network pore channel structure. The method has the advantages of wide raw material sources and simple process, can realize the recycling of high-aromatic heavy oil, and the prepared porous carbon material has the characteristics of higher specific surface area and good pore structure, and can be used in the fields of electrochemical energy storage, adsorption separation, catalytic carriers and the like.

Inventors

  • DUAN YAJIE
  • LING HAO
  • XU KEYAN
  • QIN ZHE
  • ZOU YICHAO

Assignees

  • 华东理工大学

Dates

Publication Date
20260512
Application Date
20260309

Claims (14)

  1. 1. A petroleum-based hierarchical porous carbon material and a preparation method thereof are characterized by comprising the following steps: (1) Heavy oil with high aromatic hydrocarbon content such as catalytic cracking slurry oil is used as a raw material, and thermal polycondensation reaction is carried out at 400-450 ℃ in inert atmosphere, so that an asphalt precursor containing mesophase microspheres is obtained; (2) Crushing the obtained asphalt precursor, and performing oxidation fixing treatment at 100-300 ℃ in an air atmosphere to crosslink and solidify the precursor; (3) Mixing the product of the step (2) with an alkaline activator to obtain a mixed raw material; (4) And (3) performing two-stage activation treatment on the mixed product obtained in the step (3), namely heating to 600-800 ℃ in an inert atmosphere, and performing chemical activation treatment to form micropores. Then heating to 850-950 ℃ and physically activating and developing mesoporous channels in the atmosphere of CO 2 gas and water vapor gas; (5) And (3) carrying out acid washing, water washing and drying treatment on the activated product to obtain the petroleum-based hierarchical porous carbon material with the three-dimensional communicated network pore structure.
  2. 2. The method according to claim 1, wherein the slurry oil in the step (1) is heavy oil with high aromatic content such as catalytic cracking slurry oil, vacuum residue oil, and the like, and the aromatic content is >50%.
  3. 3. The method of claim 1, wherein the inert gas in step (1) comprises nitrogen, helium, argon, or a mixture thereof.
  4. 4. The method according to claim 1, wherein the temperature rise rate of the thermal polycondensation in the step (1) is 2-5 ℃ per minute, the thermal polycondensation time is 1-6 hours, and the reaction pressure is atmospheric pressure-3 MPa.
  5. 5. The method according to claim 1, wherein the pitch obtained in step (1) contains mesophase microspheres and has an aromatic carbon content of 60% to 80%.
  6. 6. The method according to claim 1, wherein the temperature rise rate in the step (2) is 2 to 5 ℃ per minute, and the oxidation fixation time is 0.5 to 5 hours.
  7. 7. The method according to claim 1, wherein the basic activator in the step (3) is any one of KOH、K 2 CO 3 、NaOH、K 3 C 6 H 5 O 7 、KC 2 H 3 O 2 、K 2 C 2 O 4 .
  8. 8. The method according to claim 1, wherein the mass ratio of the product of step (3) to the activator is 1:3-1:6.
  9. 9. The method according to claim 1, wherein the temperature rise rate in the step (4) is 5 to 10 ℃ per minute, the chemical activation time is 3 to 6 hours, and the physical activation time is 1 to 3 hours.
  10. 10. The method according to claim 1, wherein the physical activation loss ratio in the step (4) is 10% -40%, and the loss ratio is the ratio of the product quality difference before and after the reaction to the product quality before the reaction.
  11. 11. The method of claim 1, wherein the inert gas in step (4) comprises nitrogen, helium, argon, or a mixture thereof.
  12. 12. The preparation method according to claim 1, wherein the activated product prepared in the step (4) and acid are subjected to acid washing according to a mass ratio of 1 (2-5), wherein the acid washing temperature is 10-70 ℃, the acid washing is 0.5-5h, deionized water is adopted to wash the activated product to be neutral after the acid washing, and the activated product is finally dried at 80-120 ℃ for 1-3h.
  13. 13. The method according to claim 1, wherein the acid used in the acid washing in the step (5) is at least one of dilute sulfuric acid, dilute nitric acid, dilute hydrochloric acid, dilute acetic acid and hydrofluoric acid, and the acid concentration is 1-5mol/L.
  14. 14. The method for preparing the petroleum-based hierarchical porous carbon material according to any one of claims 1 to 13, wherein the material has a three-dimensional communicated network-shaped pore canal structure and a hierarchical pore structure composed of micropores and mesopores, wherein the micropore ratio is 40% -80%, and the medium Kong Zhanbi is 20% -60%.

Description

Petroleum-based hierarchical porous carbon material and preparation method thereof Technical Field The invention belongs to the technical field of carbon material preparation, and particularly relates to a petroleum-based hierarchical porous carbon material prepared by taking petroleum-based slurry oil as a raw material and further carrying out oxidation fixation and two-step activation treatment and a preparation method thereof. Background Petroleum-based slurries are a widely available and relatively low cost industrial by-product that is rich in aromatic components. Mesophase pitch can be obtained by thermal polycondensation of the slurry oil, and further a porous carbon material is obtained by carbonization and activation treatment. Therefore, the preparation of the graded porous carbon material by taking the slurry oil as the raw material has good application prospect. The porous carbon material has high specific surface area, adjustable pore structure and good chemical stability, and has wide application in the fields of energy storage, adsorption separation, catalysis, environmental management and the like. In particular, in the fields of supercapacitors, battery electrode materials, gas storage and the like, the structure and pore characteristics of the porous carbon material have important influences on the performance of the porous carbon material. However, the porous carbon materials prepared by the traditional method are mostly in disordered pore structures, and the pore channel connectivity is poor, so that the porous carbon materials are not beneficial to substance transmission. In recent years, research shows that the porous carbon material with the three-dimensional communication structure can remarkably improve the diffusion efficiency of ions and molecules, thereby improving the material performance. Therefore, the development of the method for preparing the graded porous carbon material with the three-dimensional communicated network-shaped pore canal structure in a large scale with simple process has important significance. Disclosure of Invention Aiming at the problems in the prior art, the invention aims to provide a preparation method of a petroleum-based porous carbon material with a three-dimensional communicated network-shaped pore canal structure, which overcomes the defects and the shortcomings of the prior art. In order to achieve the above purpose, the present invention provides the following technical solutions. The preparation method of the petroleum-based hierarchical porous carbon specifically comprises the following steps: (1) Taking petroleum slurry as a raw material, and performing thermal polycondensation reaction at 400-450 ℃ in an inert atmosphere to obtain an asphalt precursor containing mesophase microspheres; (2) Crushing the obtained asphalt, and performing oxidation fixing treatment at 100-300 ℃ in an air atmosphere to crosslink and solidify the precursor; (3) Mixing the product of the step (2) with an alkaline activator to obtain a mixed raw material; (4) And (3) performing two-stage activation treatment on the mixed product obtained in the step (3), namely heating to 600-800 ℃ in an inert atmosphere, and performing chemical activation treatment to form micropores. Then heating to 850-950 ℃ and activating and developing mesoporous channels in the atmosphere of CO 2 gas and water vapor gas; (5) And (3) carrying out acid washing, water washing and drying treatment on the activated product to obtain the petroleum-based hierarchical porous carbon material with the three-dimensional communicated network pore structure. The invention further defines the technical scheme. Further, the slurry oil in the step (1) is catalytic cracking slurry oil, vacuum residue oil and other aromatic-rich oil, and the content of aromatic hydrocarbon is more than 50%. Further, the inert gas atmosphere of step (1) comprises nitrogen, helium, argon or a mixture thereof. Further, the temperature rise rate of the thermal polycondensation in the step (1) is 2-5 ℃ per minute, the thermal polycondensation time is 1-6h, and the reaction pressure is normal pressure-3 MPa. Further, the product pitch of step (1) should contain mesophase microspheres with an aromatic carbon content of 60% -80% (the aromatic carbon content is obtained by 13 C NMR spectral peak integral calculation). Further, in the step (2), the temperature rising rate is 2-5 ℃ per min, and the oxidation fixing time is 0.5-2h. Further, in the step (3), the kind of the alkaline activator is KOH、K2CO3、NaOH、K3C6H5O7、KC2H3O2、K2C2O4. Further, the mass ratio of the product of the step (3) to the activator is 1:3-1:6. Further, the temperature rising rate in the step (4) is 5-10 ℃ per minute, the chemical activation time is 3-6h, and the physical activation time is 1-3h. Further, the water vapor in the step (4) is introduced by CO 2 carrier gas through a water bath saturated carrying mode at 60-85 ℃, and the carrier gas flow is 200-500mL/min.