CN110683529A - Preparation method of coal-series one-dimensional porous carbon material - Google Patents
Preparation method of coal-series one-dimensional porous carbon material Download PDFInfo
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- CN110683529A CN110683529A CN201911173505.7A CN201911173505A CN110683529A CN 110683529 A CN110683529 A CN 110683529A CN 201911173505 A CN201911173505 A CN 201911173505A CN 110683529 A CN110683529 A CN 110683529A
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Abstract
A preparation method of a coal-series one-dimensional structure porous carbon material comprises the following steps: preferably selecting a coal-based byproduct as a carbon source, pretreating the coal-based byproduct by a solvent method, and recovering the solvent in a distillation mode to obtain a distillation residual solid; drying and crushing the distillation residual solid to a nanometer level, mixing the distillation residual solid with a special template agent according to a certain mass ratio, putting the mixture into a high-temperature tube furnace protected by inert atmosphere for calcining, taking out the calcined mixed product, washing, drying and grinding to obtain the porous carbon material with the one-dimensional structure. The prepared porous carbon material has higher specific surface area and proper pore size distribution, and can be used for gas adsorption, catalyst carriers, energy storage and the like.
Description
Technical Field
The invention relates to the technical field of functional carbon materials prepared from coal-based raw materials, in particular to a preparation method of a coal-series one-dimensional porous carbon material.
Technical Field
The nano carbon material has the advantages of excellent conductivity, stable structure, environmental protection and the like, and has wide application prospect in the fields of new energy, chemical industry, environment and the like. Particularly, nanocarbon materials having a one-dimensional structure, such as carbon nanotubes, carbon fibers, etc., have attracted much attention due to their high outer surface area and unique electronic confinement characteristics. The existing preparation method of the one-dimensional carbon material mainly comprises a catalytic cracking method, chemical vapor deposition, electrostatic spinning and the like. However, the preparation of such carbon materials usually has the problems of high raw material cost, low carbon residue rate, time-consuming preparation process and the like, and is not suitable for large-scale application.
The nature of the feedstock is one of the important factors affecting the quality of the carbon material. In order to obtain a high-quality porous carbon material, the raw materials need to be pretreated and modulated, the ash content is reduced, the aromatic hydrocarbon content in the raw materials is adjusted, and the polycyclic aromatic hydrocarbon is reduced. The usual methods include: solvent method, vacuum distillation method, filtration method, modification method, hydrogenation method, etc.
Coal tar is a main byproduct in the coal processing process and is rich in a large amount of polycyclic aromatic hydrocarbon. The coal tar can be distilled to obtain light oil, phenol oil, naphthalene oil, wash oil, anthracene oil and bulk product coal pitch thereof, wherein the coal tar pitch accounts for 50-60% of the coal tar. China mainly uses coal as resources, and the yield of coal tar is quite large every year. In addition to coal tar, a large amount of oily residue byproducts are generated in the coal processing and utilization processes (such as kerosene co-refining, direct liquefaction, coal pyrolysis and the like), the byproducts usually consist of unconverted components in coal, additives, heavy oil, coal tar, asphalt and inorganic impurities, and have complex components, are toxic and harmful, and lack of efficient and resource utilization approaches. The porous carbon material is prepared by using coal tar pitch or oily residue as a carbon source, so that the raw material cost can be reduced, and an important way for high-added-value utilization of coal processing byproducts is provided.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a preparation method of a coal-series one-dimensional porous carbon material with low cost, large specific surface area and high conductivity.
In order to achieve the above object, the preparation method of the present invention comprises the steps of:
1) refining the coal-based by-product by a solvent method, and recovering the solvent by a distillation mode to obtain distillation residual solid;
2) crushing the distillation residual solid obtained in the step 1) to a nano level, and mixing the crushed solid with the solvent according to the ratio of 1: mixing the crushed distillation residual solid with a template agent in a mass ratio of 0.1-30 to obtain mixed powder;
3) placing the mixed powder obtained in the step 2) in a high-temperature tubular furnace protected by inert atmosphere, heating to 500-1000 ℃ from room temperature at a heating rate of 1-50 ℃/min, and calcining to obtain a calcined product;
4) and 3) washing, drying and grinding the calcined product obtained in the step 3) to obtain the porous carbon material with the one-dimensional structure.
The coal-based by-product in the step 1) is one or more of coal tar, coal pitch or coal liquefaction residues in a coal processing by-product.
The solvent method in the step 1) is one or a combination of a solvent settling method, a solvent centrifugation method and a solvent filtration method, namely, the coal-based by-product is separated by the method to obtain upper-layer liquid, and the upper-layer liquid is distilled to recover the solvent to obtain distillation residual solid.
The solvent adopted by the solvent method in the step 1) is one or more of aromatic hydrocarbon solvent phenol oil, wash oil or anthracene oil and aliphatic hydrocarbon solvent kerosene, naphtha or gasoline.
The distillation temperature in the step 1) is 150-400 ℃.
The template agent in the step 2) adopts metal oxide or hydroxide nano-wires which are composed of one or more of potassium, magnesium, zinc or cobalt as metal elements.
The calcining time of the step 3) is 0.5-10 h.
The inert atmosphere in the step 3) is one of nitrogen, helium and argon.
And 4) repeatedly washing the calcined product to be neutral, drying and grinding to obtain the porous carbon material with the one-dimensional structure.
The porous carbon material with one-dimensional structure prepared by the preparation method can be applied to the aspects of gas adsorption, electrode materials, energy storage materials and the like.
The invention has the following beneficial technical effects:
according to the invention, coal processing byproducts are used as raw materials, metal oxide or hydroxide nanowires are used as a template agent, and the regulation and control of the one-dimensional structure of the carbon material can be realized through a high-temperature carbonization process, so that the improvement of the conductivity and the yield of the carbon material is facilitated. Compared with the conventional chemical vapor deposition method, catalytic cracking method and the like, the preparation method reduces the cost and improves the performance of the carbon material.
Detailed Description
The present invention is further illustrated by the following examples, which are provided for illustration only and are not intended to limit the scope of the present invention.
Example 1:
1) coal-based byproduct coal liquefaction residue is used as a raw material, and kerosene/wash oil (volume ratio of 1: 1) treating the mixed solvent by a solvent sedimentation method, standing and separating to obtain upper-layer liquid, and distilling the upper-layer liquid at 350 ℃ to recover the solvent to obtain distillation residual solid;
2) crushing the distillation residual solid obtained in the step 1) into powder of 100-200 nm, and mixing the powder according to the ratio of 1: 2, mixing the crushed distillation residual solid with a template agent potassium hydroxide to obtain mixed powder;
3) placing the mixed powder obtained in the step 2) in a high-temperature tubular furnace with the flow of 100ml/min under the protection of inert atmosphere nitrogen, and heating to 900 ℃ from room temperature at the heating rate of 5 ℃/min to calcine for 1h to obtain a calcined product;
4) and (3) repeatedly washing the calcined product obtained in the step 3) with water to be neutral, drying and grinding to obtain the porous carbon material with the one-dimensional structure.
Example 2:
1) coal-based byproduct coal liquefaction residue is used as a raw material, and kerosene/wash oil (volume ratio of 1: 1) treating the mixed solvent by a solvent sedimentation method, standing and separating to obtain upper-layer liquid, and distilling the upper-layer liquid at 150 ℃ to recover the solvent to obtain distillation residual solid;
2) crushing the distillation residual solid obtained in the step 1) into powder of 100-200 nm, and mixing the powder according to the ratio of 1: 4, mixing the crushed distillation residual solid with a template agent magnesium oxide according to the mass ratio to obtain mixed powder;
3) placing the mixed powder obtained in the step 2) in a high-temperature tubular furnace with the flow of 100ml/min under the protection of inert atmosphere nitrogen, and heating to 600 ℃ from room temperature at the heating rate of 20 ℃/min to calcine for 8 hours to obtain a calcined product;
4) and (3) repeatedly washing the calcined product obtained in the step 3) with water to be neutral, drying and grinding to obtain the porous carbon material with the one-dimensional structure.
Example 3:
1) coal-based byproduct coal liquefaction residue is used as a raw material, and kerosene/anthracene oil (volume ratio of 1: 1) treating the mixed solvent by a solvent sedimentation method, standing and separating to obtain upper-layer liquid, and distilling the upper-layer liquid at 380 ℃ to recover the solvent to obtain distillation residual solid;
2) crushing the distillation residual solid obtained in the step 1) into powder of 100-200 nm, and mixing the powder according to the ratio of 1: 10, mixing the crushed distillation residual solid with a template agent zinc oxide to obtain mixed powder;
3) placing the mixed powder obtained in the step 2) in a high-temperature tubular furnace with the flow of 100ml/min under the protection of inert atmosphere nitrogen, and heating to 500 ℃ from room temperature at the heating rate of 1 ℃/min to calcine for 10h to obtain a calcined product;
4) and (3) repeatedly washing the calcined product obtained in the step 3) with water to be neutral, drying and grinding to obtain the porous carbon material with the one-dimensional structure.
Example 4:
1) coal-based byproduct coal liquefaction residue and coal tar are used as raw materials, and kerosene/anthracene oil (volume ratio of 1: 1) treating the mixed solvent by a solvent sedimentation method, standing and separating to obtain upper-layer liquid, and distilling the upper-layer liquid at 200 ℃ to recover the solvent to obtain distillation residual solid;
2) crushing the distillation residual solid obtained in the step 1) into powder of 100-200 nm, and mixing the powder according to the ratio of 1: mixing the crushed distillation residual solid with a template agent cobalt oxide according to a mass ratio of 0.1 to obtain mixed powder;
3) placing the mixed powder obtained in the step 2) in a high-temperature tubular furnace with the flow of 100ml/min under the protection of helium in the inert atmosphere, and heating to 550 ℃ from room temperature at the heating rate of 10 ℃/min to calcine for 9h to obtain a calcined product;
4) and (3) repeatedly washing the calcined product obtained in the step 3) with water to be neutral, drying and grinding to obtain the porous carbon material with the one-dimensional structure.
Example 5:
1) coal-based by-product coal tar pitch is used as a raw material, and kerosene/phenol oil (volume ratio of 1: 1) treating the mixed solvent by a solvent centrifugation method, separating to obtain upper layer liquid, and distilling the upper layer liquid at 320 ℃ to recover the solvent to obtain distillation residual solid;
2) crushing the distillation residual solid obtained in the step 1) into powder of 100-200 nm, and mixing the powder according to the ratio of 1: 15, mixing the crushed distillation residual solid with a template agent zinc hydroxide to obtain mixed powder;
3) placing the mixed powder obtained in the step 2) in a high-temperature tubular furnace with the flow of 100ml/min under the protection of inert atmosphere argon, and heating to 800 ℃ from room temperature at the heating rate of 30 ℃/min to calcine for 5h to obtain a calcined product;
4) and (3) repeatedly washing the calcined product obtained in the step 3) with water to be neutral, drying and grinding to obtain the porous carbon material with the one-dimensional structure.
Example 6:
1) coal-based by-product coal tar pitch is used as a raw material, gasoline/wash oil (volume ratio of 1: 2) treating the mixed solvent by a solvent filtration method to obtain upper layer liquid, and distilling the upper layer liquid at 400 ℃ to recover the solvent to obtain distillation residual solid;
2) crushing the distillation residual solid obtained in the step 1) into powder of 100-200 nm, and mixing the powder according to the ratio of 1: 1, mixing the crushed distillation residual solid with a template agent magnesium hydroxide to obtain mixed powder;
3) placing the mixed powder obtained in the step 2) in a high-temperature tubular furnace with the flow of 100ml/min under the protection of inert atmosphere argon, and heating to 1000 ℃ from room temperature at the heating rate of 50 ℃/min to calcine for 0.5h to obtain a calcined product;
4) and (3) repeatedly washing the calcined product obtained in the step 3) with water to be neutral, drying and grinding to obtain the porous carbon material with the one-dimensional structure.
Example 7:
1) coal-based by-products coal pitch and coal tar are used as raw materials, naphtha/anthracene oil (volume ratio 1: 1) treating the mixed solvent by a solvent centrifugation method, separating to obtain upper layer liquid, and distilling the upper layer liquid at 260 ℃ to recover the solvent to obtain distillation residual solid;
2) crushing the distillation residual solid obtained in the step 1) into powder of 100-200 nm, and mixing the powder according to the ratio of 1: 20, mixing the crushed distillation residual solid with a template agent potassium oxide to obtain mixed powder;
3) placing the mixed powder obtained in the step 2) in a high-temperature tubular furnace with the flow of 100ml/min under the protection of helium in the inert atmosphere, and heating to 650 ℃ from room temperature at the heating rate of 40 ℃/min to calcine for 6h to obtain a calcined product;
4) and (3) repeatedly washing the calcined product obtained in the step 3) with water to be neutral, drying and grinding to obtain the porous carbon material with the one-dimensional structure.
Example 8:
1) coal-based by-product coal liquefaction residue and coal pitch are used as raw materials, and kerosene/wash oil (volume ratio of 1: 1) treating the mixed solvent by a solvent filtration method to obtain upper layer liquid, and distilling the upper layer liquid at 300 ℃ to recover the solvent to obtain distillation residual solid;
2) crushing the distillation residual solid obtained in the step 1) into powder of 100-200 nm, and mixing the powder according to the ratio of 1: 30, mixing the crushed distillation residual solid with a template agent potassium hydroxide to obtain mixed powder;
3) placing the mixed powder obtained in the step 2) in a high-temperature tubular furnace with the flow of 100ml/min under the protection of inert atmosphere argon, and heating to 700 ℃ from room temperature at the heating rate of 35 ℃/min to calcine for 5h to obtain a calcined product;
4) and (3) repeatedly washing the calcined product obtained in the step 3) with water to be neutral, drying and grinding to obtain the porous carbon material with the one-dimensional structure.
Claims (9)
1. A preparation method of a coal-based one-dimensional porous carbon material is characterized by comprising the following steps:
1) refining the coal-based by-product by a solvent method, and recovering the solvent by a distillation mode to obtain distillation residual solid;
2) crushing the distillation residual solid obtained in the step 1) to a nano level, and mixing the crushed solid with the solvent according to the ratio of 1: mixing the crushed distillation residual solid with a template agent in a mass ratio of 0.1-30 to obtain mixed powder;
3) placing the mixed powder obtained in the step 2) in a high-temperature tubular furnace protected by inert atmosphere, heating to 500-1000 ℃ from room temperature at a heating rate of 1-50 ℃/min, and calcining to obtain a calcined product;
4) and 3) washing, drying and grinding the calcined product obtained in the step 3) to obtain the porous carbon material with the one-dimensional structure.
2. The method for producing a coal-based one-dimensional porous carbon material according to claim 1, characterized in that: the coal-based by-product in the step 1) is one or more of coal tar, coal pitch or coal liquefaction residues in a coal processing by-product.
3. The method for producing a coal-based one-dimensional porous carbon material according to claim 1, characterized in that: the solvent method in the step 1) is one or a combination of a solvent settling method, a solvent centrifugation method and a solvent filtration method, namely, the coal-based by-product is separated by the method to obtain upper-layer liquid, and the upper-layer liquid is distilled to recover the solvent to obtain distillation residual solid.
4. The method for producing a coal-based one-dimensional structure porous carbon material according to claim 1 or 3, characterized in that: the solvent adopted by the solvent method in the step 1) is one or more of aromatic hydrocarbon solvent phenol oil, wash oil or anthracene oil and aliphatic hydrocarbon solvent kerosene, naphtha or gasoline.
5. The method for producing a coal-based one-dimensional structure porous carbon material according to claim 1 or 3, characterized in that: the distillation temperature in the step 1) is 150-400 ℃.
6. The method for producing a coal-based one-dimensional porous carbon material according to claim 1, characterized in that: the template agent in the step 2) adopts metal oxide or hydroxide nano-wires which are composed of one or more of potassium, magnesium, zinc or cobalt as metal elements.
7. The method for producing a coal-based one-dimensional porous carbon material according to claim 1, characterized in that: the calcining time of the step 3) is 0.5-10 h.
8. The method for producing a coal-based one-dimensional porous carbon material according to claim 1, characterized in that: the inert atmosphere in the step 3) is one of nitrogen, helium and argon.
9. The method for producing a coal-based one-dimensional porous carbon material according to claim 1, characterized in that: and 4) repeatedly washing the calcined product to be neutral, drying and grinding to obtain the porous carbon material with the one-dimensional structure.
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| CN102431992A (en) * | 2011-09-22 | 2012-05-02 | 安徽工业大学 | Method for preparing porous carbon material by using magnesium oxide template in cooperation with activation of potassium hydroxide |
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| JP2016191014A (en) * | 2015-03-31 | 2016-11-10 | 国立大学法人北海道大学 | Carbon nanotube-containing functional porous body |
| CN106829924A (en) * | 2017-03-15 | 2017-06-13 | 江苏理工学院 | A kind of preparation method of one-dimensional porous CNT |
| CN110127692A (en) * | 2019-05-24 | 2019-08-16 | 许皖 | A kind of preparation method of mesoporous heat-resistant activity charcoal |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102431992A (en) * | 2011-09-22 | 2012-05-02 | 安徽工业大学 | Method for preparing porous carbon material by using magnesium oxide template in cooperation with activation of potassium hydroxide |
| JP2016191014A (en) * | 2015-03-31 | 2016-11-10 | 国立大学法人北海道大学 | Carbon nanotube-containing functional porous body |
| CN105819419A (en) * | 2016-03-09 | 2016-08-03 | 安徽工业大学 | Preparation method of two-dimensional porous carbon nanosheet for super capacitors |
| CN106829924A (en) * | 2017-03-15 | 2017-06-13 | 江苏理工学院 | A kind of preparation method of one-dimensional porous CNT |
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