CN114348988A - Preparation method of coal-based porous carbon - Google Patents
Preparation method of coal-based porous carbon Download PDFInfo
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Abstract
The invention discloses a preparation method of coal-based porous carbon, which comprises the following steps: (1) crushing raw coal, mixing with ethanol and cane sugar, and performing ball milling to obtain a mixed material; (2) placing the mixture in acid liquor, heating in water bath, stirring, acid leaching, filtering, washing to neutrality, and drying to obtain deashed coal powder; (3) and carbonizing the deashed coal powder to obtain the coal-based porous carbon. The coal-based porous carbon prepared by the method has three structures of macropores, mesopores and micropores, and takes the micropores as main components, so that the specific surface area of the activated carbon is further improved.
Description
Technical Field
The invention relates to the technical field of coal-based porous carbon, in particular to a preparation method of coal-based porous carbon.
Background
Among all carbon source materials, coal is most abundant in reserves and least expensive. The coal is rich in large condensed ring organic compounds, has high carbon content and rich porous structures, and can be used as a carbon source substance to prepare a high-performance mesoporous carbon material by adopting high-temperature carbonization treatment. The activated carbon has unique pore structure and huge surface structure, is various in variety, acid-resistant, alkali-resistant and heat-resistant, and is easy to regenerate, so that the activated carbon is widely applied to multiple fields. Compared with wood, the coal resource is rich and the price is low in China, so that the coal is an important raw material for preparing the activated carbon.
The activated carbon material has the characteristics of low price, high specific surface area, adjustable pore diameter, excellent electrochemical performance and environmental friendliness, is most researched in the aspect of double-layer capacitors, is various, mainly takes cheap activated carbon with rich resources (mainly used in the fields of water treatment, air purification, industrial decoloration and the like at present), and is difficult to be directly used as a supercapacitor electrode material due to the problems of poor conductivity, unreasonable pore diameter distribution and the like; the carbon material for the supercapacitor electrode prepared by using biomass as a raw material is relatively expensive (more than ten times of that of active carbon for adsorption), and has different performances due to different raw materials and preparation processes. Therefore, the cheap high-performance porous activated carbon material which is prepared by taking the cheap activated carbon with rich resources as the raw material and can be used for the electrode of the super capacitor has important application prospect. Meanwhile, the specific surface area and pore volume indexes of the activated carbon prepared in the prior art are generally low, and the method cannot adapt to the development of the super capacitor.
Disclosure of Invention
In view of the prior art, the invention aims to provide a preparation method of coal-based porous carbon. The coal-based porous carbon prepared by the method has three structures of macropores, mesopores and micropores, and takes the micropores as main components, so that the specific surface area of the activated carbon is further improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of coal-based porous carbon, which comprises the following steps:
(1) crushing raw coal, mixing with ethanol and cane sugar, and performing ball milling to obtain a mixed material;
(2) placing the mixture in acid liquor, heating in water bath, stirring, acid leaching, filtering, washing to neutrality, and drying to obtain deashed coal powder;
(3) and carbonizing the deashed coal powder to obtain the coal-based porous carbon.
Preferably, in the step (1), the raw coal is taixi coal; the pulverization is to pulverize the taixi coal to 200 meshes.
Preferably, in the step (1), the mass ratio of the coal dust to the sucrose is 2: (0.1 to 0.5); the adding amount ratio of the coal powder to the ethanol is 30 g: 30 mL; the grain size of the sucrose is less than or equal to 80 meshes.
Preferably, in the step (1), the grinding balls used for ball milling are zirconia; the ball-material ratio of the ball mill is 5-20:1.
Preferably, in the step (1), the grinding ball grading is controlled to be that the number ratio of 2mm balls to 1mm balls is 1: 1; the ball milling time is 2-4 h, and the rotating speed is 300 r/min.
Preferably, in the step (2), the acid solution is 6mol/L hydrochloric acid solution; the adding amount ratio of the mixture to the acid liquor is 30 g: (400-500) mL.
Preferably, in the step (2), the water bath temperature is 60 ℃, and the acid leaching time is 2 h; the drying temperature is 110 ℃, and the drying time is 12 h.
Preferably, in the step (3), the carbonization is carried out at a temperature rise rate of 5 ℃/min to 850-900 ℃ and is kept for 1-2 h.
The invention has the beneficial effects that:
(1) according to the invention, ethanol is added as an active agent in ball milling, and sucrose is added for ball milling, so that the ball milling time can be reduced, and the ball milling granularity is smaller; and sucrose is partially hydrolyzed in subsequent acidification, which can further increase the number of pores during carbonization.
(2) The preparation method is simple, short in time consumption, large in specific surface area of the obtained activated carbon, reasonable in pore size distribution and suitable for being used as an electrode material of a super capacitor.
Drawings
FIG. 1: XRD patterns of example 3 and comparative examples 1 to 3.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
As described in the background section, activated carbon is difficult to be directly used as an electrode material of a supercapacitor due to the problems of poor conductivity, unreasonable pore size distribution and the like. Based on the above, the invention aims to provide a preparation method of coal-based porous carbon. In order to make the particle size of the coal powder smaller and prepare more micropores, the invention takes ethanol as an active agent and adds sucrose, thereby not only preventing the coal powder from agglomerating, but also improving the grinding force; meanwhile, the gradation of the grinding balls is controlled, the coal powder with smaller particle size is obtained by ball milling, and the ball milling time is shorter. And then, carrying out deliming treatment by acid leaching, and carrying out acid leaching on the pulverized coal containing ethanol and hydrochloric acid after ball milling, wherein the ethanol can ensure that the pulverized coal is more fully contacted with the hydrochloric acid. The cane sugar and the hydrochloric acid are gradually hydrolyzed and release heat under the water bath heating, the structure of the coal dust is influenced to a certain extent, the ash content is lower, the mineral content in the coal is less, the good deashing effect is obtained, and more micropores can be obtained in the subsequent carbonization.
In order to make the technical solutions of the present application more clearly understood by those skilled in the art, the technical solutions of the present application will be described in detail below with reference to specific embodiments.
The test materials used in the examples of the present invention are all conventional in the art and commercially available.
Description of the drawings: the compositions of the taixi coals used in the examples of the present invention and the comparative examples are shown in tables 1 and 2.
TABLE 1 Industrial analysis of Taixi anthracite
TABLE 2 analysis of chemical element content of ash of Taixi anthracite
Example 1
(1) 30g of Taixi coal is crushed to 200 meshes, 30mL of Taixi coal is mixed with ethanol and 1.5g of cane sugar with the fineness of 100 meshes, zirconia balls are used, and the number ratio of the zirconia grinding balls to the 2mm balls to the 1mm balls is controlled to be 1:1, the ball-to-feed ratio is 10: 1. the rotating speed of the planetary ball mill is 300r/min, and the ball milling time is 4 hours, so that a mixed material is obtained;
(2) placing 30g of the mixture in 450mL of 6mol/L hydrochloric acid solution, heating and stirring the mixture in a water bath at 60 ℃, carrying out acid leaching for 2 hours, filtering the mixture, washing the mixture to be neutral by using deionized water, and drying the mixture for 12 hours at 110 ℃ to obtain coal powder;
(3) heating the deashing coal powder to 850 ℃ at the heating rate of 5 ℃/min, preserving the heat for 1h, carbonizing to obtain coal-based porous carbon, and detecting that the specific surface area of the coal-based porous carbon is 3011m2Between/g, pore volume is 1.66cm3/g。
Example 2
(1) 30g of Taixi coal is crushed to 200 meshes, 30mL of Taixi coal is mixed with ethanol and 3.0g of cane sugar with the fineness of 80 meshes, zirconia balls are used, and the number ratio of the zirconia grinding balls to the 2mm balls to the 1mm balls is controlled to be 1:1, the ball-to-feed ratio is 10: 1. the rotating speed of the planetary ball mill is 300r/min, and the ball milling time is 3h, so that a mixed material is obtained;
(2) placing 30g of the mixture in 400mL of 6mol/L hydrochloric acid solution, heating and stirring the mixture in a water bath at 60 ℃, carrying out acid leaching for 2 hours, filtering the mixture, washing the mixture to be neutral by using deionized water, and drying the mixture for 12 hours at 110 ℃ to obtain deashed coal powder;
(3) heating the deashed coal powder to 850 ℃ at the heating rate of 5 ℃/min, preserving the heat for 1.5h, carbonizing to obtain coal-based porous carbon, and detecting that the specific surface area of the coal-based porous carbon is 3034m2Between/g, pore volume is 1.69cm3/g。
Example 3
(1) 30g of Taixi coal is crushed to 200 meshes, 30mL of Taixi coal is mixed with ethanol and 6.0g of cane sugar with the fineness of 100 meshes, zirconia balls are used, and the number ratio of the zirconia grinding balls to the 2mm balls to the 1mm balls is controlled to be 1:1, the ball-to-feed ratio is 10: 1. the rotating speed of the planetary ball mill is 300r/min, and the ball milling time is 2 hours, so that a mixed material is obtained;
(2) placing 30g of the mixture into 500mL of 6mol/L hydrochloric acid solution, heating and stirring the mixture in a water bath at 60 ℃, carrying out acid leaching for 2 hours, filtering the mixture, washing the mixture to be neutral by using deionized water, and drying the mixture for 12 hours at 110 ℃ to obtain deashed coal powder;
(3) heating the deashed coal powder to 850 ℃ at the heating rate of 5 ℃/min, preserving the heat for 2 hours, carbonizing to obtain coal-based porous carbon, and detecting that the specific surface area of the coal-based porous carbon is 3101m2Between/g, pore volume is 1.75cm3/g。
Comparative example 1: prepared according to the method of example 1 in application No. 201910738787.4
A preparation method of hydrogen peroxide modified coal-based porous carbon comprises the following steps:
crushing raw coal to obtain coal powder, adding the coal powder, nickel nitrate, ferric nitrate, ethanol and ball grinding balls into a planetary ball mill for ball milling to obtain a mixed material; the mass ratio of the coal powder to the nickel nitrate to the ferric nitrate is 2:1: 1.5; the mass ratio of the coal powder to the ethanol is 1: 4; the ball grinding ball is made of silicon carbide; the ball grinding ball comprises a big ball, a middle ball and a small ball, the diameter of the big ball is 12mm, the diameter of the middle ball is 8mm, the diameter of the small ball is 5mm, and the mass ratio of the big ball to the middle ball to the small ball is 7: 5: 3; the mass ratio of the ball grinding balls to the pulverized coal is 25: 1, ball milling and mixing time is 3h, and ball milling rotating speed is 300 r/min;
secondly, placing the ball-milled mixed material in a microwave device under the nitrogen atmosphere, and carbonizing under the conditions that the microwave power is 500W and the microwave time is 20 min;
step three, adding the carbonized material into a 30 wt% hydrogen peroxide solution for soaking for 3 hours, and introducing ozone into the hydrogen peroxide solution in the soaking process; filtering, washing and drying after soaking, and adding the dried material into an alkaline solution for ultrasonic soaking; filtering and drying the ultrasonically soaked materials, then placing the materials in a sealed glass tank, irradiating the materials by adopting an electron beam irradiation device, then washing the materials by using water, and drying the materials to obtain hydrogen peroxide modified activated carbon; the mass ratio of the carbonized material to the hydrogen peroxide solution is 1: 6; voltage range for irradiation: 10MeV, number rate range: 10mA, irradiation dose range: 800 kGy; the concentration of the alkaline solution is 3 mol/L; the alkaline solution is an aqueous solution of potassium sulfide, urea and ethylenediamine; the weight ratio of the potassium sulfide to the urea to the ethylenediamine is 1:5: 1; the aeration rate of the ozone is 100 mL/min; the frequency of ultrasonic soaking is 120 kHz; the carbonized material is treated by the synergistic action of hydrogen peroxide and ozone and the irradiation of electron beams, so that the specific surface area of the activated carbon can be further improved.
The activated carbon prepared in this example was tested to have a specific surface area of 2615m2Per g, pore volume 1.12cm3/g。
Comparative example 2
(1) 30g of taixi coal is crushed to 200 meshes, 30mL of taixi coal is mixed with ethanol, 15g of nickel nitrate and 15g of ferric nitrate, zirconia balls are used, and the number ratio of the zirconia grinding ball grade to the 1mm balls is controlled to be 1:1. the rotating speed of the planetary ball mill is 300r/min, and the ball milling time is 2 hours, so that a mixed material is obtained;
(2) similar to the steps (2) to (3) of example 3, the specific surface area was 2451m2Between/g, pore volume is 1.35cm3/g。
Comparative example 3
(1) Crushing and screening the Taixi coal to obtain a raw material with a particle size of less than 200 meshes, and drying the Taixi coal for 12 hours by using a 110-DEG C air-blast drying oven. Taking 30g of dried Taixi coal and 7.5mol/L of sodium hydroxide according to the liquid-solid ratio of 3: 8, and placing the mixture in a hydrothermal kettle. To this was added 10ml of alcohol. And then reacting for 12h at 210 ℃, filtering, washing with deionized water to be neutral, and drying for 12h at 110 ℃ to obtain the alkali-treated coal powder treated by sodium hydroxide. 30g of dried alkali-treated coal powder is taken to be dissolved in 450ml of hydrochloric acid with the concentration of 6mol/L, and 10ml of alcohol is added at the same time. And then stirring in a water bath at 60 ℃, carrying out acid leaching for 2h, filtering, washing to be neutral by deionized water, and drying at 110 ℃ for 12h to obtain the deashed coal powder.
(2) As in step (3) of example 3, the specific surface area was found to be 2751m2Between/g, pore volume is 1.55cm3/g。
XRD detection is carried out on the deashed coal powder prepared in the example 3 and the comparative examples 1-3, and the obtained result is shown in figure 1. As can be seen from FIG. 1, the XRD pattern of the delimed coal powder prepared in example 1 is smoother, and the diffraction peaks corresponding to minerals in the coal disappear. As can be seen from fig. 1, the deliming has a large influence on the kind and content of residual elements in the coal. After the acid leaching of the embodiment 3, the mineral impurities can be effectively removed, the ash content is lowest, and the content of all impurity elements is very low.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (8)
1. The preparation method of the coal-based porous carbon is characterized by comprising the following steps:
(1) crushing raw coal, mixing with ethanol and cane sugar, and performing ball milling to obtain a mixed material;
(2) placing the mixture in acid liquor, heating in water bath, stirring, acid leaching, filtering, washing to neutrality, and drying to obtain deashed coal powder;
(3) and carbonizing the deashed coal powder to obtain the coal-based porous carbon.
2. The method according to claim 1, wherein in the step (1), the raw coal is taixi coal; the pulverization is to pulverize the taixi coal to 200 meshes.
3. The preparation method according to claim 1, wherein in the step (1), the mass ratio of the pulverized coal to the sucrose is 2: (0.1 to 0.5); the adding amount ratio of the coal powder to the ethanol is 30 g: 30 mL; the grain size of the sucrose is less than or equal to 80 meshes.
4. The preparation method according to claim 1, wherein in the step (1), the grinding balls used for ball milling are zirconia; the ball-material ratio of the ball mill is 5-20:1.
5. The production method according to claim 1, wherein in the step (1), the grinding ball gradation is controlled such that the number ratio of the 2mm balls to the 1mm balls is 1: 1; the ball milling time is 2-4 h, and the rotating speed is 300 r/min.
6. The preparation method according to claim 1, wherein in the step (2), the acid solution is 6mol/L hydrochloric acid solution; the adding amount ratio of the mixture to the acid liquor is 30 g: (400-500) mL.
7. The preparation method according to claim 1, characterized in that in the step (2), the water bath temperature is 60 ℃, and the acid leaching time is 2-4 h; the drying temperature is 110 ℃, and the drying time is 12 h.
8. The preparation method according to claim 1, wherein in the step (3), the carbonization is performed by raising the temperature to 850-900 ℃ at a temperature raising rate of 5 ℃/min and keeping the temperature for 1-2 h.
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