CN114348988B - Preparation method of coal-based porous carbon - Google Patents
Preparation method of coal-based porous carbon Download PDFInfo
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Abstract
The application discloses a preparation method of coal-based porous carbon, which comprises the following steps: (1) Crushing raw coal, mixing with ethanol and sucrose, and performing ball milling to obtain a mixed material; (2) Placing the mixture into acid liquor, heating in water bath, stirring, pickling, filtering, washing to neutrality, and drying to obtain deashing pulverized coal; and (3) carbonizing the deashing pulverized coal 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 mainly comprises micropores, so that the specific surface area of the activated carbon is further improved.
Description
Technical Field
The application 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 is least expensive. The coal is rich in large condensed ring organic compounds, has high carbon content and rich porous structure, and can be used as a carbon source substance to prepare a high-performance mesoporous carbon material by high-temperature carbonization treatment. Activated carbon has a unique pore structure and a huge surface structure, is various in variety, resistant to acid, alkali and heat, and easy to regenerate, and is widely applied to various fields. Compared with woody materials, the coal resources of China are rich and the price is low, so the coal is an important raw material for preparing the activated carbon.
The active carbon material has the characteristics of low price, high specific surface area, adjustable aperture, excellent electrochemical performance and environmental friendliness, has the most research on the aspect of double-layer capacitors, is various, mainly takes cheap active carbon with abundant resources (mainly used in the fields of water treatment, air purification, industrial decoloration and the like at present), and is difficult to directly use as an electrode material of the supercapacitor due to the problems of poor conductivity, unreasonable aperture distribution and the like; the carbon material for the supercapacitor electrode prepared by taking biomass as a raw material is relatively expensive (ten times or more than that of active carbon for adsorption), and has uneven performance due to different raw materials and preparation processes. Therefore, the preparation of the cheap high-performance porous activated carbon material which can be used for the supercapacitor electrode by taking the cheap activated carbon with abundant resources as the raw material 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 activated carbon cannot adapt to the development of super capacitors.
Disclosure of Invention
Aiming at the prior art, the application 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 mainly comprises micropores, so that the specific surface area of the activated carbon is further improved.
In order to achieve the above purpose, the application adopts the following technical scheme:
the application provides a preparation method of coal-based porous carbon, which comprises the following steps:
(1) Crushing raw coal, mixing with ethanol and sucrose, and performing ball milling to obtain a mixed material;
(2) Placing the mixture into acid liquor, heating in water bath, stirring, pickling, filtering, washing to neutrality, and drying to obtain deashing pulverized coal;
(3) Carbonizing the deashing pulverized coal to obtain coal-based porous carbon.
Preferably, in the step (1), the raw coal is taixi coal; the crushing is to crush the Taixi coal to 200 meshes.
Preferably, in the step (1), the mass ratio of the pulverized coal to the sucrose is 2: (0.1 to 0.5); the ratio of the addition amount of the pulverized coal to the addition amount of the ethanol is 30g:30mL; the grain diameter of the sucrose is less than or equal to 80 meshes.
Preferably, in the step (1), the grinding balls used for ball milling are zirconium oxide; the ball-milling ball-material ratio is 5-20:1.
Preferably, in the step (1), the grading of the grinding balls is controlled to be 2mm balls and the number ratio of the 1mm balls is 1:1, a step of; the ball milling time is 2-4 h, and the rotating speed is 300r/min.
Preferably, in the step (2), the acid liquor is a hydrochloric acid solution with the concentration of 6 mol/L; the ratio of the addition amount of the mixture to the acid solution is 30g: (400-500) mL.
Preferably, in the step (2), the water bath temperature is 60 ℃, and the acid leaching time is 2 hours; the drying temperature is 110 ℃, and the drying time is 12 hours.
Preferably, in the step (3), the carbonization is performed by heating to 850-900 ℃ at a heating rate of 5 ℃/min, and preserving heat for 1-2 hours.
The application has the beneficial effects that:
(1) According to the application, 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 the sucrose is partially hydrolyzed in the subsequent acidification, and the process can further increase the number of micropores in carbonization.
(2) The preparation method is simple, short in time consumption, large in specific surface area and reasonable in pore size distribution of the obtained activated carbon, and is suitable for serving as an electrode material of the supercapacitor.
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 illustrative and is intended to provide further explanation of the application. 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 art, the activated carbon is difficult to be directly used as an electrode material of the supercapacitor due to the problems of poor conductivity, unreasonable pore size distribution and the like. Based on this, the application aims to provide a preparation method of coal-based porous carbon. In order to make the particle size of the pulverized coal smaller and the prepared micropores more, the application takes ethanol as an active agent, and sucrose is added, so that the pulverized coal agglomeration can be prevented, and the grinding force can be improved; meanwhile, the grading of grinding balls is controlled, coal powder with smaller particle size is obtained through ball milling, and the ball milling time is shorter. Then carrying out deashing treatment by acid leaching, carrying out acid leaching on the pulverized coal containing ethanol and hydrochloric acid after ball milling, wherein the pulverized coal can be fully contacted with the hydrochloric acid by the ethanol. Sucrose and hydrochloric acid are gradually hydrolyzed and released under water bath heating, so that a certain influence is generated on the structure of coal dust, the ash content is lower, the mineral content in coal is less, a good ash removal effect is achieved, and more micropores can be obtained in subsequent carbonization.
In order to enable those skilled in the art to more clearly understand the technical scheme of the present application, the technical scheme of the present application will be described in detail with reference to specific embodiments.
The test materials used in the examples of the present application are all conventional in the art and are commercially available.
Description: the components of the taixi coals used in the examples and comparative examples of the present application are shown in tables 1 and 2.
TABLE 1 industrial analysis of anthracite coal
TABLE 2 analysis of ash content of anthracite
Example 1
(1) Crushing 30g of Taixi coal to 200 meshes, mixing 30mL of Taixi coal with ethanol and 1.5g of sucrose with fineness of 100 meshes, and controlling the grading of the zirconia grinding balls into 2mm balls and the number ratio of 1mm balls to 1 by using zirconia balls: 1, the ball-to-material 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 into 450mL of 6mol/L hydrochloric acid solution, heating in a water bath at 60 ℃, stirring, pickling for 2h, filtering, washing with deionized water to neutrality, and drying at 110 ℃ for 12h to obtain coal dust;
(3) Heating the deashing coal dust to 850 ℃ at a heating rate of 5 ℃/min, preserving heat for 1h, carbonizing to obtain coal-based porous carbon, and detecting that the specific surface area of the coal-based porous carbon is 3011m 2 Between/g, pore volume of 1.66cm 3 /g。
Example 2
(1) Pulverizing 30g of Taixi coal to 200 meshes, mixing 30mL of Taixi coal with ethanol and 3.0g of sucrose with fineness of 80 meshes, and controlling the grading of the zirconia grinding balls into 2mm balls and 1mm balls according to the number ratio of 1:1, the ball-to-material 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 into 400mL of 6mol/L hydrochloric acid solution, heating in a water bath at 60 ℃, stirring, pickling for 2h, filtering, washing with deionized water to neutrality, and drying at 110 ℃ for 12h to obtain deashing pulverized coal;
(3) Heating the deashing coal dust to 850 ℃ at a heating rate of 5 ℃/min, preserving 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 3034m 2 Between/g, pore volume of 1.69cm 3 /g。
Example 3
(1) Crushing 30g of Taixi coal to 200 meshes, mixing 30mL of Taixi coal with ethanol and 6.0g of sucrose with fineness of 100 meshes, and controlling the grading of the zirconia grinding balls into 2mm balls and 1mm balls according to the number ratio of 1:1, the ball-to-material ratio is 10:1. the rotating speed of the planetary ball mill is 300r/min, and the ball milling time is 2h, so that a mixed material is obtained;
(2) Placing 30g of the mixture into 500mL of 6mol/L hydrochloric acid solution, heating in a water bath at 60 ℃, stirring, pickling for 2h, filtering, washing with deionized water to neutrality, and drying at 110 ℃ for 12h to obtain deashing pulverized coal;
(3) Heating the deashing coal dust to 850 ℃ at a heating rate of 5 ℃/min, preserving 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 3101m 2 Between/g, pore volume of 1.75cm 3 /g。
Comparative example 1: prepared according to the method of example 1 in application number 201910738787.4
The preparation method of the hydrogen peroxide modified coal-based porous carbon comprises the following steps:
firstly, crushing raw coal to obtain coal dust, and adding the coal dust, 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 pulverized coal to the nickel nitrate to the ferric nitrate is 2:1:1.5; the mass ratio of the pulverized coal to the ethanol is 1:4; the ball milling balls are made of silicon carbide; the ball milling ball comprises a big ball, a middle ball and a small ball, wherein 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, a step of; the mass ratio of the ball grinding ball to the pulverized coal is 25:1, ball milling mixing time is 3 hours, and ball milling rotating speed is 300r/min;
step two, placing the ball-milled mixed material in a microwave device under the nitrogen atmosphere, and carbonizing under the condition that the microwave power is 500W and the microwave time is 20 min;
step three, adding the carbonized material into a 30wt% 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 alkaline solution for ultrasonic soaking; filtering and drying the material after ultrasonic soaking, then placing the material in a sealed glass tank, irradiating the material by adopting an electron beam irradiation device, then washing the material by using water, and drying the material 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: 800kGy; the concentration of the alkaline solution is 3mol/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 100mL/min; the ultrasonic soaking frequency is 120kHz; the carbonized material is treated by the synergistic effect of hydrogen peroxide and ozone and the irradiation effect of electron beams, so that the specific surface area of the activated carbon can be further improved.
The specific surface area of the activated carbon prepared in this example was 2615m 2 Per g, pore volume of 1.12cm 3 /g。
Comparative example 2
(1) 30g of Taixi coal is crushed to 200 meshes, 30mL is mixed with ethanol, 15g of nickel nitrate and 15g of ferric nitrate, zirconia balls are used, and the grading of the zirconia balls is controlled to be 2mm balls and the number ratio of 1mm balls is 1:1. the rotating speed of the planetary ball mill is 300r/min, and the ball milling time is 2h, so that a mixed material is obtained;
(2) As shown in the steps (2) to (3) of example 3, the specific surface area was 2451m 2 Between/g, pore volume of 1.35cm 3 /g。
Comparative example 3
(1) Crushing and screening the Taixi coal to obtain a raw material smaller than 200 meshes, and drying the Taixi coal for 12 hours by using a 110 ℃ blast drying box. Taking 30g of dried Taixi coal and 7.5mol/L sodium hydroxide according to a liquid-solid ratio of 3:8, uniformly mixing the materials according to the proportion, and placing the mixture in a hydrothermal kettle. 10ml of alcohol was added thereto. Then reacting for 12 hours at 210 ℃, filtering, washing to neutrality by deionized water, and drying for 12 hours at 110 ℃ to obtain the alkali-treated coal dust treated by sodium hydroxide. 30g of dried alkali-treated coal dust is taken and added into 450ml of hydrochloric acid with the concentration of 6mol/L, and 10ml of alcohol is added. Then stirring in water bath at 60 ℃, pickling for 2h, filtering, washing with deionized water to neutrality, and drying at 110 ℃ for 12h to obtain the deashing pulverized coal.
(2) As in step (3) of example 3, the specific surface area was examined to be 2751m 2 Between/g, pore volume of 1.55cm 3 /g。
XRD measurements were carried out on the deashing coal fines prepared in example 3 and comparative examples 1 to 3, and the results are shown in FIG. 1. As can be seen from fig. 1, the XRD pattern of the deashed coal powder prepared in example 1 is smoother, and the diffraction peak corresponding to the mineral substances in the coal disappears. As can be seen from fig. 1, the deashing has a large influence on the kind and content of residual elements in the coal. The mineral impurities can be effectively removed after the acid leaching in the embodiment 3, the ash content is the lowest, and the content of all impurity elements is very low.
The above description is only of the preferred embodiments of the present application and is not intended to limit the present application, but various modifications and variations can be made to the present application by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (1)
1. The preparation method of the coal-based porous carbon is characterized by comprising the following steps of:
(1) Pulverizing 30g of Taixi coal to 200 meshes, mixing with 30mL of ethanol and 6.0g of sucrose with fineness of 100 meshes, and controlling the grading of the zirconia grinding balls into 2mm balls and 1mm balls according to the number ratio of 1:1, the ball-to-material ratio is 10:1, a step of; the rotating speed of the planetary ball mill is 300r/min, and the ball milling time is 2h, so that a mixed material is obtained;
(2) Placing 30g of the mixture into 500mL of 6mol/L hydrochloric acid solution, heating in a water bath at 60 ℃, stirring, pickling for 2h, filtering, washing with deionized water to neutrality, and drying at 110 ℃ for 12h to obtain deashing pulverized coal;
(3) Heating the deashing coal dust to 850 ℃ at a heating rate of 5 ℃/min, preserving heat for 2 hours, and carbonizing to obtain the coal-based porous carbon.
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