CN113371708A - Method for preparing semicoke-based activated carbon by ball milling assisted organic fermentation technology - Google Patents
Method for preparing semicoke-based activated carbon by ball milling assisted organic fermentation technology Download PDFInfo
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- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
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- C01B32/318—Preparation characterised by the starting materials
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Abstract
The invention discloses a method for preparing semicoke-based activated carbon by a ball milling assisted organic fermentation technology, which comprises the following steps: 1) ball-milling the blocky semicoke to obtain semicoke powder; 2) dissolving organic matters in water, adding semi-coke powder, stirring uniformly, and fermenting to obtain fermented semi-coke; 3) and (3) activating the fermented semicoke at high temperature, and then washing and drying to obtain the semicoke-based activated carbon.
Description
Technical Field
The invention belongs to the field of preparation of activated carbon and treatment and application of Cr (VI) -containing wastewater, and relates to a method for preparing semicoke-based activated carbon by using a ball milling assisted organic fermentation technology.
Background
Semicoke is also called semi-coke, is a solid carbonaceous product obtained by pyrolyzing high-volatile coal without cohesiveness or with weak cohesiveness under the condition of medium and low temperature, is formally incorporated into the clean energy ranks in 2016 by China, and is comprehensively popularized and used nationwide. According to data statistics of China semi-coke association, the yield of the semi-coke in China is 7000 ten thousand tons and 3890 ten thousand tons by 2019, the yield of the semi-coke is estimated to be 5473.6 ten thousand tons in 2026, while the market price of the semi-coke is only 600 yuan/ton in 2020. The price is low, the stock is increased, and a large number of carbocoal production enterprises in China are in a state of comprehensive loss. Therefore, the development of the semicoke utilization technology with high economic added value and the product have strong social value and economic significance.
Various heavy metal pollutants, such as copper (Cu), cadmium (Cd), nickel (Ni), and chromium (Cr), generated in the industries of electroplating, printing, dyeing, metallurgy, and leather, etc., cause pollution to the global environment. Chromium (Cr) is one of the most toxic heavy metals harmful to the human body, and exists in the form of Cr (iii) and Cr (vi) in the natural environment, but the physicochemical properties and toxicity of both are completely different. Cr (iii) is considered to be a micronutrient that maintains the normal function of living organisms, while Cr (vi) compounds have extremely harmful effects on the biochemical system, with a toxicity of about 100 times that of Cr (iii). Short term exposure of people above the maximum contaminant level of Cr (vi) can lead to skin and stomach allergies or ulcers; prolonged exposure above maximum contaminant levels can result in damage to liver, kidney and neural tissue, and even death in large doses. The U.S. environmental protection agency has listed Cr (vi) as one of the 17 chemical substances that pose the greatest threat to humans, and the world health organization has issued strict emission limit standards that control the Cr (vi) content below 0.05 mg/L. Therefore, a treatment technique for industrial wastewater containing Cr (VI) or the like is indispensable.
The activated carbon adsorption material is a common commercial adsorption material, has a good pore structure, a large specific surface area and easily-regulated surface chemical properties, and is widely applied to treatment of wastewater containing Cr (VI). However, in recent years, the cost price of the traditional activated carbon raw materials such as coconut shells rises year by year, so that the price of the activated carbon rises year by year, and the cost for producing one ton of activated carbon is up to 8000-. The semicoke is an ideal active carbon raw material due to high fixed carbon content and less volatile components, and has low priceThe attention of the researchers is wide. Through calculation, if the semicoke is used as a raw material, the cost for producing one ton of activated carbon is only 3000-4000 yuan, and the method has extremely high economic value. However, the semicoke raw material has compact structure and large hole expanding difficulty, and is a main problem faced by researchers at present. At present, the commercial activated carbon activation method mainly comprises two methods of physical activation and chemical activation, wherein, water vapor and CO are used2The activation method which is taken as an activation medium is called as a physical activation method, but the single physical activation method is difficult to excite the carbon substrate on the surface of the semicoke to react with the activation gas, so that the problems of incomplete hole expansion, low specific surface area and the like are caused, and the quality is poor; in addition, by means of KOH, ZnCl2And H3PO4The chemical agent assisted activation method is called chemical activation method, but the activation process not only consumes a large amount of chemical agent, but also causes great pollution to the environment.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a method for preparing semicoke-based activated carbon by using a ball milling assisted organic fermentation technology, which has the characteristic of low pollution and can prepare high-quality semicoke-based activated carbon.
In order to achieve the aim, the method for preparing the semicoke-based activated carbon by the ball-milling assisted organic fermentation technology comprises the following steps:
1) ball-milling the blocky semicoke to obtain semicoke powder;
2) dissolving organic matters in water, adding semi-coke powder, stirring uniformly, and fermenting to obtain fermented semi-coke;
3) and (3) activating the fermented semicoke at high temperature, and then washing and drying to obtain the semicoke-based activated carbon.
In the step 1), ball milling is carried out on the blocky carbocoal by a high-energy ball mill, wherein the rotating speed of the high-energy ball mill is 100-500rpm, and the ball milling time is 4-10 h.
The mesh number of the semi-coke powder is less than or equal to 200 meshes.
The organic matter is one or a mixture of more of starch, glucose and maltose.
Fermentation powder is added in the fermentation process.
The mass ratio of the fermentation powder, the organic matter, the water and the semicoke is (0.01-0.05): (0.1-0.3): (1-3): (1-2).
The temperature of the fermentation process is 20-60 ℃.
The specific operation of the step 3) is as follows:
and (3) activating the fermented semicoke at high temperature by adopting a high-temperature tube furnace, washing by using hydrochloric acid and distilled water, then carrying out vacuum drying, and finally carrying out sealed preservation.
In the high-temperature activation process, the temperature rise time of the high-temperature tube furnace is 40-160min, the activation temperature is 800-900 ℃, the activation time is 120-180min, and the activation gas is CO2The gas flow of the gas and the activating gas is 30-80 mL.
The invention has the following beneficial effects:
the method for preparing the semicoke-based activated carbon by the ball-milling assisted organic fermentation technology comprises the following steps of performing ball milling on block semicokes to open possible pore network structures in the semicokes, increasing the specific surface area in the semicokes, performing fermentation treatment on the semicokes and organic matters, and performing crosslinking reaction on organic acid generated by metabolism during organic matter fermentation and the surface of a semicoke raw material so as to promote the adhesion effect of semicoke-based carbon materials and adhesives, increase active sites on the semicoke surface and achieve the purpose of reducing activation difficulty, and finally performing high-temperature activation treatment on the fermented semicokes, wherein in the high-temperature activation treatment process, CO is used for activating the semicokes at high temperature2Reacting with disordered carbon in the semicoke to generate CO, wherein a micropore structure appears on the surface of the semicoke along with the escape of CO gas, and then CO2The activated carbon enters micropores to continuously react with a deeper carbon substrate, and semicoke-based activated carbon with rich micropore structure is finally generated, so that semicoke-based activated carbon with developed pore structure and high specific surface area is obtained.
Drawings
FIG. 1 is a comparative view of a scanning electron microscope showing a semicoke raw material, a semicoke raw material after fermentation, and semicoke-based activated carbon in example III;
FIG. 2 is a Fourier transform infrared spectrum of the semicoke-based activated carbon and semicoke raw material in example III;
FIG. 3 is a graph showing the adsorption and desorption curves of the semicoke-based activated carbon and the semicoke raw material in the third example;
FIG. 4 is a graph showing the pore size distribution of the semicoke-based activated carbon and semicoke raw materials in the third example;
FIG. 5 is a graph showing the adsorption capacity of semicoke-based activated carbon and semicoke raw material for Cr (VI) in example III;
FIG. 6 is a graph showing the adsorption capacity of semicoke-based activated carbon on Cr (VI) -containing wastewater as a function of time in the first embodiment;
FIG. 7 is a graph showing the adsorption capacity of semicoke-based activated carbon on Cr (VI) -containing wastewater as a function of time in example II;
FIG. 8 is a graph showing the adsorption capacity of semicoke-based activated carbon on Cr (VI) -containing wastewater as a function of time in the third embodiment;
FIG. 9 is a graph showing the adsorption capacity of semicoke-based activated carbon with respect to Cr (VI) -containing wastewater with time, in the fourth embodiment.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, not all of the embodiments, and are not intended to limit the scope of the present disclosure. Moreover, in the following description, descriptions of well-known structures and techniques are omitted so as to not unnecessarily obscure the concepts of the present disclosure. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The method for preparing the semicoke-based activated carbon by the ball-milling assisted organic fermentation technology comprises the following steps:
1) ball-milling the blocky semicoke to obtain semicoke powder;
2) dissolving organic matters in water, adding semi-coke powder, stirring uniformly, and fermenting to obtain fermented semi-coke;
3) and (3) activating the fermented semicoke at high temperature, and then washing and drying to obtain the semicoke-based activated carbon.
In the step 1), ball milling is carried out on the blocky carbocoal by a high-energy ball mill, wherein the rotating speed of the high-energy ball mill is 100-500rpm, and the ball milling time is 4-10 h.
The mesh number of the semi-coke powder is less than or equal to 200 meshes.
The organic matter is one or a mixture of more of starch, glucose and maltose.
Fermentation powder is added in the fermentation process.
The mass ratio of the fermentation powder, the organic matter, the water and the semicoke is (0.01-0.05): (0.1-0.3): (1-3): (1-2).
The temperature of the fermentation process is 20-60 ℃.
The specific operation of the step 3) is as follows:
and (3) activating the fermented semicoke at high temperature by adopting a high-temperature tube furnace, washing by using hydrochloric acid and distilled water, then carrying out vacuum drying, and finally carrying out sealed preservation.
In the high-temperature activation process, the temperature rise time of the high-temperature tube furnace is 40-160min, the activation temperature is 800-900 ℃, the activation time is 120-180min, and the activation gas is CO2The gas flow of the gas and the activating gas is 30-80 mL.
The adsorption performance of the sample is used as the adsorption capacity of the wastewater containing Cr (VI) as an index for evaluation, and the adsorption process is as follows: first, 100mg/L of K is prepared2Cr2O7The solution simulates wastewater containing Cr (VI), semicoke-based activated carbon is added under the constant temperature condition, the rotating speed of a rotor is adjusted to 250rpm, an ultraviolet spectrophotometer (UV1900PPC, Shanghai Asia-research electronic technology Co., Ltd.) is used for testing by intermittent sampling, and the tested samples are filtered by a water system (PES) filter membrane of Jinteng 13 x 0.22 mu m. In the experiment, the pH value of the solution is adjusted to 2-7, the mass of the adsorbent is 0.05-0.25g, and the adsorption temperature is adjusted toThe optimal adsorption condition of the semicoke-based activated carbon for adsorbing Cr (VI) is explored at the temperature of 25-45 ℃ for 240min, and the saturated adsorption quantity and the removal rate of the sample are calculated by the following formulas:
wherein q iseThe amount of Cr (VI) adsorbed per unit mass of adsorbent when equilibrium is reached, c0Is the initial concentration of Cr (VI) in the solution, ceConcentration of Cr (VI) in solution for equilibrium adsorption, ctThe concentration of Cr (VI) in the solution at the moment of adsorption t, V, the volume of the solution, m, the dosage of the adsorbent and R, the removal rate of the adsorbent to the Cr (VI) at the moment of adsorption t.
Example one
The method for preparing the semicoke-based activated carbon by the ball-milling assisted organic fermentation technology comprises the following steps:
1) taking 30g of block semicoke, and then placing the block semicoke in a ball mill for ball milling for 4 hours to obtain powdery semicoke;
2) dissolving 3g of starch and 0.3g of fermentation powder in 30mL of aqueous solution, uniformly stirring, adding 30g of semi-coke powder, fermenting at 40 ℃, sampling after fermenting for 14 days, and then drying, sealing and storing;
3) taking 5g of fermented semicoke material, and performing high temperature activation treatment, wherein the activation temperature is controlled at 800 deg.C, the temperature rise time is 90min, the activation time is 120min, and CO is used2And (3) taking the gas flow as an activating agent, wherein the gas flow is 30mL/min, and after activation, carrying out vacuum drying on the obtained semicoke-based activated carbon at 120 ℃, and then sealing and storing to obtain the semicoke-based activated carbon.
FIG. 6 shows the relationship between the adsorption capacity of semicoke-based activated carbon for Cr (VI) -containing wastewater with time, and the specific conditions for adsorption were as follows: the solution containing Cr (VI) is 100mL, the pH value is 2, the mass of the adsorbent is 0.1g, the adsorption temperature is 25 ℃, and the adsorption time is 240 min.
The preparation and performance parameters of the activated carbon in the first example are summarized in table 1:
TABLE 1
Example two
The method for preparing the semicoke-based activated carbon by the ball-milling assisted organic fermentation technology comprises the following steps:
1) placing 30g of block semicoke in a ball mill for ball milling for 6 hours to obtain powdery semicoke;
2) dissolving 3g of starch and 0.3g of fermentation powder in 30mL of aqueous solution, uniformly stirring, adding 30g of semi-coke powder, fermenting at 40 ℃, sampling after fermenting for 14 days, and then drying, sealing and storing;
3) performing high-temperature activation treatment on 5g of fermented semi-coke material, wherein the activation temperature is controlled to be 800 ℃, the temperature rise time is 90min, the activation time is 180min, and CO is used2The gas flow is 30mL/min as an activating agent, and the activated semicoke-based activated carbon is dried in vacuum at 120 ℃ and then sealed for storage.
FIG. 7 is a graph showing the relationship between the adsorption capacity of a semicoke-based adsorbent for Cr (VI) -containing wastewater with time, wherein the specific adsorption conditions are as follows: the solution containing Cr (VI) is 100mL, the pH value is 2, the mass of the adsorbent is 0.1g, the adsorption temperature is 25 ℃, and the adsorption time is 240 min.
The preparation of activated carbon and summary of performance parameters in example two are shown in Table 2
TABLE 2
EXAMPLE III
The method for preparing the semicoke-based activated carbon by the ball-milling assisted organic fermentation technology comprises the following steps:
1) grinding 30g of block semicoke in a ball mill for 8 hours to obtain powdery semicoke;
2) dissolving 3g of starch and 0.3g of fermentation powder in 30mL of aqueous solution, uniformly stirring, adding 30g of semi-coke powder, fermenting at 40 ℃, sampling after fermenting for 14 days, and drying, sealing and storing the sample;
3) performing high-temperature activation treatment on 5g of fermented semi-coke material, wherein the activation temperature is controlled to be 850 ℃, the temperature rise time is 90min, the activation time is 120min, and CO is used2The gas flow is 30mL/min as an activating agent, and the activated semicoke-based activated carbon is dried in vacuum at 120 ℃ and then sealed for storage.
FIG. 8 shows the relationship between the adsorption capacity of the semicoke-based adsorbent for Cr (VI) -containing wastewater with time, and specific adsorption conditions were as follows: the solution containing Cr (VI) is 100mL, the pH value is 2, the mass of the adsorbent is 0.1g, the adsorption temperature is 25 ℃, and the adsorption time is 240 min.
The preparation and performance parameters of the activated carbon in the third example are summarized in table 3;
TABLE 3
Fig. 1 is a scanning electron microscope image of a semicoke raw material, fermented semicoke and semicoke-based activated carbon in example three, wherein (a1-a2) in fig. 1 is the semicoke raw material, b1-b2 is the semicoke raw material after fermentation, and c1-c2 is the semicoke-based activated carbon, and it can be seen from fig. 1 that the semicoke raw material has a smooth and dense surface, the semicoke surface after fermentation is slightly rough, the semicoke-based activated carbon has a rough surface and a developed pore structure, which shows that the present invention has a good pore-enlarging effect on the semicoke-based activated carbon.
Fig. 2 is a fourier transform infrared spectrum of a semicoke-based activated carbon and a semicoke raw material sample in example three, and as can be seen from fig. 2, the infrared spectrum of the semicoke raw material is almost a straight line, which shows that the surface of the semicoke raw material is almost free from functional groups, but the surface of the semicoke-based activated carbon contains abundant active functional groups such as-OH, C-C, C-O, C-OH and the like, which shows that the surface chemical properties of the semicoke-based activated carbon can be greatly improved by the present invention.
FIG. 3 is the adsorption and desorption curves of the semicoke-based activated carbon and the semicoke raw material in the third example, and the BET calculation formula can obtain that the specific surface area of the semicoke-based activated carbon reaches 844.2m2Per g, compared with the specific surface area of the raw material of 46.9m2The specific surface area of the semi-coke activated carbon is 18 times higher than that of the semi-coke activated carbon.
Fig. 4 is a pore size distribution graph of the semicoke-based activated carbon and the semicoke raw material in the third example, and it can be seen from fig. 4 that the semicoke-based activated carbon has a good micro-mesoporous structure.
FIG. 5 is a graph showing the adsorption of Cr (VI) by the semicoke-based activated carbon and the semicoke raw material in example III. As can be seen from FIG. 5, Cr (VI) is rapidly adsorbed by the semicoke-based activated carbon 200min before adsorption, and the adsorption equilibrium is substantially reached within 20 min. Under the optimal condition of adsorption, the adsorption capacity of the semicoke-based adsorption material on Cr (VI) is 102.4mg/g, and the adsorption capacity of the semicoke raw material on Cr (VI) is 12.6mg/g, which indicates that the semicoke-based activated carbon prepared by the method has good adsorption effect.
Example four
The method for preparing the semicoke-based activated carbon by the ball-milling assisted organic fermentation technology comprises the following steps:
1) grinding 30g of block semicoke in a ball mill for 10 hours to obtain powdery semicoke;
2) dissolving 3g of starch and 0.3g of fermentation powder in 30mL of aqueous solution, uniformly stirring, adding 30g of semi-coke powder, fermenting at 40 ℃, sampling after fermenting for 14 days, and finally drying, sealing and storing the sample;
3) performing high temperature activation treatment on 5g of fermented semicoke material, controlling the activation temperature to be 850 ℃, the temperature rise time to be 90min, the activation time to be 180min, and using CO2The gas flow is 30mL/min as an activating agent, and the activated semicoke-based activated carbon is subjected to vacuum drying at 120 DEG CDrying, and sealing for storage.
FIG. 9 shows the relationship between the adsorption capacity of the semicoke-based adsorbent for Cr (VI) -containing wastewater with time, and specific adsorption conditions were as follows: the solution containing Cr (VI) is 100mL, the pH value is 2, the mass of the adsorbent is 0.1g, the adsorption temperature is 25 ℃, and the adsorption time is 240 min.
The preparation and performance parameters of the activated carbon in the fourth example are summarized in table 4;
TABLE 4
EXAMPLE five
The method for preparing the semicoke-based activated carbon by the ball-milling assisted organic fermentation technology comprises the following steps:
1) ball-milling the blocky semicoke to obtain semicoke powder;
2) dissolving organic matters in water, adding semi-coke powder, stirring uniformly, and fermenting to obtain fermented semi-coke;
3) and (3) activating the fermented semicoke at high temperature, and then washing and drying to obtain the semicoke-based activated carbon.
In the step 1), ball milling is carried out on the blocky semicoke by a high-energy ball mill, wherein the rotating speed of the high-energy ball mill is 100rpm, and the ball milling time is 4 h.
The mesh number of the semi-coke powder is less than or equal to 200 meshes.
The organic matter is starch.
Fermentation powder is added in the fermentation process.
The mass ratio of the fermentation powder to the organic matter to the water to the semicoke is 0.01: 0.1: 1: 1.
the temperature during the fermentation was 20 ℃.
The specific operation of the step 3) is as follows:
and (3) activating the fermented semicoke at high temperature by adopting a high-temperature tube furnace, washing by using hydrochloric acid and distilled water, then carrying out vacuum drying, and finally carrying out sealed preservation.
During the high temperature activation, highThe temperature rise time of the warm tube furnace is 40min, the activation temperature is 800 ℃, the activation time is 120min, and the activation gas is CO2The gas flow rate of the gas and the activating gas was 30 mL.
EXAMPLE six
The method for preparing the semicoke-based activated carbon by the ball-milling assisted organic fermentation technology comprises the following steps:
1) ball-milling the blocky semicoke to obtain semicoke powder;
2) dissolving organic matters in water, adding semi-coke powder, stirring uniformly, and fermenting to obtain fermented semi-coke;
3) and (3) activating the fermented semicoke at high temperature, and then washing and drying to obtain the semicoke-based activated carbon.
In the step 1), ball milling is carried out on the blocky semicoke by a high-energy ball mill, wherein the rotating speed of the high-energy ball mill is 500rpm, and the ball milling time is 10 hours.
The mesh number of the semi-coke powder is less than or equal to 200 meshes.
The organic matter is glucose.
Fermentation powder is added in the fermentation process.
The mass ratio of the fermentation powder to the organic matter to the water to the semicoke is 0.05: 0.3: 3: 2.
the temperature during the fermentation was 60 ℃.
The specific operation of the step 3) is as follows:
and (3) activating the fermented semicoke at high temperature by adopting a high-temperature tube furnace, washing by using hydrochloric acid and distilled water, then carrying out vacuum drying, and finally carrying out sealed preservation.
In the high-temperature activation process, the temperature rise time of the high-temperature tube furnace is 160min, the activation temperature is 900 ℃, the activation time is 180min, and the activated gas is CO2The gas flow rate of the gas, activation gas was 80 mL.
EXAMPLE seven
The method for preparing the semicoke-based activated carbon by the ball-milling assisted organic fermentation technology comprises the following steps:
1) ball-milling the blocky semicoke to obtain semicoke powder;
2) dissolving organic matters in water, adding semi-coke powder, stirring uniformly, and fermenting to obtain fermented semi-coke;
3) and (3) activating the fermented semicoke at high temperature, and then washing and drying to obtain the semicoke-based activated carbon.
In the step 1), ball milling is carried out on the blocky semicoke by a high-energy ball mill, wherein the rotating speed of the high-energy ball mill is 300rpm, and the ball milling time is 6 h.
The mesh number of the semi-coke powder is less than or equal to 200 meshes.
The organic matter is maltose.
Fermentation powder is added in the fermentation process.
The mass ratio of the fermentation powder to the organic matter to the water to the semicoke is 0.030.2: 2: 1.5.
the temperature during the fermentation was 45 ℃.
The specific operation of the step 3) is as follows:
and (3) activating the fermented semicoke at high temperature by adopting a high-temperature tube furnace, washing by using hydrochloric acid and distilled water, then carrying out vacuum drying, and finally carrying out sealed preservation.
In the high-temperature activation process, the temperature rise time of the high-temperature tube furnace is 100min, the activation temperature is 850 ℃, the activation time is 150min, and the activated gas is CO2The gas flow rate of the gas, activation gas was 60 mL.
Example eight
The method for preparing the semicoke-based activated carbon by the ball-milling assisted organic fermentation technology comprises the following steps:
1) ball-milling the blocky semicoke to obtain semicoke powder;
2) dissolving organic matters in water, adding semi-coke powder, stirring uniformly, and fermenting to obtain fermented semi-coke;
3) and (3) activating the fermented semicoke at high temperature, and then washing and drying to obtain the semicoke-based activated carbon.
In the step 1), ball milling is carried out on the blocky semicoke by a high-energy ball mill, wherein the rotating speed of the high-energy ball mill is 100rpm, and the ball milling time is 10 hours.
The mesh number of the semi-coke powder is less than or equal to 200 meshes.
The organic matter is a mixture of glucose and maltose.
Fermentation powder is added in the fermentation process.
The mass ratio of the fermentation powder to the organic matter to the water to the semicoke is 0.01: 0.3: 3: 1.
the temperature during the fermentation was 60 ℃.
The specific operation of the step 3) is as follows:
and (3) activating the fermented semicoke at high temperature by adopting a high-temperature tube furnace, washing by using hydrochloric acid and distilled water, then carrying out vacuum drying, and finally carrying out sealed preservation.
In the high-temperature activation process, the temperature rise time of the high-temperature tube furnace is 160min, the activation temperature is 800 ℃, the activation time is 180min, and the activated gas is CO2The gas flow rate of the gas and the activating gas was 30 mL.
Example nine
The method for preparing the semicoke-based activated carbon by the ball-milling assisted organic fermentation technology comprises the following steps:
1) ball-milling the blocky semicoke to obtain semicoke powder;
2) dissolving organic matters in water, adding semi-coke powder, stirring uniformly, and fermenting to obtain fermented semi-coke;
3) and (3) activating the fermented semicoke at high temperature, and then washing and drying to obtain the semicoke-based activated carbon.
In the step 1), ball milling is carried out on the blocky semicoke by a high-energy ball mill, wherein the rotating speed of the high-energy ball mill is 500rpm, and the ball milling time is 4 hours.
The mesh number of the semi-coke powder is less than or equal to 200 meshes.
The organic matter is a mixture of starch, glucose and maltose.
Fermentation powder is added in the fermentation process.
The mass ratio of the fermentation powder to the organic matter to the water to the semicoke is 0.020.15: 1.8: 1.8.
the temperature during the fermentation was 30 ℃.
The specific operation of the step 3) is as follows:
and (3) activating the fermented semicoke at high temperature by adopting a high-temperature tube furnace, washing by using hydrochloric acid and distilled water, then carrying out vacuum drying, and finally carrying out sealed preservation.
In the high-temperature activation process, the temperature rise time of the high-temperature tube furnace is 40-160min, the activation temperature is 820 ℃, the activation time is 170min, and the activated gas is CO2The gas flow rate of the gas, activation gas was 70 mL.
Claims (9)
1. A method for preparing semicoke-based activated carbon by a ball milling assisted organic fermentation technology is characterized by comprising the following steps:
1) ball-milling the blocky semicoke to obtain semicoke powder;
2) dissolving organic matters in water, adding semi-coke powder, stirring uniformly, and fermenting to obtain fermented semi-coke;
3) and (3) activating the fermented semicoke at high temperature, and then washing and drying to obtain the semicoke-based activated carbon.
2. The method for preparing semicoke-based activated carbon by using the ball-milling assisted organic fermentation technology as claimed in claim 1, wherein in the step 1), the blocky semicoke is ball-milled by using a high-energy ball mill, wherein the rotating speed of the high-energy ball mill is 100-500rpm, and the ball-milling time is 4-10 h.
3. The method for preparing semicoke-based activated carbon by using ball milling assisted organic fermentation technology as claimed in claim 1, wherein the mesh number of the semicoke powder is not more than 200 meshes.
4. The method for preparing semicoke-based activated carbon by using the ball milling assisted organic fermentation technology as claimed in claim 1, wherein the organic matter is one or a mixture of starch, glucose and maltose.
5. The method for preparing semicoke-based activated carbon by using ball milling assisted organic fermentation technology as claimed in claim 1, wherein fermentation powder is added during the fermentation process.
6. The method for preparing semicoke-based activated carbon by using ball milling assisted organic fermentation technology as claimed in claim 5, wherein the mass ratio of the fermentation powder, the organic matter, the water and the semicoke is (0.01-0.05): (0.1-0.3): (1-3): (1-2).
7. The method for preparing semicoke-based activated carbon by using ball milling assisted organic fermentation technology as claimed in claim 1, wherein the temperature of the fermentation process is 20-60 ℃.
8. The method for preparing semicoke-based activated carbon by using ball milling assisted organic fermentation technology as claimed in claim 1, wherein the specific operation of the step 3) is as follows:
and (3) activating the fermented semicoke at high temperature by adopting a high-temperature tube furnace, washing by using hydrochloric acid and distilled water, then carrying out vacuum drying, and finally carrying out sealed preservation.
9. The method for preparing semicoke-based activated carbon by ball milling assisted organic fermentation technology as claimed in claim 8, wherein in the high temperature activation process, the temperature rise time of the high temperature tube furnace is 40-160min, the activation temperature is 800-2The gas flow of the gas and the activating gas is 30-80 mL.
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| CN114804104A (en) * | 2022-02-21 | 2022-07-29 | 江苏联兴成套设备制造有限公司 | Organic fermentation reinforced CO 2 Method for regenerating waste active carbon by activating pore-forming |
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