CN110745824A - Method for regulating and controlling coal-based porous carbon pore matching based on trace potassium source catalytic activation - Google Patents
Method for regulating and controlling coal-based porous carbon pore matching based on trace potassium source catalytic activation Download PDFInfo
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Abstract
A method for regulating and controlling coal-based porous carbon pore matching based on trace potassium source catalytic activation relates to a preparation method of a porous carbon material. The invention aims to solve the problems of insufficient specific surface area/pore structure development in the traditional physical activation preparation process of the coal-based porous carbon and large dosage of an activating agent in the chemical activation process. The method takes coal as a raw material, utilizes the catalytic action of potassium-based metal salt on the physical activation process, and strengthens the development of the pore volume and the specific surface area of the porous carbon in the preparation process. Comprises (1) refining raw materials, (2) adding potassium-based substances, (3) activating at high temperature, (4) cleaning activated products, (5) and drying. The depth regulation and control of the average pore diameter and the pore matching are realized by changing the species and the addition proportion of the sylvite, and the specific surface area can reach 1283.6m at most2(g) total pore volume can be up to 0.93cm3(ii) in terms of/g. The method can be used for synthesizing coal base with excellent performance in different fields of catalysis, gas adsorption, separation and the likeA porous carbon material.
Description
Technical Field
The invention relates to a preparation method of a porous carbon material, and particularly relates to a method for regulating and controlling coal-based porous carbon pore matching based on trace potassium source catalytic activation.
Background
The porous carbon material is a carbon material with pore structures of different sizes, and the size and the shape of the internal pores can be regulated and controlled according to the actual application requirements. The porous carbon material has the advantages of high chemical stability, adjustable physical and chemical structure, wide raw material source and the like, and is widely applied to the fields of pollutant adsorption, gas storage, water purification, catalysis and photocatalysis. The definition of the international union of pure and applied chemistry divides the pores within carbon materials into three categories by pore size: micropores (pore diameter <2nm), mesopores (pore diameter 2-50 nm) and macropores (pore diameter >50 nm). According to the structure-action mechanism, the main functions exerted by pores of different sizes in the reaction process are different, and taking the adsorption process as an example, the adsorption storage performance of the porous carbon material depends on the matching relationship between the pore structure and the kinetic diameter of adsorbates (gas molecules, liquid phase molecules). For porous carbon materials, one of the most critical evaluation parameters is pore size distribution, and porous carbon materials can be classified into microporous carbon, mesoporous carbon and hierarchical porous carbon according to the proportion of mesoporous and macroporous structures in the materials. Generally, microporous carbon materials are commonly used for adsorbing small molecular gas pollutants, medium-large porous carbon materials are commonly used for purifying high molecular water pollutants or carrying catalysts, and graded porous carbon materials can be used as excellent electrochemical cathode materials or have the excellent characteristics of microporous carbon and medium-large porous carbon.
The common preparation methods of porous carbon mainly comprise a carbonization activation method and a soft-hard template method, wherein the carbonization activation method can be further divided into a physical activation method, a chemical activation method, a hydrothermal method and the like. Among the various production methods, how to realize cost-effective production of porous carbon based on a simple process and a wide range of raw materials has been a problem of attention. Coal is a fossil fuel with huge reserves, and by 2017, the resource reserves of 16666.73 hundred million tons of coal in China are found out, the resource reserves are increased by 4.3 percent on a par, the cost can be greatly reduced by using the coal as a raw material to produce porous carbon, and the method has wide and continuous development prospects. At present, home and abroad coal-based porous carbon production enterprises basically adopt a physical/chemical activation process, but the traditional physical/chemical activation method for preparing the coal-based porous carbon material still has the following problems:
(1) due to the complexity of the intrinsic physicochemical structure of the feed coal, pore formation by traditional physical activation is generally limited by the lower reactivity between the coal structure and the gaseous activating agent, resulting in insufficient development of the specific surface area/pore structure of the coal-based activated coke. At the moment, the methods of increasing the temperature, increasing the dosage of the activating agent and the like can cause more serious ineffective ablation of the carbon structure, so that the overall yield of the porous carbon is reduced, and the production economy is reduced.
(2) The traditional chemical activation method usually needs to additionally add an activating agent (KOH, H) which is about 4 to 8 times of the mass of the carbonaceous precursor3PO4、K2CO3Or ZnCl2Etc.), the subsequent treatment also requires the consumption of large amounts of water/acid, greatly increasing the production costs and the risk of environmental pollution. And the method is difficult to realize the depth adjustment of the pore matching group, and the application prospect of industrial large-scale production is limited.
Aiming at the key problems in the production process of the coal-based porous carbon, the development of the preparation method of the high-performance porous carbon with adjustable physicochemical structure, simple process and low cost is an important research direction.
Disclosure of Invention
The invention aims to solve the problems of insufficient specific surface area/pore development, large dosage of activating agent required by a chemical activation method and high cost in the traditional method for preparing the coal-based porous carbon by physical activation, and provides a method for regulating and controlling pore composition of the coal-based porous carbon by catalytic activation based on a trace potassium source.
The invention provides a method for regulating and controlling pore matching of coal-based porous carbon by adding catalytic activation based on a trace potassium source by utilizing the catalytic action of potassium-based metal salt on carbon gasification reaction, and the development of pore volume and specific surface area of the porous carbon in the preparation process is enhanced. The average pore diameter and pore matching of the porous carbon are deeply regulated and controlled by changing the variety and the addition proportion of the potassium salt, and the high-performance porous carbon material suitable for different fields (such as adsorption, catalysis and the like) is obtained based on the simple, feasible and low-cost synthesis method.
The invention relates to a method for regulating and controlling coal-based porous carbon pore matching based on trace potassium source catalytic activation, which comprises the following steps:
firstly, refining raw materials
Sequentially crushing, grinding and screening raw coal to obtain refined coal powder or coal particles;
addition of potassium-based substance
Adding a potassium-based substance into the refined coal powder or coal particles by physical mixing, liquid-phase impregnation, ultrasonic penetration or mechanical ball milling to obtain a uniform mixture;
the potassium-based substance is one or a mixture of more of potassium carbonate, potassium chloride, potassium sulfate, potassium nitrate, potassium acetate, tripotassium phosphate, monopotassium phosphate and potassium citrate according to any proportion;
third, high temperature activation
Placing the mixture in the second step into an atmosphere furnace, heating to raise the temperature, keeping the mixture at a constant temperature, and naturally cooling the atmosphere furnace to room temperature after the constant temperature is finished to obtain an activated product;
fourthly, cleaning the activated product
Carrying out acid washing treatment and deionized water washing treatment on the activated product in sequence until the pH of the supernatant is 6.5-7.5 to obtain a washed activated product;
fifthly, drying
Drying the activated product after cleaning in the fourth step to obtain the coal-based porous carbon material;
the mass ratio of the refined coal powder or coal particles to the potassium element in the potassium-based substance is 1: (0.001-0.1).
The principle and the beneficial effects of the invention are as follows:
the invention provides a method for regulating and controlling coal-based porous carbon pore matching based on trace potassium source catalytic activation. The previous research of the invention shows that the content of potassium-based mineral substances in the inherent ash content of the coal is only about 1 wt-%, and the promotion effect of trace potassium on the development of pore structures is very large, so that the conclusion that the addition of potassium-based substances has better catalysis effect on the traditional physical activation coke making process can be inferred. The discovery lays a foundation for providing a method for regulating and controlling the pore matching of the coal-based porous carbon by the catalytic activation of the trace potassium source.
The specific method comprises the following steps: coal is used as a raw material, and trace potassium-based substances are uniformly distributed in the structure of the coal through liquid-phase impregnation, ultrasonic treatment or mechanochemical ball milling and mixing. And then, carrying out high-temperature activation treatment on the sample in an active atmosphere, and promoting the development of the specific surface area and the pore structure of the sample in the preparation process by utilizing the catalytic action of potassium. And the deep regulation and control of porous carbon pore matching are realized by changing the species and proportion of the added potassium-based substances, and microporous carbon with a developed structure or hierarchical porous carbon with coexistent micropores, mesopores and macropores is obtained.
Compared with the prior art, the method has the advantages that:
firstly, the raw material for synthesizing the porous carbon can adopt one or more mixed coal of lignite, bituminous coal, subbituminous coal or anthracite, and has wide adaptability to coal types. The coal is the most common fossil energy in China, has the advantages of low cost, wide source, large reserve and the like, and has lower cost and wider application prospect compared with other raw materials (such as high molecular polymers) for synthesizing the porous carbon material by taking the coal as a carbon source.
Secondly, the invention introduces a very trace amount of potassium-based substances to CO2The reaction process of activating pore-forming with coal matrix plays a role of catalysis, the development of specific surface area and pore volume is promoted, and the specific surface area of the obtained graded pore carbon can reach 1283.6m2Per g, total pore volume 0.93cm3The pore grading degree (the proportion of the mesopore volume to the total pore volume) is 43 percent, and the specific surface area of the obtained microporous carbon can reach 1036.6m at most2(ii) in terms of/g. The amount of the potassium-based substances added in the method is only one hundred times of that of the traditional chemical activation process, and the subsequent treatment process only needs a very small amount of acid/water washing, so that the method is relatively simple in process and has little pollution to the ecological environment. Compared with the traditional chemical activation method, the method reduces the production cost and has the potential of enlarging production.
The invention finds that the addition amount of the potassium salt plays a crucial role in the porous carbon pore structure: when the addition ratio of the potassium salt is more than 2%, the catalytic effect on the traditional physical activation process is stronger, the reaction process is quicker and more violent, even the collapse of pores and the increase of ineffective ablation are caused, and the development of the pore structure is not facilitated; further increasing the addition rate to above 10% leads to a deterioration in the overall economics of the technology, does not meet the concept of trace additions, and suffers from more severe ineffective ablation during coke making, reducing the final yield.
Thirdly, the traditional porous carbon preparation usually needs to be performed with pre-carbonization treatment and then activation, and the process is complicated. According to the invention, the potassium-based substance and the coal are mixed and then directly subjected to one-step activation treatment in the atmosphere furnace, so that the porous carbon with a developed structure can be obtained, the method is simple, and the process difficulty is reduced.
Compared with the traditional physical/chemical activation process, the porous carbon material with different pore size distributions and pore matching groups can be obtained only by regulating and controlling the variety and content of the potassium-based substance, which is the innovative discovery of the invention, and no relevant report is given in the existing method. The invention successfully obtains the microporous carbon and the hierarchical porous carbon with coexisting micropores/mesopores by utilizing the difference of the performances of different potassium salts in the catalytic activation process, and realizes the deep regulation and control of the pore matching by setting different addition amounts. The invention can be used for synthesizing the porous carbon material with excellent performance in different fields such as electrochemistry, catalysis, gas adsorption separation and the like.
Drawings
FIG. 1 is a nitrogen adsorption isotherm of a coal-based porous carbon material prepared in example 1;
FIG. 2 is a nitrogen adsorption isotherm of the coal-based porous carbon material prepared in example 2;
FIG. 3 is a nitrogen adsorption isotherm of the coal-based porous carbon material prepared in example 3;
FIG. 4 is a nitrogen adsorption isotherm of a coal-based porous carbon material prepared in a comparative example.
Detailed Description
The first embodiment is as follows: the method for regulating and controlling the pore matching of the coal-based porous carbon based on the catalytic activation of the trace potassium source comprises the following steps:
firstly, refining raw materials
Sequentially crushing, grinding and screening raw coal to obtain refined coal powder or coal particles;
addition of potassium-based substance
Adding a potassium-based substance into the refined coal powder or coal particles by physical mixing, liquid-phase impregnation, ultrasonic penetration or mechanical ball milling to obtain a uniform mixture;
the potassium-based substance is one or a mixture of more of potassium carbonate, potassium chloride, potassium sulfate, potassium nitrate, potassium acetate, tripotassium phosphate, monopotassium phosphate and potassium citrate according to any proportion;
third, high temperature activation
Placing the mixture in the second step into an atmosphere furnace, heating to raise the temperature, keeping the mixture at a constant temperature, and naturally cooling the atmosphere furnace to room temperature after the constant temperature is finished to obtain an activated product;
fourthly, cleaning the activated product
Carrying out acid washing treatment and deionized water washing treatment on the activated product in sequence until the pH of the supernatant is 6.5-7.5 to obtain a washed activated product;
fifthly, drying
Drying the activated product after cleaning in the fourth step to obtain the coal-based porous carbon material;
the mass ratio of the refined coal powder or coal particles to the potassium element in the potassium-based substance is 1: (0.001-0.1).
The second embodiment is as follows: the same as the first embodiment is that: step one, the raw coal is one or a mixture of more of lignite, bituminous coal, subbituminous coal or anthracite according to any proportion. The rest is the same as the first embodiment.
The third concrete implementation mode: the same as the first embodiment is that: and step two, the mass ratio of the refined coal powder or coal particles to the potassium element in the potassium-based substance is 1: (0.001-0.05). The rest is the same as the first embodiment.
The fourth concrete implementation mode: the same as the first embodiment is that: heating in water bath, heat tracing or platform contact heating is adopted in the liquid phase impregnation method; the ball milling tank in the ball milling method is made of agate, corundum or stainless steel. The rest is the same as the first embodiment.
The fifth concrete implementation mode: the same as the first embodiment is that: and step three, the temperature rise and constant temperature treatment is to raise the temperature of the atmosphere furnace to 600-1000 ℃ and keep the temperature for 0.1-10 h. The rest is the same as the first embodiment.
The sixth specific implementation mode: the same as the first embodiment is that: and step three, the temperature rise rate of the atmosphere furnace is 0.1-100 ℃/min. The rest is the same as the first embodiment.
The seventh embodiment: the same as the first embodiment is that: step three, the atmosphere in the atmosphere furnace is CO2Mixed atmosphere consisting of water vapor and inert gas or mixed atmosphere consisting of water vapor and inert gas; the CO is2CO in mixed atmosphere with inert gas2And the volume ratio of the inert gas to the inert gas is (0.1-10): 1; the volume ratio of the water vapor to the inert gas in the mixed atmosphere consisting of the water vapor and the inert gas is (0.1-10): 1. the rest is the same as the first embodiment.
The specific implementation mode is eight: the same as the first embodiment is that: and step three, the inert gas is high-purity nitrogen or high-purity argon. The rest is the same as the first embodiment.
The specific implementation method nine: the same as the first embodiment is that: and step four, adopting a pickling solution of glacial acetic acid, dilute hydrochloric acid, dilute sulfuric acid or dilute nitric acid during pickling treatment. The rest is the same as the first embodiment.
The detailed implementation mode is ten: the same as the first embodiment is that: and fifthly, the temperature during drying treatment is 60-200 ℃, and the drying mode is vacuum drying, hot air drying, flat contact drying and natural drying. The rest is the same as the first embodiment.
The invention is not limited to the above embodiments, and one or a combination of several embodiments may also achieve the object of the invention.
The following examples were used to demonstrate the beneficial effects of the present invention:
example 1: in this embodiment, the method for regulating and controlling the coal-based porous carbon pore matching through the catalytic activation of the trace potassium source is performed according to the following steps:
firstly, refining raw materials
Sequentially crushing, grinding and screening the east-west bituminous coal to obtain refined coal powder;
the grain size of the refined coal powder is 160 meshes;
addition of potassium-based substance
Will be provided withPotassium carbonateAdding the mixture into the refined coal powder or coal particles by a liquid phase impregnation method to obtain a uniform mixture;
the mass ratio of the refined coal powder or coal particles to potassium element in potassium carbonate is1：0.001(ii) a The liquid phase impregnation method adopts water bath heating;
third, high temperature activation
Placing the mixture in the second step into an atmosphere furnace, heating the atmosphere furnace to 900 ℃, preserving heat for 1h, and naturally cooling the atmosphere furnace to room temperature after the heat preservation is finished to obtain an activated product;
the temperature rise rate of the atmosphere furnace is 10 ℃/min;
the atmosphere in the atmosphere furnace is CO2And inert gas; the CO is2CO in mixed atmosphere with inert gas2And inert gas in a volume ratio of 0.67: 1; the inert gas is high-purity nitrogen;
fourthly, cleaning the activated product
Sequentially carrying out acid washing treatment and deionized water washing treatment on the activated product until the supernatant is nearly neutral to obtain a washed activated product;
the pickling solution adopted in the pickling treatment is dilute hydrochloric acid;
fifthly, drying
Drying the activated product after cleaning in the fourth step to obtain the coal-based porous carbon material;
the drying mode is hot air drying.
FIG. 1 is an adsorption isotherm of coal-based porous carbon prepared by catalytic activation with trace potassium carbonate in example 1, and based on FIG. 1, it can be calculated that the specific surface area of the porous activated carbon material obtained in example 1 is as high as 1029.3m2Per g, pore volume of 0.66cm3The/g, adsorption isotherm is type I, indicating that the porous carbon is a microporous material.
Example 2: in this embodiment, the method for regulating and controlling the coal-based porous carbon pore matching through the catalytic activation of the trace potassium source is performed according to the following steps:
firstly, refining raw materials
Sequentially crushing, grinding and screening the east-west bituminous coal to obtain refined coal powder;
the grain size of the refined coal powder is 160 meshes;
addition of potassium-based substance
Will be provided withTripotassium phosphateAdding the mixture into the refined coal powder or coal particles by a liquid phase impregnation method to obtain a uniform mixture;
the mass ratio of the refined coal powder or coal particles to the potassium element in the tripotassium phosphate is1：0.001(ii) a The liquid phase impregnation method adopts water bath heating;
third, high temperature activation
Placing the mixture in the second step into an atmosphere furnace, heating the atmosphere furnace to 900 ℃, preserving heat for 1h, and naturally cooling the atmosphere furnace to room temperature after the heat preservation is finished to obtain an activated product;
the temperature rise rate of the atmosphere furnace is 10 ℃/min;
the atmosphere in the atmosphere furnace is CO2And inert gas; the CO is2CO in mixed atmosphere with inert gas2And inert gas in a volume ratio of 0.67: 1; the inert gas is high-purity nitrogen;
fourthly, cleaning the activated product
Sequentially carrying out acid washing treatment and deionized water washing treatment on the activated product until the supernatant is nearly neutral to obtain a washed activated product;
the pickling solution adopted in the pickling treatment is dilute hydrochloric acid;
fifthly, drying
Drying the activated product after cleaning in the fourth step to obtain the coal-based porous carbon material;
the drying mode is hot air drying.
FIG. 2 is an adsorption isotherm of coal-based porous carbon obtained by catalytic activation with trace amounts of tripotassium phosphate in example 2, and based on FIG. 2, it can be calculated that the specific surface area of the porous activated carbon material obtained in example 2 is as high as 1103.9m2Per g, pore volume of 0.73cm3In/g, adsorption isotherm partial pressure (p/p)0) When the carbon pore volume is larger than 0.4, the carbon pore has a typical hysteresis loop, which indicates that the porous carbon is a hierarchical pore type carbon material with both micropores and mesopores, and the proportion of the mesopore volume to the total pore volume is 34% calculated by a BJH method. The structure is obviously different from the microporous carbon structure obtained by the catalytic activation of trace potassium carbonate in the example 1, which shows that the pore matching of the prepared porous carbon can be regulated and controlled by changing the type of the potassium source.
Example 3: in this embodiment, the method for regulating and controlling the coal-based porous carbon pore matching through the catalytic activation of the trace potassium source is performed according to the following steps:
firstly, refining raw materials
Sequentially crushing, grinding and screening the east-west bituminous coal to obtain refined coal powder;
the grain size of the refined coal powder is 160 meshes;
addition of potassium-based substance
Will be provided withTripotassium phosphateAdding the mixture into the refined coal powder or coal particles by a liquid phase impregnation method to obtain a uniform mixture;
the mass ratio of the refined coal powder or coal particles to the potassium element in the tripotassium phosphate is1：0.002(ii) a The liquid phase impregnation method adopts water bath heating;
third, high temperature activation
Placing the mixture in the second step into an atmosphere furnace, heating the atmosphere furnace to 900 ℃, preserving heat for 1h, and naturally cooling the atmosphere furnace to room temperature after the heat preservation is finished to obtain an activated product;
the temperature rise rate of the atmosphere furnace is 10 ℃/min;
the atmosphere in the atmosphere furnace isCO2And inert gas; the CO is2CO in mixed atmosphere with inert gas2And inert gas in a volume ratio of 0.67: 1; the inert gas is high-purity nitrogen;
fourthly, cleaning the activated product
Sequentially carrying out acid washing treatment and deionized water washing treatment on the activated product until the supernatant is nearly neutral to obtain a washed activated product;
the pickling solution adopted in the pickling treatment is dilute hydrochloric acid;
fifthly, drying
Drying the activated product after cleaning in the fourth step to obtain the coal-based porous carbon material;
the drying mode is hot air drying.
FIG. 3 is an adsorption isotherm of coal-based porous carbon obtained by catalytic activation with trace amounts of tripotassium phosphate in example 3, and based on FIG. 3, it can be calculated that the specific surface area of the porous activated carbon material obtained in example 3 is as high as 1283.6m2Per g, pore volume of 0.94cm3In/g, adsorption isotherm partial pressure (p/p)0) When the carbon material is larger than 0.4, the carbon material has an obvious hysteresis loop, which indicates that the porous carbon is a hierarchical pore type carbon material with both micropores and mesopores. Compared with the microporous carbon structure obtained by adding 1 wt-% of tripotassium phosphate for catalytic activation in example 2, the porous carbon with larger pore grading degree can be obtained by increasing the adding proportion of the tripotassium phosphate to 2 wt-%, and the proportion of the macroporous volume in the total pore volume is 44% calculated by the BJH method. This shows that the adjustment and control of the porous carbon pore matching can be realized by changing the addition amount of the trace potassium source.
Comparative example: in this embodiment, the method for regulating and controlling the coal-based porous carbon pore matching through the catalytic activation of the trace potassium source is performed according to the following steps:
firstly, refining raw materials
Sequentially crushing, grinding and screening the Dongdong acid-washed coal to obtain refined coal powder;
the grain size of the refined coal powder is 160 meshes;
second, high temperature activation
Placing the refined coal powder in the step one into an atmosphere furnace, heating the atmosphere furnace to 900 ℃, preserving heat for 1h, and naturally cooling the atmosphere furnace to room temperature after the heat preservation is finished to obtain an activated product;
the temperature rise rate of the atmosphere furnace is 10 ℃/min;
the atmosphere in the atmosphere furnace is CO2And inert gas; the CO is2CO in mixed atmosphere with inert gas2And inert gas in a volume ratio of 0.67: 1; the inert gas is high-purity nitrogen;
fourthly, cleaning the activated product
Sequentially washing the activated product with deionized water to obtain a washed activated product;
fifthly, drying
Drying the activated product after cleaning in the fourth step to obtain the coal-based porous carbon material;
the drying mode is hot air drying.
FIG. 4 shows the reaction of a conventional CO in a comparative example2The adsorption isotherm of the coal-based porous carbon prepared by the physical activation method can be calculated based on fig. 4, and the specific surface area of the porous activated carbon material obtained in the comparative example is only 478.9m2Per g, pore volume of 0.32cm3(ii) in terms of/g. Compared with the embodiments 1-3, the specific surface area and the pore volume of the porous carbon sample obtained in the comparative embodiment are far smaller than those of the porous carbon sample catalytically activated by the potassium-based substance, so that the superiority of the method provided by the invention compared with the traditional physical activation method is fully proved, and the development of the pore structure and the specific surface area in the activation process is promoted.
Claims (10)
1. A method for regulating and controlling coal-based porous carbon pore matching based on trace potassium source catalytic activation is characterized by comprising the following steps:
firstly, refining raw materials
Sequentially crushing, grinding and screening raw coal to obtain refined coal powder or coal particles;
addition of potassium-based substance
Adding a potassium-based substance into the refined coal powder or coal particles by physical mixing, liquid-phase impregnation, ultrasonic penetration or mechanical ball milling to obtain a uniform mixture;
the potassium-based substance is one or a mixture of more of potassium carbonate, potassium chloride, potassium sulfate, potassium nitrate, potassium acetate, tripotassium phosphate, monopotassium phosphate and potassium citrate according to any proportion;
third, high temperature activation
Placing the mixture in the second step into an atmosphere furnace, heating to raise the temperature, keeping the mixture at a constant temperature, and naturally cooling the atmosphere furnace to room temperature after the constant temperature is finished to obtain an activated product;
fourthly, cleaning the activated product
Carrying out acid washing treatment and deionized water washing treatment on the activated product in sequence until the pH of the supernatant is 6.5-7.5 to obtain a washed activated product;
fifthly, drying
Drying the activated product after cleaning in the fourth step to obtain the coal-based porous carbon material;
the mass ratio of the refined coal powder or coal particles to the potassium element in the potassium-based substance is 1: (0.001-0.1).
2. The method for regulating and controlling the pore composition of the coal-based porous carbon based on the catalytic activation of the trace potassium source according to claim 1, wherein in the step one, the raw coal is a mixture of one or more of lignite, bituminous coal, sub-bituminous coal or anthracite coal in any proportion.
3. The method for regulating and controlling the pore matching of the coal-based porous carbon based on the catalytic activation of the trace potassium source according to claim 1 or 2, wherein the mass ratio of the refined coal powder or coal particles to potassium element in the potassium-based substance in the step two is 1: (0.001-0.05).
4. The method for regulating and controlling the pore composition of the coal-based porous carbon based on the catalytic activation of the trace potassium source according to claim 1, wherein the liquid-phase impregnation method in the second step adopts water bath heating, heat tracing heating or platform contact heating; the ball milling tank in the ball milling method is made of agate, corundum or stainless steel.
5. The method for regulating and controlling the pore composition of the coal-based porous carbon based on the catalytic activation of the trace potassium source according to claim 1, wherein the heating and constant-temperature treatment in the third step is to heat an atmosphere furnace to 600-1000 ℃ and keep the temperature for 0.1-10 h.
6. The method for regulating and controlling the pore composition of the coal-based porous carbon based on the catalytic activation of the trace potassium source according to claim 1, wherein the temperature rise rate of the atmosphere furnace in the third step is 0.1 ℃/min to 100 ℃/min.
7. The method for regulating and controlling the pore composition of the coal-based porous carbon based on the catalytic activation of the trace potassium source according to claim 1 or 6, wherein the atmosphere in the atmosphere furnace in the step three is CO2Mixed atmosphere consisting of water vapor and inert gas or mixed atmosphere consisting of water vapor and inert gas; the CO is2CO in mixed atmosphere with inert gas2And the volume ratio of the inert gas to the inert gas is (0.1-10): 1; the volume ratio of the water vapor to the inert gas in the mixed atmosphere consisting of the water vapor and the inert gas is (0.1-10): 1.
8. the method for regulating and controlling the pore composition of the coal-based porous carbon based on the catalytic activation of the trace potassium source according to claim 7, wherein the inert gas in the third step is high-purity nitrogen or high-purity argon.
9. The method for regulating and controlling the pore composition of the coal-based porous carbon based on the catalytic activation of the trace potassium source according to claim 1, wherein the pickling solution adopted in the pickling treatment in the step four is glacial acetic acid, diluted hydrochloric acid, diluted sulfuric acid or diluted nitric acid.
10. The method for regulating and controlling the pore matching of the coal-based porous carbon based on the catalytic activation of the trace potassium source according to claim 1, wherein the temperature during the drying treatment in the fifth step is 60-200 ℃, and the drying mode is vacuum drying, hot air drying, flat contact drying and natural drying.
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| CN114804100B (en) * | 2022-05-13 | 2023-10-27 | 中南大学 | Porous carbon with ultrahigh specific surface area and preparation method thereof |
| CN116282014A (en) * | 2023-03-13 | 2023-06-23 | 中国矿业大学 | Preparation method and application of coal-based porous carbon material |
| CN117383539A (en) * | 2023-10-30 | 2024-01-12 | 北京市科学技术研究院城市安全与环境科学研究所 | Preparation of modified straw-based hydrothermal carbon and application of modified straw-based hydrothermal carbon in carbon dioxide fixation |
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