CN115893410A - Semi-coke-based activated carbon and preparation method thereof - Google Patents
Semi-coke-based activated carbon and preparation method thereof Download PDFInfo
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Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Carbon And Carbon Compounds (AREA)
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Abstract
The invention relates to semi-coke-based activated carbon and a preparation method thereof, wherein the preparation method of the semi-coke-based activated carbon comprises the following steps: 1) Preparing a core-shell structure composite material with semi-coke powder as a core and an auxiliary agent as a shell; wherein the auxiliary agent is a pyrolyzable material with cohesiveness; 2) Carbonizing the core-shell structure composite material to obtain a carbonized material; 3) And activating the carbonized material to obtain the semi-coke-based activated carbon. The invention can better solve the problems of small specific surface area and large pore size in the preparation of activated carbon by semi-coke. The invention selects proper auxiliary agent to ensure that the specific surface area of the prepared semi-coke-based activated carbon is 1000-1600m 2 The adjustment in the range of/g, the micro-porosity can be adjusted and controlled between 60-85%, and the preparation of serial semi-coke-based activated carbon can be ensured. The inventionThe method has simple process and strong operability, is suitable for industrial production, and has certain practical significance for the preparation and production of serial semi-coke-based activated carbon.
Description
Technical Field
The invention relates to the technical field of activated carbon, in particular to semi-coke-based activated carbon and a preparation method thereof.
Background
Under the era background of 'carbon neutralization and carbon peak reaching', the social and economic development has higher and higher requirements on 'three wastes' treatment and new energy storage equipment performance. The activated carbon has various types, and at present, the activated carbon is often used for adsorbing and removing metal ions, sulfur, nitrate and organic matters in industrial wastewater and waste gas; meanwhile, high-quality activated carbon is also used in high-end fields such as blood purification, electrochemical energy storage, catalyst carriers and the like.
The precursors of the active carbon mainly comprise biomass base, wood and coal. Wherein, the traditional activated carbon preparation taking wood as raw material is restricted by the development of forestry, so that the biomass is mostly used as raw material to prepare the activated carbon at present. However, the preparation of activated carbon from biomass has relatively high requirements for equipment and devices, and compared with activated carbon prepared from coal, biomass activated carbon has low mechanical strength, poor abrasion resistance, low adsorption performance and poor regeneration performance. In addition, when the biomass is adopted to prepare the activated carbon material, the problem of low yield is generally existed.
In contrast, the kinds of coal and its by-products are various, and peat, bituminous coal, lignite, coke, etc. can be used for the preparation of the activated carbon material. As an important byproduct of coal chemical industry, the semi-coke has high fixed carbon content, but the strength and the crushing resistance are poor, a large amount of scraps can be generated in the transportation process, a large amount of waste is caused, and the preparation of a relatively high-value product by using the scraps plays an important role in the development of the semi-coke industry.
The inventor of the invention finds that the semi-coke has relatively large pores and is difficult to activate conventionally, but the porosity of the semi-coke-based activated carbon can be effectively improved by kneading the semi-coke with an auxiliary agent. At present, no patent and literature report about the preparation of activated carbon by using semi-coke as a raw material exists, and the work of adjusting the porosity of the semi-coke activated carbon by using an auxiliary agent is more fresh.
Disclosure of Invention
In view of the above, the invention provides a semi-coke-based activated carbon and a preparation method thereof, and mainly aims to solve the technical problems of serious semi-coke pulverization and difficult activation in activated carbon preparation by using semi-coke as a raw material.
In order to achieve the purpose, the invention mainly provides the following technical scheme:
in one aspect, an embodiment of the present invention provides a method for preparing semi-coke-based activated carbon, including the following steps:
1) Preparing a core-shell structure composite material with semi-coke powder as a core and an auxiliary agent as a shell; wherein the auxiliary agent is a pyrolyzable material with cohesiveness;
2) Carbonizing the core-shell structure composite material to obtain a carbonized material;
3) And activating the carbonized material to obtain the semi-coke-based activated carbon.
Preferably, in the step 1): the auxiliary agent is one or more of polyvinylpyrrolidone, polyacrylonitrile, phenolic resin, urea resin, melamine resin, polyvinyl alcohol, coal tar pitch and petroleum pitch.
Preferably, the step 1) includes: dissolving the auxiliary agent in a solvent, adding semi-coke powder into the solvent, and stirring the mixture for a set time at a set temperature to obtain a mixed solution; filtering the mixed solution to obtain a filter cake; and drying the filter cake to obtain the core-shell structure composite material. (ii) a Preferably, the semi-coke powder has a particle size of 60-200 meshes; preferably, the mass ratio of the auxiliary agent to the semi-coke powder is (5) - (50. The solvent is one or more of water, ethanol, tetrahydrofuran and dimethylformamide; and/or the set temperature is between room temperature and 80 ℃. Preferably, the stirring treatment time is 0.5-12h. Preferably, the temperature of the drying treatment is 80-120 ℃, and the time of the drying treatment is 6-24h.
Preferably, in the step 2): under the condition of inert atmosphere, heating the core-shell structure composite material to a carbonization treatment temperature, and performing carbonization treatment; wherein the temperature of the carbonization treatment is 600-1000 ℃, preferably 700-900 ℃. Preferably, the carbonization treatment time is 0.5-4h, preferably 1-2h; and/or the inert atmosphere is a nitrogen atmosphere or an argon atmosphere; and/or the temperature rise rate of heating the core-shell structure composite material to the temperature of carbonization treatment is 1-10 ℃/min, preferably 2-5 ℃/min.
Preferably, in the step 3): mixing the carbonized material with an activating agent to obtain a mixture; then activating the mixture under an inert atmosphere; and finally, cleaning and drying the activated product to obtain the semi-coke-based activated carbon. Preferably, the mass ratio of the carbonized material to the activating agent is 1. Preferably, the activating agent is one or more of potassium hydroxide, sodium hydroxide, zinc chloride and phosphoric acid. Preferably, the temperature of the activation treatment is 600-1000 ℃, preferably 700-900 ℃; the time of the activation treatment is 0.5-4h, preferably 2-3h; and/or the inert atmosphere is an argon atmosphere or a nitrogen atmosphere; and/or the heating rate of heating the mixture to the temperature of the activation treatment is 1-10 ℃/min, preferably 2-3 ℃/min.
On the other hand, the embodiment of the invention provides semi-coke-based activated carbon, wherein the semi-coke-based activated carbon is a core-shell structure composite material with semi-coke powder as a core layer and a carbon material as a shell layer; wherein the carbon material is obtained by pyrolyzing an auxiliary agent; the auxiliary agent is a pyrolysis material with cohesiveness; wherein the semi-coke-based activated carbon is of a hierarchical pore structure with macropores, mesopores and micropores; wherein the pore diameter of the macropores is 50-500nm, the pore diameter of the mesopores is 2-50nm, and the pore diameter of the micropores is 0.5-2nm; wherein the pore structure on the nuclear layer comprises macropores and micropores, and the micropores are positioned on the pore walls of the macropores; the pore structure on the shell layer comprises mesopores and micropores; preferably, the specific surface area of the semi-coke-based activated carbon is 1000-1600m 2 (ii) preferably 60 to 85% in microporosity (micropore ratio), and the semi-coke-based activated carbonIs prepared by the preparation method of the semi-coke-based activated carbon.
Compared with the prior art, the semi-coke-based activated carbon and the preparation method thereof have the following beneficial effects:
the embodiment of the invention provides semi-coke-based activated carbon and a preparation method thereof, and firstly proposes that semi-coke powder which is difficult to activate and easy to pulverize is mixed with an auxiliary agent with certain cohesiveness, and liquid phase coating is carried out to form a core-shell structure composite material taking the semi-coke powder as a core and the auxiliary agent as a shell. Then, the core-shell structure composite material is carbonized, wherein, in the carbonization process, the auxiliary agent is pyrolyzed to form a carbon material which is called a pre-carbon layer (the pores distributed on the carbon material are mainly micropores). Then, activating the carbonized material; wherein, in the process of activation treatment, the activating agent etches the pre-carbon layer, so that the pre-carbon layer has micropores and mesopores; due to the coating effect of the pre-carbon layer, the effect of the activating agent and the core layer semi-coke is improved, and the etching effect of the activating agent on the hole wall of the semi-coke is improved. After activation treatment, the obtained semi-coke-based activated carbon is a core-shell structure composite material with semi-coke powder as a core layer and a carbon material as a shell layer; wherein the carbon material is obtained by pyrolyzing an auxiliary agent; the semi-coke-based activated carbon is of a hierarchical pore structure (also called a hierarchical pore structure or a hierarchical pore structure) with macropores (macropores inside), mesopores and micropores; the pore structure on the nuclear layer comprises macropores and micropores positioned on the walls of the macropores; the pore structure on the shell layer comprises mesopores and micropores. The semi-coke-based activated carbon with the structure has a large specific surface area, so that the adsorption effect is remarkably excellent; meanwhile, the nuclear layer is provided with macropores (micropores are arranged at the edge of the pore wall of the macropore), the shell layer is provided with micropores and mesopores, and the external pores are smaller than the internal pores, so that the semi-coke-based activated carbon can be prevented from being discharged after being adsorbed and even saturated, and the adsorption effect is further enhanced.
Compared with the direct activation of the semi-coke, the semi-coke-based activated carbon prepared by the preparation method of the semi-coke-based activated carbon has richer porosity, higher specific surface area and more micropore space, and effectively improves the adsorption capacity of the semi-coke-based activated carbon. Furthermore, the semi-coke-based activated carbon materials with different porosities and specific surface areas can be obtained by adjusting the type and content of the auxiliary agent, the activating agent and the heat treatment conditions, so that the preparation of activated carbon with different specifications is realized.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to implement them in accordance with the contents of the description, the following detailed description is given with reference to the preferred embodiments of the present invention and the accompanying drawings.
Drawings
FIG. 1 is a scanning electron micrograph of activated carbon obtained by direct activation of semi coke;
FIG. 2 is a scanning electron micrograph of a semi-coke-based activated carbon prepared in example 1 of the present invention;
FIG. 3 shows N in semi-coke-based activated carbon prepared in example 1 of the present invention 2 Adsorption and desorption curves and pore structure distribution curves.
Detailed Description
To further explain the technical means and effects of the present invention adopted to achieve the predetermined object, the following detailed description of the embodiments, structures, features and effects according to the present invention will be made with reference to the accompanying drawings and preferred embodiments. In the following description, different "one embodiment" or "an embodiment" refers to not necessarily the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
In order to overcome the technical problems of difficult activation and serious pulverization of semi-coke, the invention provides a preparation method of semi-coke-based activated carbon with strong operability and easy large-scale production.
It should be noted here that: if the semi coke is directly activated to prepare the activated carbon; because the pores on the semi-coke are relatively large (too large), the semi-coke is difficult to activate (the activating agent can only act on the part contacted with the pore wall, and the activating agent dispersed in the pores can not act on the activating action), so the semi-coke is directly activated to prepare the activated carbon, the obtained activated carbon has small specific surface area and large pore size, the adsorption effect is low, and the activated carbon is easy to discharge after adsorption.
Therefore, the scheme of the invention is provided aiming at the problems of serious pulverization of the semi-coke, difficult activation of the semi-coke and the performance of the activated carbon prepared by direct activation.
The main concept of the scheme of the invention is as follows: mixing the semi-coke powder which is difficult to activate and easy to pulverize with an auxiliary agent with certain cohesiveness, and carrying out liquid phase coating to form the core-shell structure composite material. Then, the core-shell structure composite material is carbonized, wherein, in the carbonization process, the auxiliary agent is pyrolyzed to form a carbon material which is called a pre-carbon layer (the pores distributed on the carbon material are mainly micropores). Then, activating the carbonized material; wherein, in the process of activation treatment, the activating agent etches the pre-carbon layer, so that the pre-carbon layer has micropores and mesopores; due to the coating effect of the pre-carbon layer, the effect of the activating agent and the core layer semi-coke is improved, and the etching effect of the activating agent on the semi-coke hole wall is improved. After activation treatment, the obtained semi-coke-based activated carbon is a core-shell structure composite material with semi-coke powder as a core layer and a carbon material as a shell layer; wherein the carbon material is obtained by pyrolyzing an auxiliary agent; the semi-coke-based activated carbon is of a multi-level pore structure (with macropores inside) with macropores, mesopores and micropores; the pore structure on the nuclear layer comprises macropores and micropores positioned on the walls of the macropores; the pore structure on the shell layer comprises mesopores and micropores. The semi-coke-based activated carbon with the structure has a large specific surface area, so that the adsorption effect is remarkably excellent; meanwhile, the nuclear layer is provided with macropores (micropores are arranged at the edge of the pore wall of the macropore), the shell layer is provided with micropores and mesopores, and the external pores are smaller than the internal pores, so that the semi-coke-based activated carbon can be prevented from being discharged after being adsorbed and even saturated, and the adsorption effect is further enhanced.
Here, the pore size distribution is divided into macropores (> 50 nm), mesopores (also called mesopores, 2-50 nm) and micropores (< 2 nm) according to IUPAC division.
The main scheme of the invention is as follows:
in one aspect, an embodiment of the present invention provides a method for preparing semi-coke-based activated carbon, including the following steps:
1) Preparing a core-shell structure composite material with semi-coke powder as a core and an auxiliary agent as a shell; wherein the auxiliary agent is a pyrolyzable material with cohesiveness.
In this step: the auxiliary agent is one or more of polyvinylpyrrolidone, polyacrylonitrile, phenolic resin, urea resin, melamine resin, polyvinyl alcohol, coal pitch and petroleum pitch. Any obvious alternative of a thermally decomposable, adhesive polymeric material without departing from the spirit of the present invention is intended to be within the scope of the present invention. Here, it should be noted that: there is no particular requirement for the viscosity range of the adjuvant, and the specific experiments and examples are focused on, but not limited to, 500 to 700 mPas.
The method comprises the following steps: dissolving the auxiliary agent in a solvent, then adding semi-coke powder into the solvent, stirring the mixture for 0.5 to 12 hours at a set temperature (room temperature to 80 ℃), filtering the mixture to obtain a filter cake, and then drying the filter cake for 6 to 24 hours at a temperature of between 80 and 120 ℃ to obtain the core-shell structure composite material taking the semi-coke powder as a core and the auxiliary agent as a shell. Preferably, the solvent may be one or more of water, ethanol, tetrahydrofuran, dimethylformamide and the like.
Preferably, the mass ratio of the auxiliary agent to the semi-coke powder is (5. Preferably (15.
2) And (3) carbonizing the core-shell structure composite material to obtain a carbonized material.
The method comprises the following steps: and (3) placing the core-shell structure composite material in an atmosphere furnace, and carbonizing the product in an inert atmosphere to obtain the carbonized material.
In this step: the inert atmosphere may be a nitrogen atmosphere or an argon atmosphere.
Wherein the carbonization treatment temperature is 600-1000 deg.C (preferably 700-900 deg.C), the carbonization treatment time is 0.5-4h (preferably 1-2 h), and the heating rate is 1-10 deg.C/min, preferably 2-5 deg.C/min.
3) And activating the carbonized material to obtain the semi-coke-based activated carbon.
In this step: the mass ratio of the carbonized material to the activating agent is 1.
Preferably, the activating agent is potassium hydroxide, sodium hydroxide, zinc chloride, phosphoric acid, or the like. Any obvious substitution of inorganic salts or acids with activating action without departing from the inventive concept shall fall within the scope of protection of the present invention.
Preferably, in this step, the atmosphere is argon or nitrogen.
Preferably, in this step, the activation temperature is 600-1000 ℃, preferably 700-900 ℃; the time of the activation treatment is 0.5-4h, preferably 2-3h; the heating rate is 1-10 deg.C/min, preferably 2-3 deg.C/min.
The invention is further illustrated below by means of specific examples:
example 1
The embodiment provides a preparation method of semi-coke-based activated carbon, which comprises the following steps:
1) At room temperature, 15g of medium temperature coal tar pitch was dissolved in tetrahydrofuran to form a homogeneous solution a with a concentration of 20%. 100g of semi-coke powder (with a particle size of 60-200 meshes) is added into the solution A with stirring, and stirring is continued for 2h. Then filtering and drying the mixture to obtain the core-shell structure composite material taking semi-coke as a core and coal tar pitch as a shell.
2) Placing the core-shell structure composite material taking the semi-coke as a core and the coal pitch as a shell in a tubular furnace filled with nitrogen, heating to 700 ℃ at the speed of 5 ℃/min, keeping the temperature at 700 ℃ for 1h, and cooling to room temperature to obtain a carbonized material (the carbon-coated semi-coke composite material).
3) And (3) uniformly mixing 10g of carbonized material (carbon-coated semi-coke composite material) and 40g of potassium hydroxide, putting the mixture into a tubular furnace filled with nitrogen, heating to 800 ℃ at the speed of 2 ℃/min, keeping the temperature for 2 hours, and cooling to room temperature. The obtained activated product is soaked in deionized water, and then a proper amount of hydrochloric acid is added to neutralize the pH value to be neutral. Washing with a large amount of water, filtering, and drying at 100 deg.C to obtain semi-coke-based activated carbon.
FIG. 1 is a scanning electron micrograph of activated carbon obtained by direct activation of semi coke; fig. 2 is a scanning electron micrograph of the semi-coke-based activated carbon prepared in example 1. Comparing fig. 1 and fig. 2, it is evident that: the semi-coke-based activated carbon prepared in example 1 had a rougher surface and exhibited a pore structure.
FIG. 3 is N of semi-coke-based activated carbon prepared in example 1 2 Adsorption and desorption curves and pore structure distribution curves. FIG. 3 shows that the semi-coke-based activated carbon obtained in example 1 is an activated carbon mainly having micropores.
The semi-coke-based activated carbon prepared in the embodiment 1 has a hierarchical pore structure with macropores, mesopores and micropores; wherein the pore structure on the nuclear layer comprises macropores and micropores, and the micropores are positioned on the pore walls of the macropores; the pore structure on the shell layer comprises mesopores and micropores.
The semi-coke-based activated carbon prepared in example 1 had a specific surface area of 1382m 2 The microporosity is 76%.
Table 1 shows some adsorption indexes of activated carbon obtained by direct activation of semi-coke (referred to as direct activation method) and semi-coke-based activated carbon prepared in example 1. As can be seen from Table 1, the specific surface area and pore volume of the semi-coke-based activated carbon prepared in example 1 were 1382m each 2 G and 0.7cm 3 The water content is about 6 percent, the iodine adsorption value and the carbon tetrachloride adsorption rate are 1100mg/g and 75 percent respectively, which are both superior to the activated carbon sample prepared by the direct activation method. In addition, the ash content and pH of the samples prepared by the two methods do not differ much.
TABLE 1
Example 2
The embodiment provides a preparation method of semi-coke-based activated carbon, which comprises the following steps:
1) 20g of polyvinyl alcohol are dissolved in deionized water at a temperature of 80 ℃ to form a homogeneous solution A having a concentration of 15%. 100g of semi-coke powder (with a particle size of 60-200 meshes) is added into the solution A with stirring, and stirring is continued for 2h. Then filtering and drying the semi-finished product to obtain the core-shell structure composite material taking semi-finished product as a core and polyvinyl alcohol as a shell.
2) Placing the core-shell structure composite material taking the semi-coke as a core and the polyvinyl alcohol as a shell in a tubular furnace filled with nitrogen, heating to 700 ℃ at the speed of 3 ℃/min, keeping the temperature at 700 ℃ for 1.5h, and cooling to room temperature to obtain the carbonized material (the carbon-coated semi-coke composite material).
3) And (3) uniformly mixing 10g of carbonized material (carbon-coated semi-coke composite material) and 40g of sodium hydroxide, putting the mixture into a tubular furnace filled with nitrogen, heating to 800 ℃ at the speed of 3 ℃/min, keeping the temperature for 2 hours, and cooling to room temperature. The obtained activated product is soaked in deionized water, and then a proper amount of hydrochloric acid is added to neutralize the pH value to be neutral. Washing with a large amount of water, filtering, and drying at 100 deg.C to obtain semi-coke-based activated carbon.
The specific surface area of the semi-coke-based activated carbon prepared in the embodiment is 1270m 2 Per g, pore volume of 0.63cm 3 (ii) a water content of about 5%, and iodine adsorption value and carbon tetrachloride adsorption rate of 930mg/g and 70%, respectively; ash content was only 1.2% and pH was about 7.
The semi-coke-based activated carbon prepared in the embodiment 2 has a hierarchical pore structure with macropores, mesopores and micropores; wherein the pore structure on the nuclear layer comprises macropores and micropores, and the micropores are positioned on the pore walls of the macropores; the pore structure on the shell layer comprises mesopores and micropores.
The semi-coke-based activated carbon prepared in example 2 had a microporosity of 67%.
Example 3
The embodiment provides a preparation method of semi-coke-based activated carbon, which comprises the following steps:
1) 20g of polyacrylonitrile were dissolved in dimethylformamide at a temperature of 80 ℃ to form a homogeneous solution A having a concentration of 15%. 100g of semi-coke powder (with the particle size of 60-200 meshes) is added into the solution A with stirring, and the stirring is continued for 2h. Then filtering and drying the composite material to obtain the core-shell structure composite material taking the semi-coke as a core and the polyacrylonitrile as a shell.
2) Placing the core-shell structure composite material taking the semi-coke as a core and the polyacrylonitrile as a shell in a tubular furnace filled with argon, heating to 800 ℃ at the speed of 5 ℃/min, keeping the temperature at 800 ℃ for 1h, and cooling to room temperature to obtain a carbonized material (carbon-coated semi-coke composite material).
3) And (3) uniformly mixing 10g of carbonized material (carbon-coated semi-coke composite material) and 40g of zinc chloride, putting the mixture into a tubular furnace filled with argon, heating to 700 ℃ at the speed of 2 ℃/min, keeping the temperature for 2 hours, and cooling to room temperature. Washing the obtained activated product with a large amount of water, filtering to neutrality, and drying at 100 ℃ to obtain the semi-coke-based activated carbon.
The specific surface area of the semi-coke-based activated carbon prepared in the embodiment is 1280m 2 G, pore volume of 0.63cm 3 The water content is about 8 percent, and the iodine adsorption value and the carbon tetrachloride adsorption rate are 950mg/g and 72 percent respectively; ash content was only 3.1% and pH was about 7.
The semi-coke-based activated carbon prepared in example 3 has a hierarchical pore structure with macropores, mesopores and micropores; wherein the pore structure on the nuclear layer comprises macropores and micropores, and the micropores are positioned on the pore walls of the macropores; the pore structure on the shell layer comprises mesopores and micropores.
The semi-coke-based activated carbon prepared in example 3 had a microporosity of 65%.
Example 4
The embodiment provides a preparation method of semi-coke-based activated carbon, which comprises the following steps:
1) At room temperature, 15g of phenolic resin was dissolved in ethanol to form a 25% strength homogeneous solution A. 100g of semi-coke powder (with a particle size of 60-200 meshes) is added into the solution A with stirring, and stirring is continued for 2h. Then filtering and drying the mixture to obtain the core-shell structure composite material taking the semi-coke as a core and the phenolic resin as a shell.
2) Placing the core-shell structure composite material taking the semi-coke as a core and the phenolic resin as a shell in a tubular furnace filled with argon, heating to 900 ℃ at the speed of 3 ℃/min, keeping the temperature at 900 ℃ for 1h, and cooling to room temperature to obtain a carbonized material (the carbon-coated semi-coke composite material).
3) And (3) uniformly mixing 10g of carbonized material (carbon-coated semi-coke composite material) and 30g of phosphoric acid, putting the mixture into a tubular furnace filled with argon, heating to 700 ℃ at the speed of 2 ℃/min, keeping the temperature for 2 hours, and cooling to room temperature. Washing the obtained activated product with a large amount of water, filtering to neutrality, and drying at 100 ℃ to obtain the semi-coke-based activated carbon.
The specific surface area of the semi-coke-based activated carbon prepared in the embodiment is 1180m 2 G, pore volume of 0.59cm 3 The water content is about 8 percent, and the iodine adsorption value and the carbon tetrachloride adsorption rate are 900mg/g and 68 percent respectively; the ash content was only 4.3% and the pH was about 6.
The semi-coke-based activated carbon prepared in example 4 has a hierarchical pore structure with macropores, mesopores and micropores; wherein the pore structure on the nuclear layer comprises macropores and micropores, and the micropores are positioned on the pore walls of the macropores; the pore structure on the shell layer comprises mesopores and micropores.
The semi-coke-based activated carbon prepared in example 4 had a microporosity of 64%.
Example 5
The embodiment provides a preparation method of semi-coke-based activated carbon, which comprises the following steps:
1) 20g of low-temperature coal tar pitch was dissolved in tetrahydrofuran to form a 30% strength homogeneous solution A. 100g of semi-coke powder (with a particle size of 60-200 meshes) is added into the solution A with stirring, and stirring is continued for 2h. And then filtering and drying the mixture to obtain the core-shell structure composite material taking semi-coke as a core and low-temperature coal pitch as a shell.
2) Placing the core-shell structure composite material taking the semi-coke as a core and the low-temperature coal pitch as a shell in a tubular furnace filled with argon, heating to 900 ℃ at the speed of 5 ℃/min, keeping the temperature at 900 ℃ for 1h, and cooling to room temperature to obtain a carbonized material (carbon-coated semi-coke composite material).
3) And (3) uniformly mixing 10g of carbonized material (carbon-coated semi-coke composite material) and 30g of potassium hydroxide, placing the mixture in a tubular furnace filled with argon, heating to 800 ℃ at the speed of 3 ℃/min, keeping the temperature for 2 hours, and cooling to room temperature. The obtained activated product is soaked in deionized water, and then a proper amount of hydrochloric acid is added to neutralize the pH value to be neutral. Washing with a large amount of water, filtering to neutrality, and drying at 100 deg.C to obtain semi-coke-based activated carbon.
The specific surface area of the semi-coke-based activated carbon prepared in the embodiment is 1330m 2 Per g, pore volume of 0.67cm 3 The water content is about 5 percent, and the iodine adsorption value and the carbon tetrachloride adsorption rate are respectively 1000mg/g and 72 percent; ash content was only 1.3% and pH was about 7.
The semi-coke-based activated carbon prepared in example 5 has a hierarchical pore structure with macropores, mesopores and micropores; wherein the pore structure on the core layer comprises macropores and micropores, and the micropores are positioned on the pore walls of the macropores; the pore structure on the shell layer comprises mesopores and micropores.
The semi-coke-based activated carbon prepared in example 5 had a microporosity of 71%.
Example 6
The embodiment provides a preparation method of semi-coke-based activated carbon, which comprises the following steps:
1) 20g of high-temperature coal tar pitch was dissolved in tetrahydrofuran to form a homogeneous solution A having a concentration of 20%. 100g of semi-coke powder (with a particle size of 60-200 meshes) is added into the solution A with stirring, and stirring is continued for 2h. Then filtering and drying the semi-coke to obtain the core-shell structure composite material taking the semi-coke as a core and the high-temperature coal pitch as a shell.
2) Placing the core-shell structure composite material taking the semi-coke as a core and the high-temperature coal pitch as a shell in a tubular furnace filled with argon, heating to 800 ℃ at the speed of 3 ℃/min, keeping the temperature at 800 ℃ for 2h, and cooling to room temperature to obtain a carbonized material (carbon-coated semi-coke composite material).
3) And (3) uniformly mixing 10g of carbonized material (carbon-coated semi-coke composite material) and 30g of potassium hydroxide, placing the mixture in a tubular furnace filled with argon, heating to 800 ℃ at the speed of 3 ℃/min, keeping the temperature for 2 hours, and cooling to room temperature. The obtained activated product is soaked in deionized water, and then a proper amount of hydrochloric acid is added to neutralize the pH value to be neutral. Washing with a large amount of water, filtering to neutrality, and drying at 100 deg.C to obtain semi-coke-based activated carbon.
The specific surface area of the semi-coke-based activated carbon prepared in the example is 1292m 2 Per g, pore volume of 0.69cm 3 The water content is about 7 percent, and the iodine adsorption value and the carbon tetrachloride adsorption rate are 980mg/g and 70 percent respectively; ash content was only 1.8% and pH was about 7.
The semi-coke-based activated carbon prepared in example 6 has a hierarchical pore structure with macropores, mesopores and micropores; wherein the pore structure on the nuclear layer comprises macropores and micropores, and the micropores are positioned on the pore walls of the macropores; the pore structure on the shell layer comprises mesopores and micropores.
The semi-coke-based activated carbon prepared in example 6 had a microporosity of 73%.
In conclusion, the preparation method of the semi-coke-based activated carbon provided by the invention can better solve the problems of small specific surface area and large pore size in the preparation of activated carbon from semi-coke. The invention selects proper auxiliary agent to ensure that the specific surface area of the prepared semi-coke-based activated carbon is 1000-1600m 2 The/g is adjusted, the microporosity can be adjusted and controlled between 60 percent and 85 percent, and the preparation of serial semi-coke-based activated carbon can be ensured. The preparation method adopted by the invention has the advantages of simple process and strong operability, and is suitable for industrial production. Has certain practical significance for the preparation and production of series semi-coke-based activated carbon.
In addition, it should be noted that: if the auxiliary agents (such as asphalt, high polymer, resin and the like) are directly prepared into the activated carbon, the problems of low yield and high cost exist, and the method is only suitable for the field which requires large adsorption capacity and does not need to consider the use cost. The semi-coke-based activated carbon prepared by the method is an activated carbon material taking semi-coke as a core and a carbon material subjected to assistant pyrolysis as a shell, so that the defect of low porosity of a semi-coke directly activated product is overcome, a high specific surface area and porosity can be obtained only by a small amount of assistant, and the pore distribution range can be regulated and controlled by regulating the using conditions of the assistant. The method is favorable for preparing the semi-coke-based activated carbon material with multiple application ranges at low cost, and realizes high-quality utilization of semi-coke products.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent change and modification made to the above embodiment according to the technical spirit of the present invention are still within the scope of the technical solution of the present invention.
Claims (10)
1. A preparation method of semi-coke-based activated carbon is characterized by comprising the following steps:
1) Preparing a core-shell structure composite material with semi-coke powder as a core and an auxiliary agent as a shell; wherein the auxiliary agent is a pyrolyzable material with cohesiveness;
2) Carbonizing the core-shell structure composite material to obtain a carbonized material;
3) And activating the carbonized material to obtain the semi-coke-based activated carbon.
2. The method for producing a semi-coke-based activated carbon as claimed in claim 1, wherein in the step 1): the auxiliary agent is one or more of polyvinylpyrrolidone, polyacrylonitrile, phenolic resin, urea resin, melamine resin, polyvinyl alcohol, coal pitch and petroleum pitch.
3. The method for producing a semi-coke-based activated carbon as claimed in claim 1 or 2, wherein said step 1) comprises:
dissolving the auxiliary agent in a solvent, adding semi-coke powder into the solvent, and stirring the mixture at a set temperature to obtain a mixed solution; filtering the mixed solution to obtain a filter cake; drying the filter cake to obtain a core-shell structure composite material; preferably, the particle size of the semi-coke powder is 60-200 meshes.
4. The process for producing a semi-coke-based activated carbon as claimed in claim 3,
the mass ratio of the auxiliary agent to the semi-coke powder is (5; and/or
The solvent is one or more of water, ethanol, tetrahydrofuran and dimethylformamide; and/or
The set temperature is room temperature-80 ℃; and/or
The stirring treatment time is 0.5-12h; and/or
The temperature of the drying treatment is 80-120 ℃, and the time of the drying treatment is 6-24h.
5. A process for producing a semi-coke-based activated carbon as claimed in any one of claims 1 to 4, wherein in said step 2):
heating the core-shell structure composite material to the carbonization temperature under the condition of inert atmosphere, and performing carbonization treatment; wherein the temperature of the carbonization treatment is 600-1000 ℃, preferably 700-900 ℃.
6. The process for producing a semi-coke-based activated carbon as claimed in claim 5,
the carbonization time is 0.5-4h, preferably 1-2h; and/or
The inert atmosphere is nitrogen atmosphere or argon atmosphere; and/or
The heating rate of heating the core-shell structure composite material to the temperature of carbonization treatment is 1-10 ℃/min, preferably 2-5 ℃/min.
7. The process for producing a semi-coke-based activated carbon as claimed in any one of claims 1 to 6, wherein in said step 3):
mixing the carbonized material with an activating agent to obtain a mixture; then activating the mixture under an inert atmosphere; and finally, cleaning and drying the activated product to obtain the semi-coke-based activated carbon.
8. The process for producing a semi-coke-based activated carbon as claimed in claim 7,
the mass ratio of the carbonized material to the activating agent is 1; and/or
The activating agent is one or more of potassium hydroxide, sodium hydroxide, zinc chloride and phosphoric acid.
9. The process for producing a semi-coke-based activated carbon as claimed in claim 7,
the temperature of the activation treatment is 600-1000 ℃, preferably 700-900 ℃; the time of the activation treatment is 0.5-4h, preferably 2-3h; and/or
The inert atmosphere is argon atmosphere or nitrogen atmosphere; and/or
The rate of heating of the mixture to the temperature of the activation treatment is 1-10 ℃/min, preferably 2-3 ℃/min.
10. The semi-coke-based activated carbon is characterized in that the semi-coke-based activated carbon is a core-shell structure composite material with semi-coke powder as a core layer and a carbon material as a shell layer; wherein the carbon material is obtained by pyrolyzing an auxiliary agent; the auxiliary agent is a pyrolysis material with cohesiveness;
wherein the semi-coke-based activated carbon is of a hierarchical pore structure with macropores, mesopores and micropores; wherein the pore diameter of the macropores is 50-500nm, the pore diameter of the mesopores is 2-50nm, and the pore diameter of the micropores is 0.5-2nm; wherein the pore structure on the nuclear layer comprises macropores and micropores, and the micropores are positioned on the pore walls of the macropores; the pore structure on the shell layer comprises mesopores and micropores;
preferably, the semi-coke-based activated carbon has a specific surface area of 1000-1600m 2 (ii)/g, microporosity of 60-85%;
preferably, the semi-coke-based activated carbon is produced by the method for producing a semi-coke-based activated carbon according to any one of claims 1 to 9.
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