CN109019591B - Preparation method of asphalt-based spherical activated carbon with low cost and hierarchical pore structure - Google Patents
Preparation method of asphalt-based spherical activated carbon with low cost and hierarchical pore structure Download PDFInfo
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- CN109019591B CN109019591B CN201811113343.3A CN201811113343A CN109019591B CN 109019591 B CN109019591 B CN 109019591B CN 201811113343 A CN201811113343 A CN 201811113343A CN 109019591 B CN109019591 B CN 109019591B
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Abstract
The invention relates to a preparation method of low-cost asphalt-based spherical activated carbon with a hierarchical pore structure, which is characterized in that coal pitch with a softening point of 130-230 ℃ is used as a raw material, low-temperature easily-decomposed organic matters are used as a pore forming agent, and the asphalt-based spherical activated carbon is prepared by mixing, crushing, spheroidizing, air oxidation, liquid-phase oxidation, carbonization, steam activation and acid washing. Wherein the prepared asphalt-based spherical activated carbon has a sphere diameter of 0.4-1.5 mm, a density of 0.5-0.85 g/cm3, a specific surface area of 800-1500 m2/g, a vibration resistance of higher than 95%, a micropore content of 60-83%, a mesopore content of 30-5%, a macropore content of 10-12% and a sphericity of higher than 99%. The invention has important significance for promoting the engineering of the asphalt-based spherical activated carbon and promoting the application of the spherical activated carbon in the fields of civil use, industry, aerospace, aviation and the like.
Description
Technical Field
The invention relates to a preparation method of asphalt-based spherical activated carbon, in particular to a preparation method of asphalt-based spherical activated carbon with low cost and a hierarchical pore structure.
Background
The new material for military and civil integration is upgraded to the national strategy, and the demand of national defense key engineering, high-precision weapon equipment, medicine, electronics, air and water purification on high-end adsorption materials is urgent. The asphalt-based spherical activated carbon is prepared by taking coal asphalt with a high softening point (the softening point is 240-280 ℃) as a raw material and refined naphthalene as a pore-forming agent through spheroidization, extraction, oxidation without melting, carbonization and steam activation. The carbon adsorption material is a carbon adsorption material with a particle size of 0.1-1.5 mm, a spherical structure, high strength and a structure rich in micropores (the aperture is 0.4-2 nm). Compared with the existing commercial granular, columnar and powdery activated carbon, the asphalt-based spherical activated carbon not only has good adsorption selectivity, high adsorption capacity and high strength, but also has the advantages of high filling density and rapid adsorption and desorption by adopting an electrolytic adsorption technology in the actual use process; compared with resin-based spherical activated carbon, the resin-based spherical activated carbon needs to be subjected to a sulfuric acid sulfonation reaction in the preparation process to improve the heat-resistant temperature of the resin ball, and therefore, the problems of serious equipment corrosion and difficult engineering amplification are brought. Therefore, the asphalt-based spherical activated carbon has better development prospect than resin-based spherical activated carbon, has wider application field than commercially available activated carbon, and has important significance for promoting the development of national defense, medicine, electronics, chemical industry and other industries in China.
It is noted that the existing asphalt-based spherical activated carbon has higher preparation cost due to the limitations of raw materials and preparation processes. The specific factors and drawbacks that lead to high costs are as follows:
(1) the raw material is high-softening-point coal pitch with a softening point of 240-280 ℃, and the current market price is more than 8 times of that of medium-temperature coal pitch;
(2) in order to reduce the balling temperature and generate original pores in the asphalt balls, 10-50% of refined naphthalene must be uniformly mixed in the high-softening-point coal asphalt;
(3) the method for removing naphthalene in the naphthalene-containing asphalt ball by adopting an organic solvent extraction method needs a large amount of organic solvent, and the used organic solvents (such as petroleum ether and the like) are industrial class A substances;
(4) when the porous asphalt balls are oxidized by adopting the fixed bed reactor and are not melted, the diffusion resistance of oxygen in the fixed bed reactor is too large, the reaction time is long, the energy consumption is high, and the productivity is low;
(5) the refined naphthalene and the organic solvent extractant are flammable and explosive, have strict requirements on plant structures and equipment layout, and further increase the fixed asset cost.
Disclosure of Invention
The invention designs a preparation method of asphalt-based spherical activated carbon with low cost and a hierarchical pore structure, and aims to provide a preparation method of asphalt-based spherical activated carbon with low cost, a sphere diameter of 0.4-1.5 mm and dense densityThe degree of the reaction is 0.5 to 0.85g/cm3The specific surface area is 900 to 1300m2The preparation method of the asphalt-based spherical activated carbon has the vibration resistance strength higher than 95 percent and has a hierarchical pore structure of macroporous, mesoporous and microporous.
The method has the following characteristics: (1) coal pitch which is low in price, high in quinoline insoluble content and 130-230 ℃ in softening point is used as a raw material; 2) taking coal tar substances which are low in price and easy to decompose at low temperature as pore-forming agents; 3) by air pre-oxidation, on one hand, the pore-forming agent is subjected to cracking reaction to form a proper amount of original pores in the matrix of the asphalt ball, and on the other hand, the strength of the asphalt ball containing pores is improved; 4) the oxidation non-melting time of the porous asphalt ball is shortened by adopting a liquid phase oxidation method; 5) the trace metal existing in the special coal pitch is used as a catalyst, so that the steam activation temperature and time of the carbonized pitch ball are reduced.
In order to solve the technical problems, the invention adopts the following scheme:
a preparation method of asphalt-based spherical activated carbon with low cost and a hierarchical pore structure comprises the following steps:
step 2, crushing the pore-forming agent/coal tar pitch strips prepared in the step 1 by using a double-roller crusher to prepare pore-forming agent/coal tar pitch particles with the particle size of 0.6-2 mm;
step 3, putting every 500kg of pore-forming agent/coal pitch particles prepared in the step 2 into a 5000L high-pressure reaction kettle, adding 3000L of deionized water and 10-50 kg of polyvinyl alcohol, and introducing 99.99% of high-purity nitrogen to keep the pressure in the reaction kettle at 0.2-2 MPa; heating the high-pressure reaction kettle to 70-135 ℃ at a heating rate of 5 ℃/min, and keeping the temperature for 30 min; then naturally cooling to 30-65 ℃ to obtain pore-forming agent/coal pitch balls with the diameter of 0.6-2 mm;
step 4, placing the pore agent/coal tar pitch balls prepared in the step 3 into a rotary furnace (the volume of an inner cavity is 10-20 m)3) In the middle, 5-50 m of the mixture is introduced3H emptyHeating to 300-360 ℃ at a heating rate of 0.5-2 ℃/min, and carrying out decomposition or cracking reaction on a pore-forming agent or light components in the special coal pitch to generate a proper amount of pores in the coal pitch ball to prepare the coal pitch ball containing pores; and the light components and pore-forming agent in the coal tar pitch can generate proper amount of macropores, mesopores and micropores in the decomposition or cracking process;
step 5, placing the asphalt ball containing the holes prepared in the step 4 into an acid aqueous solution with the concentration of 5-50%, wherein the concentration is the mass concentration; liquid phase oxidation is carried out for 2-8 h at 20-80 ℃. Filtering and separating, washing the coal tar pitch balls with the pores for 5 times by using deionized water, and then drying at 100-150 ℃ for 2-6 h to prepare oxidized pitch balls with the pores;
step 6, after the liquid phase oxidation in the step 5 is finished, placing the oxidized asphalt ball containing the holes in a rotary furnace, and introducing nitrogen with the purity of 99.99 percent; then heating to 800-900 ℃ at a heating rate of 5-10 ℃/min, and keeping the temperature for 2-4 hours at the temperature to prepare carbonized asphalt balls;
step 7, after the carbonization in the step 6 is finished, automatically cooling to 700-800 ℃, keeping the temperature for 30min, and switching nitrogen to 30-60 m3Water vapor with flow rate per hour, and reacting for 2-10 hours at the temperature to prepare the asphalt-based spherical activated carbon;
step 8, carrying out acid washing on the spherical activated carbon prepared in the step 7 at normal temperature, wherein the concentration of an acidic aqueous solution is 5-65%, and the concentration is a mass concentration; then washing, filtering and drying are carried out to obtain the pitch-based spherical active carbon.
Further, the special coal pitch in the step 1 comprises one or a mixture of high-temperature coal pitch with a softening point of 130-170 ℃ and heavy pitch slag (bottom material of impregnant coal pitch) with a softening point of 170-230 ℃, wherein the coking value of the special coal pitch is 60-78%, the content of quinoline insoluble substances is 15-48%, and the ash content of the special pitch is 0.1-3%.
Further, the pore-forming agent in the step 1 is one of coal tar, coal pitch with a softening point of 30-45 ℃, petroleum pitch with a softening point of 30-45 ℃, ethylene residual oil, phenolic resin, polyethylene, polypropylene and polybutylene.
Further, the acid in the acidic aqueous solution in step 5 is one or a mixed solution of two of hydrochloric acid, nitric acid and sulfuric acid.
A preparation method of asphalt-based spherical activated carbon with low cost and a hierarchical pore structure comprises the following steps:
mixing the special coal tar pitch and pore-forming agent to prepare pore-forming agent/coal tar pitch strip;
crushing the pore-forming agent/coal tar pitch strips to prepare pore-forming agent/coal tar pitch particles;
pelletizing the pore-forming agent/coal pitch particles into pore-forming agent/coal pitch balls;
pre-oxidizing pore-forming agent/coal pitch ball air into pore-containing coal pitch balls;
carrying out liquid phase oxidation on the coal-containing pitch balls to obtain oxidized pitch balls containing pores;
carbonizing the oxidized asphalt balls containing the pores into carbonized asphalt balls;
activating the carbonized asphalt balls into asphalt-based spherical activated carbon by using water vapor;
and (3) pickling, washing and drying the asphalt-based spherical activated carbon to obtain the asphalt-based spherical activated carbon.
Further, the special coal pitch comprises one or a mixture of high-temperature coal pitch with a softening point of 130-170 ℃ and heavy pitch slag (bottom material of impregnant coal pitch) with a softening point of 170-230 ℃, wherein the coking value of the special coal pitch is 60-78%, the content of quinoline insoluble substances is 15-48%, and the ash content of the special pitch is 0.1-3%.
Further, the pore-forming agent is one of coal tar, coal pitch with a softening point of 30-45 ℃, petroleum pitch with a softening point of 30-45 ℃, ethylene residual oil, phenolic resin, polyethylene, polypropylene and polybutylene.
An asphalt-based spherical activated carbon is characterized in that: prepared using any of the methods described above. Wherein the spherical diameter of the asphalt-based spherical activated carbon is 0.4-1.5 mm, and the density is 0.5-0.85 g/cm3The specific surface area is 800-1500 m2The vibration resistance is higher than 95%, the micropore content is 60-83%, and the mesopore content is30-5%, the content of macropores is 10-12%, and the sphericity is higher than 99%.
The preparation method of the asphalt-based spherical activated carbon with low cost and the hierarchical pore structure has the following beneficial effects:
(1) the invention takes the special coal pitch with low cost as the raw material, greatly reduces the raw material cost of the pitch-based spherical activated carbon, not only can shorten the production process of the pitch-based spherical activated carbon, greatly reduce the production cost thereof and effectively reduce the use level of a production factory, but also can widely apply the pitch-based spherical activated carbon to the fields of civil use, industry, electronics, aerospace, aviation and the like due to the lower production cost thereof.
(2) The invention adopts coal tar and other substances which are easy to decompose or crack at low temperature as the pore-forming agent, has simple process, and saves a plurality of problems caused by the conventional refined naphthalene as the pore-forming agent, such as complex structure of balling equipment caused by easy volatilization of naphthalene, subsequent extraction and replacement by adopting organic solvents such as petroleum ether, separation of naphthalene and organic solvent, recovery and reutilization of naphthalene and the like.
(3) The invention takes substances such as coal tar and the like as pore-forming agents, thereby effectively reducing the use level of asphalt-based spherical activated carbon production plants.
(4) In the invention, the light components and the pore-forming agent in the coal pitch can generate a proper amount of macropores, mesopores and micropores in the decomposition or cracking process, so that the contact area between the pitch matrix and a subsequent liquid-phase reaction medium can be increased, the diffusion resistance of the liquid-phase reaction medium in a pore channel is further reduced, and the reaction time of the pitch ball in the liquid-phase oxidation process is finally effectively shortened.
(5) According to the invention, as part of macropores, mesopores and micropores are generated in the oxidized asphalt sphere before liquid-phase oxidation, the method is more favorable for escaping of cracked gas in the carbonization process, further favorable for controlling the surface appearance of the carbonized asphalt sphere and especially favorable for inhibiting the generation of microcracks.
(6) In the steam activation process, the macropores, the mesopores and the micropores in the oxidized asphalt spheres can improve the contact area of an asphalt matrix and a steam reaction medium, so that the diffusion resistance of the steam reaction medium in a pore channel is reduced, the steam activation time can be effectively shortened, and the energy consumption in the activation process is reduced.
(7) The ash content of the special asphalt is high (0.1-3%), the use of the special asphalt in a binder and an impregnant is limited to a certain extent, but the ash content is mostly metallic nickel, magnesium, cobalt and the like, and the metallic components can play the function of a catalyst in the steam activation process, so the activation reaction temperature of matrix carbon and steam can be effectively reduced, and the preparation cost of the asphalt-based spherical activated carbon is further reduced.
(8) The invention utilizes the advantages of the raw materials and the process, effectively reduces the production cost of the asphalt-based spherical activated carbon, and further expands the wide application of the asphalt-based spherical activated carbon in the fields of civilian use, industry, aerospace, aviation and the like.
Drawings
FIG. 1: the surface topography of the rock asphalt base spherical active carbon prepared by the invention;
FIG. 2: the surface topography of the naphthalene-containing asphalt ball prepared by the second embodiment of the invention;
FIG. 3: the surface topography of the naphthalene-containing asphalt ball prepared by the fourth embodiment of the invention;
FIG. 4: the surface topography of the asphalt-based spherical activated carbon prepared by the fifth embodiment of the invention.
Detailed Description
The invention is further illustrated below with reference to comparative examples and examples:
as shown in figure 1, the sphere diameter of the asphalt-based spherical activated carbon prepared by the method is 0.4-1.5 mm, and the density is 0.5-0.85 g/cm3The specific surface area is 800-1500 m2The vibration resistance is higher than 95%, the micropore content is 60-83%, the mesopore content is 30-5%, the macropore content is 10-12%, and the sphericity is higher than 99%.
[ EXAMPLES one ]
Taking high-temperature coal tar pitch with a softening point of 130 ℃ as a raw material, crushing 1000kg of medium-temperature coal tar pitch into coal tar pitch particles with the diameter of 0.6-0.8 mm by adopting a double-roll crusher, sequentially placing 3000L of deionized water, 10kg of polyvinyl alcohol and 500kg of coal tar pitch particles into a 5000L high-pressure reaction kettle, and introducing 99.99 percentThe pressure in the reaction vessel was maintained at 0.5MPa by the high-purity nitrogen gas of (2). Heating the reaction medium to 140 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 30min, and then naturally cooling to 50 ℃. Because the balling temperature is 10 ℃ higher than the self softening point of the high-temperature coal tar pitch, and all the high-temperature coal tar pitch particles are changed into coal tar pitch balls with spherical structures under the action of surface tension and polyvinyl alcohol surfactant. Then the pitch ball is placed in a rotary furnace and 20m of gas is introduced3After the temperature is raised to 330 ℃ at a temperature rising speed of 0.5 ℃/min and kept constant for 2 hours, although light components in the coal asphalt ball can escape in the process, the porosity per unit area in the asphalt ball is low due to the low amount of the light components, so that the oxidation is insufficient, and finally all the asphalt balls are melted for the second time to become an asphalt block structure.
[ example two ]
The heavy asphalt slag is used as a raw material, the softening point of the raw material is 226 ℃, the coking value is 76.8 percent, and the content of quinoline insoluble substances is 43.9 percent. 1000kg of heavy asphalt slag and 100kg of coal tar are uniformly mixed by adopting a double-screw extruder to prepare coal tar/heavy asphalt slag strips with the diameter of 3 mm. And (3) crushing 1100kg of coal tar/heavy asphalt slag strips into coal tar/heavy asphalt slag particles with the diameter of 0.6-0.8 mm by using a double-roller crusher. 3000L of deionized water, 10kg of polyvinyl alcohol and 500kg of coal tar/heavy asphalt slag particles are sequentially placed in a 5000L high-pressure reaction kettle, and 99.99 percent of high-purity nitrogen is introduced to keep the pressure in the reaction kettle at 0.5 MPa. Then heating the reaction medium to 93 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 30min, and then naturally cooling to 50 ℃. 1100kg of the prepared product is coal tar/heavy pitch slag balls with smooth surface and high sphericity, and the ball diameter is distributed in the range of 0.6-0.8 mm, as shown in figure 2.
[ EXAMPLE III ]
The heavy asphalt slag with the softening point of 226 ℃ is used as a raw material, and 1000kg of heavy asphalt slag and 270kg of coal tar are uniformly mixed by a double-screw extruder to prepare coal tar/heavy asphalt slag strips with the diameter of 3 mm. And (3) adopting a double-roller crusher to crush 1270kg of coal tar/heavy asphalt slag strips into coal tar/heavy asphalt slag particles with the diameter of 0.6-0.8 mm. 3000L of deionized water, 10kg of polyvinyl alcohol and 500kg of coal tar/heavy asphalt slag particles are sequentially placed in a 5000L high-pressure reaction kettle, and 99.99 percent of high-purity nitrogen is introduced to keep the pressure in the reaction kettle at 0.5 MPa. Then heating the reaction medium to 193 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 30min, and then naturally cooling to 50 ℃. Due to the high spheroidization temperature, the coal tar/heavy asphalt slag particles are dissolved at the spheroidization temperature, and only the ellipsoidal coal tar/heavy asphalt slag product with the particle size of 30-50 mm is prepared.
[ EXAMPLE IV ]
The heavy asphalt slag with the softening point of 226 ℃ is used as a raw material, and 1000kg of heavy asphalt slag and 50kg of coal tar are uniformly mixed by a double-screw extruder to prepare coal tar/heavy asphalt slag strips with the diameter of 3 mm. And (3) crushing 1100kg of coal tar/heavy asphalt slag strips into coal tar/heavy asphalt slag particles with the diameter of 0.6-0.8 mm by using a double-roller crusher. 3000L of deionized water, 10kg of polyvinyl alcohol and 1050kg of coal tar/heavy asphalt slag particles are sequentially placed in a 5000L high-pressure reaction kettle, and 99.99% of high-purity nitrogen is introduced to keep the pressure in the reaction kettle at 0.5 MPa. Then heating the reaction medium to 107 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 30min, and then naturally cooling to 50 ℃. 1050kg of the prepared product is coal tar/heavy pitch slag balls with smooth surface and high sphericity, and the ball diameter is distributed in the range of 0.6-0.8 mm, as shown in figure 3.
[ EXAMPLE V ]
1000kg of coal tar/heavy pitch pellets produced in EXAMPLE II were placed in a rotary kiln and 10m of air was passed through3Heating to 330 deg.C at a heating rate of 1 deg.C/min, and keeping the temperature for 2h to obtain 873kg of coal-tar pitch ball with smooth surface. 873kg of the coal tar pitch ball containing the holes is put into a nitric acid water solution with the concentration of 15 percent and is oxidized for 6 hours in a liquid phase at the temperature of 45 ℃. The porous coal tar pitch spheres were separated by filtration, washed 5 times with deionized water, and then dried at 120 ℃ for 2 hours to obtain 871kg of porous oxidized coal tar pitch spheres. 871kg of porous oxidized coal pitch balls are placed in a rotary furnace, nitrogen with the purity of 99.99 percent is introduced, and the temperature is continuously increased from the room temperature to 900 ℃ at the temperature increasing speed of 5 ℃/min. Keeping the temperature at 900 ℃ for 2h, and then keeping the temperature at 5 ℃/mThe temperature reduction speed of in is reduced to 850 ℃, and then the nitrogen is switched to 35m3Steam at a flow rate of/h, and steam activation was carried out at 850 ℃ for 6h, to obtain 436kg of pitch-based spherical activated carbon. Wherein the specific surface area of the asphalt-based spherical activated carbon is 1231m2(ii)/g, vibration resistance of 99%, density of 0.71g/cm3The content of 0.4-2 nm micropores is 72.7%, the content of 2-50 nm mesopores is 19.3%, and the content of 50nm macropores is 8%, as shown in FIG. 4.
[ EXAMPLE six ]
436kg of pitch-based spherical activated carbon manufactured by [ example five ] was placed in a 20% nitric acid aqueous solution and acid-washed at 45 ℃ for 6 hours. The 431kg of pitch-based spherical activated carbon was prepared by separating by filtration, washing the pitch-based spherical activated carbon with deionized water for 5 times, and then drying at 120 ℃ for 2 hours. Wherein the specific surface area of the asphalt-based spherical activated carbon is 1249m2G, vibration resistance of 95% and density of 0.69g/cm3The content of 0.4-2 nm micropores is 74.1%, the content of 2-50 nm mesopores is 19.2%, and the content of 50nm macropores is 7.7%.
[ EXAMPLE VII ]
1000kg of coal tar/heavy pitch pellets produced in EXAMPLE II were placed in a rotary kiln and 10m of air was passed through3Heating to 330 deg.C at a heating rate of 1 deg.C/min, and keeping the temperature for 2h to obtain 873kg of coal-tar pitch ball with smooth surface. 873kg of the oxidized coal pitch ball containing the holes is directly placed in a rotary furnace, nitrogen with the purity of 99.99 percent is introduced, and the temperature is continuously increased from the room temperature to 900 ℃ at the temperature increasing speed of 5 ℃/min. Keeping the temperature at 900 deg.C for 2h, cooling to 850 deg.C at 5 deg.C/min, and switching nitrogen to 35m3Steam flow/h, and steam activation at 850 ℃ for 6h, the product does not have any pitch-based spherical activated carbon or coke, and only 12kg of ash. The reason is that the coal pitch ball containing pores is not oxidized in liquid phase, the average molecular weight of the coal pitch ball containing pores is low, and the coal pitch ball containing pores is subjected to cracking reaction in the carbonization process of 900 ℃ to form rich macroporous channels. During the activation of residual carbon by water vapor at 850 ℃, the water vapor fully reacts with the matrix carbon through rich macroporous pore channels and is completely reactedPartially converted into carbon dioxide or carbon monoxide, and the rest substances are all inorganic substances which do not chemically react with water molecules, such as metallic nickel, magnesium, cobalt and the like.
[ example eight ]
1000kg of coal tar/heavy pitch pellets produced by [ example two ] were placed in a 15% strength nitric acid aqueous solution and subjected to liquid phase oxidation at 45 ℃ for 26 hours. Filtering and separating, washing the porous coal tar pitch balls with deionized water for 5 times, and drying at 120 ℃ for 2 hours to prepare 59kg of porous oxidized coal tar pitch balls, wherein the diameter of the balls is reduced from 0.6-0.8 mm to 0.1-0.2 mm; the remaining coal tar/heavy pitch slag balls are dissolved in an aqueous nitric acid solution.
[ EXAMPLE ninth ]
1000kg of coal tar/heavy pitch pellets prepared in [ example four ] were placed in a rotary kiln, 10m of air 3/h was introduced, the temperature was raised from room temperature to 330 ℃ at a rate of 1 ℃/min and kept constant at that temperature for 2h, yielding 939kg of pore-containing coal pitch pellets having a smooth surface. 939kg of coal tar pitch balls containing pores are put into a nitric acid aqueous solution with the concentration of 15 percent and are subjected to liquid phase oxidation for 6 hours at the temperature of 45 ℃. The porous coal tar pitch spheres were separated by filtration, washed 5 times with deionized water, and then dried at 120 ℃ for 2 hours to prepare 938kg of porous oxidized coal tar pitch spheres. 938kg of oxidized coal pitch ball containing holes is placed in a rotary furnace, nitrogen with the purity of 99.99 percent is introduced, and the temperature is continuously increased from room temperature to 900 ℃ at the temperature increasing speed of 5 ℃/min. Keeping the temperature at 900 deg.C for 2h, cooling to 850 deg.C at 5 deg.C/min, and switching nitrogen to 35m3Steam with flow rate/h, and steam activation is carried out for 6h at 850 ℃ to obtain 181kg of asphalt-based spherical activated carbon and 96kg of powdered activated carbon. Wherein, the prepared asphalt-based spherical activated carbon has a large number of microcracks on the surface and a specific surface area of 1509m2A vibration resistance of 43% and a density of 0.53g/cm358.6 percent of micropores with the diameter of 0.4-2 nm, 29.3 percent of mesopores with the diameter of 2-50 nm and 12.1 percent of macropores with the diameter of more than 50 nm.
[ EXAMPLE eleven ]
1000kg of coal tar/heavy pitch pellets produced in EXAMPLE II were placed in a rotary kiln and 10m of air was passed through3H ofAnd (3) heating the mixture to 330 ℃ from room temperature at a heating rate of 1 ℃/min and keeping the temperature constant at the temperature for 2 hours to obtain 873kg of the coal tar pitch ball with smooth surface and containing pores. 873kg of the coal tar pitch ball containing the holes is put into 25 percent sulfuric acid water solution and is oxidized for 6 hours in a liquid phase at 45 ℃. 863kg of the oxidized coal tar pitch ball containing the pores is prepared by filtering and separating, washing the coal tar pitch ball containing the pores with deionized water for 5 times, and then drying at 120 ℃ for 2 h. 863kg of oxidized coal pitch balls containing holes are placed in a rotary furnace, nitrogen with the purity of 99.99 percent is introduced, and the temperature is continuously increased from room temperature to 900 ℃ at the temperature increasing speed of 5 ℃/min. Keeping the temperature at 900 deg.C for 2h, cooling to 850 deg.C at 5 deg.C/min, and switching nitrogen to 35m3Steam with flow rate/h and steam activation for 6h at 850 ℃ to obtain 381kg of asphalt-based spherical activated carbon, but the surface of the asphalt-based spherical activated carbon has a certain amount of microcracks. Wherein the specific surface area of the pitch-based spherical activated carbon is 1397m2G, vibration resistance of 82%, density of 0.64g/cm3The content of 0.4-2 nm micropores is 63.1%, the content of 2-50 nm mesopores is 24.3%, and the content of 50nm macropores is 12.6%.
The invention is described above with reference to the accompanying drawings, it is obvious that the implementation of the invention is not limited in the above manner, and it is within the scope of the invention to adopt various modifications of the inventive method concept and solution, or to apply the inventive concept and solution directly to other applications without modification.
Claims (6)
1. A preparation method of asphalt-based spherical activated carbon with low cost and a hierarchical pore structure comprises the following steps:
step 1, mixing the special coal tar pitch and the pore-forming agent according to a mass ratio of 1: 0.1-0.3, uniformly mixing the mixture by a double-screw extruder at normal temperature, and then preparing a pore-forming agent/coal tar pitch strip with the diameter of 2-3 mm;
step 2, crushing the pore-forming agent/coal tar pitch strips prepared in the step 1 by using a double-roller crusher to prepare pore-forming agent/coal tar pitch particles with the particle size of 0.6-2 mm;
step 3, putting every 500kg of pore-forming agent/coal pitch particles prepared in the step 2 into a 5000L high-pressure reaction kettle, adding 3000L of deionized water and 10-50 kg of polyvinyl alcohol, and introducing 99.99% of high-purity nitrogen to keep the pressure in the reaction kettle at 0.2-2 MPa; heating the high-pressure reaction kettle to 70-135 ℃ at a heating rate of 5 ℃/min, and keeping the temperature for 30 min; then naturally cooling to 30-65 ℃ to obtain pore-forming agent/coal pitch balls with the diameter of 0.6-2 mm;
step 4, placing the pore agent/coal tar pitch ball manufactured in the step 3 into a rotary furnace, and introducing 5-50 m3Heating to 300-360 ℃ in air at a heating rate of 0.5-2 ℃/min, and carrying out decomposition or cracking reaction on a pore-forming agent or a light component in the special coal pitch to generate a proper amount of pores in the coal pitch ball so as to prepare the coal pitch ball containing pores; and the light components and pore-forming agent in the coal tar pitch can generate proper amount of macropores, mesopores and micropores in the decomposition or cracking process;
step 5, placing the asphalt balls containing the holes prepared in the step 4 into an acid aqueous solution with the concentration of 5-50%, and carrying out liquid-phase oxidation for 2-8 h at the temperature of 20-80 ℃; filtering and separating, washing the coal tar pitch balls with the pores for 5 times by using deionized water, and then drying at 100-150 ℃ for 2-6 h to prepare oxidized pitch balls with the pores;
step 6, after the liquid phase oxidation in the step 5 is finished, placing the oxidized asphalt ball containing the holes in a rotary furnace, and introducing nitrogen with the purity of 99.99 percent; then heating to 800-900 ℃ at a heating rate of 5-10 ℃/min, and keeping the temperature for 2-4 hours at the temperature to prepare carbonized asphalt balls;
step 7, after the carbonization in the step 6 is finished, automatically cooling to 700-850 ℃, keeping the temperature for 30min, and switching nitrogen to 30-60 m3Water vapor with flow rate per hour, and reacting for 2-10 hours at the temperature to prepare the asphalt-based spherical activated carbon;
and 8, carrying out acid washing on the spherical activated carbon prepared in the step 7 at normal temperature, wherein the concentration of an acidic aqueous solution is 5-65%, and then carrying out water washing, filtering and drying to obtain the asphalt-based spherical activated carbon.
2. The method for preparing the asphalt-based spherical activated carbon with low cost and hierarchical pore structure according to claim 1 is characterized in that:
the special coal pitch in the step 1 comprises one or a mixture of high-temperature coal pitch with a softening point of 130-170 ℃ and heavy pitch slag with a softening point of 170-230 ℃, namely a bottom material of impregnant coal pitch, wherein the coking value of the special coal pitch is 60-78%, the content of quinoline insoluble substances is 15-48%, and the ash content of the special pitch is 0.1-3%.
3. The method for preparing the asphalt-based spherical activated carbon with low cost and hierarchical pore structure according to claim 1 is characterized in that:
the pore-forming agent in the step 1 is one of coal tar, coal pitch with a softening point of 30-45 ℃, petroleum pitch with a softening point of 30-45 ℃, ethylene residual oil, phenolic resin, polyethylene, polypropylene and polybutylene.
4. The method for preparing the asphalt-based spherical activated carbon with low cost and hierarchical pore structure according to claim 1 is characterized in that:
and 5, the acid in the acidic aqueous solution is one or a mixed solution of nitric acid and sulfuric acid.
5. An asphalt-based spherical activated carbon is characterized in that: prepared using the process of any of the claims 1-4.
6. The pitch-based spherical activated carbon according to claim 5, characterized in that: the spherical diameter of the asphalt-based spherical activated carbon is 0.4-1.5 mm, and the density is 0.5-0.85 g/cm3The specific surface area is 800-1500 m2The vibration resistance is higher than 95%, the micropore content is 60-83%, the mesopore content is 30-5%, the macropore content is 10-12%, and the sphericity is higher than 99%.
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| CN113443625B (en) * | 2021-06-30 | 2023-01-24 | 华东理工大学 | Preparation method of polystyrene resin-based spherical activated carbon |
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