CN107720747B - Preparation method of mesoporous-asphalt-based spherical activated carbon - Google Patents
Preparation method of mesoporous-asphalt-based spherical activated carbon Download PDFInfo
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Abstract
A process for preparing the spherical activated carbon rich in mesoporous asphalt base includes such steps as mixing asphalt with Lewis acid catalyst, grinding, high-pressure reaction while sealing, heating to reaction temp, stirring, constant-temp reaction to obtain asphalt containing part of mesophase, grinding, ultrasonic treating in organic solvent, loading in reactor, adding polyvinyl alcohol as surfactant and water, stirring, heating, suspension to become balls, oxidizing, and steam activating. The invention has the advantages of simple method, no additive, high specific surface area, good thermal conductivity and high mesopore content.
Description
Technical Field
The invention belongs to the field of preparation of spherical activated carbon, and particularly relates to a preparation method of mesoporous-asphalt-based spherical activated carbon.
Background
The spherical activated carbon has a series of excellent characteristics of high specific surface area, large pore volume, high bulk density, good biocompatibility, good fluid mechanical property and the like, so that the spherical activated carbon has wide application in the fields of catalyst carriers, adsorbents, drug carriers and the like.
The pitch has the advantages of high carbon content, good fluidity, easy graphitization, excellent compatibility with carbonaceous aggregate, and the like, and is generally used as a precursor of spherical active carbon. In patent CN1224034A, asphalt, organic metal compound and aromatic solvent are mixed in a high-temperature autoclave according to a certain proportion to prepare asphalt material containing metal particles, which is then pelletized by emulsification. In patent CN102795624A, benzoyl peroxide, divinylbenzene, styrene, diethylbenzene and asphalt powder with softening point of 240-280 ℃ and particle size of 150-200 meshes are mixed and suspended into balls in polyvinyl alcohol dispersion. The above patent has complex balling process, and the prepared asphalt ball has compact inside and is lack of mesopores and macropores. When the oxidation is not melted, the oxygen diffusion is not facilitated, the stabilization time and the energy consumption are increased, and the later activation process is also not facilitated.
Traditionally, asphalt-based spherical activated carbon is mainly microporous, has a small proportion of mesopores and macropores, and limits the application of the activated carbon in liquid phase adsorption, industrial catalysis and other occasions. In order to prepare a spherical activated carbon rich in mesopores, patent CN1250024A discloses that the pitch-based spherical activated carbon obtained by primary activation is immersed in a solution of different metal compounds for a period of time, dried and then subjected to secondary activation by steam at 900 ℃. In the method, the pitch ball is activated for the second time, so that the production period and the reaction energy consumption are increased, and the mesopore rate and the macropore rate of the prepared product are still low. In addition, CN103787331A uses mesophase pitch as raw material, and firstly, the mesophase pitch is mixed by adding additives such as aromatic hydrocarbon substances and thermosetting phenolic resin, and the prepared product is prepared into pitch spheres by a suspension method, and finally, pitch-based spherical activated carbon is prepared by conventional pre-oxidation, carbonization, activation and other processes. Although the product obtained by the method has high mesoporous rate, the asphalt needs to be modulated by adding the additive, and the degree of mixing and dissolving of the asphalt and the additive is poor due to large molecular polarity difference, which is directly related to whether the pore structure of the final product can be uniformly developed. In addition, the process is complicated to operate.
Patent CN106348290A discloses a highly thermal conductive pitch-based spherical activated carbon, which requires the addition of a thermal conductive agent such as one or a mixture of mesophase pitch powder, mesophase pitch carbon fiber, graphite powder and graphite worms. Although the spherical activated carbon with better heat conductivity can be prepared by the method, the introduction of the heat-conducting agent increases the production cost and has the problem of uneven dispersion possibly, and the pore structure of the spherical activated carbon prepared by the method is mainly microporous. The prior literature shows that the carbonized product of the mesophase pitch has the characteristics of good electrical and thermal conductivity, high strength and the like. Therefore, in order to combine the advantages of both isotropic pitch and mesophase pitch, the pitch containing a part of mesophase is used as a raw material, or a product with low price and high quality can be prepared, but there are only related patent reports.
Disclosure of Invention
Aiming at the defects at present, the invention aims to provide a method for preparing mesopore-rich spherical activated carbon by using asphalt as a raw material, which has the advantages of simple method, no additive, high specific surface area and high mesopore content.
The invention firstly prepares isotropic asphalt containing partial mesophase, the asphalt powder is dispersed in organic solvent by ultrasonic, then transferred to a reaction kettle, added with proper amount of water and polyvinyl alcohol, stirred and heated to suspend to form balls. When the organic solvent is volatilized, mesopores are preserved in the asphalt balls. After the ball is oxidized and not melted, the generation of micropores and further hole expansion of the ball are promoted by water vapor activation.
The preparation method comprises the following steps:
grinding the mixture of the asphalt raw material and the Lewis acid catalyst into 80-200 meshes of micro powder, then putting the micro powder into a high-pressure reaction kettle, directly sealing and heating the mixture to the reaction temperature of 250-400 ℃, stirring the mixture, reacting the mixture at constant temperature for 1-4h to obtain the asphalt containing partial mesophase, grinding and screening the asphalt into 10-100 meshes of powder, carrying out ultrasonic treatment in an organic solvent for 10-100min, then pouring the powder into the reaction kettle, adding the surfactant polyvinyl alcohol and water, stirring and heating the mixture to the temperature of 100-150 ℃, and suspending the powder into balls. The sphere is oxidized and not melted and then is activated by water vapor for 0.5 to 3 hours at the temperature of 750 ℃ and 950 ℃ to obtain the spherical activated carbon rich in the mesoporous asphalt base.
As mentioned above, the asphalt material comprises one or more of petroleum asphalt, coal asphalt and natural asphalt.
As mentioned above, the Lewis acid catalyst is anhydrous AlCl3Anhydrous FeCl3Anhydrous CoCl2、BF3One or a mixture of more of the above, and the addition amount of the additive accounts for 0.5-5% of the weight fraction of the raw material asphalt, and preferably 2-4%.
As mentioned above, the mixture of the asphalt and the Lewis acid catalyst is ground into fine powder, and the reaction temperature of the mixture is preferably 300-350 ℃.
As mentioned above, the organic solvent comprises one or more of methanol, ethanol, ethylene glycol and acetone, and the weight ratio of the added solvent to the mesophase-containing pitch powder is 0.5 to 3, preferably 1.5 to 2.
As mentioned above, the surfactant polyvinyl alcohol and water are added in the amounts of polyvinyl alcohol: water: the weight ratio of the mesophase-containing pitch powder is 2.5-50: 500-1000: 10. preferably 10 to 30: 600-800: 10.
the method of the invention is different from the prior art in that: the asphalt raw material and the Lewis acid catalyst are mixed and ground into micro powder, which is favorable for full contact between the materials, improves the catalytic effect and reduces the dosage of the catalyst. The method is completed in a high-pressure reaction kettle, nitrogen does not need to be introduced in advance, and the method adopts shorter reaction time, thereby reducing the energy consumption and the requirements on equipment. More importantly, the method can ensure that part of the generated mesophase exists in a mosaic structure in the matrix of the isotropic pitch, and avoid the massive fusion of mesophase globules and the generation of domain-type mesophase. Before the asphalt ball is prepared by a suspension method, the materials are firstly dispersed in an organic solvent by ultrasonic. The operation is simple and easy to implement, so that the organic solvent is easy to diffuse into the asphalt particles, and the possibility of leaving mesopores and macropores for later solvent volatilization is provided. If the operation is not carried out, medium and large pores cannot be obtained, and specific differences are detailed in examples.
Furthermore, the invention has the advantages that: in the process of synthesizing the spheres, the pitch is preformed with mesopores, which is beneficial to reducing the diffusion resistance of water vapor and shortening the diffusion distance, and promotes the development of the pore structure, so that the pitch spheres can be activated at lower temperature in shorter time, and the proportion of macropores in the prepared spherical activated carbon is higher. In addition, part of the mesophase is generated in situ in the isotropic pitch and is uniformly distributed. The asphalt-based spherical activated carbon prepared by using the asphalt as a raw material possibly has good electric and thermal conductivity, and the application potential of the activated carbon is expanded.
The specific surface area of the active carbon obtained by the invention is 825.1m2/g-1325.9m2The mesoporous rate is 37.3 to 47.7 percent, which is far higher than the specific surface area of 372.9m of the activated carbon prepared by the conventional method in the comparative example2/g-731.2m2G and a mesopore ratio of 7.5-17.3%.
Detailed Description
The process of the present invention will be further illustrated by the following examples.
Example 1
200g of coal tar pitch and 4g of anhydrous AlCl3Mixing, grinding into 200 mesh powder, putting into a high pressure reaction kettle, uniformly mixing, heating to 400 ℃, keeping the temperature for 4 hours to obtain the asphalt containing partial mesophase, wherein the content of the mesophase is 22.9 wt%. It was ground to 60 mesh powder. Taking 20g of the powder, carrying out ultrasonic treatment in 10g of ethanol for 30min, then pouring the powder into a reaction kettle, adding 2000ml of water and 100g of polyvinyl alcohol, stirring and heating to 150 ℃ to obtain the asphalt balls. Oxidizing the ball without melting, and activating with water vapor at 800 deg.C for 1h to obtain spherical active carbon rich in mesoporous asphalt base and with surface area of active carbonIs 875.1m2The mesopore ratio was 38.3% by weight.
Comparative example 1
The same batch of mesophase-containing pitch is directly suspended into balls without solvent dispersion ultrasound, the batching and subsequent process conditions are kept unchanged, and the surface area of the prepared pitch-based spherical activated carbon is 625.1m2The mesopore ratio was 12.3% in terms of/g.
Example 2
200g of natural asphalt and 8g of anhydrous FeCl3Mixing, grinding into 120 mesh powder, adding into a high pressure reaction kettle, stirring, heating to 300 deg.C, maintaining the temperature for 3 hr to obtain asphalt containing partial mesophase, wherein the content of mesophase is 25.5 wt%. It was ground and sieved to 20 mesh powder. Taking 20g of the powder, carrying out ultrasonic treatment for 10min in 40g of mixed solvent of ethanol and ethylene glycol (the weight ratio of the ethanol to the ethylene glycol is 1:2), then pouring the mixture into a reaction kettle, adding 1200ml of water and 30g of polyvinyl alcohol, and stirring and heating to 110 ℃. Oxidizing the ball without melting, and activating with steam at 850 deg.C for 1.5 hr to obtain spherical activated carbon rich in mesoporous asphalt base with surface area of 835.4m2The mesopore ratio was 37.3% in terms of/g.
Comparative example 2
The same batch of mesophase-containing pitch is directly suspended into balls without solvent dispersion ultrasound, the batching and subsequent process conditions are kept unchanged, and the surface area of the prepared pitch-based spherical activated carbon is 572.8m2The mesopore ratio was 9.3% by weight.
Example 3
200g of petroleum asphalt was mixed with 10g of anhydrous CoCl2Mixing, grinding into 80 mesh powder, adding into a high pressure reaction kettle, stirring, heating to 350 deg.C, maintaining the temperature for 4 hr to obtain asphalt containing partial mesophase, wherein the content of mesophase is 37.3 wt%. It was ground and sieved to 20 mesh powder. Taking 20g of the powder, carrying out ultrasonic treatment in 30g of methanol solvent for 60min, then pouring the powder into a reaction kettle, adding 1000ml of water and 5g of polyvinyl alcohol, and stirring and heating to 150 ℃. Oxidizing the ball without melting, and activating with water vapor at 750 deg.C for 0.5h to obtain spherical activated carbon rich in mesoporous asphalt base with surface area of 885.1m2A mesopore ratio of 43.7/g％。
Comparative example 3
The same batch of mesophase-containing pitch is directly suspended into balls without solvent dispersion ultrasound, the batching and subsequent process conditions are kept unchanged, and the surface area of the prepared pitch-based spherical activated carbon is 395.1m2The mesopore ratio was 9.1% per g.
Example 4
200g of coal tar pitch was mixed with 2g of anhydrous CoCl2Mixing, grinding into 80 mesh powder, adding into a high pressure reaction kettle, stirring, heating to 320 deg.C, maintaining the temperature for 3 hr to obtain asphalt containing partial mesophase, wherein the content of mesophase is 19.3 wt%. It was ground and sieved to 20 mesh powder. Taking 20g of the powder, carrying out ultrasonic treatment in 30g of glycol solvent for 60min, then pouring the powder into a reaction kettle, adding 1600ml of water and 60g of polyvinyl alcohol, and stirring and heating to 150 ℃. Oxidizing the ball without melting, and activating with water vapor at 800 deg.C for 0.5h to obtain spherical activated carbon rich in mesoporous asphalt base with surface area of 1325.9m2The mesopore ratio was 47.7% by weight.
Comparative example 4
The same batch of mesophase-containing pitch is directly suspended into balls without solvent dispersion ultrasound, the batching and subsequent process conditions are kept unchanged, and the surface area of the prepared pitch-based spherical activated carbon is 715.3m2The mesopore ratio was 14.1% by weight.
Example 5
200g of petroleum asphalt and 1g of anhydrous AlCl3Mixing, grinding into 140 mesh powder, adding into a high pressure reaction kettle, stirring, heating to 300 deg.C, maintaining the temperature for 2 hr to obtain asphalt containing partial mesophase, wherein the content of mesophase is 15.3 wt%. It was ground and sieved to 20 mesh powder. Taking 20g of the powder, carrying out ultrasonic treatment in 30g of methanol solvent for 60min, then pouring the powder into a reaction kettle, adding 1600ml of water and 20g of polyvinyl alcohol, and stirring and heating to 150 ℃. Oxidizing the ball without melting, and activating with water vapor at 750 deg.C for 0.5h to obtain spherical active carbon rich in mesoporous asphalt base with surface area of 990.0m2The mesopore ratio was 41.6% in terms of/g.
Comparative example 5
The same batch of mesophase-containing pitch is directly suspended into spheres without solvent dispersion ultrasound, the batching and subsequent process conditions are kept unchanged, and the surface area of the prepared pitch-based spherical active carbon is 731.2m2The mesopore ratio was 17.3% in terms of/g.
Example 6
200g of petroleum asphalt and 4g of anhydrous FeCl3Mixing, grinding into 80 mesh powder, adding into a high pressure reaction kettle, stirring, heating to 350 deg.C, maintaining the temperature for 4 hr to obtain asphalt containing partial mesophase, wherein the content of mesophase is 31.1 wt%. It was ground and sieved to 20 mesh powder. Taking 20g of the powder, carrying out ultrasonic treatment in 30g of acetone solvent for 60min, then pouring the powder into a reaction kettle, adding 1800ml of water and 40g of polyvinyl alcohol, and stirring and heating to 150 ℃. Oxidizing the ball without melting, and activating with water vapor at 750 deg.C for 0.5h to obtain spherical activated carbon rich in mesoporous asphalt base with surface area of 825.7m2The mesopore ratio was 45.7% by weight.
Comparative example 6
The same batch of mesophase-containing pitch is directly suspended into balls without solvent dispersion ultrasound, the batching and subsequent process conditions are kept unchanged, and the surface area of the prepared pitch-based spherical activated carbon is 479.9m2The mesopore ratio was 9.1% per g.
Example 7
200g of a mixture of coal pitch and petroleum pitch (1: 3 by weight) was mixed with 6g of BF3Mixing, grinding into 100 mesh powder, adding into a high pressure reaction kettle, stirring, heating to 250 deg.C, maintaining the temperature for 2 hr to obtain asphalt containing partial mesophase, wherein the content of mesophase is 22.7 wt%. It was ground and sieved to 60 mesh powder. Taking 20g of the powder, carrying out ultrasonic treatment in 60g of acetone solvent for 100min, then pouring the powder into a reaction kettle, adding 1500ml of water and 50g of polyvinyl alcohol, and stirring and heating to 120 ℃. The ball is oxidized and not melted and then is activated by water vapor for 3 hours at 750 ℃ to obtain the spherical activated carbon rich in the mesoporous asphalt base, and the surface area of the activated carbon is 935.4m2The mesopore ratio was 43.1% by weight.
Comparative example 7
The same batch containing the intermediateDirectly suspending phase asphalt into spheres without solvent dispersion ultrasound, keeping the ingredients and subsequent process conditions unchanged, and obtaining the asphalt-based spherical activated carbon with the surface area of 674.8m2The mesopore ratio was 13.4% in terms of/g.
Example 8
200g of a mixture of coal pitch and petroleum pitch (1: 1 by weight) and 8g of AlCl3Mixing, grinding into 140 mesh powder, adding into a high pressure reaction kettle, stirring, heating to 280 deg.C, and maintaining the temperature for 2 hr to obtain asphalt containing partial mesophase, wherein the content of mesophase is 32.7 wt%. It was ground and sieved to 60 mesh powder. Taking 20g of the powder, carrying out ultrasonic treatment in 60g of methanol solvent for 100min, then pouring the powder into a reaction kettle, adding 1600ml of water and 60g of polyvinyl alcohol, and stirring and heating to 120 ℃. Oxidizing the ball without melting, and activating with water vapor at 950 deg.C for 1h to obtain spherical activated carbon rich in mesoporous asphalt base with surface area of 986.4m2The mesopore ratio was 45.8% by weight.
Comparative example 8
The same batch of mesophase-containing pitch is directly suspended into balls without solvent dispersion ultrasound, the batching and subsequent process conditions are kept unchanged, and the surface area of the prepared pitch-based spherical active carbon is 520.8m2The mesopore ratio was 8.0% in terms of/g.
Example 9
200g of coal tar pitch and 3g of anhydrous AlCl3And anhydrous FeCl3Grinding the mixture (the weight ratio of the two is 1:2) into powder of 120 meshes, putting the powder into a high-pressure reaction kettle, uniformly stirring, heating to 360 ℃, and keeping the temperature for 1 hour to obtain the asphalt containing partial mesophase, wherein the content of the mesophase is 25.9 wt%. It was ground and sieved to 60 mesh powder. Taking 20g of the powder, carrying out ultrasonic treatment in 60g of acetone solvent for 100min, then pouring the powder into a reaction kettle, adding 1200ml of water and 25g of polyvinyl alcohol, and stirring and heating to 120 ℃. The ball is oxidized and not melted and then is activated by water vapor for 2.5 hours at the temperature of 750 ℃ to obtain the spherical activated carbon rich in the mesoporous asphalt base, and the surface area of the activated carbon is 950.4m2The mesopore ratio was 44.6% by weight.
Comparative example 9
The same batch is adoptedDirectly suspending the mesophase pitch into spheres without solvent dispersion ultrasound, keeping the ingredients and subsequent process conditions unchanged, and obtaining the pitch-based spherical active carbon with the surface area of 601.2m2The mesopore ratio was 9.1% per g.
Example 10
200g of a mixture of coal pitch and natural pitch (1: 1 by weight) and 3g of anhydrous AlCl3And anhydrous FeCl3Grinding the mixture (the weight ratio of the two is 1:2) into powder of 80 meshes, putting the powder into a high-pressure reaction kettle, uniformly stirring, heating to 300 ℃, and keeping the temperature for 4 hours to obtain the asphalt containing partial mesophase, wherein the content of the mesophase is 20.2 wt%. It was ground and sieved to 10 mesh powder. Taking 20g of the powder, carrying out ultrasonic treatment for 20min in 20g of a mixed solvent of methanol, ethanol and glycol (the weight ratio of the methanol to the ethanol to the glycol is 1:2:1), then pouring the mixture into a reaction kettle, adding 1200ml of water and 50g of polyvinyl alcohol, and stirring and heating to 100 ℃. Oxidizing the ball without melting, and activating with water vapor at 950 deg.C for 0.5h to obtain spherical activated carbon rich in mesoporous asphalt base with surface area of 1124.4m2The mesopore ratio was 42.1% by weight.
Comparative example 10
The same batch of mesophase-containing pitch is directly suspended into balls without solvent dispersion ultrasound, the batching and subsequent process conditions are kept unchanged, and the surface area of the prepared pitch-based spherical activated carbon is 690.3m2The mesopore ratio was 14.3% in terms of/g.
Example 11
200g of coal tar pitch, petroleum pitch and natural asphalt mixture (the weight ratio of the three is 1:1:1) and 3g of anhydrous AlCl3And anhydrous CoCl2Grinding the mixture (the weight ratio of the two is 2:1) into 140 meshes of powder, putting the powder into a high-pressure reaction kettle, uniformly stirring, heating to 330 ℃, and keeping the temperature for 3 hours to obtain the asphalt containing partial mesophase, wherein the content of the mesophase is 27.2 wt%. It was ground and sieved to 50 mesh powder. Taking 20g of the powder, carrying out ultrasonic treatment for 70min in 30g of a mixed solvent of methanol, ethanol and acetone (the weight ratio of the three is 1:1:1), then pouring the mixture into a reaction kettle, adding 1500ml of water and 45g of polyvinyl alcohol, and stirring and heating to 130 ℃. The ball is oxidized and not melted and then is activated by water vapor at 850 DEG C1h, obtaining the mesoporous asphalt-based spherical activated carbon with the surface area of 927.6m2The mesopore ratio was 41.6% in terms of/g.
Comparative example 11
The same batch of mesophase-containing pitch is directly suspended into balls without solvent dispersion ultrasound, the batching and subsequent process conditions are kept unchanged, and the surface area of the prepared pitch-based spherical active carbon is 524.1m2The mesopore ratio was 8.8% in terms of/g.
Example 12
200g of petroleum asphalt and natural asphalt mixture (weight ratio of the petroleum asphalt to the natural asphalt mixture is 1:3) and 8g of anhydrous FeCl3And BF3Grinding the mixture (the weight ratio of the two is 1:1) into powder of 170 meshes, putting the powder into a high-pressure reaction kettle, uniformly stirring, heating to 360 ℃, and keeping the temperature for 1 hour to obtain the asphalt containing partial mesophase, wherein the content of the mesophase is 36.2 wt%. It was ground and sieved to 40 mesh powder. Taking 20g of the powder, carrying out ultrasonic treatment for 80min in 30g of a mixed solvent of methanol and acetone (the weight ratio of the two is 2:1), then pouring the mixture into a reaction kettle, adding 1500ml of water and 90g of polyvinyl alcohol, and stirring and heating to 150 ℃. The ball is oxidized and not melted and then is activated by water vapor for 2.5 hours at 800 ℃, thus obtaining the spherical activated carbon rich in the mesoporous asphalt base, and the surface area of the activated carbon is 897.6m2The mesopore ratio was 42.7% by weight.
Comparative example 12
The same batch of mesophase-containing pitch is directly suspended into balls without solvent dispersion ultrasound, the batching and subsequent process conditions are kept unchanged, and the surface area of the prepared pitch-based spherical active carbon is 422.6m2The mesopore ratio was 8.3% in terms of/g.
Example 13
200g of coal tar pitch, petroleum pitch and natural asphalt mixture (the weight ratio of the three is 3:1:1) and 6g of anhydrous AlCl3、FeCl3And CoCl2Grinding the mixture (the weight ratio of the three is 1:1:1) into 140-mesh powder, putting the powder into a high-pressure reaction kettle, uniformly stirring, heating to 350 ℃, and keeping the temperature for 3 hours to obtain the asphalt containing partial mesophase, wherein the content of the mesophase is 39.2 wt%. It was ground and sieved to 100 mesh powder. Taking 20g of the powder, adding 30g of methanol,Carrying out ultrasonic treatment on a mixed solvent of ethanol (the weight ratio of the two is 4:1) for 90min, then pouring the mixture into a reaction kettle, adding 1500ml of water and 75g of polyvinyl alcohol, and stirring and heating to 150 ℃. Oxidizing the ball without melting, and activating with water vapor at 850 deg.C for 2 hr to obtain spherical activated carbon rich in mesoporous asphalt base with surface area of 987.8m2The mesopore ratio was 42.6% in terms of/g.
Comparative example 13
The same batch of mesophase-containing pitch is directly suspended into balls without solvent dispersion ultrasound, the batching and subsequent process conditions are kept unchanged, and the surface area of the prepared pitch-based spherical activated carbon is 372.9m2The mesopore ratio was 7.5% in terms of/g.
Example 14
Mixing 200g of coal pitch, petroleum pitch and natural pitch mixture (weight ratio of 1:2:2) with 4g of anhydrous AlCl3、FeCl3And CoCl2Grinding the mixture (the weight ratio of the three is 1:1:2) into powder of 100 meshes, putting the powder into a high-pressure reaction kettle, uniformly stirring the powder, heating the powder to 300 ℃, and keeping the temperature for 2.5 hours to obtain the asphalt containing partial mesophase, wherein the content of the mesophase is 29.2 wt%. It was ground and sieved to 100 mesh powder. Taking 20g of the powder, carrying out ultrasonic treatment for 90min in 30g of a mixed solvent of methanol and acetone (the weight ratio of the two is 4:1), then pouring the mixture into a reaction kettle, adding 1600ml of water and 60g of polyvinyl alcohol, and stirring and heating to 150 ℃. Oxidizing the ball without melting, and activating with water vapor at 830 deg.C for 2 hr to obtain spherical activated carbon rich in mesoporous asphalt base with surface area of 1027.8m2The mesopore ratio was 44.5% by weight.
Comparative example 14
The same batch of mesophase-containing pitch is directly suspended into balls without solvent dispersion ultrasound, the batching and subsequent process conditions are kept unchanged, and the surface area of the prepared pitch-based spherical activated carbon is 685.7m2The mesopore ratio was 12.8% in terms of/g.
Example 15
Mixing 210g of coal pitch, petroleum pitch and natural pitch mixture (weight ratio of the three is 1:1:1) with 8g of anhydrous AlCl3、FeCl3、CoCl2And BF3Mixture of (IV)According to the weight ratio of 1:1:1:1), grinding into powder of 100 meshes, putting into a high-pressure reaction kettle, uniformly stirring, heating to 300 ℃, and keeping the temperature for 3 hours to obtain the asphalt containing partial mesophase, wherein the content of the mesophase is 24.2 wt%. It was ground and sieved to 100 mesh powder. Taking 20g of the powder, carrying out ultrasonic treatment for 90min in 30g of a mixed solvent of methanol, ethanol and acetone (the weight ratio of the three is 1:1:1), then pouring the mixture into a reaction kettle, adding 2000ml of water and 80g of polyvinyl alcohol, and stirring and heating to 150 ℃. Oxidizing the ball without melting, and activating with water vapor at 780 deg.C for 1.5 hr to obtain spherical activated carbon rich in mesoporous asphalt base with surface area of 897.8m2The mesopore ratio was 42.9% in terms of/g.
Comparative example 15
The same batch of mesophase-containing pitch is directly suspended into balls without solvent dispersion ultrasound, the batching and subsequent process conditions are kept unchanged, and the surface area of the prepared pitch-based spherical activated carbon is 630.6m2The mesopore ratio was 8.5% in terms of/g.
Claims (8)
1. A method for preparing mesoporous asphalt-based spherical activated carbon is characterized by comprising the following steps:
grinding the mixture of the asphalt raw material and the Lewis acid catalyst into 80-200 meshes of micro powder, then putting the micro powder into a high-pressure reaction kettle, directly sealing and heating the mixture to the reaction temperature of 250-400 ℃, stirring the mixture, reacting the mixture at constant temperature for 1-4h to obtain asphalt containing partial mesophase, grinding and screening the asphalt into 10-100 meshes of powder, carrying out ultrasonic treatment in an organic solvent for 10-100min, then pouring the powder into the reaction kettle, adding polyvinyl alcohol and water serving as surfactants, stirring and heating the mixture to the temperature of 100-150 ℃, and suspending the mixture into balls; after the sphere is oxidized and not melted, the sphere is activated by water vapor for 0.5 to 3 hours at the temperature of 750 ℃ and 950 ℃ to obtain the spherical activated carbon rich in the mesoporous asphalt base;
the Lewis acid catalyst is anhydrous AlCl3Anhydrous FeCl3Anhydrous CoCl2、BF3One or a plurality of mixtures in the asphalt mixture, and the addition amount accounts for 0.5 to 5 percent of the weight of the raw material asphalt;
the organic solvent comprises one or more of methanol, ethanol, glycol and acetone.
2. The process for the preparation of a mesoporous asphalt based spherical activated carbon enriched in as claimed in claim 1, wherein said pitch feedstock comprises one or a mixture of petroleum pitch, coal pitch, natural pitch.
3. The process for producing a mesoporous asphalt based spherical activated carbon rich in as claimed in claim 1, wherein the amount of Lewis acid catalyst added is 2 to 4% by weight of the raw material asphalt.
4. The method for preparing mesoporous asphalt based spherical activated carbon as defined in claim 1, wherein the reaction temperature of said asphalt with Lewis acid catalyst mixture is 300-350 ℃.
5. A process for producing a mesoporous asphalt based spherical activated carbon rich in as much as possible in claim 1, wherein the weight ratio of the organic solvent added to the mesophase-containing pitch powder is 0.5 to 3.
6. A process for the preparation of a mesoporous asphalt based spherical activated carbon enriched in as much as possible in claim 5, wherein the weight ratio of said organic solvent to said mesophase-containing pitch powder is 1.5 to 2.
7. A process for the preparation of a mesoporous and pitch-based spherical activated carbon rich in as claimed in claim 1, characterized by that
The addition amount of the surfactant polyvinyl alcohol and water is polyvinyl alcohol: water: the weight ratio of the mesophase-containing pitch powder is 2.5-50: 500-1000: 10.
8. a process for the preparation of a mesoporous and pitch-based spherical activated carbon rich in as claimed in claim 1, characterized by that
The polyvinyl alcohol: water: the weight ratio of the mesophase-containing pitch powder is 10-30: 600-800: 10.
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