CN115893409A - Method for preparing meso-microporous biomass super-activated carbon based on combined activation of carbon dioxide-phosphoric anhydride-copper complex - Google Patents

Method for preparing meso-microporous biomass super-activated carbon based on combined activation of carbon dioxide-phosphoric anhydride-copper complex Download PDF

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CN115893409A
CN115893409A CN202211326887.4A CN202211326887A CN115893409A CN 115893409 A CN115893409 A CN 115893409A CN 202211326887 A CN202211326887 A CN 202211326887A CN 115893409 A CN115893409 A CN 115893409A
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activated carbon
biomass
phosphoric anhydride
microporous
copper
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CN115893409B (en
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张宗波
李大伟
张煜
孟楠
李金�
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China University of Petroleum East China
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China University of Petroleum East China
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Abstract

The invention provides a method for preparing meso-microporous biomass super activated carbon based on carbon dioxide-phosphoric anhydride-copper complex combined activation, which comprises the following steps: sieving a biomass raw material, drying to constant weight, mixing with phosphoric anhydride and a complex copper activator, and performing ultrasonic treatment to obtain a mixture; drying the mixture, and activating at high temperature in a carbon dioxide atmosphere to obtain a carbide; and cooling the carbide to room temperature, washing with deionized water, and drying to obtain the meso-microporous biomass super activated carbon. Compared with the prior art, the invention has the following beneficial effects: 1. the adopted phosphoric anhydride and the complexing copper activator can simultaneously improve the specific surface area and the surface modification functional group of the super activated carbon, thereby improving the adsorption performance of the super activated carbon; 2. the ultrasonic treatment can accelerate the mass transfer between the biomass raw material and the activating agent, thereby greatly shortening the activation time; 3. the sample is directly transferred to a high-temperature activation temperature environment from room temperature without a heating process and an intermediate carbonization process, so that the preparation steps are simplified, and continuous production can be realized.

Description

Method for preparing meso-microporous biomass super-activated carbon based on combined activation of carbon dioxide-phosphoric anhydride-copper complex
Technical Field
The invention relates to a method for preparing meso-microporous biomass super activated carbon based on carbon dioxide-phosphoric anhydride-copper complex combined activation, and belongs to the technical field of porous carbon preparation.
Background
The super activated carbon has a specific surface area of more than 2000m 2 A porous carbon material per gram. Compared with the traditional activated carbon, the activated carbon has larger specific surface area and pore volume, is considered as a high-performance strategic raw material, and has huge application value in the aspects of energy storage, environmental management, seawater desalination, sewage treatment and the like. At present, the preparation method of the super activated carbon mainly comprises three methods, namely a physical activation method, a chemical activation method and a physical-chemical combined activation method. Among them, most of the activated carbon produced by physical activation is microporous activated carbon, which has insufficiently developed mesopores and unsatisfactory adsorption performance. Use of KOH and ZnCl in chemical activation processes 2 The activator is easy to prepare the product with the specific surface area of more than 3000m 2 The activator has serious corrosion to equipment, and the intermediate product is inflammable and explosive, has larger danger, and is difficult to be applied to industrialized mass production. Compared with the two activation methods, the physical-chemical combined activation method can simultaneously obtain higher specific surface area and pore volume, but the method generally has the problems of complex operation process, long preparation time, low performance of finished products and the like, so that a new method needs to be found to simplify the activation process, shorten the activation time and simultaneously improve the adsorption performance of the super activated carbon.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a method for preparing meso-microporous biomass super activated carbon.
The invention is realized by the following technical scheme:
the invention provides a method for preparing meso-microporous biomass super activated carbon based on combined activation of carbon dioxide-phosphoric anhydride-copper complex, which comprises the following steps:
sieving a biomass raw material, drying to constant weight, mixing with phosphoric anhydride and a complex copper activator, and performing ultrasonic treatment to obtain a mixture;
drying the mixture, and then performing carbon activation in a carbon dioxide atmosphere to obtain a carbide;
cooling the carbide to room temperature, washing with deionized water, and drying to obtain the meso-microporous biomass super activated carbon
Preferably, the flow rate of the carbon dioxide is 50 to 150mL/min.
Preferably, the mass fraction of the phosphoric anhydride activator is 40 to 60wt%.
Preferably, the impregnation ratio of the biomass raw material and the phosphoric anhydride activator is 1:1-3.
Preferably, the carbon activation temperature is 650-850 ℃.
Preferably, the impregnation ratio of the biomass raw material and the complex copper activator is 1.25-25.
Preferably, the concentration of the complexing copper activator is 0.05-1 mol/L.
Preferably, the ultrasonic treatment frequency is 40-60 kHz, and the power is 200-600W.
Preferably, the biomass material is coconut shell.
The realization principle of the invention is as follows:
at high temperature, the carbon dioxide and the carbon carry out elimination reaction, the carbon matrix is corroded, the surface of the inner microcrystal is exposed and further reacts with the carbon dioxide, and a huge specific surface area is formed; phosphoric anhydride can catalytically crack the biopolymer in coconut shell at high temperature, and link biopolymer fragments through cyclization and condensation reactions to form phosphate and polyphosphate, and after the phosphate and polyphosphate are removed, a rich meso-microporous structure can be formed. The complex copper can be decomposed at high temperature and can be subjected to oxidation reaction with the carbon surface, so that the copper is dispersed on the surface and in pores of the activated carbon in the form of compound molecules, the content of surface functional groups is increased, and the number of internal micropores is increased. Therefore, the carbon dioxide-phosphoric anhydride-complex copper ion combined activation method is adopted to prepare the biochar, so that the specific surface area of the super activated carbon can be increased, and the chemical property of the surface can be improved, thereby obtaining the meso-microporous biomass super activated carbon with ultrahigh adsorption property.
Compared with the prior art, the invention has the following beneficial effects:
1. the adopted phosphoric anhydride and the complexing copper activator can simultaneously improve the specific surface area and the surface modification functional group of the super activated carbon, thereby improving the adsorption performance of the super activated carbon;
2. the ultrasonic treatment can accelerate the mass transfer between the biomass raw material and the activating agent, thereby greatly shortening the activation time;
3. the sample is directly transferred to a high-temperature activation temperature environment from room temperature without a temperature rise process and an intermediate carbonization process, so that the preparation steps are simplified, and continuous production can be realized.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1 is a nitrogen adsorption and desorption curve of super activated carbon prepared by activating and non-activating activated carbon with different concentrations of activating agent under the same activating conditions.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the concept of the invention. All falling within the scope of the present invention.
Example 1
The embodiment provides a method for preparing meso-microporous biomass super activated carbon based on carbon dioxide-phosphoric anhydride-copper complex combined activation, which specifically comprises the following steps:
sieving coconut shells with the grain size of 0.22-0.90 mm, and drying to constant weight. Mixing coconut shells, 50wt% of sulfuric anhydride and 0.2mol/L of complex copper activator according to the mass ratio of 1. And cooling to room temperature, washing a sample obtained by carbon activation with deionized water at 40-50 ℃ until a washing liquid is neutral, and drying to obtain the meso-microporous biomass super activated carbon product. And testing the desalting performance of the prepared biomass super activated carbon by adopting a capacitance deionization method. According to the international standard, the desalting amount of most biomass activated carbon is less than or equal to 40mg/g, and the desalting amount of the biomass super activated carbon product produced by the embodiment can reach 49.3mg/g which is far higher than the international standard.
Example 2
Other experimental parameters of this example were the same as those of example 1 except that the copper activation treatment was not performed.
Comparative example 1
The other experimental parameters of this comparative example were the same as those of example 1, except that the impregnation ratio of the biomass raw material to the complex copper activator was 1.
Comparative example 2
The other experimental parameters of this comparative example were the same as those of example 1, except that the impregnation ratio of the biomass raw material to the complex copper activator was 1.
Under the condition that other experimental parameters are the same, the impregnation ratio of the biomass raw material to the complex copper activator is changed (the total impregnation time is unchanged), and the pore parameters of the prepared super activated carbon are shown in table 1.
Table 1: performance characterization results of the super activated carbon sample
Sample (I) Specific surface area (m) 2 /g) Total pore volume (cm) 3 /g) Pore volume (cm) of micropores 3 /g) Pore volume of mesopores (cm) 3 /g)
SAC 2617 2.36 0.87 1.49
0.05-CU-SAC 2707 2.07 0.86 1.21
0.2-CU-SAC 3287 2.38 1.05 1.33
1-CU-SAC 2785 2.09 0.90 1.19
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.

Claims (6)

1. A method for preparing meso-microporous biomass super activated carbon based on carbon dioxide-phosphoric anhydride-copper complex combined activation is characterized by comprising the following steps:
sieving a biomass raw material, drying to constant weight, mixing with phosphoric anhydride and a complex copper activator, and performing ultrasonic treatment to obtain a mixture;
drying the mixture, and then performing carbon activation in a carbon dioxide atmosphere at 650-850 ℃ to obtain a carbide;
and cooling the carbide to room temperature, washing with deionized water, and drying to obtain the meso-microporous biomass super-activated carbon.
2. The method for preparing the meso-microporous biomass super activated carbon based on carbon dioxide-phosphoric anhydride-copper complex combined activation as claimed in claim 1, wherein the mass fraction of the phosphoric anhydride activator is 40-60wt%.
3. The method for preparing the meso-microporous biomass super activated carbon based on carbon dioxide-phosphoric anhydride-copper complex combined activation according to claim 1, wherein the impregnation ratio of the biomass raw material mixed with the phosphoric anhydride activator is 1:1-3.
4. The method for preparing meso-microporous biomass super activated carbon based on carbon dioxide-phosphoric anhydride-copper complex combined activation according to claim 1, wherein the copper complex activator is amino acid complex copper, phosphorus complex copper and chlorine complex copper.
5. The method for preparing the meso-microporous biomass super activated carbon based on the combined activation of carbon dioxide-phosphoric anhydride-copper complex as claimed in claim 1, wherein the concentration of the copper complex activator is 0.05-1 mol/L.
6. The method for preparing the meso-microporous biomass super activated carbon based on the combined activation of carbon dioxide-phosphoric anhydride-copper complex as claimed in claim 1, wherein the impregnation ratio of the biomass raw material and the complex copper activator is 1.25-25.
CN202211326887.4A 2022-10-26 2022-10-26 Method for preparing mesoporous-microporous biomass super-activated carbon based on carbon dioxide-phosphoric anhydride-copper complex combined activation Active CN115893409B (en)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103474253A (en) * 2013-09-30 2013-12-25 武汉理工大学 Porous carbon microsphere electrode materials based on surface function functional group, preparing method of materials, super capacitor of materials, and preparing method of super capacitor
CN104512891A (en) * 2013-09-26 2015-04-15 中国钢铁股份有限公司 Activated carbon microsphere with high specific surface area, manufacturing method thereof, electrode plate and capacitor
CN108178141A (en) * 2018-01-17 2018-06-19 大连理工大学 A kind of preparation method of highly conductive, high-tap density, high specific surface micro-pore charcoal
CN109534342A (en) * 2019-01-18 2019-03-29 中国石油大学(华东) The preparation method of biomass super-activated carbon
CN109850866A (en) * 2019-01-30 2019-06-07 青岛大学 A kind of classifying porous carbon material and preparation method thereof for flexible super capacitor
CN112467109A (en) * 2020-11-27 2021-03-09 西安建筑科技大学 Activated carbon material, composite material, cathode material and cathode sheet of zinc ion energy storage device and zinc ion energy storage device
US20220259049A1 (en) * 2020-12-23 2022-08-18 Zhejiang University Bio-oil light fraction-based bread-shaped porous activated carbon, method for preparing the same and use thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104512891A (en) * 2013-09-26 2015-04-15 中国钢铁股份有限公司 Activated carbon microsphere with high specific surface area, manufacturing method thereof, electrode plate and capacitor
CN103474253A (en) * 2013-09-30 2013-12-25 武汉理工大学 Porous carbon microsphere electrode materials based on surface function functional group, preparing method of materials, super capacitor of materials, and preparing method of super capacitor
CN108178141A (en) * 2018-01-17 2018-06-19 大连理工大学 A kind of preparation method of highly conductive, high-tap density, high specific surface micro-pore charcoal
CN109534342A (en) * 2019-01-18 2019-03-29 中国石油大学(华东) The preparation method of biomass super-activated carbon
CN109850866A (en) * 2019-01-30 2019-06-07 青岛大学 A kind of classifying porous carbon material and preparation method thereof for flexible super capacitor
CN112467109A (en) * 2020-11-27 2021-03-09 西安建筑科技大学 Activated carbon material, composite material, cathode material and cathode sheet of zinc ion energy storage device and zinc ion energy storage device
US20220259049A1 (en) * 2020-12-23 2022-08-18 Zhejiang University Bio-oil light fraction-based bread-shaped porous activated carbon, method for preparing the same and use thereof

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