阅读说明：本技术 一种生物质基活性炭材料 (Biomass-based activated carbon material ) 是由 赵培玉 袁文鹏 王金 魏广帅 尹延超 徐先莽 于 2021-10-10 设计创作，主要内容包括：一种生物质基活性炭材料,包括如下重量份数的原料组成：牡丹仔粕1份；杉树皮1-2份。本发明以富含牡丹仔油的牡丹仔粕为原料制备生物质基活性炭材料能够提高牡丹籽粕的利用价值。本发明使用脱硫废液为活化剂即能较好的解决脱硫废液难处理的问题,又能降低工业活化剂用量,降低活性炭材料制备成本。本发明使用牡丹仔粕为原料,可充分利用牡丹仔粕内的剩余牡丹仔油,在碳化活化过程中对所得生物质基活性炭材料进行原位氮元素掺杂,调节材料的表面性能,改善活性炭材料表面酸碱度,为活性炭吸附CO-(2)提供大量的活性位点。本发明使用脱硫废液和胺基钠两步法活化制备生物质基活性炭材料可降低活化温度至450-550℃,进而降低活性炭制备能耗。(A biomass-based active carbon material comprises the following raw materials in parts by weight: 1 part of peony seed meal; 1-2 parts of fir bark. The biomass-based activated carbon material prepared by taking the peony seed meal rich in peony seed oil as a raw material can improve the utilization value of the peony seed meal. The method can better solve the problem of difficult treatment of the desulfurization waste liquid by using the desulfurization waste liquid as the activating agent, and can reduce the using amount of the industrial activating agent and the preparation cost of the activated carbon material. The method uses the peony seed meal as the raw material, can fully utilize residual peony seed oil in the peony seed meal, carries out in-situ nitrogen element doping on the obtained biomass-based active carbon material in the carbonization and activation process, adjusts the surface performance of the material, improves the surface pH value of the active carbon material, and takes the active carbon material as the active materialCarbon adsorption of CO 2 Providing a large number of active sites. The method for preparing the biomass-based activated carbon material by using the desulfurization waste liquid and the amino sodium through two-step activation can reduce the activation temperature to 450-550 ℃, and further reduce the energy consumption for preparing the activated carbon.)

1. A biomass-based activated carbon material, characterized in that: the composite material comprises the following raw materials in parts by weight: 1 part of peony seed meal; 1-2 parts of fir bark.

2. A biomass-based activated carbon material as claimed in claim 1 wherein: the preparation method comprises the following steps:

the method comprises the following steps: drying the peony seed meal and the cedar bark at 120 ℃, respectively, crushing to 300-mesh and 500-mesh powder, and then mixing to obtain a mixed raw material A;

step two: mixing the mixed raw material A and the desulfurization waste liquid according to the proportion of 1g/5-20ml of solid and liquid, ultrasonically dipping for 2-6h under the condition that the ultrasonic frequency is 25-40KHz, drying at the temperature of 100-150 ℃, and then carrying out carbonization and activation for 2-4h under the conditions that the temperature is 500-700 ℃ and the temperature rise rate of carbonization and activation is 5-8 ℃/min, wherein the carbonization and activation is carried out under the condition of air isolation; obtaining a mixed carbon material B;

step three: mixing the obtained mixed carbon material B and sodium amide according to the mass ratio of 1:1-2, and then carrying out air isolation activation for 1.5-3h under the conditions that the temperature is 450-550 ℃ and the activation heating rate is 5-8 ℃/min, thus obtaining the biomass-based activated carbon material.

3. A biomass-based activated carbon material as claimed in claim 1 wherein: the specific surface area is 1033-2951cm²/g。

4. A biomass-based activated carbon material as claimed in claim 1 wherein: the total pore volume is 0.57-1.60cm³/g。

5. A biomass-based activated carbon material as claimed in claim 1 wherein: the total volume of micropores is 0.52-1.25cm³/g。

6. A biomass-based activated carbon material as claimed in claim 1 wherein: the adsorption temperature is 0-50 deg.C, and the adsorption pressure is 0.01-0.1 MPa.

7. A biomass-based activated carbon material as claimed in claim 1 wherein: it is applied to adsorbing and capturing carbon dioxide.

Technical Field

The invention belongs to the field of preparation of activated carbon materials, and particularly relates to a biomass-based activated carbon material.

Background

With the continuous development of society, the increasingly serious greenhouse effect causes climate abnormity, and the wide attention of the world is attracted; CO discharged by coal-fired power plant flue gas₂Is an important reason for the increasing severity of greenhouse effect. Therefore, how to effectively capture CO from flue gas₂Reduction of artificial CO₂The emission has important significance for relieving global climate change. The activated carbon has the advantages of large specific surface area, adjustable pore diameter, good surface hydrophobicity, low price, easy obtaining and the like, and is widely applied to separation of gases such as flue gas, carbon dioxide and the like. At present, the pore structure and CO of the activated carbon are improved₂Adsorption performance, using large amount of KOH or K in the preparation process of the activated carbon₂CO₃And the like industrial activators. The great use of the activating agent for a long time not only causes equipment corrosion and serious environmental pollution, but also increases the preparation cost of the activated carbon. Meanwhile, the research of the literature finds that the N atoms have structural characteristics similar to those of the carbon atoms, and when the N atoms are used for substituting certain carbon atoms in the carbon material by adopting N doping, the pore structural performance of the activated carbon adsorbent can be adjusted, the surface performance of the material can also be adjusted, the pH value of the surface of the activated carbon material is improved, and CO is adsorbed by the activated carbon adsorbent₂Providing a large number of active sites.

In addition, the desulfurization waste liquid generated in the desulfurization process of the coke oven gas is a mixed pollutant containing various toxic substances, mainly contains components such as ammonium thiosulfate, ammonium thiocyanate, ammonium sulfate, ammonium sulfite, hydroquinone, suspended sulfur and the like, cannot be directly treated by a biochemical method, and cannot be directly discharged. Therefore, how to effectively treat the coking desulfurization waste liquid is a difficult problem to be solved urgently in coking enterprises.

Sher et al prepared carbon dioxide adsorbents using walnut shells as a carbon source and KOH as an activator, but the mass ratio of KOH to walnut shells reached 4(Sher et al, development of biological derived high viscosity soil adsorbents for postcom destruction CO2 capture, Fuel 282(2020) 118506-118518). Cai et al purify styrene and divinylbenzene to prepare a carbon precursor, and then use KOH as an activating agent to prepare a spherical carbon material for carbon dioxide adsorption, so that not only is the synthesis process complicated, but also the mass ratio of KOH to the carbon source reaches 4(Cai et al₂capture, Carbon150(2019) 43-51). Therefore, the development of an activated carbon material which can be simply prepared and has high adsorption capacity and low cost is very important for capturing carbon dioxide.

Disclosure of Invention

The invention provides a biomass-based activated carbon material, which is used for overcoming the defects in the prior art.

The invention is realized by the following technical scheme:

a biomass-based active carbon material comprises the following raw materials in parts by weight: 1 part of peony seed meal; 1-2 parts of fir bark.

The preparation method of the biomass-based activated carbon material comprises the following steps:

the method comprises the following steps: drying the peony seed meal and the cedar bark at 120 ℃, respectively, crushing to 300-mesh and 500-mesh powder, and then mixing to obtain a mixed raw material A;

step two: mixing the mixed raw material A and the desulfurization waste liquid according to the proportion of 1g/5-20ml of solid and liquid, ultrasonically dipping for 2-6h under the condition that the ultrasonic frequency is 25-40KHz, drying at the temperature of 100-150 ℃, and then carrying out carbonization and activation for 2-4h under the conditions that the temperature is 500-700 ℃ and the temperature rise rate of carbonization and activation is 5-8 ℃/min, wherein the carbonization and activation is carried out under the condition of air isolation; obtaining a mixed carbon material B;

step three: mixing the obtained mixed carbon material B and sodium amide according to the mass ratio of 1:1-2, and then carrying out air isolation activation for 1.5-3h under the conditions that the temperature is 450-550 ℃ and the activation heating rate is 5-8 ℃/min, thus obtaining the biomass-based activated carbon material.

The biomass-based activated carbon material has the specific surface area of 1033-2951cm²/g。

The total pore volume of the biomass-based activated carbon material is 0.57-1.60cm³/g。

The total volume of the micropores of the biomass-based activated carbon material is 0.52-1.25cm³/g。

The biomass-based activated carbon material has the adsorption temperature of 0-50 ℃ and the adsorption pressure of 0.01-0.1 MPa.

The biomass-based activated carbon material is applied to adsorbing and capturing carbon dioxide.

The invention has the advantages that: the biomass-based activated carbon material prepared by taking the peony seed meal rich in peony seed oil as the raw material can improve the utilization value of the peony seed meal, and the fir bark as the raw material can improve the pore structure performance of the activated carbon material. The method can better solve the problem of difficult treatment of the desulfurization waste liquid by using the desulfurization waste liquid as the activating agent, and can reduce the using amount of the industrial activating agent and the preparation cost of the activated carbon material. The method uses the peony seed meal as a raw material, can fully utilize residual peony seed oil in the peony seed meal, carries out in-situ nitrogen element doping on the obtained biomass-based active carbon material in the carbonization and activation process, adjusts the surface performance of the material, improves the surface pH value of the active carbon material, and adsorbs CO for the active carbon₂Providing a large number of active sites. The method for preparing the biomass-based activated carbon material by using the desulfurization waste liquid and the amino sodium through two-step activation can reduce the activation temperature to 450-550 ℃, and further reduce the energy consumption for preparing the activated carbon.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.

FIG. 1 is a diagram of a peony seed meal of the present invention;

FIG. 2 is a pore size distribution diagram of biomass-based activated carbon material prepared by the present invention;

FIG. 3 shows CO of biomass-based activated carbon material prepared by the present invention₂Adsorption capacity graph.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1:

(1) preparing a biomass-based active carbon material:

drying 25g of peony seed meal and 25g of fir bark at 120 ℃, then respectively crushing to 300 meshes, and then mixing the crushed peony seed meal and the fir bark raw material to obtain a mixed raw material A; ultrasonically dipping the mixed raw material A in 500ml of desulfurization waste liquid for 2 hours at the ultrasonic frequency of 25KHz, and then drying at the temperature of 100 ℃; then carbonizing and activating for 2 hours at the temperature of 600 ℃ under the nitrogen condition, wherein the carbonization and activation temperature rate is 5 ℃/min, and obtaining a mixed carbon material B; then, physically mixing the obtained mixed carbon material B and sodium amide according to the mass ratio of 1:1, then carrying out activation again for 1.5 hours under the condition of nitrogen at 450 ℃, wherein the activation heating rate is 5 ℃/min, and finally obtaining about 12g of biomass-based activated carbon material, wherein the pore structure distribution of the biomass-based activated carbon material is shown in figure 2;

(2) testing the performance of the biomass-based active carbon material:

the CO of the sample at 25 ℃ was measured using a specific surface and pore size analyzer model 3H-2000PS2, manufactured by Beijing Behcard instruments science and technology Ltd₂Adsorption isotherms. 0.15g of biomass-based activated carbon was packed in a test tube, and the activated carbon was heated to 200 ℃ and maintained for 4 hours to removeRemoving impurity gases in the sample. Then the temperature is reduced to 25 ℃ at 99.99% CO₂Adsorption is carried out in the atmosphere. The carbon dioxide adsorption amount of the biomass-based activated carbon under these conditions was 3.3mmol/g, and the carbon dioxide adsorption amount curve thereof is shown in FIG. 3.

The 3H-2000PS2 specific surface and pore size analyzer is used for performing carbon dioxide adsorption and analysis test on biomass-based activated carbon material for 10 times, wherein the adsorption process is at 25 deg.C and 99.99% CO₂The analysis is carried out under the atmosphere and the analysis is carried out at 200 ℃. 0.15g of adsorbent was packed in the test tube and the temperature was raised to 200 ℃ for 4 hours. The temperature was then reduced to 25 ℃ and adsorption was carried out under carbon dioxide atmosphere. After the adsorption process is finished, the temperature is increased to 200 ℃, and the biomass-based activated carbon is desorbed for 4 hours at 200 ℃. Then, the temperature is reduced to 25 ℃, the adsorption reaction is carried out again under the carbon dioxide atmosphere, and the process is repeated for 10 times. Under the condition, after 10 times of adsorption/desorption cycle processes, the adsorption capacity of the biomass-based composite activated carbon can still reach 3.296mmol/g, and the adsorption capacity is only reduced by 0.12%. The biomass-based composite activated carbon has better carbon dioxide adsorption cycle stability.

Example 2:

(1) preparing a biomass-based active carbon material:

drying 20g of peony seed meal and 30g of fir bark at 120 ℃, then respectively crushing to 400 meshes, and then mixing the crushed peony seed meal and the fir bark raw material to obtain a mixed raw material A; ultrasonically dipping the mixed raw material A in 500ml of desulfurization waste liquid for 2 hours at the ultrasonic frequency of 25KHz, and then drying at the temperature of 100 ℃; then carbonizing and activating for 2 hours at the temperature of 600 ℃ under the nitrogen condition, wherein the carbonization and activation temperature rate is 5 ℃/min, and obtaining a mixed carbon material B; then, physically mixing the obtained mixed carbon material B and sodium amide according to the mass ratio of 1:1, and then activating again for 1.5 hours under the condition of nitrogen at 450 ℃, wherein the activation heating rate is 5 ℃/min, and finally obtaining about 13g of biomass-based activated carbon material;

(2) testing the performance of the biomass-based active carbon material:

technology limited public of Beijing Beschild instrument3H-2000PS2 model specific surface and pore size Analyzer manufactured by Producer for testing CO of samples at 25 deg.C₂Adsorption isotherms. 0.15g of biomass-based composite activated carbon was packed in the test tube, and the activated carbon was heated to 200 ℃ and maintained for 4 hours to remove impurity gases in the sample. The temperature was then reduced to 25 ℃ and adsorption was carried out under carbon dioxide atmosphere. Under the condition, the carbon dioxide adsorption capacity of the biomass-based composite activated carbon is 3.24 mmol/g.

The 3H-2000PS2 specific surface and pore size analyzer is used for performing carbon dioxide adsorption analysis test on the biomass-based composite activated carbon material for 10 times, wherein the adsorption process is performed at 25 ℃ and 99.99% CO₂The analysis is carried out under the atmosphere and the analysis is carried out at 200 ℃. 0.15g of adsorbent was packed in the test tube and the temperature was raised to 200 ℃ for 4 hours. The temperature was then reduced to 25 ℃ and adsorption was carried out under carbon dioxide atmosphere. After the adsorption process was completed, the temperature was again raised to 200 ℃ and the adsorbent was allowed to desorb at 200 ℃ for 4 hours. Then, the temperature is reduced to 25 ℃, the adsorption reaction is carried out again under the carbon dioxide atmosphere, and the process is repeated for 10 times. Under the condition, after 10 times of adsorption/desorption circulation processes, the adsorption capacity of the biomass-based composite activated carbon can still reach 3.237mmol/g, and the adsorption capacity is only reduced by 0.1%. The biomass-based activated carbon has better carbon dioxide adsorption cycle stability.

Example 3:

preparing a biomass-based active carbon material:

drying 15g of peony seed meal and 30g of fir bark at 120 ℃, then respectively crushing to 400 meshes, and then mixing the crushed peony seed meal and the fir bark raw material to obtain a mixed raw material A; ultrasonically dipping the mixed raw material A in 450ml of desulfurization waste liquid for 2 hours at the ultrasonic frequency of 25KHz, and then drying at the temperature of 120 ℃; then carbonizing and activating for 2 hours at the temperature of 600 ℃ under the nitrogen condition, wherein the carbonization and activation temperature rate is 5 ℃/min, and obtaining a mixed carbon material B; then, physically mixing the obtained mixed carbon material B and sodium amide according to the mass ratio of 1:1, and then activating again for 1.5 hours under the condition of nitrogen at 450 ℃, wherein the activation heating rate is 5 ℃/min, and finally obtaining about 14g of biomass-based activated carbon material;

(2) testing the performance of the biomass-based active carbon material:

the CO of the sample at 25 ℃ was measured using a specific surface and pore size analyzer model 3H-2000PS2, manufactured by Beijing Behcard instruments science and technology Ltd₂Adsorption isotherms. 0.15g of biomass-based activated carbon was packed in the test tube, and the activated carbon was heated to 200 ℃ and maintained for 4 hours to remove impurity gases in the sample. The temperature was then reduced to 25 ℃ and adsorption was carried out under carbon dioxide atmosphere. Under the condition, the carbon dioxide adsorption capacity of the biomass-based composite activated carbon is 3.28 mmol/g.

The 3H-2000PS2 specific surface and pore size analyzer is used for performing carbon dioxide adsorption analysis test on the biomass-based composite activated carbon material for 10 times, wherein the adsorption process is performed at 25 ℃ and 99.99% CO₂The analysis is carried out under the atmosphere and the analysis is carried out at 200 ℃. 0.15g of adsorbent was packed in the test tube and the temperature was raised to 200 ℃ for 4 hours. The temperature was then reduced to 25 ℃ and adsorption was carried out under carbon dioxide atmosphere. After the adsorption process was completed, the temperature was again raised to 200 ℃ and the adsorbent was allowed to desorb at 200 ℃ for 4 hours. Then, the temperature is reduced to 25 ℃, the adsorption reaction is carried out again under the carbon dioxide atmosphere, and the process is repeated for 10 times. Under the condition, after 10 times of adsorption/desorption circulation processes, the adsorption capacity of the biomass-based composite activated carbon can still reach 3.276mmol/g, and the adsorption capacity is only reduced by 0.12%. The biomass-based composite activated carbon has better carbon dioxide adsorption cycle stability.

Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.