CN107108232B - Activated carbon, hydrothermal carbon and preparation method thereof - Google Patents
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Abstract
Activated carbon, hydrothermal carbon, and methods of making the same are provided. A method (10) for producing hydrothermal and activated carbon includes providing (10) biomass and mixing (14) the biomass with an oxidant to form a biomass-oxidant mixture. Subjecting (16) the biomass-oxidant mixture to a hydrothermal carbonization process to form a hydrothermal char having an increased content of oxygenated functional groups as compared to the biomass. Mixing (18) the hydrothermal char with an activator to form a hydrothermal char-activator mixture. Subjecting (20) the hydrothermal carbon-activator mixture to a chemical activation process to form activated carbon.
Description
Technical Field
The present invention relates to carbonaceous materials, and more particularly, to activated carbon, hydrothermal carbon (hydrocar) and methods of making the same.
Background
As environmental concerns have increased, the use of sustainable and renewable resources such as biomass has attracted much attention. Research has shown that carbonaceous materials such as biomass-derived activated carbon and hydrothermal carbon have wide application, but are limited by the characteristics of the carbonaceous material. Accordingly, it is desirable to provide carbonaceous materials having improved properties and methods of making the same.
Disclosure of Invention
Accordingly, in a first aspect, the present invention provides a process for the preparation of activated carbon. The method includes providing a biomass and mixing the biomass with an oxidant to form a biomass-oxidant mixture. Subjecting the biomass-oxidant mixture to a hydrothermal carbonization process to form a hydrothermal char having an increased content of oxygenated functional groups as compared to the biomass. Mixing the hydrothermal carbon with an activator to form a hydrothermal carbon-activator mixture. Subjecting the hydrothermal carbon-activator mixture to a chemical activation process to form activated carbon.
In a second aspect, the present invention provides an activated carbon having a mesoporous surface area of about 1300 square meters per gram (m)2Per g) to about 2000m2(ii) a mesopore volume of about 1.9 cubic centimeters per gram (cm)3Per g) to about 3.8cm3(iv)/g, and a mesoporous porosity greater than 70 (%).
In a third aspect, the present invention provides a process for preparing a hydrothermal char. The method includes providing a biomass and mixing the biomass with an oxidant to form a biomass-oxidant mixture. Subjecting the biomass-oxidant mixture to a hydrothermal carbonization process to form a hydrothermal char having an increased content of oxygenated functional groups as compared to the biomass.
In a fourth aspect, the present invention provides a hydrothermal char having an increased content of oxygenated functional groups as compared to a biomass from which the hydrothermal char is prepared.
Other aspects and advantages of the invention will become apparent from the following detailed description, taken in conjunction with the accompanying drawings, illustrating by way of example the principles of the invention.
Drawings
Embodiments of the invention will now be described, by way of example only, with reference to the accompanying drawings, in which:
FIG. 1 is a schematic flow diagram illustrating a process for making hydrothermal carbon and activated carbon according to one embodiment of the present invention;
FIG. 2 is a photograph showing biomass of coconut shells;
FIG. 3 is a photograph showing a hydrothermal char produced from biomass of coconut shells according to one embodiment of the present invention;
FIG. 4 is a photograph showing the hydrothermal carbon of FIG. 3 mixed with an activating agent;
FIG. 5 is a schematic diagram showing an apparatus (set-up) for a chemical activation process according to one embodiment of the present invention;
fig. 6 is a graph showing nitrogen adsorption-desorption isotherms at 77 kelvin (K) for commercial mesoporous carbon and activated carbon prepared from biomass of coconut shells with and without pre-chemical activation treatment;
FIG. 7 is a graph showing pore size distribution of commercially available mesoporous carbon and activated carbon prepared from biomass of coconut shells with and without pre-chemical activation treatment;
FIG. 8 shows a graph of pore size distribution of activated carbon prepared from biomass of sawdust with and without pre-chemical activation treatment;
fig. 9 is a graph showing pore size distribution of activated carbon produced from biomass of palm kernel shells with and without pre-chemical activation treatment; and
fig. 10 is a graph showing rhodamine b (rhodamine b) adsorption curves for commercially available mesoporous carbon and activated carbon prepared from biomass of coconut shells with and without pre-chemical activation treatment.
Detailed Description
The detailed description set forth below in connection with the appended drawings is intended as a description of the presently preferred embodiments of the invention and is not intended to represent the only forms in which the present invention may be practiced. It is to be understood that the same or equivalent functions may be accomplished by different embodiments that are intended to be encompassed within the scope of the invention.
Referring now to fig. 1, a process 10 for making hydrothermal and activated carbon will now be described. The method begins with step 12 of providing biomass.
Biomass may include horticultural waste. In this embodiment, the biomass may be one or more of: coconut shells, palm kernel shells, sawdust, wood, nut shells, pods, fruit pits, seeds, husks, bagasse, peat, lignite and subbituminous coals and may be provided in the form of coarse particles having a particle diameter of from about 0.5 millimeters (mm) to about 5 mm. In one embodiment, biomass having a high hardness can be selected to improve yield.
At step 14, biomass is mixed with an oxidant to form a biomass-oxidant mixture.
The oxidizing agent may be one or more of: hydrogen peroxide, carboxylic acids, peroxy acids, dibasic acids, and humic acids.
The biomass-oxidant mixture may comprise from about 60 mass% (wt%) to about 80 wt% biomass.
The biomass-oxidant mixture is subjected to a hydrothermal carbonization process at step 16 to form a hydrothermal char (char) obtained after hydrothermal treatment) having an increased content of oxygenated functional groups as compared to the biomass from which the hydrothermal char was prepared. Incorporation of the oxidant during hydrothermal treatment of the biomass induces formation of oxygen-containing functional groups (OFG) on the hydrothermal char.
The hydrothermal carbonization process may be performed at a temperature of about 200 degrees celsius (° c) to about 300 ℃ for a time of about 20 minutes (min) to about 200 minutes. Hydrothermal carbonization of biomass is used to improve the chemical properties of the hydrothermal char product (i.e., high concentration of oxygenated functional groups and low degree of aromatization), which makes the hydrothermal char an effective precursor for subsequent chemical activation.
The hydrothermal char formed may have an oxygenated functional group content of about 30 percent (%) to about 70% more than the biomass. In one embodiment, the hydrothermal char has an oxygenated functional group content of about 40% to about 60% more than the biomass. The hydrothermal carbon may have an oxygen-containing functional group content of about 1.2 milliequivalents per gram (meq/g) to about 1.6 meq/g. In particular embodiments, the oxygen-containing functional group content may be about 1.29meq/g, about 1.42meq/g, or about 1.58 meq/g. The oxygen-containing functional group content may comprise one or more of carboxyl groups, lactone groups, and phenol groups.
At step 18, the hydrothermal carbon is mixed with an activator to form a hydrothermal carbon-activator mixture.
The activator may be one or more of: zinc chloride, phosphoric acid, metal chlorides, inorganic acids, sodium phosphate and bases. The ratio of activator to hydrothermal charcoal in the hydrothermal charcoal-activator mixture may be from about 2:1 to about 10: 1.
At step 20, the hydrothermal carbon-activator mixture is subjected to a chemical activation process to form activated carbon.
The chemical activation process may be performed at a treatment temperature of about 350 ℃ to about 650 ℃ for a period of about 0.5 hours (h) to about 3 hours. The chemical activation process may be ramped up (ramp to) to the treatment temperature at a rate of about 5 degrees celsius per minute (c/min) to about 15 c/min. In one embodiment, the chemical activation process may be performed in the presence of nitrogen at a flow rate of about 20 milliliters per minute (ml/min) to about 100 ml/min.
The mesoporous surface area of the formed activated carbon may be about 1300 square meters per gram (m)2Per g) to about 2000m2The mesopore volume can be about 1.9 cubic centimeters per gram (cm)3Per g) to about 3.8cm3The mesoporous porosity can be more than 70 (%), wherein the mesoporous porosity is the mesoporous surface area (A) of the activated carbonme) Relative Brunauer-Emmett-Teller (BET) surface area (A)t) The ratio of. In one embodiment, the mesoporous surface area may be about 1331m2The mesoporous volume may be about 1.98cm3And the mesoporous porosity may be about 76%. In another embodiment, the mesoporous surface area may be about 1780m2Per g, the mesopore volume can be about 3.5cm3And the mesoporous porosity may be about 100%. In yet another embodiment, the mesoporous surface area may be about 1815m2Per g, the mesopore volume can be about 2.8cm3And the mesoporous porosity may be about 98%.
By this method 10, activated carbon having high or increased mesoporous porosity and high or increased mesoporous surface area can be obtained from waste biomass. An increase in the porosity of the activated carbon is highly desirable and is obtained in method 10 by selecting biomass, selecting an oxidizing agent, selecting a chemical activating agent, optimizing activation conditions such as temperature, rate of temperature rise, and gas flow, and selecting a pretreatment method.
In method 10, hydrothermal treatment of biomass in the presence of an oxidant is used as a pretreatment step to produce a hydrothermal char with high or increased OFG content as a precursor for subsequent chemical activation. The pretreatment step induces the formation of more oxygen-containing functional groups on the hydrothermal carbon, making the hydrothermal carbon precursor more reactive during subsequent chemical activation. Chemical activation of hydrothermal carbon with high or increased OFG content thus results in activated carbon with high or increased mesoporous porosity and high or increased mesoporous surface area.
The high mesoporous carbon is applied to the field of immobilization of biomolecules such as enzymes, vitamins and the like. High mesoporous porosity is also highly desirable for energy storage applications, electrocatalysis, electrode materials, and environmental remediation applications.
Examples
Coconut shell (cocoa), palm kernel shell and sawdust are used as waste biomass sources. Coconut shells (after trimming fiber), palm kernel shells (after depulping) and sawdust were dried at 105 ℃ for 24 hours, comminuted using a commercial laboratory blender (Waring), and then ground and sieved to produce coarse particles of about 10 mesh to 20 mesh. A photograph of biomass from coconut shells is shown in figure 2.
The biomass is then mixed with an oxidant to form a biomass-oxidant mixture. Hydrogen peroxide (30% GR, Merck) was used as the oxidant to induce OFG formation on the char during pretreatment of the feedstock biomass. Pretreatment with hydrogen peroxide imparts more OFG content to the hydrothermal carbon precursor, making it more reactive to subsequent chemical activation.
Biomass-Hydrogen peroxide mixture (90mL H) at 200 ℃ in a Parr 4848 autoclave2O215g biomass in (10 wt.%) was subjected to hydrothermal treatment for 20 minutes. The reactor was then cooled to room temperature and the product was dried at 105 ℃ for 12 hours. A photograph of a hydrothermal char produced from biomass of coconut shells is shown in fig. 3.
Followed by zinc chloride (ZnCI)2Reagent grade (Scharlab)) activated carbon was prepared by chemical activation.
More specifically, the hydrothermal char precursor was mixed with a zinc chloride solution (equivalent to 90mL of water in 15g of precursor of the starting biomass) at a zinc chloride to shell ratio of 5:1 and dried at 105 ℃ for 12 hours. A photograph showing the hydrothermal carbon mixed with the activator is shown in fig. 4. The effect of adding zinc chloride as a chemical activator appears in the form of two competing mechanisms: pore formation and pore enlargement. At low zinc chloride-to-feed ratios, pore formation is the predominant effect. Pore enlargement occurs at the expense of micropore formation at high zinc chloride-to-feed ratios, thus reducing the micropore content. In addition, the amount of activator used depends on the starting materials, the surface functional groups present, the processing conditions and the desired properties of the product such as pore size, surface area, hardness, etc.
Referring now to fig. 5, a schematic diagram of an apparatus 50 for a chemical activation process is shown. The apparatus 50 includes a nitrogen source 52 in fluid communication with a furnace 54 (Carbolite). A flow meter 56 is provided to detect the flow of gas from the nitrogen source 52 to the furnace 54. The outlet of the oven 54 is in fluid communication with a scrubber 58.
The hydrothermal carbon-activator mixture 60 is loaded onto an alumina boat in a quartz tube and then placed in the furnace 54. The temperature in the furnace 54 was raised to 500 ℃ at a rate of 10 ℃/min and held for 2 hours in the presence of nitrogen at a flow rate of 50 mL/min. The temperature in the furnace 54 is then cooled to room temperature in the presence of nitrogen at a flow rate of 50 mL/min. The resulting product was stirred in 250mL of hydrochloric acid (37%, Panreac) (about 0.1mol/L) for 30 minutes and washed with a large amount of distilled water until the pH obtained from the washing solution was 6. Finally, the activated carbon was dried at 105 ℃ for 24 hours and used for analysis.
Sodium hydroxide (Merck, EMSURE,>99%) OFG content was measured. Boehm titration was performed to evaluate oxygen containing functional groups, typically carboxyl, lactone and phenolic groups. More specifically, under nitrogen (N)2) The biomass and hydrothermal char are heated in the presence of an inert atmosphere up to 150 ℃ for 24 hours. After cooling to room temperature, 1.5g of the sample was mixed with 50mL of NaOH (0.05M), and the mixture was stirred with shaking for 24 hours. The sample was then removed by filtration and a 10mL aliquot was titrated with 0.05M HCl to obtain the OFG content.
Adsorption-desorption isotherms, Brunauer-Emmett-Teller (BET) surface areas (A) were obtained by using a gas adsorption analyzer (Nova-3000 series, Quantachrome)t) And the pore volume of the adsorbent. The pore size distribution was obtained using NLDFT (non-localized density function theory) method. Further, mesoporous surface area (A) was measured by a t-plot methodme) And micropore volume, wherein the total pore volume is estimated as the liquid volume of nitrogen at a relative pressure of about 0.98. Then by subtracting the total pore volume (V)t) Minus micropore volume (V)mi) To calculate the mesoporous volume (V)me). Rhodamine B was selected as a model adsorbate to evaluate the adsorption capacity of activated carbon. Adsorption experiments were performed using equilibrium shaking (batch equilibration) and the concentration of the dye was assessed by using a UV-visible spectrometer (Shimadzu-3600).
Table 1 shows the OFG content of the biomass before and after the hydrothermal carbonization process.
TABLE 1
| Sample (I) | OFG content (meq/g) |
| Coconut Shell (CS) | 1.04 |
| CS hydrothermal charcoal | 1.58 |
| Sawdust (SD) | 0.95 |
| SD hydrothermal carbon | 1.42 |
| Palm Kernel Shell (PKS) | 0.89 |
| PKS hydrothermal charcoal | 1.29 |
As can be seen from table 1 above, the hydrothermal char formed has an increased content of oxygenated functional groups compared to the biomass from which the hydrothermal char was prepared. It can also be seen from the experimental data that the hydrothermal char formed as a result of the pretreatment step has about 40% to about 60% more oxygenated functional group content than the biomass from which the hydrothermal char was prepared.
Table 2 below shows the characteristics of the following various carbon samples: commercially available mesoporous carbon (Sigma Aidrich), activated carbon prepared by direct chemical activation of raw coconut shell (CS-ZP), activated carbon prepared from raw coconut shell subjected to hydrothermal pretreatment in the presence of hydrogen peroxide (CS-HHTZP), activated carbon prepared by direct chemical activation of palm kernel shell (PKS-ZP), activated carbon prepared from palm kernel shell subjected to hydrothermal pretreatment in the presence of hydrogen peroxide (PKS-HHTZP), activated carbon prepared by direct chemical activation of sawdust (SD-ZP), and activated carbon prepared from sawdust subjected to hydrothermal pretreatment in the presence of hydrogen peroxide (SD-HHTZP).
TABLE 2
As can be seen from table 2 above, the activated carbon obtained by hydrothermal treatment with hydrogen peroxide and chemical activation with zinc chloride has high mesoporous area, mesoporous volume, and mesoporous porosity. It can also be seen from table 2 above that a significant increase in these properties is observed when the biomass is pretreated with hydrogen peroxide in a hydrothermal environment. In fact, as can be seen from table 2 above, the use of hydrogen peroxide in the hydrothermal step results in activated carbon having a high mesoporous porosity (mesopore area/BET area) of up to 100%, up to 1815m2High mesoporous surface area per gram, up to 3.5cm3High mesopore volume per g.
The results confirm the inference that including an oxidant pretreatment process improves the effectiveness of the activator and achieves higher mesopore area and higher mesopore porosity. The high OFG content on the hydrothermal carbon, and subsequent activation with zinc chloride, promotes the formation of significantly higher mesopore porosity compared to carbons prepared in the absence of hydrogen peroxide pretreatment. The significant increase in mesoporous surface area and volume is attributed to improved chemical activation due to increased OFG formation on hydrothermal carbon by hydrogen peroxide induced surface functionalization.
Referring now to fig. 6, a graph of nitrogen adsorption-desorption isotherms for commercial mesoporous carbon at 77 kelvin (K) and activated carbon prepared from biomass of coconut shells with and without pre-chemical activation treatment is shown. The continuous line indicates adsorption and the symbol indicates desorption. Hysteresis confirms the presence of mesopores. As is apparent from fig. 6, the adsorption volume of activated carbon (CS-HHTZP) prepared from biomass subjected to hydrothermal pretreatment in the presence of hydrogen peroxide is higher compared to activated carbon (CS-ZP) prepared by direct chemical activation of biomass and commercially available mesoporous carbon. This demonstrates the importance of hydrothermal pretreatment of biomass in the presence of an oxidant prior to chemical activation.
Referring now to fig. 7, 8 and 9, a graph of pore size distribution of commercially available mesoporous carbon and activated carbon prepared from biomass of coconut shells with and without pre-chemical activation treatment is shown in fig. 7, a graph of pore size distribution of activated carbon prepared from biomass of sawdust with and without pre-chemical activation treatment is shown in fig. 8, and a graph of pore size distribution of activated carbon prepared from biomass of palm kernel shells with and without pre-chemical activation treatment is shown in fig. 9. These results show that activated carbon prepared by hydrothermal pretreatment in the presence of an oxidant provides better mesoporous porosity and larger mesoporous volume, 50 angstroms, than activated carbon prepared by direct chemical activation of biomass
To
Referring now to FIG. 10, there is shown a commercial mesoporous carbonAnd a plot of the rhodamine B adsorption curve for activated carbon prepared from biomass of coconut shells with and without pre-chemical activation treatment. The figure shows in liquid phase (C)e) The amount of dye adsorbed per gram of activated carbon at different equilibrium concentrations of adsorbate (q)e). The results of the equilibrium shock study shown in fig. 10 confirm that the adsorption capacity of activated carbon (CS-HHTZP) prepared from biomass subjected to hydrothermal pretreatment in the presence of hydrogen peroxide is higher compared to activated carbon (CS-ZP) prepared by direct chemical activation of biomass and commercially available mesoporous carbon. It can also be observed from FIG. 10 that the saturated capacities of CS-HHTZP, CS-ZP and commercially available mesoporous carbon are 913mg/g, 715mg/g and 176mg/g, respectively. Notably, the saturation capacity of mesoporous carbon, CS-HHTZP, is 28% higher than that of CS-ZP. This increase in adsorption again indicates the contribution of higher mesopore porosity achieved by the hydrothermal treatment with hydrogen peroxide prior to chemical activation.
The results show the significant beneficial effects of the hydrothermal pretreatment step in the presence of hydrogen peroxide and its role in significantly increasing the mesoporous area of the resulting activated carbon. Hydrothermal carbonization using hydrogen peroxide generates more oxygen-containing functional groups, facilitating easy chemical activation. The oxygen-containing functional group (carboxyl, lactone, and phenolic) content in the precursor is an important indicator of the reactivity of the control chemical activation and therefore can be used as a predictor of activated carbon porosity. Studies have shown the importance of surface modification of raw biomass waste to form excellent precursors with increased OFG (oxygen-containing functional group) content, which facilitates chemical activation and thus has a strong beneficial effect in preparing the mesoporous area of the resulting carbon. A significant increase in mesoporous area is achieved by supplementing the chemical activator with an oxidizing agent.
Although specific compositions and parameters have been described in detail in the foregoing embodiments, it will be apparent to those skilled in the art that modifications and variations can be made therein without departing from the scope of the invention.
As is apparent from the foregoing discussion, the present invention provides a process for producing hydrothermal carbon with increased oxygenated functional group content and activated carbon with high or increased mesoporous porosity and surface area from waste biomass. Advantageously, the incorporation of an oxidizing agent during hydrothermal treatment of the biomass induces the formation of oxygen-containing functional groups (OFG) on the resulting hydrothermal char. The high or increased OFG content on hydrothermal carbons promotes formation of carbons with significantly higher mesoporous porosity after chemical activation.
The mesoporous carbon produced according to the present invention is suitable for use in many fields such as energy storage, water treatment, gas separation and purification, and electrocatalysis.
While the preferred embodiments of the invention have been illustrated and described, it will be clear that the invention is not limited to the described embodiments only. Numerous modifications, changes, variations, substitutions and equivalents will be apparent to those skilled in the art without departing from the scope of the invention as described in the claims.
In addition, throughout the description and claims, the words "comprise," "comprising," and the like are to be construed in an inclusive (as opposed to an exclusive or exhaustive) sense, that is, in a sense "including, but not limited to," unless the context clearly requires otherwise.
Claims (15)
1. A method for making activated carbon, comprising:
providing a biomass;
mixing the biomass with an oxidant to form a biomass-oxidant mixture;
subjecting the biomass-oxidant mixture to a hydrothermal carbonization process to form a hydrothermal char having an increased content of oxygenated functional groups as compared to the biomass;
mixing the hydrothermal carbon with an activator to form a hydrothermal carbon-activator mixture; and
subjecting the hydrothermal carbon-activator mixture to a chemical activation process to form activated carbon,
wherein the oxidant is hydrogen peroxide, wherein the hydrothermal char has an oxygen-containing functional group content of 30% to 70% more than the biomass,
wherein the activator is zinc chloride, and
wherein the ratio of the activator to the hydrothermal charcoal in the hydrothermal charcoal-activator mixture is from 2:1 to 10: 1.
2. The process for making activated carbon of claim 1, wherein the biomass comprises one or more of: wood, nut shells, pods, fruit pits, skins.
3. The process for making activated carbon of claim 1, wherein the biomass comprises one or more of: coconut shell, palm kernel shell, sawdust, seeds, bagasse, peat, lignite, and subbituminous coal.
4. The method for producing activated carbon according to claim 1, wherein the biomass is provided in the form of coarse particles having a particle diameter of 0.5mm to 5 mm.
5. The process for making activated carbon of claim 1, wherein the biomass-oxidant mixture comprises 60 to 80 wt% of the biomass.
6. The method for preparing activated carbon according to claim 1, wherein the hydrothermal carbonization process is performed at a temperature of 200 ℃ to 300 ℃ for a time of 20 minutes to 200 minutes.
7. The process for making activated carbon of claim 1, wherein the hydrothermal char has 40% to 60% more oxygenated functional group content than the biomass.
8. The process for producing an activated carbon according to claim 1, wherein the content of the oxygen-containing functional group of the hydrothermal carbon is from 1.2meq/g to 1.6 meq/g.
9. The method for producing activated carbon according to claim 8, wherein the oxygen-containing functional group content is 1.29meq/g, 1.42meq/g, or 1.58 meq/g.
10. The process for producing activated carbon of claim 8, wherein the oxygen-containing functional group content comprises one or more of: carboxyl, lactone and phenolic groups.
11. The method for preparing activated carbon according to claim 1, wherein the chemical activation process is performed at a treatment temperature of 350 ℃ to 650 ℃ for a time of 0.5 hours to 3 hours.
12. The method of making activated carbon of claim 11, wherein the chemical activation process is ramped up to the treatment temperature at a rate of 5 ℃/minute to 15 ℃/minute.
13. The method for preparing activated carbon according to claim 1, wherein the chemical activation process is performed in the presence of nitrogen gas at a flow rate of 20 ml/min to 100 ml/min.
14. The process for producing activated carbon according to claim 1, wherein the activated carbon has 1300m2G to 2000m2Mesoporous surface area per g, 1.9cm3G to 3.8cm3A mesopore volume per gram, and a mesopore porosity of greater than 70%.
15. The process for producing activated carbon according to claim 14, wherein for the activated carbon:
the mesoporous surface area is 1331m2The mesoporous volume is 1.98cm3(iv)/g, and the mesoporous porosity is 76%;
the mesoporous surface area is 1780m2(g), the mesoporous volume is 3.5cm3(ii)/g, and the mesoporous porosity is 100%; or
The mesoporous surface area is 1815m2(g), the mesoporous volume is 2.8cm3(iv)/g, and the mesoporous porosity is 98%.
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| CN116443849B (en) * | 2023-04-27 | 2024-07-12 | 安徽建筑大学 | Porous carbon material with high specific surface area and preparation method and application thereof |
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| US6057262A (en) * | 1995-05-19 | 2000-05-02 | University Of Kentucky Research Foundation | Activated carbon and process for making same |
| CN100509141C (en) * | 2004-06-24 | 2009-07-08 | 中国海洋大学 | Method for preparing active carbon materials SO* absorbent by medicament activation method |
| CN101439857B (en) * | 2008-12-11 | 2011-03-02 | 武汉科技大学 | Mesoporous activated carbon and preparation process thereof |
| CN101759181A (en) * | 2009-12-15 | 2010-06-30 | 李广朝 | Method for producing activated carbon for super capacitors |
| CN102205963A (en) * | 2011-03-16 | 2011-10-05 | 吉林大学 | Method for preparing activated carbon for biomass-based super capacitor |
| CN103962097A (en) * | 2014-04-02 | 2014-08-06 | 中国石油大学(华东) | Method for preparing CO2 carbon-based absorbent on basis ofenteromorpha |
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