CN110064367B - Biomass-based activated carbon microsphere and preparation method and application thereof - Google Patents
Biomass-based activated carbon microsphere and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a biomass-based activated carbon microsphere and a preparation method and application thereof. The preparation method comprises the following steps: mixing waste biomass powder with various reagents and fully stirring the mixture at room temperature until the mixture is uniform to obtain a suspension; transferring the suspension to a reaction kettle for hydrothermal reaction to obtain hydrothermal carbon spheres; cooling the hydrothermal carbon spheres, washing with water, and drying to obtain a carbon precursor; mixing and grinding a carbon precursor, a nitrogenous substance and an activating agent according to a certain proportion, and then roasting, washing and drying to prepare the biomass-based activated carbon microsphere, wherein the specific surface area of the biomass-based activated carbon microsphere can reach 1349.17-1685.68 m2(ii) in terms of/g. The invention has the advantages of cheap raw materials, simple formula, mild preparation conditions, spherical product and capability of preparing the activated carbon microspheres with CO at room temperature2Has excellent adsorption performance, stable cyclic regeneration adsorption performance and better CO2/N2Adsorption selectivity and the like.
Description
Technical Field
The invention belongs to CO2The field of adsorbents, in particular to biomass-based activated carbon microspheres and a preparation method and application thereof.
Background
Biomass is a general term of a certain accumulated amount of animal and plant resources and animal and plant wastes, is the only renewable carbon energy on the earth, and is known as traditional fossilFuel alternatives ", about 66 million tons per year, most of which are incinerated and used, and the utilization rate is extremely low. Thermal power plants that burn fossil fuels to generate electricity are the largest CO worldwide2Emission source, approximatively accounting for CO235% of the total emission. CO capture from post-combustion flue gas in three carbon capture processes, fuel combustion, pre-combustion, and post-combustion2Is the simplest method. Flue gas after combustion (T < 200 ℃) is mainly CO2And N2Due to CO2The separation difficulty is very high due to low partial pressure, and the method becomes a significant scientific problem restricting the world energy-saving and emission-reducing pattern in the 21 st century in a certain sense. Thus, for low temperature CO2The adsorption and recovery have very important strategic significance.
The hydrothermal carbonization (HTC) method is a process for synthesizing a carbon-rich product in a sealed pressure vessel by using biomass as a raw material and water as a solvent and a reaction medium under self pressure and at a reaction temperature of 150-375 ℃. Compared with the traditional thermochemical conversion method, the HTC temperature is low, the raw materials are not limited by the moisture content, the energy consumption is low, and CO is generated2The release amount is small, and the method becomes an efficient biomass pretreatment means and a biomass full-component conversion method; the hydrothermal carbon has rich oxygen-containing functional groups, adjustable surface chemical properties and high calorific value (HHV), and has made some progress in the fields of metal ion adsorption, preparation of porous carbon materials, solid acid catalysts, clean energy and the like (Wu beautiful and beautiful, Liwei, Wu Qiong, and the like]Chemical progression 2015,28(1): 121-. CN106629661A discloses a process for preparing carbon nanospheres from bagasse, which comprises placing bagasse in a mixed solution of sulfuric acid, phosphoric acid and water, dissolving cellulose and hemicellulose in the bagasse, filtering the solvent to obtain a filtrate, dissolving small molecular sugar in the bagasse during hydrothermal reaction of the filtrate, and preparing carbon nanospheres from the small molecular sugar solution by a hydrothermal method. The method has simple process and wide raw material source, but two acid solutions are used in the preparation process, so the method is not environment-friendly. CN102219204A discloses a method for preparing biomass-based colloidal carbon, which comprises hydrolyzing corn stalks with dilute acid and concentrated acid respectively to obtain sugar acid solution of xylose and glucose, and mixing the sugar acid solution with waterAnd (3) carrying out in-situ polycondensation and carbonization to prepare the colloidal carbon spheres taking xylose or glucose as precursors. The method has high waste utilization rate, but the operation process is complicated.
The traditional hydrothermal method for preparing carbon spheres generally uses small molecular biomass such as sucrose, glucose, etc. as carbon source, such as Sevilla Marta et al (Marta Sevilla, Antonio B. Fuerts. chemical and structural properties of carbonaous products obtained by hydrotherma carbide of saccharoides [ J]Chemistry-A European Journal,2009,15, 4195-. However, the preparation of spherical biochar materials by mild hydrothermal method using agricultural waste biomass (core, shell, skin, rod) rich in lignin and high-crystallinity cellulose as raw materials has been recently reported at home and abroad. Based on this, the preparation of CO useful at room temperature using waste biomass as raw material2The trapped micron carbon spheres have strong competitiveness and are expected to be used as cheap load matrixes of various materials.
Disclosure of Invention
The invention aims to provide a preparation method of biomass-based activated carbon microspheres.
The technical problem to be solved by the invention is as follows: provides a preparation method of biomass-based spherical activated carbon with relatively mild preparation conditions, cheap raw materials and good performance, and the prepared adsorbent can be used for treating main greenhouse gas CO at room temperature2Has excellent adsorption performance and stable cyclic regeneration adsorption performance.
The invention also aims to provide the biomass-based activated carbon microspheres obtained by the preparation method.
The invention further aims to provide application of the biomass-based activated carbon microspheres.
The purpose of the invention is realized by the following technical scheme:
a preparation method of biomass-based activated carbon microspheres comprises the following steps:
firstly, mixing waste biomass powder of 20-100 meshes with various reagents, and fully stirring the mixture at room temperature until the mixture is uniform to obtain a suspension; transferring the suspension to a reaction kettle for hydrothermal reaction to obtain hydrothermal carbon spheres; cooling the hydrothermal carbon spheres, washing with water, and drying to obtain a carbon precursor; mixing and grinding a carbon precursor, a nitrogenous substance and an activating agent according to a certain proportion, and then roasting, washing and drying to prepare the biomass-based active carbon microsphere; the multiple reagents are ammonium persulfate, sulfuric acid, and water.
The waste biomass powder is at least one of pecan shell powder, pineapple peel powder, melon seed shell powder, walnut shell powder and coconut inner shell powder; it is prepared from at least one of pecan shell, pineapple peel, melon seed shell, walnut shell and coconut inner shell by cleaning, oven drying, crushing and sieving.
The dosage of the waste biomass powder and the dosage of various reagents are respectively as follows: 1-2 parts by mass of waste biomass powder, 1-2 parts by mass of ammonium persulfate, 0.5-1 part by volume of sulfuric acid, and 40-60 parts by volume of water.
The stirring time is 0.5-1 h, and the rotating speed is 600 r/min.
The mass concentration range of the sulfuric acid is 95.0-98.0%.
The hydrothermal process conditions are as follows: reacting for 16-20 h at 120 ℃, heating to 230 ℃ from 120 ℃, and reacting for 24h at 230 ℃.
The nitrogen-containing substance is chitosan; the activating agent is one or two of potassium oxalate and potassium tartrate; the dosage of the precursor, the nitrogenous substance and the activating agent of the carbon is respectively as follows: 1 to 1.5 parts by mass of a carbon precursor, 1 to 3 parts by mass of a nitrogen-containing compound, and 3 to 4.5 parts by mass of an activating agent.
The roasting process conditions are as follows: n is a radical of2Or static roasting in inert gas atmosphere at 700-800 ℃ for 2 h.
And preserving heat for 1h at 200 ℃ before roasting.
The biomass-based activated carbon microsphere is characterized in that the hydrothermal carbon microsphere can be directly prepared from waste biomass powder by a simple hydrothermal method, and most of the carbon microsphere (the particle size is 3 +/-1 mu m) can still be reserved after high-temperature roasting and activation.
The biomass-based activated carbon microsphere has the specific surface area of 1349.17-1685.68m2/g。
The biomass-based activated carbon microspheres can be used for adsorbing CO2。
The biomass-based activated carbon microspheres can be used for treating CO at normal temperature and normal pressure2The adsorption amount of (A) is 3.86 to 4.09 mmol/g. The obtained activated carbon microsphere adsorbent adsorbs CO2And then the desorption is circularly regenerated at different temperatures.
The biomass-based activated carbon microspheres can be used for treating CO at normal temperature and normal pressure2/N2The adsorption selectivity of the catalyst is 10.71-14.37.
In the invention, 1 part by mass: 1 part by volume is 1 g/ml.
Compared with the prior art, the invention has the following main advantages:
(1) various cheap, easily-obtained, nontoxic and harmless waste biomass shells are selected as carbon sources, so that certain universality is achieved; the mild potassium tartrate or potassium oxalate is selected as an activating agent, so that the adsorption performance of the activated carbon can be greatly improved on the basis of reducing energy consumption;
(2) ammonium persulfate with strong oxidizing property is adopted to assist hydrothermal reaction to prepare hydrothermal carbon microspheres, and then the hydrothermal carbon microspheres are roasted at high temperature to obtain the activated carbon microsphere adsorbent, so that the spherical morphology can be kept, and the adsorption performance of activated carbon can be enhanced; under the combined assistance of the strong oxidizing property of ammonium persulfate and the acidity of sulfuric acid, macromolecular substances such as cellulose and lignin can be decomposed into small molecular soluble substances such as glucose, and the small molecular substances are converged into spherical particles under the hydrothermal environment (
Holger V.Lutze,Klaudiusz Grübel,et al.Chemistry of persulfates in water and wastewater treatment:a review[J].Chemical Engineering Journal,2017,330,44-62)。
(3) The prepared activated carbon microspheres are aligned to CO at room temperature2Has excellent adsorption performance, stable cyclic regeneration adsorption performance and better CO2/N2Adsorption selectivity and the like: the prepared biomass-based activated carbon microspheres (the particle size is about 3 +/-1 mu m) can react with CO at normal temperature and normal pressure2The adsorption capacity can reach 3.86-4.09 mmol/g; for CO at normal temperature and normal pressure2/N2The adsorption selectivity of the adsorbent can reach 10.71-14.37; the specific surface area can reach 1349.17-1685.68 m2/g。
(4) The prepared biomass-based activated carbon microspheres can be regenerated at a lower temperature (to adsorb CO)2The sample is degassed for 4 hours under the condition of 200 ℃ and vacuum on a degassing device of a first generation TriStar II 3020 adsorption analyzer produced by Micromerics instruments of America, so that the regeneration experiment can be completed), and the sample has excellent cyclic regeneration adsorption performance.
Drawings
In fig. 1, a, b, c, d, and e are scanning electron microscope pictures of biomass-based activated carbon microspheres prepared in examples 1 to 5, respectively.
FIG. 2 is an X-ray diffraction pattern of biomass-based activated carbon microspheres prepared in example 1.
In FIG. 3, a and b are N in biomass-based activated carbon microspheres prepared in examples 1 to 5, respectively2Adsorption-desorption curve.
In fig. 4, a and b are pore distribution curves of biomass-based activated carbon microspheres prepared in examples 1 to 5, respectively.
FIG. 5 shows that the biomass-based activated carbon microspheres prepared in examples 1 to 5 are aligned to CO at normal temperature and normal pressure2Adsorption curve of (2).
FIG. 6 shows the CO content of biomass-based activated carbon microspheres prepared in example 1 at normal temperature and pressure2The cyclic adsorption histogram of (a).
In FIG. 7, a and b are the CO pairs at normal temperature and pressure for biomass-based activated carbon microspheres prepared in example 1, respectively2And N2Adsorption curve of, for CO at normal temperature and pressure2/N2Initial slope determination of the adsorption curve.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto. The concentration range of sulfuric acid used in the examples of the present invention was 95.0-98.0%. In the test of the embodiment of the invention, the actual ranges of the normal temperature and the room temperature are 20-25 ℃.
Example 1:
firstly, pulverizing pineapple peels which are sequentially cleaned and dried for 24 hours at 100 ℃ into powder of 20-100 meshes; taking 1g of pineapple peel powder, 0.5mL of sulfuric acid, 1g of ammonium persulfate and 40mL of distilled water, and stirring at room temperature for 0.5h to obtain a suspension; transferring the suspension into a reaction kettle lined with polytetrafluoroethylene, preserving heat for 16h at 120 ℃, heating to 230 ℃ from 120 ℃, and preserving heat for 24h at 230 ℃ to obtain a hydrothermal carbon microsphere product;
secondly, cooling the hydrothermal carbon microsphere product at room temperature, washing with distilled water, and drying at 110 ℃ for 12h to obtain a carbon precursor; mixing and grinding a carbon precursor, chitosan and potassium tartrate according to a mass ratio of 1:2:3, transferring all the mixture into a crucible, and placing the crucible in N2Keeping the temperature at 200 ℃ for 1h under the atmosphere of 50ml/min, and heating to 800 ℃ for carbonization (the heating rate is 5 ℃/min) for 2h to obtain a carbide; repeatedly washing the carbide with 1mol/L hydrochloric acid and distilled water to neutrality, drying (80 ℃, 12h) to obtain biomass-based spherical activated carbon, and treating CO at normal temperature and normal pressure2The adsorption amount of (2) was 4.06mmol/g (see the curve in FIG. 1), and the adsorption was carried out on CO at normal temperature and pressure2/N2Selectivity of 11.02.
Example 2:
firstly, pulverizing the pecan shells which are sequentially cleaned and dried at 100 ℃ for 24 hours into powder of 20-100 meshes; taking 2g of pecan shell powder, 1mL of sulfuric acid, 2g of ammonium persulfate and 60mL of distilled water, and stirring for 1h at room temperature to obtain a suspension; transferring the suspension into a reaction kettle lined with polytetrafluoroethylene, preserving heat for 18 hours at 120 ℃, heating to 230 ℃ from 120 ℃, and preserving heat for 24 hours at 230 ℃ to obtain a hydrothermal carbon microsphere product;
secondly, cooling the hydrothermal carbon microsphere product at room temperature, washing with distilled water, and drying at 110 ℃ for 12h to obtain a carbon precursor; mixing and grinding a carbon precursor, chitosan and potassium tartrate in a mass ratio of 1:1:3, transferring all the mixture into a crucible, and placing the crucible in N2Keeping the temperature at 200 ℃ for 1h under the atmosphere of 50ml/min, and heating to 750 ℃ for carbonization (the heating rate is 5 ℃/min) for 2h to obtain a carbide; repeatedly washing the carbide with 1mol/L hydrochloric acid and distilled water to neutrality, drying (80 ℃, 12h) to obtain biomass-based spherical activated carbon which is at normal temperature and normal pressureReduction of CO2The adsorption amount of (2) was 3.86mmol/g (see the curve in FIG. 1), and the adsorption was carried out on CO at normal temperature and pressure2/N2The selectivity of (A) was 10.71.
Example 3:
firstly, pulverizing the melon seed shells which are cleaned and dried for 24 hours at 100 ℃ into powder of 20-100 meshes; stirring 2g of melon seed shell powder, 1mL of sulfuric acid, 2g of ammonium persulfate and 40mL of distilled water at room temperature for 0.5h to obtain a suspension; transferring the suspension into a reaction kettle lined with polytetrafluoroethylene, preserving heat for 20 hours at 120 ℃, heating to 230 ℃ from 120 ℃, and preserving heat for 24 hours at 230 ℃ to obtain a hydrothermal carbon microsphere product;
secondly, cooling the hydrothermal carbon microsphere product at room temperature, washing with distilled water, and drying at 110 ℃ for 12h to obtain a carbon precursor; mixing and grinding a carbon precursor, chitosan and potassium oxalate in a mass ratio of 1.5:1.5:4.5, transferring all the mixture into a crucible, and placing the crucible in N2Keeping the temperature at 200 ℃ for 1h under the atmosphere of 50ml/min, and heating to 700 ℃ for carbonization (the heating rate is 5 ℃/min) for 2h to obtain a carbide; repeatedly washing the carbide with 1mol/L hydrochloric acid and distilled water to neutrality, drying (80 ℃, 12h) to obtain biomass-based spherical activated carbon, and treating CO at normal temperature and normal pressure2The adsorption amount of (2) was 3.86mmol/g (see the curve in FIG. 1), and the adsorption was carried out on CO at normal temperature and pressure2/N2The selectivity of (a) was 11.04.
Example 4:
firstly, pulverizing walnut shells which are sequentially cleaned and dried at 100 ℃ for 24 hours into powder of 20-100 meshes; taking 2g of walnut shell powder, 1mL of sulfuric acid, 2g of ammonium persulfate and 40mL of distilled water, and stirring at room temperature for 0.5h to obtain a suspension; transferring the suspension into a reaction kettle lined with polytetrafluoroethylene, preserving heat for 16h at 120 ℃, heating to 230 ℃ from 120 ℃, and preserving heat for 24h at 230 ℃ to obtain a hydrothermal carbon microsphere product;
secondly, cooling the hydrothermal carbon microsphere product at room temperature, washing with distilled water, and drying at 110 ℃ for 12h to obtain a carbon precursor; mixing and grinding a carbon precursor, chitosan and potassium tartrate according to a mass ratio of 1.5:3:4.5, transferring all the mixture into a crucible, and placing the crucible in N2Keeping the temperature at 200 deg.C for 1h under 50ml/min, heating to 750 deg.C, and carbonizing for 2h at a heating rate of 5 deg.C/min to obtainTo a char; repeatedly washing the carbide with 1mol/L hydrochloric acid and distilled water to neutrality, drying (80 ℃, 12h) to obtain biomass-based spherical activated carbon, and treating CO at normal temperature and normal pressure2The adsorption amount of (2) was 4.00mmol/g (see the curve in FIG. 1), and the adsorption was carried out on CO at normal temperature and pressure2/N2The selectivity of (A) was 12.17.
Example 5:
firstly, pulverizing coconut shells which are sequentially cleaned and dried at 100 ℃ for 24 hours into powder of 20-100 meshes; stirring 2g of coconut inner shell powder, 1mL of sulfuric acid, 2g of ammonium persulfate and 40mL of distilled water at room temperature for 0.5h to obtain a suspension; transferring the suspension into a reaction kettle lined with polytetrafluoroethylene, preserving heat for 16h at 120 ℃, heating to 230 ℃ from 120 ℃, and preserving heat for 24h at 230 ℃ to obtain a hydrothermal carbon microsphere product;
secondly, cooling the hydrothermal carbon microsphere product at room temperature, washing with distilled water, and drying at 110 ℃ for 12h to obtain a carbon precursor; mixing and grinding a carbon precursor, chitosan and potassium oxalate in a mass ratio of 1:1:3, transferring all the mixture into a crucible, and placing the crucible in N2Keeping the temperature at 200 ℃ for 1h under the atmosphere of 50ml/min, and heating to 800 ℃ for carbonization (the heating rate is 5 ℃/min) for 2h to obtain a carbide; repeatedly washing the carbide with 1mol/L hydrochloric acid and distilled water to neutrality, drying (80 ℃, 12h) to obtain biomass-based spherical activated carbon, and treating CO at normal temperature and normal pressure2The adsorption amount of (2) was 4.09mmol/g (see the curve in FIG. 1), and the adsorption was carried out on CO at normal temperature and pressure2/N2The selectivity of (a) is 14.37.
Comparative example 1:
in order to investigate whether the ammonium persulfate auxiliary hydrothermal treatment method can effectively improve the CO content of the biomass-based spherical activated carbon material at room temperature2The control experiment was designed under the preferred experimental conditions (example 1):
firstly, pulverizing pineapple peels which are sequentially cleaned and dried for 24 hours at 100 ℃ into powder of 20-100 meshes; 1g of pineapple peel powder and 40mL of distilled water are taken and stirred for 0.5h at room temperature to obtain a suspension; transferring the suspension into a reaction kettle lined with polytetrafluoroethylene, preserving heat for 16h at 120 ℃, heating to 230 ℃ from 120 ℃, and preserving heat for 24h at 230 ℃ to obtain a hydrothermal product;
secondly, cooling the hydrothermal product at room temperature, washing with distilled water, and drying at 110 ℃ for 12h to obtain a carbon precursor; mixing and grinding a carbon precursor, chitosan and potassium tartrate according to a mass ratio of 1:2:3, transferring all the mixture into a crucible, and placing the crucible in N2Keeping the temperature at 200 ℃ for 1h under the atmosphere of 50ml/min, and heating to 800 ℃ for carbonization (the heating rate is 5 ℃/min) for 2h to obtain a carbide; repeatedly washing the carbide with 1mol/L hydrochloric acid and distilled water to neutrality, drying (80 ℃, 12h) to obtain biomass-based activated carbon, and treating CO at normal temperature and normal pressure2The amount of adsorbed was 3.57 mmol/g.
The samples in the above examples were analyzed using a TriStar II 3020 model adsorption Analyzer, manufactured by Micromerics instruments, USA, for comparison of surface area and pore size, and the total surface area was measured by BET method and the total pore volume was measured at relative pressure (P/P)0) The adsorption quantity is 0-0.995 calculated from the adsorption quantity of liquid nitrogen; sample for CO at normal temperature and pressure2And N2The adsorption amount of (A) was measured by using TriStar II 3020 type adsorption analyzer manufactured by Micromerics instruments, USA, CO2/N2By CO selectively2And N2Calculating the initial slope of the adsorption curve by using Henry's law; the microstructure of the sample surface was measured by a JSM-IT300 scanning electron microscope manufactured by Japan Electron Co., Ltd; the phase structure of the sample was examined using an X-ray diffractometer model D8Advance, brueck AXS, germany.
According to the scanning electron microscope picture (figure 1) of the biomass-based activated carbon microspheres prepared in the embodiments 1-5, the products of all the embodiments are spherical particles with the particle size of about 3 +/-1 μm.
The X-ray diffraction pattern (figure 2) of the biomass-based activated carbon microspheres prepared according to example 1 of the invention shows that the product is amorphous carbon.
Specific parameters of analyses such as specific surface area and pore structure of the samples of examples 1 to 5 are shown in Table 1. As can be seen from Table 1, the biomass-based activated carbon microspheres prepared according to embodiments 1 to 5 of the present invention have a high total specific surface area and a high total pore volume, which can respectively reach 1685.68m at most2/g、0.3533cm3Per g, and CO2The diameter of the molecule is 0.33nm, so the activated carbon prepared by the invention has CO pairing effect2The adsorption of gases plays an important role.
N of biomass-based activated carbon microspheres prepared according to embodiments 1 to 5 of the present invention2The adsorption-desorption curve (fig. 3) and the pore distribution curve (fig. 4) show typical microporous structures. Combining the main texture Property parameters with CO in Table 12The tendency of change in the amount of adsorption may be presumed to be that physical factors such as the specific surface area and the pore structure of the sample may play a determining role in the adsorption performance.
The samples of examples 1-5 were subjected to CO adsorption2Then, the mixture was degassed under vacuum at 200 ℃ for 4 hours on a degasser of TriStar II 3020 adsorption analyzer manufactured by Micromerics instruments, USA. Then, the degassed samples were subjected to cyclic adsorption experiments for 10 cycles with room temperature CO2The adsorption capacity is still as high as 3.54-3.59 mmol/g, the adsorption capacity is respectively 87.2%, 86.3%, 87.0%, 87.3% and 87.8% of the initial adsorption capacity, and the excellent cyclic regeneration and use capacity is shown (see figure 6).
The biomass-based activated carbon microspheres prepared according to the embodiment 1 of the invention contain CO at normal temperature and pressure2And N2Adsorption curve (FIG. 7) showing very low N at 25 ℃ and 1bar2The adsorption capacity, which is only 0.6525mmol/g, indicates that the sample can be used for selective adsorption of CO in flue gas2。CO2/N2Is selected by CO2And N2The initial slope of the adsorption curve was calculated using henry's law, see fig. 7, and the selectivity thus calculated was 11.02. The biomass-based activated carbon microspheres prepared according to embodiments 1-5 of the invention can be used for treating CO at normal temperature and pressure2/N2Specific adsorption selectivity parameters of (A) are shown in Table 1.
In the above embodiment, the book of the old can be adopted
And crushing the dried solution product before activation by using a multifunctional crusher, wherein the crushed product is 20-100 meshes.
Table 1 main texture property parameters, CO at normal temperature and pressure, of biomass-based activated carbon microspheres prepared in examples 1 to 52Adsorption amount, N2Adsorption amount and CO2/N2Adsorption selectivity
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (6)
1. A preparation method of biomass-based activated carbon microspheres is characterized by comprising the following steps:
firstly, mixing waste biomass powder with various reagents and fully stirring the mixture at room temperature until the mixture is uniform to obtain a suspension; transferring the suspension to a reaction kettle for hydrothermal reaction to obtain hydrothermal carbon spheres; cooling the hydrothermal carbon spheres, washing with water, and drying to obtain a carbon precursor; mixing and grinding a carbon precursor, a nitrogenous substance and an activating agent, and then roasting, washing and drying to prepare the biomass-based active carbon microspheres; the multiple reagents are ammonium persulfate, sulfuric acid and water; the hydrothermal process conditions are as follows: reacting for 16-20 h at 120 ℃, heating to 230 ℃ from 120 ℃, and reacting for 24h at 230 ℃; the dosage of the waste biomass powder and the dosage of various reagents are respectively as follows: 1-2 parts by mass of waste biomass powder, 1-2 parts by mass of ammonium persulfate, 0.5-1 part by volume of sulfuric acid and 40-60 parts by volume of water; the nitrogen-containing substance is chitosan; the activating agent is one or two of potassium oxalate and potassium tartrate; the dosage of the precursor, the nitrogenous substance and the activating agent of the carbon is respectively as follows: 1-1.5 parts by mass of a carbon precursor, 1-3 parts by mass of a nitrogen-containing compound and 3-4.5 parts by mass of an activating agent; the waste biomass powder is at least one of pecan shell powder, pineapple peel powder, melon seed shell powder, walnut shell powder and coconut inner shell powder.
2. A method of making activated carbon microspheres based on biomass as claimed in claim 1 wherein the process conditions of said calcination are: n is a radical of2Or static roasting in inert gas atmosphere at 700-800 ℃ for 2 h.
3. Biomass-based activated carbon microspheres produced by the production method according to any one of claims 1 to 2.
4. The biomass-based activated carbon microspheres of claim 3, wherein the biomass-based activated carbon microspheres have a specific surface area of 1349.17-1685.68 m2/g。
5. Use of biomass-based activated carbon microspheres as claimed in claim 3 or 4 in adsorption of CO2The use of (1).
6. The use of claim 5, wherein said biomass-based activated carbon microspheres are compatible with CO at ambient temperature and pressure2The adsorption capacity of the adsorbent is 3.86-4.09 mmol/g, and the adsorbent can adsorb CO at normal temperature and normal pressure2/N2The adsorption selectivity of the catalyst is 10.71-14.37.
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| CN110918063B (en) * | 2019-12-26 | 2020-09-11 | 宁夏浦士达环保科技有限公司 | Preparation process of environment-friendly adsorption material and adsorption testing system |
| CN111298767A (en) * | 2020-02-17 | 2020-06-19 | 安徽工业大学 | Biomass-based carbon material for adsorbing heavy metal ions, preparation method and application |
| CN111408348A (en) * | 2020-04-28 | 2020-07-14 | 南阳师范学院 | Preparation method of straw-based porous biochar nanospheres |
| CN112441837A (en) * | 2020-12-09 | 2021-03-05 | 安徽工业大学 | High-performance (VNbTaMoW) C high-entropy carbide ceramic and preparation method thereof |
| CN112973628B (en) * | 2021-02-06 | 2023-03-17 | 重庆文理学院 | Preparation method of activated carbon rich in basic functional groups |
| CN114180553B (en) * | 2021-12-03 | 2023-10-20 | 曲阜师范大学 | Method for preparing nitrogen-doped porous carbon by taking waste crop root system as raw material and application |
| CN115028155B (en) * | 2022-05-30 | 2024-03-08 | 上海安朵生物医学科技有限公司 | Preparation method of biomass porous carbon material, carbon material prepared by method and application of carbon material |
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