CN114130361A - Adsorb CO2The nitrogen-doped porous carbon granular material and the preparation method thereof - Google Patents
Adsorb CO2The nitrogen-doped porous carbon granular material and the preparation method thereof Download PDFInfo
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- CN114130361A CN114130361A CN202111600177.1A CN202111600177A CN114130361A CN 114130361 A CN114130361 A CN 114130361A CN 202111600177 A CN202111600177 A CN 202111600177A CN 114130361 A CN114130361 A CN 114130361A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 52
- 239000008187 granular material Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 241000219000 Populus Species 0.000 claims abstract description 37
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 14
- 238000001125 extrusion Methods 0.000 claims abstract description 13
- 239000011230 binding agent Substances 0.000 claims abstract description 12
- 238000003763 carbonization Methods 0.000 claims abstract description 11
- 230000004913 activation Effects 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims description 51
- 238000001035 drying Methods 0.000 claims description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- 239000008367 deionised water Substances 0.000 claims description 35
- 229910021641 deionized water Inorganic materials 0.000 claims description 35
- 239000000203 mixture Substances 0.000 claims description 34
- 239000002023 wood Substances 0.000 claims description 34
- 238000010438 heat treatment Methods 0.000 claims description 24
- 238000000197 pyrolysis Methods 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 14
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 14
- 238000004140 cleaning Methods 0.000 claims description 12
- 239000011363 dried mixture Substances 0.000 claims description 12
- 238000002791 soaking Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 241000219782 Sesbania Species 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
- 238000001994 activation Methods 0.000 claims description 10
- 238000005520 cutting process Methods 0.000 claims description 7
- 230000003213 activating effect Effects 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000003463 adsorbent Substances 0.000 claims description 4
- 238000012216 screening Methods 0.000 claims description 3
- 238000007605 air drying Methods 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 21
- 239000003575 carbonaceous material Substances 0.000 abstract description 11
- 239000002028 Biomass Substances 0.000 abstract description 4
- 238000005469 granulation Methods 0.000 abstract description 2
- 230000003179 granulation Effects 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 244000275012 Sesbania cannabina Species 0.000 abstract 1
- 239000000047 product Substances 0.000 description 35
- 229910002092 carbon dioxide Inorganic materials 0.000 description 19
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 10
- 239000001569 carbon dioxide Substances 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 238000005303 weighing Methods 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
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- 238000000921 elemental analysis Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005201 scrubbing Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
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- 230000006835 compression Effects 0.000 description 1
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- 239000000428 dust Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
- 230000009919 sequestration Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- B01J20/3007—Moulding, shaping or extruding
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Abstract
The invention discloses a method for adsorbing CO2The nitrogen-doped porous carbon granular material and the preparation method thereof belong to the field of preparation of biomass porous carbon materials; using poplar sawdust as carbon source, microalgae as nitrogen source and sesbania powder as binder, high-temp. carbonization, KOH activation and extrusion granulation so as to obtain the invented product with ideal CO content2A nitrogen-doped porous carbon granular material with adsorption stability and good mechanical properties; the preparation method is simple, the production process is environment-friendly, and the preparation method is suitable for large-scale production.
Description
Technical Field
The invention belongs to the technical field of preparation of biomass porous carbon materials, and particularly relates to a method for adsorbing CO2The nitrogen-doped porous carbon particle material and the preparation method thereof.
Background
Global warming due to excessive carbon dioxide emissions has attracted a high degree of attention. The capture, utilization and sequestration of carbon dioxide is an important strategy for alleviating the global warming threat at present. Among them, the capture of carbon dioxide is the most indispensable step. Amine scrubbing is currently the most mature technology for carbon dioxide capture in industry, but not only is the energy consumption high, but also harmful by-products are produced in the amine scrubbing process. Therefore, there is a need to develop alternative carbon dioxide capture technologies.
Various solid adsorbent materials promising alternatives to amine-based solvents have been developed. The biomass porous carbon is rich in raw materials, has high specific surface area and pore volume, is easy to adjust pore structure, has good thermochemistry property and thermal stability, and is an excellent solid adsorbent material applied to carbon dioxide capture. For porous carbon adsorbents, both the porous structure and the surface characteristics affect their ability to capture carbon dioxide. The introduction of heteroatoms (such as N, P, B, S and the like) into the structure of the porous carbon can obviously improve the adsorption capacity of the porous carbon. Particularly, the introduction of nitrogen atoms enhances the surface polarity and alkalinity of the porous carbon and improves the reaction of the porous carbon and the acid gas. At present, nitrogen-containing organic chemicals (such as melamine, urea, tetraethylenepentamine and the like) are generally used as nitrogen sources for doping. However, these organic chemical reagents are not only high in cost, toxic and environmentally unfriendly, so that the use of biomass microalgae as a nitrogen source instead of nitrogen-containing organic chemical reagents is of great significance in improving the ability of porous carbon to capture carbon dioxide.
While researchers have done a great deal of work in the preparation of porous carbons, the porous carbons produced are typically in powder form. The practical application of the porous carbon is seriously influenced by the problem that large pressure drop is easily generated in a large fixed bed adsorption device in industrial application. In order to break through the bottleneck, the porous carbon powder is prepared into particles, and the granulation not only improves the mechanical strength of the porous carbon, but also reduces the transportation cost and the storage cost.
Disclosure of Invention
In order to solve the problems, the invention discloses a method for adsorbing CO2The nitrogen-doped porous carbon particle material and the preparation method thereof. By doping a proper amount of microalgae in the poplar wood chips, nitrogen is introduced and optimizedA pore structure. The introduction of nitrogen can increase the surface polarity and alkalinity of the nitrogen, thereby improving the adsorption of CO2Ability, mechanical properties and cycle stability.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the invention aims to provide a method for adsorbing CO2The nitrogen-doped porous carbon granular material comprises a carbon source material, a nitrogen source material and a binder; the carbon source material is poplar wood chips; the nitrogen source material is microalgae; the binder is sesbania powder.
Further, the nitrogen-doped porous carbon granular material is columnar granules, the length of the columnar granules is 0.8-1mm, and the diameter of the columnar granules is 0.8-1.0 mm.
It is still another object of the present invention to provide a method for adsorbing CO as described above2The preparation method of the nitrogen-doped porous carbon granular material comprises the following steps:
step 1: pretreating poplar sawdust and microalgae;
step 2: mixing the pretreated poplar wood chips with microalgae, soaking the mixture in deionized water, magnetically stirring the mixture at the rotation speed of 150-plus-200 rpm for 24-36h, then placing the mixture in an oven for drying, placing the dried mixture in a tubular furnace, carrying out pyrolysis carbonization in nitrogen atmosphere, cooling the mixture to 20-25 ℃, repeatedly cleaning the product with deionized water, and drying the product at the temperature of 100-plus-110 ℃ to obtain a carbonized product;
and step 3: mixing the carbonized product obtained in the step 2 with an activating agent, soaking the mixture in deionized water, magnetically stirring the mixture for 24 to 36 hours at the rotating speed of 150-200rpm, then placing the mixture in a drying oven for drying, placing the dried mixture in a tubular furnace, carrying out pyrolysis activation in a nitrogen atmosphere, cooling the activated product to 20 to 25 ℃, cleaning the product with HCl, then repeatedly washing the product with deionized water to neutrality, and drying the product at the temperature of 100-110 ℃ to obtain nitrogen-doped porous carbon powder;
and 4, step 4: and (3) mixing the nitrogen-doped porous carbon powder obtained in the step (3) with a binder, adding a proper amount of deionized water, fully stirring to form a wet material with uniform humidity, putting the mixture into an extruder for extrusion forming, extruding the material into a long cylindrical material with the diameter of 0.8-1mm, and cutting the long cylindrical material to obtain a cylindrical material with the length of 0.8-1mm, so as to obtain the nitrogen-doped porous carbon granular material.
Further, in step 1, the pretreatment comprises the following steps: repeatedly cleaning poplar wood chips with water, placing the poplar wood chips in a forced air drying oven for drying at 110 ℃ for 24-36h, crushing the dried poplar wood chips, and screening the crushed poplar wood chips to 500 mu m at 300 ℃ for later use; and (3) drying the microalgae for 24-36h in a blast drying oven at the temperature of 30-45 ℃.
Further, in the step 2, the mass ratio of the poplar wood chips to the microalgae is 1: 0.25-2, preferably, the mass ratio of the poplar wood chips to the microalgae is 1: 0.5; the pyrolysis carbonization conditions are as follows: the heating rate is 5-10 ℃/min, the temperature is increased to 550 ℃ and 600 ℃, and the constant temperature is kept for 1-1.5 h.
Further, in the step 3, the mass ratio of the carbonized product obtained in the step 2 to the activating agent is 1:2-4, preferably, the mass ratio of the carbonized product to the activating agent is 1: 2; the pyrolysis activation conditions are as follows: the heating rate is 5-10 ℃/min, the temperature is raised to 650-700 ℃, and the constant temperature is kept for 1-1.5 h.
Further, the activator is KOH.
Further, in the step 4, the mass ratio of the nitrogen-doped porous carbon powder obtained in the step 3 to the binder is 5-20:1, and preferably, the mass ratio of the nitrogen-doped porous carbon powder to the binder is 10: 1; the binder is sesbania powder.
Further, in the step 4, the mass ratio of the deionized water to the sesbania powder is 20:1-30: 1.
Further, in the step 4, the rotating speed of the extruder is 10r/min-120 r/min.
The invention has the beneficial effects that:
1. the invention uses poplar wood dust as raw material, thus reducing cost. Poplar wood chips and microalgae are mixed and are subjected to CO-pyrolysis in the carbonization and activation processes, more micropores and channels are provided for the porous carbon, the pore structure of the porous carbon prepared from pure poplar wood chips is changed, and the obviously increased microporosity obviously improves CO of the porous carbon2Adsorption capacity. Meanwhile, microalgae is used as a nitrogen source to replace a chemical reagent nitrogen source, so that the environment is protectedIs more friendly.
2. The nitrogen-doped porous carbon particles can overcome the pressure drop problem of the porous carbon powder in a fixed bed adsorption device, and have ideal CO2The adsorption stability, and the forming method is simple and easy to operate, and is suitable for industrial amplification technical routes.
3. The nitrogen-doped porous carbon material has better CO content2The adsorption capacity, the preparation method is simple, the production process is environment-friendly, and the method is suitable for large-scale production.
Drawings
FIG. 1 shows CO at 0 ℃ and 1bar ambient pressure for comparative examples 1-2 and examples 1-32The amount of adsorption;
FIG. 2 is a crushing load distribution of comparative examples 1 to 2 and examples 1 to 3;
FIG. 3 is a schematic representation of the CO of example 2, cycled 5 times at 25 ℃ and 1bar ambient pressure2The amount of adsorption.
Detailed Description
The present invention will be further illustrated with reference to the accompanying drawings and specific embodiments, which are to be understood as merely illustrative of the invention and not as limiting the scope of the invention.
Example 1
Preparation of nitrogen-doped porous carbon material doped with 25% of microalgae
The method for preparing the nitrogen-doped porous carbon material based on the poplar wood chips based on the in-situ synthesis method specifically comprises the following steps:
step 1, pretreating poplar wood chips and microalgae, repeatedly cleaning the poplar wood chips with water, drying the poplar wood chips in a blast drying oven at 105 ℃ for 24 hours, crushing the dried poplar wood chips, and screening the crushed poplar wood chips to a size of 500 microns for later use; drying the microalgae in a blast drying oven at 45 ℃ for 24 hours;
step 3, weighing the carbonized product and KOH according to the mass ratio of 1:2, soaking the carbonized product and KOH in 100mL of deionized water, magnetically stirring the mixture at the rotating speed of 200rpm for 24 hours, then placing the mixture in an oven for drying, placing the dried mixture in a tubular furnace, heating the mixture to 700 ℃ at the heating rate of 10 ℃/min under the nitrogen atmosphere, and keeping the temperature for 1 hour for pyrolysis activation; cooling the activated product to 20-25 ℃, washing with HCl, repeatedly washing with deionized water to neutrality, and drying at 110 ℃ to obtain nitrogen-doped porous carbon powder PSC-NM-0.25;
step 4, adding 14mL of deionized water into 5g of nitrogen-doped porous carbon powder PSC-NM-0.25 and 0.5g of sesbania powder, and fully stirring to obtain a wet material with uniform humidity; putting the obtained wet material into a single-screw extruder, wherein the aperture of an extrusion template is 1mm, and the extrusion speed is 90r/min, so as to obtain a long cylindrical material; and drying the obtained long cylindrical material in an oven at 60 ℃ for 12h, and cutting the long cylindrical material into short cylindrical materials with the length of 0.8-1mm, namely the final nitrogen-doped porous carbon granular material PSC-NM0.25 (E).
Example 2
Preparation of nitrogen-doped porous carbon material doped with 50% of microalgae
The method for preparing the nitrogen-doped porous carbon material based on the poplar wood chips based on the in-situ synthesis method specifically comprises the following steps:
step 1, same as example 1;
step 3, weighing the carbonized product and KOH according to the mass ratio of 1:2, soaking the carbonized product and KOH in 100mL of deionized water, magnetically stirring the mixture at the rotating speed of 200rpm for 24 hours, then placing the mixture in an oven for drying, placing the dried mixture in a tubular furnace, heating the mixture to 700 ℃ at the heating rate of 10 ℃/min under the nitrogen atmosphere, and keeping the temperature for 1 hour for pyrolysis activation; cooling the activated product to 20-25 ℃, washing with HCl, then repeatedly washing with deionized water to neutrality, and drying at 110 ℃ to obtain nitrogen-doped porous carbon powder PSC-NM-0.5;
step 4, adding 14mL of deionized water into 5g of nitrogen-doped porous carbon powder PSC-NM-0.5 and 0.5g of sesbania powder, and fully stirring to obtain a wet material with uniform humidity; putting the obtained wet material into a single-screw extruder, wherein the aperture of an extrusion template is 1mm, and the extrusion speed is 90r/min, so as to obtain a long cylindrical material; and drying the obtained long cylindrical material in an oven at 60 ℃ for 12h, and cutting the long cylindrical material into short cylindrical materials with the length of 0.8-1mm, namely the final nitrogen-doped porous carbon granular material PSC-NM0.5 (E).
Example 3
Preparation of nitrogen-doped porous carbon material doped with 200% of microalgae
The method for preparing the nitrogen-doped porous carbon material based on the poplar wood chips based on the in-situ synthesis method specifically comprises the following steps:
step 1, same as example 1;
step 3, weighing the carbonized product and KOH according to the mass ratio of 1:2, soaking the carbonized product and KOH in 100mL of deionized water, magnetically stirring the mixture at the rotating speed of 200rpm for 24 hours, then placing the mixture in an oven for drying, placing the dried mixture in a tubular furnace, heating the mixture to 700 ℃ at the heating rate of 10 ℃/min under the nitrogen atmosphere, and keeping the temperature for 1 hour for pyrolysis activation; cooling the activated product to 20-25 ℃, washing with HCl, then repeatedly washing with deionized water to neutrality, and drying at 110 ℃ to obtain nitrogen-doped porous carbon powder PSC-NM-2;
step 4, adding 14mL of deionized water into 5g of nitrogen-doped porous carbon powder PSC-NM-2 and 0.5g of sesbania powder, and fully stirring to obtain a wet material with uniform humidity; putting the obtained wet material into a single-screw extruder, wherein the aperture of an extrusion template is 1mm, and the extrusion speed is 90r/min, so as to obtain a long cylindrical material; and drying the obtained long cylindrical material in an oven at 60 ℃ for 12h, and cutting the long cylindrical material into short cylindrical materials with the length of 0.8-1mm, namely the final nitrogen-doped porous carbon granular material PSC-NM2 (E).
Comparative example 1
Preparing a pure poplar wood chip-based porous carbon material.
Step 1, same as example 1;
step 3, weighing the carbonized product and KOH according to the mass ratio of 1:2, soaking the carbonized product and KOH in 100mL of deionized water, magnetically stirring the mixture at the rotating speed of 200rpm for 24 hours, then placing the mixture in an oven for drying, placing the dried mixture in a tubular furnace, heating the mixture to 700 ℃ at the heating rate of 10 ℃/min under the nitrogen atmosphere, and keeping the temperature for 1 hour for pyrolysis activation; cooling the activated product to 20-25 ℃, washing with HCl, then repeatedly washing with deionized water to neutrality, and drying at 110 ℃ to obtain pure poplar wood chip-based porous carbon powder PSC;
step 4, adding 14mL of deionized water into 5g of nitrogen-doped porous carbon powder PSC and 0.5g of sesbania powder, and fully stirring to obtain a wet material with uniform humidity; putting the obtained wet material into a single-screw extruder, wherein the aperture of an extrusion template is 1mm, and the extrusion speed is 90r/min, so as to obtain a long cylindrical material; and drying the obtained long cylindrical material in an oven at 60 ℃ for 12 hours, and cutting the long cylindrical material into short cylindrical materials with the length of 0.8-1mm, namely the final nitrogen-doped porous carbon particle material PSC (E).
Comparative example 2
And (3) preparing a pure microalgae-based porous carbon material.
Step 1, same as example 1;
step 3, weighing the carbonized product and KOH according to the mass ratio of 1:2, soaking the carbonized product and KOH in 100mL of deionized water, magnetically stirring the mixture at the rotating speed of 200rpm for 24 hours, then placing the mixture in an oven for drying, placing the dried mixture in a tubular furnace, heating the mixture to 700 ℃ at the heating rate of 10 ℃/min under the nitrogen atmosphere, and keeping the temperature for 1 hour for pyrolysis activation;
step 4, cooling the activated product to 20-25 ℃, washing with HCI, then repeatedly washing with deionized water to neutrality, and drying at 110 ℃ to obtain pure microalgae-based porous carbon powder MC;
step 5, adding 14mL of deionized water into 5g of nitrogen-doped porous carbon powder MC and 0.5g of sesbania powder, and fully stirring to obtain a wet material with uniform humidity; putting the obtained wet material into a single-screw extruder, wherein the aperture of an extrusion template is 1mm, and the extrusion speed is 90r/min, so as to obtain a long cylindrical material; drying the obtained long cylindrical material in an oven at 60 ℃ for 12h, and cutting the long cylindrical material into short cylindrical materials with the length of 0.8-1mm, namely the final nitrogen-doped porous carbon particle material MC (E).
Performance testing
By N2The adsorption-desorption characterization test gave pore structure parameters for each comparative example and example, as shown in table 1. Microporous structure in CO2Plays a main role in the adsorption process, and the higher microporosity is beneficial to improving the CO content of the porous carbon2The potential energy of gas-solid interaction between adjacent walls in the micropores are mutually overlapped, so that CO in the micropores is enabled2The adsorption capacity is remarkably enhanced. In addition, CO2Spatial structural features (CO) inherent to molecules2Has a kinetic diameter of about 0.33nm, CO2More readily adsorbed by micropores of similar pore size) and CO2The molecular polarity of (A) is more favorable for being adsorbed by the porous carbon rich in micropores. Obviously, only with a higher ratioPorous carbon with surface area and microporosity will have better CO2The specific surface area of the nitrogen-doped porous carbon granular material is as high as 1553m2The micro-porosity is 90.36%. In addition, it can be found through the elemental analysis results (as shown in table 1) that the nitrogen content of the porous carbon is increased by doping the microalgae, compared with the nitrogen content of comparative example 1 which is only 0.15%, the nitrogen content of the invention is as high as 0.91%, and the CO content of example 2 is effectively increased2And (4) adsorption performance.
TABLE 1 pore parameters and elemental analysis for comparative and example
aCalculating a specific surface area using a BET method;brelative pressure P/P0Total pore volume at = 0.99;cthe micropore volume was calculated using the t-plot method.
The porous carbon powders prepared in examples 1-3 and comparative examples 1-2 of the present invention were subjected to CO adsorption analysis using an adsorption analyzer2And (3) testing the adsorption capacity, wherein the weight of the sample is 10-20 mg, and a degassing step is required before testing, and is carried out at 250 ℃ for 6 h. The adsorption conditions were at 0 ℃, 1bar ambient pressure; as shown in FIG. 1, CO of the porous carbon powder prepared in example 2 of the present invention2The adsorption capacity is highest.
The porous carbon particles prepared in examples 1 to 3 of the present invention and comparative examples 1 to 2 were subjected to a crushing load test of crushing individual particles on a micro precision compression tester, and the number of samples per group was 50. Examples 1 to 3 and comparative examples 1 to 2 the crushing load test of the porous carbon particles is shown in fig. 2, and they have good mechanical properties.
The porous carbon particles of example 2 of the present invention were circulated on an adsorption analyzer for 5 times for CO2Testing adsorption capacity, wherein the sample weight is 10-20 mg, degassing at 250 deg.C for 6 hr, and adsorbing at 25 deg.C and 1bar under the environment pressure shown in FIG. 32And (4) adsorption stability.
It should be noted that the above-mentioned contents only illustrate the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and it is obvious to those skilled in the art that several modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations fall within the protection scope of the claims of the present invention.
Claims (10)
1. Adsorb CO2The nitrogen-doped porous carbon granular material is characterized by comprising a carbon source material, a nitrogen source material and a binder; the carbon source material is poplar wood chips; the nitrogen source material is microalgae; the binder is sesbania powder.
2. The method of claim 1 for adsorbing CO2The nitrogen-doped porous carbon granular material is characterized in that the nitrogen-doped porous carbon granular material is columnar granules, the length of the columnar granules is 0.8-1mm, and the diameter of the columnar granules is 0.8-1.0 mm.
3. An adsorbent CO according to any one of claims 1-22The preparation method of the nitrogen-doped porous carbon granular material is characterized by comprising the following steps:
step 1: pretreating poplar sawdust and microalgae;
step 2: mixing the pretreated poplar wood chips with microalgae, soaking the mixture in deionized water, magnetically stirring the mixture at the rotation speed of 150-plus-200 rpm for 24-36h, then placing the mixture in an oven for drying, placing the dried mixture in a tubular furnace, carrying out pyrolysis carbonization in nitrogen atmosphere, cooling the mixture to 20-25 ℃, repeatedly cleaning the product with deionized water, and drying the product at the temperature of 100-plus-110 ℃ to obtain a carbonized product;
and step 3: mixing the carbonized product obtained in the step 2 with an activating agent, soaking the mixture in deionized water, magnetically stirring the mixture for 24 to 36 hours at the rotating speed of 150-plus-200 rpm, then placing the mixture in a drying oven for drying, placing the dried mixture in a tubular furnace, carrying out pyrolysis activation in a nitrogen atmosphere, cooling the activated product to 20 to 25 ℃, then cleaning the product with HCl, then repeatedly washing the product with deionized water to neutrality, and drying the product at the temperature of 100-plus-110 ℃ to obtain nitrogen-doped porous carbon powder;
and 4, step 4: and (3) mixing the nitrogen-doped porous carbon powder obtained in the step (3) with a binder, adding a proper amount of deionized water, fully stirring to form a wet material with uniform humidity, putting the mixture into an extruder for extrusion forming, and cutting to obtain the nitrogen-doped porous carbon granular material.
4. The method of claim 3, wherein the adsorbed CO is CO2The preparation method of the nitrogen-doped porous carbon granular material is characterized in that in the step 1, the pretreatment comprises the following steps: repeatedly cleaning poplar wood chips with water, placing the poplar wood chips in a forced air drying oven for drying at 110 ℃ for 24-36h, crushing the dried poplar wood chips, and screening the crushed poplar wood chips to 500 mu m at 300 ℃ for later use; and (3) drying the microalgae for 24-36h in a blast drying oven at the temperature of 30-45 ℃.
5. The method of claim 3, wherein the adsorbed CO is CO2The preparation method of the nitrogen-doped porous carbon granular material is characterized in that in the step 2, the mass ratio of the poplar wood chips to the microalgae is 1: 0.25-2; the pyrolysis carbonization conditions are as follows: the heating rate is 5-10 ℃/min, the temperature is increased to 550 ℃ and 600 ℃, and the constant temperature is kept for 1-1.5 h.
6. The method of claim 3, wherein the adsorbed CO is CO2The preparation method of the nitrogen-doped porous carbon granular material is characterized in that in the step 3, the mass ratio of the carbonized product obtained in the step 2 to the activating agent is 1: 2-4; the pyrolysis activation conditions are as follows: the heating rate is 5-10 ℃/min, the temperature is raised to 650-700 ℃, and the constant temperature is kept for 1-1.5 h.
7. The method of claim 6, wherein the adsorbed CO is CO2The preparation method of the nitrogen-doped porous carbon granular material is characterized in that the activating agent is KOH.
8. The method of claim 3, wherein the adsorbed CO is CO2The preparation method of the nitrogen-doped porous carbon granular material,characterized in that in the step 4, the mass ratio of the nitrogen-doped porous carbon powder obtained in the step 3 to the binder is 5-20: 1; the binder is sesbania powder.
9. The method of claim 3, wherein the adsorbed CO is CO2The preparation method of the nitrogen-doped porous carbon particle material is characterized in that in the step 4, the mass ratio of the deionized water to the sesbania powder is 20:1-30: 1.
10. The method of claim 3, wherein the adsorbed CO is CO2The preparation method of the nitrogen-doped porous carbon granular material is characterized in that in the step 4, the rotating speed of the extruder is 10r/min-120 r/min.
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