CN117228657A - Preparation method of molded porous carbon - Google Patents
Preparation method of molded porous carbon Download PDFInfo
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- CN117228657A CN117228657A CN202311336593.4A CN202311336593A CN117228657A CN 117228657 A CN117228657 A CN 117228657A CN 202311336593 A CN202311336593 A CN 202311336593A CN 117228657 A CN117228657 A CN 117228657A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000002023 wood Substances 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 16
- 238000003763 carbonization Methods 0.000 claims abstract description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 12
- 239000002131 composite material Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000012046 mixed solvent Substances 0.000 claims description 10
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 10
- -1 aldehyde compounds Chemical class 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 150000001491 aromatic compounds Chemical class 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- QWBBPBRQALCEIZ-UHFFFAOYSA-N 2,3-dimethylphenol Chemical compound CC1=CC=CC(O)=C1C QWBBPBRQALCEIZ-UHFFFAOYSA-N 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 6
- 235000008331 Pinus X rigitaeda Nutrition 0.000 claims description 5
- 241000018646 Pinus brutia Species 0.000 claims description 5
- 235000011613 Pinus brutia Nutrition 0.000 claims description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 5
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 4
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 claims description 4
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 claims description 4
- 241000124033 Salix Species 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 4
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 4
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 4
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 claims description 4
- 229960001553 phloroglucinol Drugs 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 claims description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 2
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 2
- 241000218691 Cupressaceae Species 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- 244000082204 Phyllostachys viridis Species 0.000 claims description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 2
- 244000082946 Tarchonanthus camphoratus Species 0.000 claims description 2
- 235000005701 Tarchonanthus camphoratus Nutrition 0.000 claims description 2
- 240000002871 Tectona grandis Species 0.000 claims description 2
- 150000001413 amino acids Chemical class 0.000 claims description 2
- 239000011425 bamboo Substances 0.000 claims description 2
- IZALUMVGBVKPJD-UHFFFAOYSA-N benzene-1,3-dicarbaldehyde Chemical compound O=CC1=CC=CC(C=O)=C1 IZALUMVGBVKPJD-UHFFFAOYSA-N 0.000 claims description 2
- 238000010000 carbonizing Methods 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- YMHQVDAATAEZLO-UHFFFAOYSA-N cyclohexane-1,1-diamine Chemical compound NC1(N)CCCCC1 YMHQVDAATAEZLO-UHFFFAOYSA-N 0.000 claims description 2
- 229940015043 glyoxal Drugs 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 2
- BGUWFUQJCDRPTL-UHFFFAOYSA-N pyridine-4-carbaldehyde Chemical compound O=CC1=CC=NC=C1 BGUWFUQJCDRPTL-UHFFFAOYSA-N 0.000 claims description 2
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 claims description 2
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 claims description 2
- UDQLIWBWHVOIIF-UHFFFAOYSA-N 3-phenylbenzene-1,2-diamine Chemical compound NC1=CC=CC(C=2C=CC=CC=2)=C1N UDQLIWBWHVOIIF-UHFFFAOYSA-N 0.000 claims 1
- 125000003277 amino group Chemical group 0.000 claims 1
- 229960004050 aminobenzoic acid Drugs 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 19
- 239000003575 carbonaceous material Substances 0.000 abstract description 14
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 238000000926 separation method Methods 0.000 abstract description 8
- 238000012546 transfer Methods 0.000 abstract description 7
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 238000000465 moulding Methods 0.000 abstract description 3
- 238000013461 design Methods 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 description 22
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 14
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 239000007789 gas Substances 0.000 description 10
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 10
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 10
- 238000005303 weighing Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000009792 diffusion process Methods 0.000 description 7
- 239000001294 propane Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 239000003463 adsorbent Substances 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 102000020897 Formins Human genes 0.000 description 4
- 108091022623 Formins Proteins 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229910052573 porcelain Inorganic materials 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000035515 penetration Effects 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000001612 separation test Methods 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
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- 239000003814 drug Substances 0.000 description 1
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- 239000003960 organic solvent Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
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- Carbon And Carbon Compounds (AREA)
Abstract
The invention belongs to the technical field of porous carbon, and discloses a preparation method of molded porous carbon. The preparation method is characterized in that wood is used as a base frame structure, polymerizable molecules are introduced into the surface of the wood, so that the van der Waals effect between abundant hydroxyl groups on the surface of the wood and the polymerized molecules is facilitated, a layer of closely attached polymer is generated through in-situ reaction, and the formed porous carbon is directly obtained through high-temperature carbonization. The preparation method is simple, can perform directional design preparation according to application requirements, can solve the technical problems that the porous carbon material has high porosity and fast mass transfer rate and can not be obtained by lossless molding, and can realize large-scale production. The preparation method provided by the invention has expansibility, and the prepared formed porous carbon has wide application potential and market prospect in the fields of gas separation, battery materials, integral electrodes and the like.
Description
Technical Field
The invention belongs to the technical field of porous carbon (active carbon), and particularly relates to a preparation method of molded porous carbon.
Background
The porous carbon material has the advantages of large specific surface area, developed pore structure, adjustable pore diameter and surface chemical property, acid and alkali corrosion resistance, good thermal stability and chemical stability, insolubility in water and organic solvents, easy regeneration and the like, is widely applied to the fields of gas phase adsorption, liquid phase adsorption, catalysts, energy, medicines and the like, and plays an important role in industrial production and people's life. However, the porous carbon material prepared and synthesized at present is in a powder shape, and in order to meet the actual application requirements, the porous carbon material must be molded by a binder, so that the mechanical strength and the wear resistance are improved. The porosity of the molded porous carbon is significantly reduced due to the presence of the binder, resulting in a decrease in the performance of the molded porous carbon produced (CN 106794443B). For this reason, the shaped carbon is usually further activated for reaming, but this in turn reduces the mechanical strength and abrasion resistance of the shaped carbon (new carbon materials, 2000, 15:6-10). Direct preparation of self-supporting monolithic shaped porous carbon has received considerable attention and there have been related literature and patent reports (CN 109734449B, CN 110354803B) in recent years. The integral forming porous carbon is basically prepared by taking a phenolic aldehyde alkaline polymer as a precursor through a sol-gel process and a carbonization process. These self-supporting monolithic porous carbons, while having a rich microporous structure and a certain mechanical strength, lack large pore channels that facilitate diffusion of the species in which the diffusion behavior of the species molecules may be limited. It is therefore necessary to explore new preparation methods.
Disclosure of Invention
The invention aims at the problems and provides a preparation method of molded porous carbon with through macropores. The porous carbon prepared by the method has the advantages of rich pore structure, high strength, high wear resistance, high mass transfer rate and the like, and has excellent performance in the aspects of adsorption separation, electrode materials, catalyst carriers and the like. According to the method, wood is used as a base frame structure, polymerizable molecules are introduced into the surface of the wood, a layer of closely attached polymer is generated by in-situ reaction by utilizing the attractive force of hydrogen bonds generated between rich hydroxyl groups on the surface of the wood and polymer molecules, and the formed porous carbon is directly obtained by high-temperature carbonization. The preparation method is simple, can perform directional design preparation according to application requirements, can solve the technical problems that the porosity and mass transfer rate of the porous carbon material and the nondestructive molding cannot be achieved, and can realize large-scale production.
The technical scheme of the invention is as follows:
a preparation method of the molded porous carbon comprises the following steps:
(1) Sequentially adding a hydroxyl-containing aromatic compound and an amino-containing compound into an alcohol-water mixed solvent, wherein the molar ratio of the hydroxyl-containing aromatic compound to the amino-containing compound is 1:10-10:1; the volume ratio of the alcohol to the water is 1:1000-1000:1;
(2) Taking wood as a base frame material, adding the wood into the solution obtained in the step (1), and standing to absorb the solution;
(3) Placing the material obtained in the step (2) in a closed container filled with aldehyde compounds, heating the closed container to 20-90 ℃, maintaining the temperature for 0.5-96h, and cooling to take out the composite material; the molar ratio of the aldehyde compound to the hydroxyl-containing aromatic compound is 2:1-10:1, a step of;
(4) Placing the composite material obtained in the step (3) into a carbonization furnace, and carbonizing under an inert gas atmosphere to obtain molded porous carbon; the carbonization condition is that the heating rate is 0.5-50 ℃/min, the temperature is raised to 500-1400 ℃, and the constant temperature is kept for 10-240min.
In the step (1), the hydroxyl-containing aromatic compound is selected from one or more of phenol, resorcinol, phloroglucinol, 2, 3-xylenol and bisphenol A, preferably resorcinol.
In the step (1), the amino-containing compound is one or more than two of aniline, p-phenylenediamine, diphenyl diamine, ethylenediamine, 1, 6-hexamethylenediamine, cyclohexanediamine, para-aminobenzoic acid, melamine and amino acid, preferably aniline.
In the step (1), the alcohol-water mixed solvent is a mixed solvent of ethanol and water, a mixed solvent of methanol and water or a mixed solvent of ethylene glycol and water.
In the step (2), the base frame material is any wood, preferably one or a combination of more than two of pine, cypress, teak, fir, camphor wood, willow, bafir and bamboo.
In the step (3), the aldehyde compound is one or more than two of formaldehyde, propionaldehyde, butyraldehyde, furfural, glyoxal, 4-pyridine formaldehyde, 2-pyridine formaldehyde, benzaldehyde, terephthalaldehyde and isophthalaldehyde.
In the step (4), the inert atmosphere is argon or nitrogen.
The invention also provides application of the formed porous carbon in separation of propylene and propane.
The invention has the beneficial effects that: according to the invention, wood is taken as a substrate, a layer of high polymer material is closely grown on the surface of the wood in situ by utilizing the hydrogen bond action between abundant hydroxyl groups on the surface of the wood and organic molecules in a gas-phase induced polymerization mode, and the formed porous carbon is directly prepared by a subsequent carbonization process. The formed porous carbon reserves the framework structure of wood, has rich and through mass transfer channels, and simultaneously has functional screening layers grown on the surface. The porous carbon material prepared by the invention has the advantages of functional screening performance, high porosity, high mechanical strength, high mass transfer rate and the like, and the size and shape of the porous carbon can be customized and formed according to target requirements. The preparation method provided by the invention has expansibility, and the prepared formed porous carbon has wide application potential and market prospect in the fields of gas separation, battery materials, integral electrodes and the like.
Drawings
FIG. 1 is a scanning electron microscope image of the molded porous carbon prepared in example 1 of the present invention.
FIG. 2 is a graph showing the penetration curve of the propylene/propane mixture separated by the shaped porous carbon prepared in example 2 of the present invention.
FIG. 3 is a graph showing the penetration of the propylene/propane gas mixture of comparative example 1 of the present invention.
FIG. 4 is a comparison of the propylene/propane diffusion kinetics curves of comparative example 2 formed porous carbon of the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples. The specific embodiments described herein are to be considered in an illustrative sense only and are not intended to limit the invention.
The preparation process of the molded polymer composite material comprises the following steps:
example 1.1
Weighing 0.06mol of resorcinol and 0.04mol of aniline, adding the resorcinol and the aniline into 5mL of absolute ethyl alcohol, dissolving and uniformly stirring; weighing 3g of fir wood, adding into the solution, standing to absorb the solution until saturation; adding 16mL of formaldehyde aqueous solution into a closed container; transferring the fir into a closed container, and heating to 90 ℃ for reaction for 18h. And after the reaction is finished, taking out the formed polymer composite material, drying the formed polymer composite material to constant weight for later use, and the sample number is named as P@B-1.
Example 1.2
Weighing 0.1mol of phloroglucinol and 0.06mol of p-phenylenediamine, adding the phloroglucinol and the p-phenylenediamine into 20mL of ethanol/water mixed solution, dissolving and uniformly stirring; weighing 9g of pine wood, adding the pine wood into the solution, and standing to absorb the solution until the solution is saturated; adding 24mL of formaldehyde aqueous solution into a closed container; transferring the pine into a closed container, and heating to 90 ℃ for reaction for 12 hours. And after the reaction is finished, taking out the formed polymer composite material, drying the formed polymer composite material to constant weight for later use, and the sample number is named as P@B-2.
Example 1.3
Weighing 0.02mol of bisphenol A and 0.03mol of 1, 6-hexamethylenediamine, adding the materials into 16mL of absolute ethyl alcohol, dissolving and uniformly stirring; weighing 7g of bafir, adding into the solution, standing and absorbing the solution until the solution is saturated; adding 12mL of formaldehyde aqueous solution into a closed container; transferring the bafir into a closed container, and heating to 90 ℃ for reaction for 6 hours. And after the reaction is finished, taking out the formed polymer composite material, drying the formed polymer composite material to constant weight for later use, and the sample number is named as P@B-3.
Example 1.4
Weighing 0.07mol of 2, 3-xylenol and 0.08mol of ethylenediamine, adding into 10mL of absolute ethyl alcohol, dissolving and uniformly stirring; weighing 6g of willow, adding into the solution, standing to absorb the solution until saturation; adding 18mL of formaldehyde aqueous solution into a closed container; transferring the willow into a closed container, and heating to 90 ℃ for reaction for 24 hours. And after the reaction is finished, taking out the formed polymer composite material, drying the formed polymer composite material to constant weight for later use, and the sample number is named as P@B-4.
The preparation process of the molded porous carbon comprises the following steps:
example 2.1
The prepared molded polymer composite material P@B-1 is placed in a porcelain boat of a carbonization furnace, and purged in argon atmosphere at 5 ℃ for min -1 The temperature rising rate of (2) is increased from room temperature to 800 ℃, and the porous carbon is prepared after 2 hours of maintainingA material. FIG. 1 is a scanning electron microscope image of the shaped porous carbon. The prepared porous carbon has orderly arranged micron-sized macroporous channels, and the average width of the channels is about 20 mu m; the surface of the carbon material is uniform, and the phenomenon of layering and splitting does not occur, which indicates that the polymer material can uniformly grow on the surface of the wood due to the action of hydrogen bonds. Sample number was designated CPB-1-800.
Example 2.2
The prepared molded polymer composite material P@B-2 is placed in a porcelain boat of a carbonization furnace, and is purged in nitrogen atmosphere at 3 ℃ for min -1 The temperature rise rate of the porous carbon material is raised to 800 ℃ from room temperature and kept for 1.5 hours, and the sample number is named CPB-2-800.
Example 2.3
The prepared molding polymer composite material P@B-3 is placed in a porcelain boat of a carbonization furnace, and purged in argon atmosphere at 10 ℃ for min -1 The temperature rise rate of the porous carbon material is raised to 700 ℃ from room temperature and kept for 2.5 hours, and the sample number is named CPB-3-700.
Example 2.4
The prepared molded polymer composite material P@B-4 is placed in a porcelain boat of a carbonization furnace, and is purged in nitrogen atmosphere at 5 ℃ for min -1 The temperature rise rate of the porous carbon material is raised to 900 ℃ from room temperature and kept for 1h, and the sample number is named CPB-4-900.
Example 3 (static Properties of porous carbon adsorbent)
Taking example 2.1 as an example, after pyrolysis treatment at different carbonization temperatures, the obtained through macroporous molded porous carbon with screening function is subjected to static adsorption test on single-component gas:
weighing 70-300mg of porous carbon, and degassing at 200 ℃ for 6-12h; the physical adsorption instrument Micromeritics ASAP 2020 was used to test the gas adsorption capacity at different equilibrium pressures to obtain adsorption isotherms at different temperatures. Sample numbers and static adsorption test performance results are shown in table 1.
Table 1 comparison of porous carbon and its corresponding static adsorption test Performance results in example 3
Example 4 (dynamic separation Property of porous carbon adsorbent)
Crushing the formed porous carbon into particles with 20-40 meshes, loading the particles into an adsorption column of a dynamic penetrating separation device, purging a pipeline of the purification device by adopting argon, and mixing propylene/propane gas mixture at 25 ℃ and 1bar at a ratio of 50: and (3) enabling the flow with the volume ratio of 50 mL/min to pass through an adsorption column, detecting the composition and the content of outlet gas at the outlet end of the adsorption column by adopting gas chromatography, and calculating the adsorption quantity and the dynamic selectivity of the porous carbon according to the composition and the content. The results of the gas mixture separation are shown in fig. 2 and table 2.
Table 2 comparison of porous carbon and its corresponding dynamic gas adsorption separation Performance results in example 4
Comparative example 1 (Segregation Selectivity comparative)
The fir frame material in example 1 was taken out alone, carbonized under the conditions of example 2.1, and a porous carbon material having only macropores was obtained as the adsorbent a. Then, a propylene-propane mixture dynamic separation test was performed according to the test conditions in example 4. The dynamic penetration curve is shown in figure 3, and the dynamic adsorption quantity of propylene is 1.66mmol/g, the dynamic adsorption quantity of propane is 0.81mmol/g and the dynamic selectivity is 2.
Porous carbon materials with only macropores without polymer compounding have only a rapid diffusion rate, but lack excellent gas selectivity.
Comparative example 2 (diffusion Rate vs)
The polymer raw materials in the example 1 are singly polymerized in the same proportion, and the macroporous carbon material without macropores is prepared under the carbonization condition of the example 2.1, and is taken as an adsorbent BThe diffusion rate at 25℃was measured by an intelligent gravimetric analyzer and compared with example 2.2, as shown in FIG. 4, the propylene diffusion rate was significantly reduced to 2.5X10 -9 m 2 S is only 60% of example 2.2, and the adsorption capacity is also only 30% of example 2.2.
Comparative example 3 (comparative different base materials)
The fir frame material in example 1 was taken out alone and was prepared under the carbonization conditions of example 2.4 to obtain a carbonaceous frame, which was used as a base material, and a molded porous carbon was prepared as an adsorbent C in the same synthesis method as in examples 1 and 2.1. Then, a propylene-propane mixture dynamic separation test was performed according to the test conditions in example 4. The dynamic adsorption capacity of propylene is calculated to be 0.32mmol/g, the dynamic adsorption capacity of propane is calculated to be 0.01mmol/g, and obviously the dynamic adsorption capacity of propylene is obviously reduced to be only 20% of that of the example 2.1. The reason why the propylene adsorption capacity is remarkably reduced is that the polymer material cannot be uniformly distributed in the carbonaceous frame material due to the lack of abundant hydroxyl functional groups on the surface of the carbonaceous frame material, the mass transfer channel is blocked, the mass transfer efficiency is remarkably reduced, and the adsorption capacity is remarkably reduced.
The foregoing is only a specific embodiment of the present invention, but the technical features of the present invention are not limited thereto. It should be noted that modifications and adaptations to the present invention may be made by one skilled in the relevant art without departing from the principles and technical characteristics thereof, and all such modifications, improvements or adaptations are intended to be within the scope of the present invention.
Claims (7)
1. The preparation method of the molded porous carbon is characterized by comprising the following steps:
(1) Sequentially adding a hydroxyl-containing aromatic compound and an amino-containing compound into an alcohol-water mixed solvent, wherein the molar ratio of the hydroxyl-containing aromatic compound to the amino-containing compound is 1:10-10:1; the volume ratio of the alcohol to the water is 1:1000-1000:1;
(2) Taking wood as a base frame material, adding the wood into the solution obtained in the step (1), and standing to absorb the solution;
(3) Placing the material obtained in the step (2) in a closed container filled with aldehyde compounds, heating the closed container to 20-90 ℃, maintaining the temperature for 0.5-96h, and cooling to take out the composite material; the molar ratio of the aldehyde compound to the hydroxyl-containing aromatic compound is 2:1-10:1, a step of;
(4) Placing the composite material obtained in the step (3) into a carbonization furnace, and carbonizing under an inert gas atmosphere to obtain molded porous carbon; the carbonization condition is that the heating rate is 0.5-50 ℃/min, the temperature is raised to 500-1400 ℃, and the constant temperature is kept for 10-240min.
2. The method according to claim 1, wherein the hydroxyl-containing aromatic compound is one or a combination of two or more selected from the group consisting of phenol, resorcinol, phloroglucinol, 2, 3-xylenol, bisphenol A.
3. The method according to claim 1, wherein the amine group-containing compound is one or a combination of two or more of aniline, p-phenylenediamine, biphenyldiamine, ethylenediamine, 1, 6-hexamethylenediamine, cyclohexanediamine, p-aminobenzoic acid, melamine, and amino acid.
4. The method according to claim 1, wherein the alcohol-water mixed solvent is one of a mixed solvent of ethanol and water, a mixed solvent of methanol and water, and a mixed solvent of ethylene glycol and water.
5. The method according to claim 1, wherein the base frame material is one or a combination of two or more of pine, cypress, teak, fir, camphorwood, willow, bafir, bamboo.
6. The preparation method of claim 1, wherein the aldehyde compound is one or more of formaldehyde, propionaldehyde, butyraldehyde, furfural, glyoxal, 4-pyridine formaldehyde, 2-pyridine formaldehyde, benzaldehyde, terephthalaldehyde and isophthalaldehyde.
7. The method of claim 1, wherein the inert atmosphere is argon or nitrogen.
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