CN114775113A - Self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber, and preparation method and application thereof - Google Patents
Self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber, and preparation method and application thereof Download PDFInfo
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- 229920002239 polyacrylonitrile Polymers 0.000 title claims abstract description 86
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 77
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 77
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 68
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000000835 fiber Substances 0.000 claims abstract description 29
- 238000001179 sorption measurement Methods 0.000 claims abstract description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 21
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 18
- 238000009987 spinning Methods 0.000 claims abstract description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 11
- 238000002166 wet spinning Methods 0.000 claims abstract description 7
- 238000010000 carbonizing Methods 0.000 claims abstract description 5
- 230000001590 oxidative effect Effects 0.000 claims abstract description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 21
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 20
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical group [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 16
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- 239000012298 atmosphere Substances 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 10
- 239000001569 carbon dioxide Substances 0.000 claims description 9
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 8
- 238000003763 carbonization Methods 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000011148 porous material Substances 0.000 abstract description 14
- 229910001414 potassium ion Inorganic materials 0.000 abstract description 4
- 238000009792 diffusion process Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 239000011159 matrix material Substances 0.000 abstract description 3
- 238000001994 activation Methods 0.000 description 15
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- 230000004913 activation Effects 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 13
- 239000000126 substance Substances 0.000 description 10
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- 239000012190 activator Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 238000010041 electrostatic spinning Methods 0.000 description 3
- 239000003546 flue gas Substances 0.000 description 3
- 239000002006 petroleum coke Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
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- 238000001000 micrograph Methods 0.000 description 2
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- 229910052700 potassium Inorganic materials 0.000 description 2
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- 239000002994 raw material Substances 0.000 description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000002009 alkene group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
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- 239000004570 mortar (masonry) Substances 0.000 description 1
- SQDFHQJTAWCFIB-UHFFFAOYSA-N n-methylidenehydroxylamine Chemical group ON=C SQDFHQJTAWCFIB-UHFFFAOYSA-N 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
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- 239000011592 zinc chloride Substances 0.000 description 1
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28023—Fibres or filaments
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D1/00—Treatment of filament-forming or like material
- D01D1/02—Preparation of spinning solutions
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/06—Wet spinning methods
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
Abstract
The invention discloses a preparation method of self-activated polyacrylonitrile-based nitrogen-containing porous carbon fibers, which comprises the following steps: (1) uniformly dispersing the potassium salt powder into a polyacrylonitrile solution to form a self-activating spinning solution, and obtaining self-activating fiber precursor through wet spinning; (2) pre-oxidizing the precursor of the self-activated fiber to obtain polyacrylonitrile-based pre-oxidized fiber;(3) carbonizing polyacrylonitrile-based pre-oxidized fiber to obtain the self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber. The self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber prepared by the method has high nitrogen content; and the introduction of potassium ions promotes the development of internal pore channels and increases CO2The diffusion path of the porous carbon fiber can improve the polarity of the material matrix and promote the porous carbon fiber of the product to react with CO2The adsorption of (2); so that the self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber pair CO2Has excellent adsorption performance and can be applied to CO2The field of adsorption.
Description
Technical Field
The invention relates to the technical field of functional fiber materials, in particular to self-activated polyacrylonitrile-based nitrogen-containing porous carbon fibers, a preparation method and application thereof.
Background
The porous carbon fiber is a carbon material between carbon fiber and activated carbon, and is prepared by carbonizing/activating organic fiber serving as a precursor. The porous carbon fiber has the characteristics of high specific surface area, developed pore structure and rich adsorption sites, and can be used for CO2In the field of adsorption, the porous carbon fiber has stable physical and chemical properties and can adsorb CO2And the regeneration can be carried out circularly and the regeneration energy consumption is low.
The preparation method of the porous carbon fiber pore structure mainly comprises physical activation and chemical activation; the physical activation mainly uses carbon dioxide, water vapor, air or the mixed gas of the gases as an activating agent, in the activation process, the precursor is heated and cracked to generate defects and gases, and the gases remove disordered carbon and tar which block the pore structure, so that the original pore diameter is enlarged and new pores are generated; for example, chinese patent publication No. CN106958053A discloses a method for preparing porous petroleum coke-based carbon fibers, which uses amphiphilic carbonaceous material prepared from petroleum coke as raw material and polyacrylonitrile as raw materials, and performs electrostatic spinning, pre-oxidation, carbonization, and physical activation to obtain porous petroleum coke-based carbon fibers.
The chemical activation is performed by chemical activating agent (KOH, K)2CO3、NaOH、H3PO3、ZnCl2Etc.) react with the fibers to form a pore structure, chemical activation is a highly efficient pore-forming method. However, in the conventional chemical activation, a large amount of chemical activating agent is required to be mixed with the precursor, and the activating agent mainly stays on the surface layer of the precursor, which easily causes uneven activation and causes consumption and waste of a large amount of activating agent.
Chinese patent document with publication number CN114267829A discloses a preparation method of a coal-based porous carbon fiber negative electrode material, which takes coal produced in Xinjiang Heishan as a carbon source, is mixed with acid to be treated, and then is dissolved in N, N-dimethylformamide together with polyacrylonitrile to prepare spinning solution, and then the coal-based porous carbon fiber is prepared through the processes of electrostatic spinning technology, pre-oxidation, carbonization, chemical activation treatment and the like. The mass ratio of the activating agent to the fiber is 4: 1 (chemical activator is KOH), there is a significant loss of activator.
Chinese patent document with publication number CN112342644A discloses a preparation method of porous carbon fiber, which comprises dissolving polyacrylonitrile in a solvent to obtain a spinning solution, performing electrostatic spinning to obtain a nanofiber felt, and heating the nanofiber felt for heat preservation and pre-oxidation and high-temperature heating to obtain nitrogen-doped carbon fiber; and mixing the obtained nitrogen-doped carbon fiber with alkali and water, drying, and then baking to obtain the porous carbon fiber. The method uses a large amount of activating agent, the activation step is carried out independently, the operation is complex and the continuous production cannot be realized.
Disclosure of Invention
The invention provides a preparation method of self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber by using polyacrylonitrile as a nitrogen source and potassium salt powder as an activating agent and utilizing a self-activating method, so that the using amount of the activating agent is reduced, the activation efficiency is improved, and the prepared self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber can be used for CO in a simulated smoke environment2The adsorption is fast and efficient, and the adsorption capacity reaches 0.69 mmol/g.
The technical scheme is as follows:
a preparation method of self-activated polyacrylonitrile-based nitrogen-containing porous carbon fibers comprises the following steps:
(1) uniformly dispersing potassium salt powder into a polyacrylonitrile solution to form a self-activating spinning solution, and obtaining self-activating fiber precursor through wet spinning;
(2) pre-oxidizing the precursor of the self-activated fiber to obtain polyacrylonitrile-based pre-oxidized fiber;
(3) carbonizing polyacrylonitrile-based pre-oxidized fiber to obtain the self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber.
Polyacrylonitrile contains a cyano (-CN) group with strong polarity, can endow the porous carbon fiber with unique nitrogen-containing functional groups, and is an excellent nitrogen source; according to the invention, potassium salt powder is used as an activator, a self-activation method is utilized, potassium salt which is uniformly distributed is introduced into a precursor spinning solution, and the potassium salt is chemically activated in fiber protofilaments in a heat treatment process to form a porous carbon material, so that the problem of activator waste can be effectively solved, the intercalation effect of potassium ions can promote the development of pore channels, and CO is increased2The diffusion path of the porous carbon fiber can improve the polarity of the material matrix and promote the porous carbon fiber of the product to react with CO2The adsorption of (2).
Preferably, the potassium salt powder is potassium carbonate, and the potassium salt powder is obtained by grinding with a mortar and sieving with a screen.
Preferably, the particle size of the potassium salt powder is less than 50 μm; the potassium salt powder with the particle size of less than 50 mu m is more beneficial to spinning.
Preferably, the solid content of the self-activating spinning solution is 18-22 wt%.
Preferably, the solvent of the polyacrylonitrile solution is dimethyl sulfoxide.
Preferably, in the self-activating spinning solution, the mass ratio of the potassium salt to the polyacrylonitrile is 1-8: 100; excessive potassium salt can cause the phenomena of uneven dispersion and aggregation and deposition, and when potassium salt is preferred to be potassium carbonate, polyacrylonitrile is easy to generate a crosslinking reaction under the alkaline condition formed by excessive potassium carbonate, so that the viscosity is increased; in the preferable range, the prepared self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber pair CO2Has excellent adsorption effect.
In the step (2), the pre-oxidation process is carried out in the air atmosphere, and the polyacrylonitrile performs cyclization reaction, oxidation reaction, dehydrogenation reaction and the like in the pre-oxidation process to form an aromatic hybrid structure, a nitrone structure, a conjugated alkene structure and the like.
Preferably, the conditions of the pre-oxidation treatment are as follows: 160-300 ℃ for 25-90 min.
Further preferably, the pre-oxidation treatment is performed in two stages, and the treatment conditions in the first stage are as follows: 160-200 ℃ for 5-30 min; the treatment conditions in the second stage were: 230-270 ℃ for 20-60 min.
Preferably, in the step (3), the carbonization process is performed in a nitrogen atmosphere, and the carbonization treatment conditions are as follows: 750-850 ℃ and 30-180 min.
The invention also provides the self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber prepared by the preparation method of the self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber, wherein the nitrogen content is 12-22%, and the self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber has an interconnected pore channel structure inside.
The invention also provides application of the self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber in the field of carbon dioxide adsorption. The self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber can quickly and efficiently adsorb carbon dioxide in a simulated flue gas environment, and the adsorption amount reaches 0.69 mmol/g.
Compared with the prior art, the invention has the beneficial effects that:
(1) the self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber prepared by the method has high nitrogen content; and the introduction of potassium ions promotes the development of internal pore channels and increases CO2The diffusion path of the porous carbon fiber can improve the polarity of the material matrix and promote the porous carbon fiber of the product to react with CO2The adsorption of (2); so that the self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber pair CO2Has excellent adsorption performance and can be applied to CO2The field of adsorption.
(2) According to the invention, the potassium salt powder of the activating agent is added into the polyacrylonitrile solution, the pore structure is regulated and controlled by regulating the proportion of polyacrylonitrile and potassium salt, the self-activating polyacrylonitrile-based nitrogen-containing porous carbon fiber is prepared, the using amount of the activating agent is reduced, the activation efficiency is improved, chemical activation of semi-finished fibers by using a large amount of the activating agent is not required, the preparation method is simple and efficient, and the energy consumption is low.
(3) According to the invention, the pore structure is formed by utilizing the precursor spinning solution with the uniformly distributed activating agent through the self-activating process, the processes of preparation of the precursor spinning solution, wet spinning and heat treatment can be continuously produced on line, and the preparation process is simple and convenient.
Drawings
Fig. 1 is an EDS energy spectrum of self-activated fiber strands of example 1.
FIG. 2 is a representation of CO of the self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber prepared in example 12Adsorption profile.
FIG. 3 is an SEM photograph of self-activated polyacrylonitrile-based nitrogen-containing porous carbon fibers obtained in example 2.
FIG. 4 is CO of the self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber prepared in example 22Adsorption profile.
FIG. 5 is an SEM photograph of self-activated polyacrylonitrile-based nitrogen-containing porous carbon fibers obtained in example 3.
FIG. 6 is a representation of CO content of the self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber prepared in example 32Adsorption profile.
FIG. 7 is CO of polyacrylonitrile-based porous carbon fiber in comparative example 12Adsorption profile.
Detailed Description
The invention is further elucidated with reference to the following figures and examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention.
The performance and preparation process analysis of the self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber are carried out by adopting the following instruments and methods: an EDS spectrometer for representing the element content of the self-activated fiber protofilament; the element analyzer is used for representing the nitrogen content of the self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber; scanning an electron microscope to represent the surface appearance of the self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber; the synchronous thermal analyzer is used for testing the CO of the self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber in the simulated flue environment2The adsorption performance of (3).
Example 1
(1) Adding ground potassium carbonate (the particle size is less than 50 mu m) into a dimethyl sulfoxide solution of polyacrylonitrile, wherein the mass ratio of the polyacrylonitrile to the potassium carbonate is 100: 1, fully blending to obtain a self-activated spinning solution with the solid content of 20 wt%;
(2) carrying out wet spinning on the self-activated spinning solution obtained in the step (1) to obtain self-activated fiber precursor;
(3) pre-oxidizing the self-activated fiber precursor in air atmosphere, treating the self-activated fiber precursor in the air atmosphere at 180 ℃ for 10min, and then treating the self-activated fiber precursor in the air atmosphere at 250 ℃ for 30min to obtain polyacrylonitrile-based pre-oxidized fiber;
(4) and carbonizing the polyacrylonitrile-based pre-oxidized fiber at 800 ℃ in a nitrogen atmosphere for 60min to obtain the self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber.
The EDS energy spectrum diagram of the self-activated fiber protofilament obtained in the step (2) is shown in figure 1, wherein a potassium element peak appears in the energy spectrum, and the relative weight fraction of the potassium element is 0.94 wt%, because part of potassium ions are lost along with a coagulation bath in the wet spinning process; the nitrogen content of the self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber prepared in the embodiment is 16.0%.
The self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber is prepared at 40 ℃ and 15% CO2/85％N2To CO under simulated flue atmosphere2The adsorption curve of (A) is shown in FIG. 2, and the adsorption amount of the self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber to carbon dioxide is 0.58 mmol/g.
Example 2
The preparation method of the self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber in the example 2 is the same as that of the example 1, except that in the preparation process of the self-activated spinning solution, the mass ratio of polyacrylonitrile to the activator potassium carbonate is adjusted to be 100: 3.
the nitrogen content of the self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber prepared in the embodiment is 15.8%; the scanning electron microscope image is shown in fig. 3, and the section of the fiber has a granular coarse structure and a pore structure.
The self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber is prepared at 40 ℃ and 15% CO2/85％N2To CO under simulated flue gas atmosphere2As shown in FIG. 4, the adsorption amount of carbon dioxide by the self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber was 0.69 mmol/g.
Example 3
The preparation method of the self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber in the example 3 is the same as that of the example 1, except that in the preparation process of the self-activated spinning solution, the mass ratio of polyacrylonitrile to the activator potassium carbonate is adjusted to be 100: 5.
the nitrogen content of the self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber prepared by the embodiment is 15.5%; the scanning electron microscope image is shown in FIG. 5, the fiber section structure is fluffy, and a large number of pores are formed.
The self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber is prepared at 40 ℃ and 15% CO2/85％N2Simulating CO in flue gas atmosphere2As shown in FIG. 6, the amount of carbon dioxide adsorbed by the self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber was 0.61 mmol/g.
Comparative example 1
Performing wet spinning on a dimethyl sulfoxide solution of polyacrylonitrile with the solid content of 20 wt% to obtain polyacrylonitrile fiber precursor, treating at 180 ℃ for 10min in an air atmosphere, treating at 250 ℃ for 30min, and treating at 800 ℃ for 60min in a nitrogen atmosphere to obtain the polyacrylonitrile-based porous carbon fiber.
The nitrogen content of the polyacrylonitrile-based porous carbon fiber is 19.3 percent, and the polyacrylonitrile-based porous carbon fiber is prepared by 15 percent CO at the temperature of 40 DEG C2/85％N2The adsorption curve of carbon dioxide under the atmosphere is shown in FIG. 7, and the adsorption amount of carbon dioxide on the polyacrylonitrile-based porous carbon fiber is 0.32 mmol/g.
The technical solutions of the present invention have been described in detail with reference to the above embodiments, it should be understood that the above embodiments are only specific examples of the present invention and should not be construed as limiting the present invention, and any modifications, additions or similar substitutions made within the scope of the principles of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A preparation method of self-activated polyacrylonitrile-based nitrogen-containing porous carbon fibers is characterized by comprising the following steps:
(1) uniformly dispersing the potassium salt powder into a polyacrylonitrile solution to form a self-activating spinning solution, and obtaining self-activating fiber precursor through wet spinning;
(2) pre-oxidizing the precursor of the self-activated fiber to obtain polyacrylonitrile-based pre-oxidized fiber;
(3) carbonizing polyacrylonitrile-based pre-oxidized fiber to obtain the self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber.
2. The method for preparing self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber according to claim 1, wherein the potassium salt powder is potassium carbonate, and the particle size is less than 50 μm.
3. The preparation method of the self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber according to claim 1, wherein the solid content of the self-activated spinning solution is 18-22 wt%.
4. The preparation method of the self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber according to claim 1, wherein in the self-activated spinning solution, the mass ratio of potassium salt to polyacrylonitrile is 1-8: 100.
5. the method for preparing self-activated polyacrylonitrile-based nitrogen-containing porous carbon fibers according to claim 1, wherein in the step (2), the pre-oxidation process is performed in an air atmosphere, and the pre-oxidation treatment conditions are as follows: 160-300 ℃ for 25-90 min.
6. The preparation method of the self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber as claimed in claim 5, wherein the pre-oxidation treatment is performed in two stages, and the treatment conditions of the first stage are as follows: 160-200 ℃ for 5-30 min; the processing conditions in the second stage were: 230-270 ℃ for 20-60 min.
7. The method for preparing self-activating polyacrylonitrile-based nitrogen-containing porous carbon fiber according to claim 1, wherein in the step (3), the carbonization process is performed in a nitrogen atmosphere, and the carbonization conditions are as follows: 750-850 ℃ and 30-180 min.
8. The self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber prepared by the preparation method of the self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber according to any one of claims 1 to 7, wherein the nitrogen content is 12-22%.
9. The use of the self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber according to claim 8 in the field of carbon dioxide adsorption.
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