CN114775113B - Self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber, preparation method and application - Google Patents
Self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber, preparation method and application Download PDFInfo
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- CN114775113B CN114775113B CN202210586461.6A CN202210586461A CN114775113B CN 114775113 B CN114775113 B CN 114775113B CN 202210586461 A CN202210586461 A CN 202210586461A CN 114775113 B CN114775113 B CN 114775113B
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- 229920002239 polyacrylonitrile Polymers 0.000 title claims abstract description 87
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 75
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 75
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000835 fiber Substances 0.000 claims abstract description 29
- 238000001179 sorption measurement Methods 0.000 claims abstract description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002243 precursor Substances 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
- 238000009987 spinning Methods 0.000 claims abstract description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 11
- 238000002166 wet spinning Methods 0.000 claims abstract description 8
- 238000010000 carbonizing Methods 0.000 claims abstract description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 18
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical group [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 16
- 239000012298 atmosphere Substances 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- 239000001569 carbon dioxide Substances 0.000 claims description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 9
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 8
- 238000003763 carbonization Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000011148 porous material Substances 0.000 abstract description 14
- 239000003345 natural gas Substances 0.000 abstract description 4
- 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 16
- 239000012190 activator Substances 0.000 description 15
- 230000004913 activation Effects 0.000 description 12
- 239000000126 substance Substances 0.000 description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 230000003213 activating effect Effects 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-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
- 229910052799 carbon Inorganic materials 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
- 239000002006 petroleum coke Substances 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002121 nanofiber Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 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
- 150000001336 alkenes Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- SQDFHQJTAWCFIB-UHFFFAOYSA-N n-methylidenehydroxylamine Chemical group ON=C SQDFHQJTAWCFIB-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
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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
-
- 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
-
- 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
-
- 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 fiber, which comprises the following steps: (1) Uniformly dispersing potassium salt powder into a polyacrylonitrile solution to form a self-activated spinning solution, and obtaining a self-activated fiber precursor through wet spinning; (2) Pre-oxidizing the self-activated fiber precursor to obtain polyacrylonitrile-based pre-oxidized fiber; (3) Carbonizing the 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 CO 2 The diffusion path of the porous carbon fiber is improved, the polarity of the material matrix is improved, and the CO of the porous carbon fiber is promoted 2 Is a natural gas, and is a natural gas; so that the self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber is opposite to CO 2 Has excellent adsorption performance and can be applied to CO 2 The adsorption field.
Description
Technical Field
The invention relates to the technical field of functional fiber materials, in particular to a self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber, a preparation method and application.
Background
The porous carbon fiber is a carbon material between carbon fiber and active carbon, and is prepared by carbonizing/activating organic fiber as a precursor. PorousThe carbon fiber has the characteristics of high specific surface area, developed pore structure and rich adsorption sites, and can be used for CO 2 In the adsorption field, the porous carbon fiber has stable physical and chemical properties and can adsorb CO 2 The waste water can be recycled and regenerated, 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 above gases as an activating agent, and in the activation process, the precursor is heated and cracked to generate defects and gas, and the gas removes disordered carbon and tar which block the pore structure, so that the original pore diameter is enlarged and new pores are generated; for example, a preparation method of porous petroleum coke-based carbon fiber is disclosed in Chinese patent document with publication number of CN106958053A, and the porous petroleum coke-based carbon fiber is prepared by using amphiphilic carbonaceous material prepared from petroleum coke and polyacrylonitrile as raw materials through electrostatic spinning, pre-oxidation, carbonization and physical activation.
The chemical activation is performed by chemical activator (KOH, K 2 CO 3 、NaOH、H 3 PO 3 、ZnCl 2 Etc.) react with the fibers to form a pore structure, chemical activation is an efficient pore-forming method. However, in the conventional chemical activation, a large amount of chemical activator is required to be mixed with the precursor, and the activator mainly stays on the surface layer of the precursor, which easily causes uneven activation and causes consumption and waste of a large amount of activator.
The invention discloses a preparation method of a coal-based porous carbon fiber anode material, which is disclosed in Chinese patent document with publication number of CN114267829A, wherein coal produced by Xinjiang black mountain is used as a carbon source, and is mixed with polyacrylonitrile to be dissolved in N, N-dimethylformamide to prepare spinning solution, and then the spinning solution is subjected to electrostatic spinning technology, pre-oxidation, carbonization, chemical activation treatment and other processes to prepare the coal-based porous carbon fiber. The mass ratio of the activator to the fiber is 4:1 (chemical activator is KOH), there is a significant loss of activator.
The Chinese patent document with publication number of CN112342644A discloses a preparation method of porous carbon fiber, which comprises the steps of dissolving polyacrylonitrile in a solvent to obtain spinning solution, carrying out electrostatic spinning to obtain nanofiber felt, heating the nanofiber felt to preserve heat for preoxidation, and heating at high temperature 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 activator, the activation step is carried out independently, the operation is complex and continuous production is not possible.
Disclosure of Invention
The invention uses polyacrylonitrile as a nitrogen source, potassium salt powder as an activator, and provides a preparation method of self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber by using a self-activation method, which reduces the dosage of the activator, improves the activation efficiency, and the prepared self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber can treat CO in a simulated flue gas environment 2 The adsorption is fast and efficient, and the adsorption quantity reaches 0.69mmol/g.
The technical scheme adopted is as follows:
the preparation method of the self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber comprises the following steps:
(1) Uniformly dispersing potassium salt powder into a polyacrylonitrile solution to form a self-activated spinning solution, and obtaining a self-activated fiber precursor through wet spinning;
(2) Pre-oxidizing the self-activated fiber precursor to obtain polyacrylonitrile-based pre-oxidized fiber;
(3) Carbonizing the polyacrylonitrile-based pre-oxidized fiber to obtain the self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber.
The polyacrylonitrile contains a cyano (-CN) group with strong polarity, can endow the porous carbon fiber with a unique nitrogen-containing functional group, and is an excellent nitrogen source; the invention takes potassium salt powder as an activator, and utilizes a self-activation method to introduce uniformly distributed potassium salt into precursor spinning solution, and the potassium salt is chemically activated in the fiber precursor to form a porous carbon material in the heat treatment process, so that on one hand, the problem of waste of the activator can be effectively solved, and on the other hand, the intercalation effect of potassium ions can promote the development of pore channels and increase CO 2 And (2) the diffusion path of the material matrix is improved, and the porous carbon fiber of the product is promotedDimension to CO 2 Is a component of the adsorption process.
Preferably, the potassium salt powder is potassium carbonate, and is obtained by grinding by a mortar and sieving by a screen.
Preferably, the particle size of the potassium salt powder is less than 50 mu m; the excessive particle size of the potassium salt powder can influence the smooth wet spinning, and the potassium salt powder with the particle size smaller than 50 μm is more beneficial to spinning.
Preferably, the solid content of the self-activated spinning solution is 18-22 wt%.
Preferably, the solvent of the polyacrylonitrile solution is dimethyl sulfoxide.
Preferably, in the self-activated spinning solution, the mass ratio of the potassium salt to the polyacrylonitrile is 1-8: 100; too much potassium salt can cause uneven dispersion and aggregation deposition, and when the potassium salt is preferably potassium carbonate, polyacrylonitrile is easy to undergo a crosslinking reaction under the alkaline condition formed by too much potassium carbonate, so that the viscosity is increased; under the preferable range, the prepared self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber is resistant to CO 2 Is excellent in adsorption.
In the step (2), the pre-oxidation process is performed in an air atmosphere, and in the pre-oxidation process, the polyacrylonitrile undergoes cyclization reaction, oxidation reaction, dehydrogenation reaction, and the like, to form an aromatic hybrid structure, a nitrone structure, a conjugated olefin structure, and the like.
Preferably, the conditions of the pre-oxidation treatment are: 160-300 ℃ and 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 second stage of treatment conditions are as follows: 230-270 ℃ and 20-60 min.
Preferably, in the step (3), the carbonization process is performed in a nitrogen atmosphere, and the carbonization conditions are as follows: 750-850 ℃ for 30-180 min.
The invention also provides the self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber prepared by the preparation method, wherein the nitrogen content of the self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber is 12-22%, and the self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber is internally provided with a pore channel structure which is mutually connected.
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 rapidly and efficiently adsorb carbon dioxide in a simulated smoke environment, and the adsorption quantity reaches 0.69mmol/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 CO 2 The diffusion path of the porous carbon fiber is improved, the polarity of the material matrix is improved, and the CO of the porous carbon fiber is promoted 2 Is a natural gas, and is a natural gas; so that the self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber is opposite to CO 2 Has excellent adsorption performance and can be applied to CO 2 The adsorption field.
(2) According to the invention, the potassium salt powder of the activating agent is added into the polyacrylonitrile solution, and the pore structure is regulated and controlled by regulating the proportion of the polyacrylonitrile to the potassium salt, so that the self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber is prepared, the dosage of the activating agent is reduced, the activating efficiency is improved, a large amount of activating agent is not required to be reused for chemical activation of semi-finished fiber, and the preparation method is simple and efficient and has low energy consumption.
(3) The invention utilizes the precursor spinning solution with uniformly distributed activator to form a pore structure through the self-activation process, the precursor spinning solution preparation, wet spinning and heat treatment processes can be continuously produced on line, and the preparation process is simple and convenient.
Drawings
FIG. 1 is an EDS spectrum of the self-activated fiber precursor of example 1.
FIG. 2 is a graph showing the CO content of the self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber obtained in example 1 2 Adsorption curve.
FIG. 3 is an SEM image of the self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber prepared in example 2.
FIG. 4 is a graph showing the CO content of the self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber obtained in example 2 2 Adsorption curve.
FIG. 5 is an SEM image of the self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber prepared in example 3.
FIG. 6 is a graph showing the CO content of the self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber obtained in example 3 2 Adsorption curve.
FIG. 7 is CO of the polyacrylonitrile-based porous carbon fiber of comparative example 1 2 Adsorption curve.
Detailed Description
The invention is further elucidated below in connection with the drawings and the examples. It is to be understood that these examples are for illustration of the invention only and are not intended to limit the scope of the 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 characterizing the elemental content of the self-activating fiber precursor; the element analyzer is used for representing the nitrogen content of the self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber; a Scanning Electron Microscope (SEM) is used for representing the surface morphology of the self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber; synchronous thermal analyzer for testing CO of self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber in simulated flue environment 2 Is used for the adsorption performance of the catalyst.
Example 1
(1) Adding ground potassium carbonate (particle size is smaller than 50 μm) 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 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 an air atmosphere, treating for 10min in the air atmosphere at 180 ℃ and then treating for 30min in the air atmosphere at 250 ℃ to obtain polyacrylonitrile-based pre-oxidized fiber;
(4) Carbonizing the polyacrylonitrile-based pre-oxidized fiber at 800 ℃ in nitrogen atmosphere for 60min to obtain the self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber.
The EDS energy spectrum of the self-activated fiber precursor obtained in the step (2) is shown in figure 1, a peak of potassium element appears in the energy spectrum, and the relative weight fraction of the potassium element is 0.94wt%, because part of potassium ions are lost along with a coagulating 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 has a CO content of 15% at 40 DEG C 2 /85％N 2 CO in simulated flue atmosphere 2 The adsorption curve of the self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber is shown in fig. 2, and the adsorption amount of the self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber to carbon dioxide is 0.58mmol/g.
Example 2
The preparation method of the self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber in example 2 is the same as that in example 1, except that in the preparation process of the self-activated spinning solution, the mass ratio of polyacrylonitrile to 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 rough structure and a pore structure.
The self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber has a CO content of 15% at 40 DEG C 2 /85％N 2 CO in simulated flue atmosphere 2 The adsorption curve of the self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber is shown in FIG. 4, and the adsorption amount of the self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber to carbon dioxide is 0.69mmol/g.
Example 3
The preparation method of the self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber in example 3 is the same as that in example 1, except that in the preparation process of the self-activated spinning solution, the mass ratio of polyacrylonitrile to activator potassium carbonate is adjusted to be 100:5.
the nitrogen content of the self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber prepared in 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 appear.
The self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber has a CO content of 15% at 40 DEG C 2 /85％N 2 CO in simulated flue atmosphere 2 The adsorption curve of (c) is shown in figure 6,the adsorption quantity of the self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber to carbon dioxide is 0.61mmol/g.
Comparative example 1
And (3) carrying out wet spinning on a dimethyl sulfoxide solution of polyacrylonitrile with the solid content of 20wt% to obtain polyacrylonitrile fiber precursor, treating the polyacrylonitrile fiber precursor for 10min at 180 ℃ and 30min at 250 ℃ in an air atmosphere, and treating the polyacrylonitrile fiber precursor for 60min at 800 ℃ 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 nitrogen content of the polyacrylonitrile-based porous carbon fiber is 15 percent CO at 40 DEG C 2 /85％N 2 The adsorption curve of carbon dioxide under atmosphere is shown in FIG. 7, and the carbon dioxide adsorption amount of the polyacrylonitrile-based porous carbon fiber is 0.32mmol/g.
While the foregoing embodiments have been described in detail in connection with the embodiments of the invention, it should be understood that the foregoing embodiments are merely illustrative of the invention and are not intended to limit the invention, and any modifications, additions, substitutions and the like made within the principles of the invention are intended to be included within the scope of the invention.
Claims (6)
1. The preparation method of the self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber is characterized by comprising the following steps of:
(1) Uniformly dispersing potassium salt powder into a polyacrylonitrile solution to form a self-activated spinning solution, and obtaining a self-activated fiber precursor through wet spinning;
(2) Pre-oxidizing the self-activated fiber precursor to obtain polyacrylonitrile-based pre-oxidized fiber;
(3) Carbonizing the polyacrylonitrile-based pre-oxidized fiber to obtain the self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber;
the potassium salt powder is potassium carbonate, and the particle size is smaller than 50 mu m; the solid content of the self-activated spinning solution is 18-22 wt%; in the self-activated spinning solution, the mass ratio of the potassium salt to the polyacrylonitrile is 1-8: 100;
the pre-oxidation process is carried out in an air atmosphere.
2. The method for preparing the self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber according to claim 1, wherein in the step (2), the conditions of the pre-oxidation treatment are as follows: 160-300 ℃ and 25-90 min.
3. The method for preparing the self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber according to claim 2, wherein 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 second stage of treatment conditions are as follows: 230-270 ℃ and 20-60 min.
4. The method for preparing the self-activated 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 treatment conditions are as follows: 750-850 ℃ for 30-180 min.
5. The self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber prepared by the method for preparing the self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber according to any one of claims 1 to 4, wherein the nitrogen content is 12 to 22%.
6. The use of the self-activated polyacrylonitrile-based nitrogen-containing porous carbon fiber according to claim 5 in the field of carbon dioxide adsorption.
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| CN110541210A (en) * | 2019-09-04 | 2019-12-06 | 中国科学院宁波材料技术与工程研究所 | Nitrogen-rich porous polyacrylonitrile-based carbon fiber and preparation method and application thereof |
| CN114381829A (en) * | 2022-01-13 | 2022-04-22 | 华南理工大学 | Microporous carbon fiber material prepared from polyacrylonitrile and used for separating multiple micromolecular gases in high selectivity manner, and preparation method and application thereof |
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