CN117418334A - Boron-doped polyacrylonitrile-based activated carbon fiber and preparation method thereof - Google Patents
Boron-doped polyacrylonitrile-based activated carbon fiber and preparation method thereof Download PDFInfo
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- CN117418334A CN117418334A CN202311447686.4A CN202311447686A CN117418334A CN 117418334 A CN117418334 A CN 117418334A CN 202311447686 A CN202311447686 A CN 202311447686A CN 117418334 A CN117418334 A CN 117418334A
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- 229920002239 polyacrylonitrile Polymers 0.000 title claims abstract description 73
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910052796 boron Inorganic materials 0.000 claims abstract description 50
- 239000000835 fiber Substances 0.000 claims abstract description 34
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- 238000001994 activation Methods 0.000 claims abstract description 21
- 230000004913 activation Effects 0.000 claims abstract description 14
- 238000003763 carbonization Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 39
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 10
- MSACGCINQCCHBD-UHFFFAOYSA-N 2,4-dioxo-4-(4-piperidin-1-ylphenyl)butanoic acid Chemical compound C1=CC(C(=O)CC(=O)C(=O)O)=CC=C1N1CCCCC1 MSACGCINQCCHBD-UHFFFAOYSA-N 0.000 claims description 9
- 238000010521 absorption reaction Methods 0.000 claims description 9
- -1 lithium tetrafluoroborate Chemical compound 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 230000003213 activating effect Effects 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 230000006641 stabilisation Effects 0.000 claims description 5
- 238000011105 stabilization Methods 0.000 claims description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000012190 activator Substances 0.000 claims description 3
- 229910021538 borax Inorganic materials 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- HDIWKNXVBQPJCO-UHFFFAOYSA-N ethyl 2-methylsulfanyl-6-oxo-1h-pyrimidine-5-carboxylate Chemical compound CCOC(=O)C1=CN=C(SC)NC1=O HDIWKNXVBQPJCO-UHFFFAOYSA-N 0.000 claims description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 239000004328 sodium tetraborate Substances 0.000 claims description 3
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 3
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 21
- 230000001681 protective effect Effects 0.000 abstract description 16
- 239000000126 substance Substances 0.000 abstract description 13
- 239000004744 fabric Substances 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 31
- 229920000049 Carbon (fiber) Polymers 0.000 description 21
- 239000011148 porous material Substances 0.000 description 10
- 239000004917 carbon fiber Substances 0.000 description 8
- 238000001000 micrograph Methods 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000002657 fibrous material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 206010019345 Heat stroke Diseases 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000008642 heat stress Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Classifications
-
- 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
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/80—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with boron or compounds thereof, e.g. borides
- D06M11/81—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with boron or compounds thereof, e.g. borides with boron; with boron halides; with fluoroborates
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/80—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with boron or compounds thereof, e.g. borides
- D06M11/82—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with boron or compounds thereof, e.g. borides with boron oxides; with boric, meta- or perboric acids or their salts, e.g. with borax
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
- D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/26—Polymers or copolymers of unsaturated carboxylic acids or derivatives thereof
- D06M2101/28—Acrylonitrile; Methacrylonitrile
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Inorganic Fibers (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
According to the boron-doped high-performance polyacrylonitrile-based activated carbon fiber and the preparation method thereof, the boron-containing compound is added in the pretreatment process of the polyacrylonitrile precursor, so that the activation process can be promoted, boron doping of the polyacrylonitrile fiber can be carried out at the high temperature of carbonization and activation, and the prepared boron-doped polyacrylonitrile-based activated carbon fiber has good adsorption performance, higher tensile strength and proper microporous structure, and is very suitable for being used for inner fabrics of breathable chemical protective clothing.
Description
Technical Field
The invention belongs to the technical field of chemical protection, and particularly relates to boron-doped polyacrylonitrile-based activated carbon fiber for an inner layer fabric of breathable chemical protective clothing and a preparation method thereof.
Background
The prior high-protection isolation type chemical protective clothing generally adopts air-proof and moisture-proof rubber or plastic as an outer layer fabric, and is generally accompanied with a large heat load problem, and the serious heat stress effect caused by long-time wearing of the protective clothing can cause heatstroke, shock and even death of operators. Therefore, the breathable chemical protective clothing capable of combining good protective performance and breathable moisture permeability is developed, so that the physiological comfort of operators is improved, expensive and heavy microclimate temperature adjusting devices are avoided, the maneuverability of the operators is improved, and the breathable chemical protective clothing is an important research point in the field of individual biochemical protection. The development of breathable chemical protective clothing based on physical adsorption has been over 60 years, and the porous carbon material adopted by the inner adsorption fabric can be divided into three stages, namely granular or powdery active carbon, spherical active carbon and active carbon fiber. Among them, the activated carbon fiber chemical protective clothing is developed by british institute of chemical protection, and is the latest type of breathable chemical protective clothing. Compared with other active carbon materials, the active carbon fiber has the advantages of higher microporosity, concentrated pore size distribution, high adsorption and desorption rate, high adsorption efficiency and the like, and is more suitable for inner fabrics of protective clothing.
The activated carbon fiber material applied to the chemical protective clothing has the characteristics of high strength, good post-processing property, easy regeneration, heat conduction and the like besides excellent adsorption performance. However, the high strength and good adsorption performance of the active carbon fiber material at present have contradiction that the high compatibility is difficult, and the mechanical property of the active carbon fiber material is reduced in the activation process. The activation process is an indispensable link in the preparation process of the activated carbon fiber material, and is a key step for obtaining good adsorption performance, but in the high-temperature activation process, the etching of the fiber by the activator brings about the increase of pores, the adsorption performance is improved, and the fiber strength is reduced due to the etching of the matrix material. Therefore, in order to solve the contradiction of mechanical property loss caused by the acquisition of the adsorption performance of the activated carbon fiber, control of the activation process conditions and research of the balance factors between the adsorption performance and the mechanical performance in the activation process, the preparation of the high-performance activated carbon fiber with both strength and adsorption capacity is necessary, and the method has important significance for upgrading and upgrading of the inner fabric of the breathable chemical protective clothing.
Disclosure of Invention
First, the technical problem to be solved
The invention provides a boron-doped polyacrylonitrile-based activated carbon fiber capable of simultaneously realizing higher tensile strength and higher benzene absorption amount and a preparation method thereof, and aims to solve the technical problem that the adsorption performance and mechanical performance of an activated carbon fiber fabric for an inner layer fabric of a breathable chemical protective garment are difficult to be highly compatible.
(II) technical scheme
In order to solve the technical problems, the invention provides a preparation method of boron-doped polyacrylonitrile-based activated carbon fiber, which comprises the following steps:
s1, cleaning polyacrylonitrile precursor fibers in clear water, soaking the polyacrylonitrile precursor fibers in a boron-containing compound aqueous solution to obtain boron-containing compound-impregnated polyacrylonitrile fibers, and airing the polyacrylonitrile precursor fibers in a natural state; fixing the polyacrylonitrile fiber impregnated with the boron-containing compound on a high-temperature-resistant stainless steel bracket, applying tension to extend the polyacrylonitrile fiber impregnated with the boron-containing compound, and then performing thermal oxidation stabilization treatment in an air atmosphere to obtain a boron-doped pre-oxidized fiber;
s2, placing the boron doped pre-oxidized fiber obtained in the step S1 into a carbonization and activation furnace, introducing nitrogen, heating to 600-750 ℃ at a heating rate of 6-12 ℃/min, and maintaining the temperature for carbonization for 1-2 hours; after carbonization, the temperature is raised to 800-900 ℃ at a heating rate of 6-12 ℃/min, and an activating agent is introduced and kept at the temperature for activation for 0.25-1.25 hours; stopping introducing the activating agent, reducing the temperature to 180 ℃ at the cooling rate of 6-12 ℃/min, stopping introducing nitrogen, taking out the boron-doped polyacrylonitrile-based activated carbon fiber after the hearth is cooled to room temperature, and washing and drying by water or ethanol to obtain a finished product.
Further, in step S1, the boron-containing compound is at least one of boric acid, potassium tetraborate tetrahydrate, borax, lithium tetrafluoroborate, sodium tetrafluoroborate, potassium tetrafluoroborate and potassium phenyltrifluoroborate.
Further, in step S1, the concentration of the aqueous solution of the boron-containing compound is 3 to 30% by weight.
Further, in the step S1, the mixture is soaked in the aqueous solution of the boron-containing compound for 12 to 36 hours.
Further, in step S1, tension is applied to elongate the boron compound impregnated polyacrylonitrile fiber by 5 to 20%.
Further, in step S1, the thermal oxidation stabilization treatment is performed at 180 to 300℃for 2 to 6 hours in an air atmosphere.
Further, in step S2, the activator is one or more of steam, carbon dioxide or air.
In addition, the invention also provides the boron-doped polyacrylonitrile-based activated carbon fiber, which is prepared by adopting the method; the boron element content in the fiber main body of the boron-doped polyacrylonitrile-based active carbon fiber is more than or equal to 0.2 weight percent.
Further, the specific surface area of the boron-doped polyacrylonitrile-based activated carbon fiber is more than or equal to 850m 2 /g; the microporosity is more than or equal to 50 percent; the tensile strength of the monofilaments is more than or equal to 0.7GPa; p/p 0 When the content of benzene absorption is 17.5%, the benzene absorption is more than or equal to 250mg/g, p/p 0 When the content of benzene is=95%, the benzene absorption amount is more than or equal to 270mg/g.
(III) beneficial effects
According to the boron-doped high-performance polyacrylonitrile-based activated carbon fiber and the preparation method thereof, the boron-containing compound is added in the pretreatment process of the polyacrylonitrile precursor, so that the activation process can be promoted, boron doping of the polyacrylonitrile fiber can be carried out at the high temperature of carbonization and activation, and the prepared boron-doped polyacrylonitrile-based activated carbon fiber has good adsorption performance, higher tensile strength and proper microporous structure, and is very suitable for being used for inner fabrics of breathable chemical protective clothing.
Drawings
FIG. 1 is a scanning electron microscope image of boron doped polyacrylonitrile-based activated carbon fibers prepared in an embodiment of the present invention; wherein the magnification is 200 times, and the scale is 40um;
FIG. 2 is a scanning electron microscope image of boron doped polyacrylonitrile-based activated carbon fibers prepared in an embodiment of the present invention; wherein the magnification is 5000 times, and the scale is 2um;
FIG. 3 is a scanning electron microscope image of boron doped polyacrylonitrile-based activated carbon fibers prepared in an embodiment of the present invention; wherein the magnification is 30000 times and the scale is 300nm;
FIG. 4 is an infrared spectrum of boron doped polyacrylonitrile-based activated carbon fibers prepared in an example of the present invention; wherein the abscissa is the infrared wave number, and the unit is cm -1 The ordinate is the transmittance in units of;
FIG. 5 is an XRD diffraction pattern of boron doped polyacrylonitrile-based activated carbon fibers prepared in the examples of the present invention; wherein, the horizontal coordinate is diffraction angle 2 theta, the unit is degrees, and the vertical coordinate is diffraction intensity;
FIG. 6 is an illustration of N of boron doped polyacrylonitrile-based activated carbon fibers prepared in an example of the present invention 2 Isothermal adsorption and desorption curves; wherein the abscissa is relative pressure, the ordinate is volume, and the unit is cm 3 /g；
FIG. 7 is a graph of the BJH pore size distribution of boron doped polyacrylonitrile-based activated carbon fibers prepared in the examples of the present invention; wherein the abscissa is the full pore diameter, the unit is nm, the ordinate is dV/dlogD, and the unit is cm 3 /g；
FIG. 8 is a graph of H-K pore width distribution of boron doped polyacrylonitrile-based activated carbon fibers prepared in an example of the present invention; wherein the abscissa is micropore width, unit nm, and the ordinate is dV/dW, unit cm 3 /g·nm；
FIG. 9 is a graph of the vapor dynamic adsorption of benzene by boron doped polyacrylonitrile-based activated carbon fibers prepared in the examples of the present invention; wherein,time in min on the abscissa and volume in mg/g on the ordinate, relative pressure p/p 0 17.5% and 95%, respectively.
Detailed Description
To make the objects, contents and advantages of the present invention more apparent, the following detailed description of the present invention will be given with reference to the accompanying drawings and examples.
The embodiment provides a boron-doped high-performance polyacrylonitrile-based activated carbon fiber and a preparation method thereof, and the specific parameters are analyzed and determined through the following steps:
1. boron-containing compound selection
S1, cleaning polyacrylonitrile precursor fibers in clear water, soaking the polyacrylonitrile precursor fibers in an aqueous solution of 5wt% of a boron-containing compound for 24 hours to obtain the polyacrylonitrile fibers impregnated with the boron-containing compound, and airing the polyacrylonitrile fibers in a natural state; fixing the polyacrylonitrile fiber impregnated with the boron-containing compound on a high-temperature-resistant stainless steel bracket, applying tension to extend the polyacrylonitrile fiber by about 8%, and then carrying out thermal oxidation stabilization treatment for 4 hours at 240 ℃ in an air atmosphere to obtain boron-doped pre-oxidized fiber; the boron-containing compound includes at least one of boric acid, potassium tetraborate tetrahydrate, borax, lithium tetrafluoroborate, sodium tetrafluoroborate, potassium tetrafluoroborate and potassium phenyltrifluoroborate.
S2, placing the boron doped pre-oxidized fiber obtained in the step S1 into a carbonization and activation furnace, and introducing protective gas (nitrogen with the flow of 30 mL/min); raising the temperature to 600-750 ℃ (the temperature raising rate is 8 ℃/min), and keeping the temperature for carbonization for 1.5 hours; heating to 820 ℃ after carbonization (heating rate is 8 ℃/min), introducing an activating agent (steam, flow rate is 0.3 g/min), and keeping the temperature for activating for 0.25-1.25 hours; and cooling to 180 ℃ (the cooling rate is 10 ℃/min), stopping introducing nitrogen, taking out the boron-doped polyacrylonitrile-based activated carbon fiber after the hearth is cooled to room temperature, washing with water, and drying to obtain a finished product. The yield, specific surface area and tensile strength were tested. The results obtained are shown in Table 1.
As can be seen from Table 1, the effect of different borides on the yield, specific surface area and tensile strength of boron-doped polyacrylonitrile-based activated carbon fibers is differentThe comprehensive performance is best when the potassium tetraborate tetrahydrate is used as an impregnant, the yield can reach 41 percent, and the specific surface area is 1027m 2 And/g, tensile strength of 1.08GPa.
TABLE 1 influence of boron-containing Compound species on the Performance of boron-doped Polyacrylonitrile-based activated carbon fibers
2. The concentration of the aqueous solution of the boron-containing compound is selected
The boron-containing compound required in the step S1 is determined as potassium tetraborate tetrahydrate, the concentration of the boron-containing compound is controlled to be 3-30wt%, other steps and conditions are unchanged, and the yield, the specific surface area and the tensile strength of the boron-doped polyacrylonitrile-based activated carbon fiber are tested. The results obtained are shown in Table 2. As shown in Table 2, as the concentration of the aqueous solution of potassium tetraborate tetrahydrate increases, the yield of the boron-doped polyacrylonitrile-based active carbon fiber obtained increases and decreases, and the specific surface area generally tends to increase, and the tensile strength generally tends to decrease. When the concentration of the aqueous solution of the potassium tetraborate tetrahydrate is 9wt%, the prepared boron-doped polyacrylonitrile-based active carbon fiber has the best overall performance, the yield can reach 40 percent, and the specific surface area is 1022m 2 And/g, tensile strength of 1.16GPa.
TABLE 2 influence of Potassium tetraborate tetrahydrate concentration on the Performance of boron doped Polyacrylonitrile-based activated carbon fibers
3. Selection of activation time
The boron-containing compound required in the step S1 is determined to be potassium tetraborate tetrahydrate, the concentration selection range is controlled to be 9wt%, the activation time of the step S2 is controlled to be 0.25-1.25 hours, other steps and conditions are unchanged, and the yield, the specific surface area and the tensile strength of the boron-doped polyacrylonitrile-based activated carbon fiber are tested. The results obtained are shown in Table 3.
TABLE 3 influence of activation time on the properties of the prepared boron doped polyacrylonitrile-based activated carbon fibers
| Activation time (hours) | Yield (%) | Specific surface area (m) 2 /g) | Tensile Strength (GPa) |
| 0.25 | 43 | 963 | 1.11 |
| 0.5 | 40 | 1022 | 1.16 |
| 0.75 | 38 | 1108 | 0.97 |
| 1.0 | 35 | 1175 | 0.85 |
| 1.25 | 31 | 1296 | 0.73 |
As shown in table 3, as the activation time increases, the yield of the prepared boron-doped polyacrylonitrile-based activated carbon fiber is continuously reduced; the specific surface area is continuously increased; the tensile strength reached a maximum of 1.16GPa at an activation time of 0.5 hours, followed by a sharp drop.
The boron doped polyacrylonitrile-based activated carbon fiber prepared in example 3 with an activation time of 0.5 hours had the best overall properties. Fig. 1 is a scanning electron microscope image photographed at a 40um scale, and it can be seen from the image that the activated carbon fiber has less broken filaments, no burrs and good quality. Fig. 2 is a scanning electron microscope image taken at a 2um scale, from which it can be seen that the surface of the activated carbon fiber is smooth, free of ash drop and free of particle residues. Fig. 3 is a scanning electron microscope image taken at 300nm scale, from which it can be observed that the surface of the activated carbon fiber has a part of fine open pores, and the adsorption performance is ensured while the appearance phase and mechanical properties thereof are maintained.
The boron-doped polyacrylonitrile-based activated carbon fiber in the embodiment is respectively subjected to infrared spectrum and X-ray diffraction characterization, and the results are respectively shown in fig. 4 and 5. As can be seen from the infrared spectrum of FIG. 4, the whole spectrum curve is smooth, and few obvious characteristic peaks, especially 1000-1500 cm, are generated -1 The interval has almost no characteristic peak, which indicates that most of organic matters are decomposed in the carbonization process, and only carbon elements are left. As can be further seen from the X-ray diffraction chart of fig. 5, the diffraction peak occurring at 25 ° 2θ is a characteristic peak represented by the (002) crystal face of the graphite structure, indicating that the fiber has a graphite-like structure; diffraction peaks occurring at 43 ° 2θ are characteristic peaks of non-graphitized carbon (100) crystal planes; both groups of diffraction peaks are not sharp, which indicates that the crystal structure of the active carbon fiber is not obvious, and the amorphous carbon content is relatively high.
Boron doped poly in this exampleThe acrylonitrile-based activated carbon fiber was subjected to test analysis of adsorption property and pore property, and the results are shown in fig. 6, fig. 7 and fig. 8, respectively. FIG. 6 is N 2 Isothermal adsorption and desorption curves, fig. 7 is a BJH pore size distribution graph, and fig. 8 is a H-K micropore width distribution graph. As can be seen in fig. 6, N 2 Isothermal adsorption desorption curve bent to p/p 0 The axis, after which the curve is horizontal or nearly horizontal, the adsorption amount approaches a limit value, which is a typical Langmuir isotherm; the type I (a) is a characteristic isothermal adsorption desorption line of a material with narrow micropores, the pore diameter width is generally smaller than 1nm, and the pore diameter distribution is mainly concentrated in the micropore range and the micropore width distribution is mainly concentrated in 0.4-0.8 nm consistent with the results shown in fig. 7 and 8.
FIG. 9 is a graph showing isothermal adsorption of boron doped polyacrylonitrile-based activated carbon fiber with respect to benzene vapor at various partial pressures in this example, showing the results at relative pressures p/p 0 Under the condition of 17.5%, the benzene absorption capacity of the activated carbon fiber can reach 338mg/g, and the relative pressure p/p 0 Under the condition of 95 percent, the benzene absorption amount of the activated carbon fiber can reach 367mg/g.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and variations could be made by those skilled in the art without departing from the technical principles of the present invention, and such modifications and variations should also be regarded as being within the scope of the invention.
Claims (9)
1. The preparation method of the boron-doped polyacrylonitrile-based activated carbon fiber is characterized by comprising the following steps of:
s1, cleaning polyacrylonitrile precursor fibers in clear water, soaking the polyacrylonitrile precursor fibers in a boron-containing compound aqueous solution to obtain boron-containing compound-impregnated polyacrylonitrile fibers, and airing the polyacrylonitrile precursor fibers in a natural state; fixing the polyacrylonitrile fiber impregnated with the boron-containing compound on a high-temperature-resistant stainless steel bracket, applying tension to extend the polyacrylonitrile fiber impregnated with the boron-containing compound, and then performing thermal oxidation stabilization treatment in an air atmosphere to obtain a boron-doped pre-oxidized fiber;
s2, placing the boron doped pre-oxidized fiber obtained in the step S1 into a carbonization and activation furnace, introducing nitrogen, heating to 600-750 ℃ at a heating rate of 6-12 ℃/min, and maintaining the temperature for carbonization for 1-2 hours; after carbonization, the temperature is raised to 800-900 ℃ at a heating rate of 6-12 ℃/min, and an activating agent is introduced and kept at the temperature for activation for 0.25-1.25 hours; stopping introducing the activating agent, reducing the temperature to 180 ℃ at the cooling rate of 6-12 ℃/min, stopping introducing nitrogen, taking out the boron-doped polyacrylonitrile-based activated carbon fiber after the hearth is cooled to room temperature, and washing and drying by water or ethanol to obtain a finished product.
2. The method for preparing boron-doped polyacrylonitrile-based activated carbon fiber according to claim 1, wherein in step S1, the boron-containing compound is at least one of boric acid, potassium tetraborate tetrahydrate, borax, lithium tetrafluoroborate, sodium tetrafluoroborate, potassium tetrafluoroborate and potassium phenyltrifluoroborate.
3. The method for preparing boron-doped polyacrylonitrile-based activated carbon fiber according to claim 1, wherein in step S1, the concentration of the boron-containing compound aqueous solution is 3-30 wt%.
4. The method for preparing boron-doped polyacrylonitrile-based activated carbon fiber according to claim 1, wherein in step S1, the fiber is immersed in an aqueous solution of a boron-containing compound for 12 to 36 hours.
5. The method for preparing boron-doped polyacrylonitrile-based activated carbon fiber according to claim 1, wherein in step S1, tension is applied to elongate the boron-containing compound-impregnated polyacrylonitrile fiber by 5 to 20%.
6. The method for preparing boron-doped polyacrylonitrile-based activated carbon fiber according to claim 1, wherein in step S1, the thermal oxidation stabilization treatment is performed at 180 to 300 ℃ for 2 to 6 hours in an air atmosphere.
7. The method for preparing boron-doped polyacrylonitrile-based activated carbon fiber according to claim 1, wherein in step S2, the activator is one or more of steam, carbon dioxide or air.
8. A boron doped polyacrylonitrile-based activated carbon fiber, characterized in that the boron doped polyacrylonitrile-based activated carbon fiber is prepared by the method of any one of the preceding claims; the boron element content in the fiber main body of the boron-doped polyacrylonitrile-based activated carbon fiber is more than or equal to 0.2 weight percent.
9. The boron-doped polyacrylonitrile-based activated carbon fiber of claim 8, wherein the specific surface area of said boron-doped polyacrylonitrile-based activated carbon fiber is greater than or equal to 850m 2 /g; the microporosity is more than or equal to 50 percent; the tensile strength of the monofilaments is more than or equal to 0.7GPa; p/p 0 When the content of benzene absorption is 17.5%, the benzene absorption is more than or equal to 250mg/g, p/p 0 When the content of benzene is=95%, the benzene absorption amount is more than or equal to 270mg/g.
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