CN114232215B - Preparation method and application of asphalt-based carbon nanofiber multistage non-woven fabric with three-dimensional cavity structure - Google Patents
Preparation method and application of asphalt-based carbon nanofiber multistage non-woven fabric with three-dimensional cavity structure Download PDFInfo
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- 239000004745 nonwoven fabric Substances 0.000 title claims abstract description 64
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000002134 carbon nanofiber Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000835 fiber Substances 0.000 claims abstract description 45
- 238000005087 graphitization Methods 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 26
- 238000009987 spinning Methods 0.000 claims abstract description 24
- 239000002086 nanomaterial Substances 0.000 claims abstract description 22
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- 238000000034 method Methods 0.000 claims description 18
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- 239000004594 Masterbatch (MB) Substances 0.000 claims description 9
- 239000013538 functional additive Substances 0.000 claims description 9
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- 239000011261 inert gas Substances 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 239000003245 coal Substances 0.000 claims description 6
- 235000021355 Stearic acid Nutrition 0.000 claims description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 5
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 5
- -1 polyoxyethylene octylphenol Polymers 0.000 claims description 5
- 239000008117 stearic acid Substances 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 4
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- 239000003208 petroleum Substances 0.000 claims description 4
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 4
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
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- 238000000227 grinding Methods 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- 239000000126 substance Substances 0.000 abstract description 5
- 230000035699 permeability Effects 0.000 abstract description 3
- 239000004753 textile Substances 0.000 abstract description 3
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 abstract description 2
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
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- 230000002411 adverse Effects 0.000 description 1
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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Classifications
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/005—Synthetic yarns or filaments
-
- 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
-
- 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
- D01F9/145—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from pitch or distillation residues
-
- 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
- D01F9/145—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from pitch or distillation residues
- D01F9/15—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from pitch or distillation residues from coal pitch
-
- 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
- D01F9/145—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from pitch or distillation residues
- D01F9/155—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from pitch or distillation residues from petroleum pitch
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Fibers (AREA)
Abstract
The invention discloses a preparation method and application of asphalt-based carbon nanofiber multistage non-woven fabric with a three-dimensional cavity structure, and belongs to the technical field of textile fibers. The carbon nanofiber multi-stage non-woven fabric is prepared by taking asphalt as a base material, adding a functional nano material to realize anisotropy of fibers, and then performing melt-jet spinning, pre-oxidation and graphitization. The non-woven fabric has high specific surface area, and simultaneously forms a large number of three-dimensional cavity structures in the non-woven fabric through the structural design of the carbon nano fibers, and anisotropy is shown among all levels of fibers, so that the gas permeability is kept while the mechanical property is ensured. Meanwhile, the carbon nanofiber multistage non-woven fabric has the advantages of high temperature stability, chemical corrosion resistance, small mass density and the like due to the fact that the main chemical structure of the carbon nanofiber multistage non-woven fabric is carbon-carbon.
Description
Technical Field
The invention belongs to the technical field of textile fibers, and particularly relates to a preparation method and application of asphalt-based carbon nanofiber multi-stage non-woven fabric with a three-dimensional cavity structure.
Background
Most of the bitumen is carbon, with some hydrogen, nitrogen, sulfur and ash. Coal resources are rich in China, the yield of coal tar pitch is high, and the pitch and processed products thereof are widely used in various fields such as roof waterproof materials, electrode materials, adhesives, surface coatings and the like. The preparation of the functional carbon material is an effective way for recycling the asphalt.
In recent years, the multistage fiber net has great application potential in the fields of individual protection, indoor air purification, industrial catalysis and the like due to the structural advantages of small pore diameter, high porosity, large specific surface area and the like. At present, the multistage fiber net is mainly prepared by an electrostatic spinning technology, and has the advantages of simple process, continuous fiber, low spinning cost and the like. The method is characterized in that a plurality of multistage fiber net materials with different structures and appearances are designed by scholars at home and abroad through electrostatic spinning, the influence of structures such as fiber diameter, surface area, surface density and thickness on the performance of the formed multistage nanofiber membrane is systematically researched, the application performance of the multistage nanofiber membrane is discussed, and partial industrialization is realized in the fields of individual protection, indoor air purification and industrial filtration. However, because the electrospun nanofiber web is limited by yield and structure, the electrospun nanofiber web still has the defects of high price, poor mechanical property, high difficulty in industrial popularization and the like.
The method has the advantages of improving the flexibility of the carrier, eliminating or weakening adverse effects generated by the expansion-contraction of the internal microstructure of the catalyst in the reaction process, optimizing the texture, reducing the aggregation of active components, fully exerting the nanometer effect of the material, and realizing the enhancement of the gas-solid reaction rate and the mass transfer efficiency, and is a problem to be solved in the field of industrial catalysts at present. With the development of science and technology, carbon fibers are widely concerned in structural materials with excellent performance, and carbon nanofiber nets show excellent prospects in the field of catalysis. However, at present, the research and preparation methods for the industrial large-scale preparation of the carbon nanofiber multi-stage non-woven fabric are not reported, so that the development of the pitch-based carbon nanofiber multi-stage non-woven fabric has wide market prospect.
Disclosure of Invention
The invention provides a preparation method and application of a carbon nanofiber multistage non-woven fabric which has a three-dimensional cavity structure, has a high specific surface area and can efficiently load a catalyst, and aims to make up for the market blank of the current industrialized carbon nanofiber multistage non-woven fabric and meet the requirements of modern chemical enterprises on carbon fiber non-woven fabrics with high specific surface areas. The carbon nanofiber multistage non-woven fabric has a high specific surface area, a large number of three-dimensional cavity structures are formed in the non-woven fabric through the structural design of the carbon nanofibers, anisotropy is shown among the fibers at each stage, and the gas permeability is kept while the mechanical performance is ensured. Meanwhile, the carbon nanofiber multistage non-woven fabric has the advantages of high temperature stability, chemical corrosion resistance, small mass density and the like due to the fact that the main chemical structure of the carbon nanofiber multistage non-woven fabric is carbon-carbon.
In order to achieve the technical purpose, the technical scheme adopted by the invention is as follows:
a preparation method of asphalt-based carbon nanofiber multistage non-woven fabric with a three-dimensional cavity structure comprises the following steps:
(1) Uniformly mixing the functional nano material and a dispersing agent according to the mass ratio of 100 to 1-20, and adding the mixture into a ball mill for grinding to obtain a functional additive suitable for asphalt melt-blown spinning;
(2) Uniformly mixing a functional additive suitable for asphalt melt-blown spinning with an asphalt material according to the mass ratio of 1-100, and then blending and granulating through a screw extruder to prepare asphalt melt-blown masterbatch;
(3) Adding the asphalt melt-blown masterbatch into a melt-blown spinning machine to form a melt, extruding the melt through a spinneret orifice, and cooling and solidifying the melt by air to form a nascent asphalt fiber web;
(4) And (3) carrying out alkali washing and water washing treatment on the nascent asphalt fiber web, and then carrying out preoxidation, drafting carbonization and graphitization heat treatment to finally prepare the asphalt-based carbon nanofiber multistage non-woven fabric with a three-dimensional cavity structure. The alkali washing and the water washing of the nascent asphalt fiber web are specifically carried out by washing with 5-10% NaOH aqueous solution and then washing to be neutral.
Preferably, the nano material in step (1) is a nano metal oxide or a nano non-metal oxide. The main function of the nano material is to make the melt-blown fiber anisotropic so as to build up a multi-stage nano fiber net structure.
More preferably, the nanomaterial in step (1) is graphene or carbon nanotubes.
Preferably, the dispersant in the step (1) is one or more of stearic acid, polyoxyethylene octyl phenol ether and fatty alcohol-polyoxyethylene ether.
Preferably, the asphalt material in the step (2) is one or more of coal-based asphalt, petroleum-based asphalt and rubber asphalt.
Preferably, the screw extruder in the step (2) is a twin-screw extruder or a single-screw extruder.
Preferably, the melt in the step (3) is extruded through a spinneret orifice and can be supplemented with high-pressure gas of about 0.3Mpa to form anisotropic melt trickle, so that spinning is facilitated.
Preferably, the specific method of the pre-oxidation, the drawing carbonization and the graphitization heat treatment in the step (4) is as follows:
A. pre-oxidation: treating with oxidizing concentrated acid under ultrasonic assistance for 0.5-10 hr, taking out non-woven fabric from the acid bath, rapidly heating to 200-500 deg.C in air, and maintaining for 0.5-1.5 hr;
B. drawing and carbonizing: rapidly heating the pre-oxidized non-woven fabric to over 1200 ℃ under the protection of high-pressure inert gas with the pressure of over 85Kpa, and keeping for 0.5-10h;
C. graphitization: after drafting and carbonization, further heating to more than 2000 ℃ and keeping for 0.5-10h to improve the graphitization degree of the product, finally carrying out ultrasonic water washing to remove impurities, and drying to obtain the final product.
Preferably, the temperature rise rate in step A and step B is more than 10 ℃/min.
Preferably, in step a, the concentrated acid is one or more of 98% concentrated sulfuric acid, 85% concentrated phosphoric acid and 68% concentrated nitric acid.
The non-woven fabric prepared by the invention can be used as a catalyst carrier to prepare a high-performance catalyst in a vapor deposition mode, or can be used as a base material to improve the functionality in other loading modes, and can be used for preparing an air filtering material, a catalytic material and an adsorbing material with multiple functions.
Advantageous effects
The method is suitable for preparing the asphalt-based carbon nanofiber multistage non-woven fabric, improves the additional value and the application field of asphalt, is convenient for large-scale processing and production, and has simple process, convenient operation and convenient implementation. The prepared asphalt-based carbon nanofiber multistage non-woven fabric with the three-dimensional cavity has excellent index performance and large specific surface area, and has a good catalytic function after being loaded with a catalyst.
Drawings
FIG. 1 is a photomicrograph of a nascent pitch web of example 1 of the present invention;
fig. 2 is a photomicrograph and a partial enlarged view of fibers in the pitch-based carbon nanofiber multi-stage non-woven fabric having a three-dimensional cavity structure obtained in example 1 of the present invention;
fig. 3 is a magnified photomicrograph of the surface of fibers in the pitch-based carbon nanofiber multi-stage nonwoven fabric having a three-dimensional cavity structure according to example 1 of the present invention.
Detailed Description
The technical solution of the present invention is further described below with reference to specific embodiments, but is not limited thereto.
Example 1
A preparation method of asphalt-based carbon nanofiber multi-stage non-woven fabric with a three-dimensional cavity structure comprises the following steps:
(1) Uniformly mixing the functional nano material and a dispersing agent according to the mass ratio of 100;
(2) Uniformly mixing a functional additive suitable for asphalt melt-blown spinning with an asphalt material according to a mass ratio of 1;
(3) Adding the asphalt melt-blown masterbatch into a melt-blown spinning machine to form a melt, extruding the melt through a spinneret orifice, and cooling and solidifying the melt by air to form a nascent asphalt fiber web;
(4) And (3) carrying out alkali washing and water washing treatment on the nascent asphalt fiber web, and then carrying out preoxidation, drafting carbonization and graphitization heat treatment to finally prepare the asphalt-based carbon nanofiber multistage non-woven fabric with a three-dimensional cavity structure. The primary asphalt fiber net is washed by alkali and water, specifically, 10% NaOH aqueous solution is used for washing, and then the water is washed to be neutral.
The main function of the nano material is to make the melt-blown fiber anisotropic so as to build up a multi-stage nano fiber net structure.
The nano material in the step (1) is graphene.
The dispersing agent in the step (1) is a mixture of stearic acid, polyoxyethylene octyl phenol ether, fatty alcohol-polyoxyethylene ether and the like in mass.
And (3) the asphalt material in the step (2) is rubber asphalt.
And (3) the screw extruder in the step (2) is a single screw extruder.
And (3) extruding the melt in the step (3) through a spinneret orifice, and assisting high-pressure gas to form anisotropic melt trickle, so that spinning is facilitated. The specific method for the pre-oxidation, the drawing carbonization and the graphitization heat treatment in the step (4) comprises the following steps:
A. pre-oxidation: treating with oxidizing concentrated acid under ultrasonic assistance for 10h, taking out the non-woven fabric from the acid bath, rapidly heating to 500 deg.C in air, and maintaining for 1.5h;
B. drawing and carbonizing: quickly heating the pre-oxidized non-woven fabric to 1500 ℃ under the protection of high-pressure inert gas with the pressure of more than 85Kpa, and keeping the temperature for 10 hours;
C. graphitization: after drafting and carbonization, further heating to 2500 ℃ and keeping for 10 hours to improve the graphitization degree of the product, finally carrying out ultrasonic water washing to remove impurities, and drying to obtain the final product.
The temperature rise rate in the step A and the step B is 50 ℃/min.
In the step A, the concentrated acid is 98% concentrated sulfuric acid.
Example 2
A preparation method of asphalt-based carbon nanofiber multistage non-woven fabric with a three-dimensional cavity structure comprises the following steps:
(1) Uniformly mixing the functional nano material and a dispersing agent according to the mass ratio of 100;
(2) Uniformly mixing a functional additive suitable for asphalt melt-blown spinning with an asphalt material according to a mass ratio of 1;
(3) Adding the asphalt melt-blown masterbatch into a melt-blown spinning machine to form a melt, extruding the melt through a spinneret orifice, and cooling and solidifying the melt by air to form a nascent asphalt fiber web;
(4) And (3) carrying out alkali washing and water washing treatment on the nascent asphalt fiber web, and then carrying out preoxidation, drafting carbonization and graphitization heat treatment to finally prepare the asphalt-based carbon nanofiber multistage non-woven fabric with a three-dimensional cavity structure. The primary asphalt fiber net is washed by alkali and water, specifically, 10% NaOH aqueous solution is used for washing, and then the water is washed to be neutral.
The nano material in the step (1) is graphene; the main function of the nano material is to make the melt-blown fiber anisotropic so as to build up a multi-stage nano fiber net structure.
The dispersant in the step (1) is stearic acid.
And (3) the asphalt material in the step (2) is coal-based asphalt.
The screw extruder in the step (2) is a double-screw extruder.
And (3) extruding the melt in the step (3) through a spinneret orifice, and assisting high-pressure gas to form anisotropic melt trickle, so that spinning is facilitated.
The specific method for the pre-oxidation, the drawing carbonization and the graphitization heat treatment in the step (4) comprises the following steps:
A. pre-oxidation: treating with oxidizing concentrated acid under ultrasonic assistance for 5h, taking out the non-woven fabric from the acid bath, rapidly heating to 300 deg.C in air, and maintaining for 0.5h;
B. drawing and carbonizing: rapidly heating the pre-oxidized non-woven fabric to 1300 ℃ under the protection of high-pressure inert gas with the pressure of more than 85Kpa, and keeping the temperature for 2 hours;
C. graphitization: after drafting and carbonization, further heating to 2000 ℃ and keeping for 0.5h to improve the graphitization degree of the product, finally carrying out ultrasonic water washing to remove impurities, and drying to obtain the final product.
The temperature rise rate in the step A and the step B is 100 ℃/min.
In the step A, the concentrated acid is 98% concentrated sulfuric acid.
Example 3
A preparation method of asphalt-based carbon nanofiber multi-stage non-woven fabric with a three-dimensional cavity structure comprises the following steps:
(1) Uniformly mixing the functional nano material and a dispersing agent according to a mass ratio of 50;
(2) Uniformly mixing a functional additive suitable for asphalt melt-blown spinning with an asphalt material according to a mass ratio of 1;
(3) Adding the asphalt melt-blown master batch into a melt-blown spinning machine to form a melt, extruding the melt through a spinneret orifice, and cooling and solidifying the melt by air to form a nascent asphalt fiber web;
(4) And (3) carrying out alkali washing and water washing treatment on the nascent asphalt fiber web, and then carrying out preoxidation, drafting carbonization and graphitization heat treatment to finally prepare the asphalt-based carbon nanofiber multistage non-woven fabric with a three-dimensional cavity structure. The alkali washing and the water washing of the nascent asphalt fiber web are specifically carried out by washing with a 5% NaOH aqueous solution and then washing to be neutral.
The nano material in the step (1) is a carbon nano tube; the main function of the nano material is to make the melt-blown fiber anisotropic so as to build up a multi-stage nano fiber net structure.
The dispersing agent in the step (1) is fatty alcohol-polyoxyethylene ether.
And (3) the asphalt material in the step (2) is petroleum-based asphalt.
The screw extruder in the step (2) is a double-screw extruder.
And (3) extruding the melt in the step (3) through a spinneret orifice, and assisting high-pressure gas to form anisotropic melt trickle, so that spinning is facilitated.
The specific method for the pre-oxidation, the drawing carbonization and the graphitization heat treatment in the step (4) comprises the following steps:
A. pre-oxidation: treating with oxidizing concentrated acid under ultrasonic assistance for 5h, taking out the non-woven fabric from the acid bath, rapidly heating to 350 deg.C in air, and maintaining for 1h;
B. drawing and carbonizing: rapidly heating the pre-oxidized non-woven fabric to 1200 ℃ under the protection of high-pressure inert gas with the pressure of more than 85Kpa, and keeping the temperature for 1h;
C. graphitizing: after drawing and carbonization, further heating to 2200 ℃ and keeping for 1h to improve the graphitization degree of the product, finally carrying out ultrasonic water washing to remove impurities, and drying to obtain the final product.
The temperature rise rate in the step A and the step B is 200 ℃/min.
In the step A, the concentrated acid is 68% concentrated nitric acid.
Example 4
A preparation method of asphalt-based carbon nanofiber multistage non-woven fabric with a three-dimensional cavity structure comprises the following steps:
(1) Uniformly mixing the functional nano material and a dispersing agent according to the mass ratio of 100;
(2) Uniformly mixing a functional additive suitable for asphalt melt-blown spinning with an asphalt material according to the mass ratio of 1;
(3) Adding the asphalt melt-blown master batch into a melt-blown spinning machine to form a melt, extruding the melt through a spinneret orifice, and cooling and solidifying the melt by air to form a nascent asphalt fiber web;
(4) And (3) carrying out alkali washing and water washing treatment on the nascent asphalt fiber web, and then carrying out preoxidation, drafting carbonization and graphitization heat treatment to finally prepare the asphalt-based carbon nanofiber multistage non-woven fabric with a three-dimensional cavity structure. The alkali washing and the water washing of the nascent asphalt fiber web are specifically carried out by washing with 10% NaOH aqueous solution and then washing to be neutral.
The nano material in the step (1) is nano metal oxide zinc oxide. The main function of the nano material is to make the melt-blown fiber anisotropic so as to build up a multi-stage nano fiber net structure.
The dispersing agent in the step (1) is polyoxyethylene octyl phenol ether.
And (3) the asphalt material in the step (2) is coal-based asphalt.
And (3) the screw extruder in the step (2) is a double-screw extruder.
And (3) extruding the melt in the step (3) through a spinneret orifice, and assisting high-pressure gas to form anisotropic melt trickle, so that spinning is facilitated.
The specific method for the pre-oxidation, drawing carbonization and graphitization heat treatment in the step (4) comprises the following steps:
A. pre-oxidation: treating with oxidizing concentrated acid under the assistance of ultrasound for 0.5-10h, taking out non-woven fabric from acid bath, rapidly heating to 300 deg.C in air, and maintaining for 1.5h;
B. drawing and carbonizing: rapidly heating the pre-oxidized non-woven fabric to 1200 ℃ under the protection of high-pressure inert gas with the pressure of more than 85Kpa, and keeping the temperature for 1h;
C. graphitization: after drafting and carbonization, further heating to 2300 ℃ and keeping for 1.5h to improve the graphitization degree of the product, finally carrying out ultrasonic water washing to remove impurities, and drying to obtain the final product.
In the step A and the step B, the temperature rise speed is 100 ℃/min.
In the step A, the concentrated acid is 85 percent concentrated phosphoric acid.
Example 5
A preparation method of asphalt-based carbon nanofiber multi-stage non-woven fabric with a three-dimensional cavity structure comprises the following steps:
(1) Uniformly mixing the functional nano material and a dispersing agent according to a mass ratio of 20;
(2) Uniformly mixing a functional additive suitable for asphalt melt-blown spinning with an asphalt material according to a mass ratio of 1;
(3) Adding the asphalt melt-blown masterbatch into a melt-blown spinning machine to form a melt, extruding the melt through a spinneret orifice, and cooling and solidifying the melt by air to form a nascent asphalt fiber web;
(4) And (3) carrying out alkali washing and water washing treatment on the nascent asphalt fiber web, and then carrying out preoxidation, drafting carbonization and graphitization heat treatment to finally prepare the asphalt-based carbon nanofiber multistage non-woven fabric with a three-dimensional cavity structure. The alkali washing and the water washing of the nascent asphalt fiber web are specifically carried out by washing with a 5% NaOH aqueous solution and then washing to be neutral.
The main function of the nano material is to make the melt-blown fiber anisotropic so as to build up a multi-stage nano fiber net structure.
The nano material in the step (1) is a carbon nano tube.
The dispersant in the step (1) is stearic acid.
And (3) mixing the asphalt material in the step (2) with coal-based asphalt, petroleum-based asphalt and rubber asphalt according to a mass ratio of 1.
And (3) the screw extruder in the step (2) is a double-screw extruder.
And (3) extruding the melt in the step (3) through a spinneret orifice, and assisting high-pressure gas to form anisotropic melt trickle, so that spinning is facilitated.
Preferably, the specific method of the pre-oxidation, the drawing carbonization and the graphitization heat treatment in the step (4) is as follows:
A. pre-oxidation: treating for 5h with oxidative concentrated acid under the assistance of ultrasound, taking out the non-woven fabric from an acid bath, rapidly heating to 250 ℃ in the air, and keeping for 1h;
B. drawing and carbonizing: quickly heating the pre-oxidized non-woven fabric to 1500 ℃ under the protection of high-pressure inert gas with the pressure of more than 85Kpa, and keeping the temperature for 5 hours;
C. graphitization: after drafting and carbonization, further heating to more than 2000 ℃ and keeping for 5 hours to improve the graphitization degree of the product, finally carrying out ultrasonic water washing to remove impurities, and drying to obtain the final product.
The temperature rise rate in the step A and the step B is 30 ℃/min.
In the step A, the concentrated acid is 98% concentrated sulfuric acid.
Performance test
(1) Fiber fineness: analysis by scanning Electron microscopy
(2) Mass per unit volume: measuring the volume with a vernier caliper, and then weighing the mass with an analytical balance
(3) Strength: GB/T24218.6-2010 textile non-woven fabric test method determination of breaking strength and breaking elongation (strip sample method)
(4) Young's modulus of single fiber: the single fiber in the non-woven fabric is separated and then measured by a single fiber strength tester
(5) Specific surface area: nitrogen adsorption process
The test results are shown in Table 1
Table 1 results of performance testing
As can be seen from the experimental data in Table 1, the asphalt-based carbon nanofiber multi-stage non-woven fabric obtained by the invention has the advantages of higher mechanical strength, larger specific surface area and smaller fiber fineness. Meanwhile, electron microscope analysis is carried out on the non-woven fabric obtained in the embodiment 1 of the invention, and as can be seen from the attached drawings 1-3, the nascent pitch fibers are anisotropic, a large number of three-dimensional cavity structures are formed in the non-woven fabric after subsequent treatment, and anisotropy is shown among all levels of fibers, so that the mechanical property is guaranteed, and the gas permeability can be kept.
It should be noted that the above-mentioned embodiments are only some of the preferred modes for implementing the invention, and not all of them. Obviously, all other embodiments obtained by persons skilled in the art based on the above embodiments of the present invention without making creative efforts shall fall within the protection scope of the present invention.
Claims (8)
1. A preparation method of asphalt-based carbon nanofiber multi-stage non-woven fabric with a three-dimensional cavity structure is characterized by comprising the following steps:
(1) Uniformly mixing the functional nano material and a dispersing agent according to the mass ratio of 100 to 1-20, and adding the mixture into a ball mill for grinding to obtain a functional additive suitable for asphalt melt-blown spinning;
(2) Uniformly mixing a functional additive suitable for asphalt melt-blown spinning with an asphalt material according to the mass ratio of 1-100, and then blending and granulating through a screw extruder to prepare asphalt melt-blown masterbatch;
(3) Adding the asphalt melt-blown master batch into a melt-blown spinning machine to form a melt, extruding the melt through a spinneret orifice, and cooling and solidifying the melt by air to form a nascent asphalt fiber web;
(4) After alkali washing and water washing treatment, pre-oxidation, drawing carbonization and graphitization heat treatment are carried out on the nascent asphalt fiber web, and finally asphalt-based carbon nanofiber multi-stage non-woven fabric with a three-dimensional cavity structure is prepared;
the nano material in the step (1) is graphene or a carbon nano tube.
2. The preparation method of the asphalt-based carbon nanofiber multistage non-woven fabric with the three-dimensional cavity structure as claimed in claim 1, wherein the dispersing agent in step (1) is one or more of stearic acid, polyoxyethylene octylphenol ether and fatty alcohol-polyoxyethylene ether.
3. The method for preparing the asphalt-based carbon nanofiber multistage non-woven fabric with the three-dimensional cavity structure as claimed in claim 1, wherein the asphalt material in the step (2) is one or more of coal-based asphalt, petroleum-based asphalt and rubber asphalt.
4. The method for preparing the asphalt-based carbon nanofiber multistage nonwoven fabric with a three-dimensional cavity structure as claimed in claim 1, wherein the screw extruder in the step (2) is a twin-screw extruder or a single-screw extruder.
5. The preparation method of the asphalt-based carbon nanofiber multistage non-woven fabric with the three-dimensional cavity structure according to claim 1, wherein the specific methods of the pre-oxidation, the drawing carbonization and the graphitization heat treatment in the step (4) are as follows:
A. pre-oxidation: treating with oxidizing concentrated acid under ultrasonic assistance for 0.5-10 hr, taking out non-woven fabric from the acid bath, rapidly heating to 200-500 deg.C in air, and maintaining for 0.5-1.5 hr;
B. drawing and carbonizing: rapidly heating the pre-oxidized non-woven fabric to over 1200 ℃ under the protection of high-pressure inert gas of more than 85 kilopascals, and keeping for 0.5-10 hours;
C. graphitization: after drafting and carbonization, further heating to more than 2000 ℃ and keeping for 0.5-10h to improve the graphitization degree of the product, finally carrying out ultrasonic water washing to remove impurities, and drying to obtain the final product.
6. The method for preparing the asphalt-based carbon nanofiber multistage non-woven fabric with the three-dimensional cavity structure as claimed in claim 5, wherein the temperature rise rate in the step A and the step B is greater than 10 ℃/min.
7. The method for preparing the asphalt-based carbon nanofiber multistage non-woven fabric with the three-dimensional cavity structure according to claim 5, wherein in the step A, the concentrated acid is one or more of 98% concentrated sulfuric acid, 85% concentrated phosphoric acid and 68% concentrated nitric acid.
8. A non-woven fabric obtained by applying the preparation method of the asphalt-based carbon nanofiber multistage non-woven fabric with the three-dimensional cavity structure according to any one of claims 1 to 7 can be used as a carrier for an air filtering material, a catalytic material or an adsorbing material.
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