KR20170062276A - Apparatus for preparing carbon nanotube fiber - Google Patents

Apparatus for preparing carbon nanotube fiber Download PDF

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KR20170062276A
KR20170062276A KR1020150167891A KR20150167891A KR20170062276A KR 20170062276 A KR20170062276 A KR 20170062276A KR 1020150167891 A KR1020150167891 A KR 1020150167891A KR 20150167891 A KR20150167891 A KR 20150167891A KR 20170062276 A KR20170062276 A KR 20170062276A
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carbon nanotube
nanotube fibers
catalyst
carbon
fibers
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KR101990385B1 (en
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오유진
송동수
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주식회사 엘지화학
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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
    • D01F9/127—Carbon filaments; Apparatus specially adapted for the manufacture thereof by thermal decomposition of hydrocarbon gases or vapours or other carbon-containing compounds in the form of gas or vapour, e.g. carbon monoxide, alcohols
    • C01B31/022—
    • 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
    • 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
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
    • D06B1/00—Applying liquids, gases or vapours onto textile materials to effect treatment, e.g. washing, dyeing, bleaching, sizing or impregnating
    • D06B1/02—Applying liquids, gases or vapours onto textile materials to effect treatment, e.g. washing, dyeing, bleaching, sizing or impregnating by spraying or projecting
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
    • D06B3/00—Passing of textile materials through liquids, gases or vapours to effect treatment, e.g. washing, dyeing, bleaching, sizing, impregnating
    • D06B3/04—Passing of textile materials through liquids, gases or vapours to effect treatment, e.g. washing, dyeing, bleaching, sizing, impregnating of yarns, threads or filaments
    • 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
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • 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
    • D06M2101/40—Fibres of carbon

Abstract

The present invention relates to an apparatus for producing carbon nanotube fibers.

Description

TECHNICAL FIELD [0001] The present invention relates to a carbon nanotube fiber manufacturing apparatus,

The present invention relates to an apparatus for producing carbon nanotube fibers.

Carbon nanotubes (CNTs), a kind of carbon isotopes, have a diameter of several to several tens of nanometers and are several hundreds of micrometers to several millimeters long. They have been reported in the journal Nature in 1991 by Dr. Iijima, , Physical properties and high aspect ratio have been studied in various fields. The inherent properties of these carbon nanotubes are due to the sp 2 bonds of carbon, stronger than iron, lighter than aluminum, and exhibit electrical conductivity similar to that of metals. According to the number of nanotubes, single-wall carbon nanotubes (SWNTs), double-wall carbon nanotubes (DWNTs), multi-walled carbon nanotubes (Multi- Wall carbon nanotube (MWNT), and can be divided into zigzag, armchair, and chiral structures depending on the asymmetry / chirality.

Methods for fabricating carbon nanotube (CNT) fibers include forest radiation and direct radiation. The forest radiation is obtained by depositing a catalyst on a substrate, synthesizing a CNT fork in a direction perpendicular to the substrate, and pulling the CNT at the end of the substrate with a tweezers or a tape to form CNTs connected by van der Waals attraction between the CNTs It is a method to radiate CNT fiber while coming out. This method has the disadvantage that it can not increase the production amount because the continuous process is impossible.

On the other hand, carbon nanotube (CNT) fibers contain various kinds of impurities. When carbon nanotube (CNT) fibers are fabricated and analyzed, the most abundant impurities in the fibers are catalyst particles formed on the outside of the fibers. These impurities must be removed because they degrade the quality of the fibers. To date, there has been a method for removing catalyst impurities using a strong acid. However, this method is problematic in that a large amount of strong acid is generated as a waste liquid, which causes not only environmental problems but also expensive wastewater treatment costs. In addition, the strong acid does not only dissolve the catalyst but also attack the CNT to form defects on the surface of the CNT, thereby deteriorating the physical properties of the carbon nanotube fibers. As another method, there is a method of melting catalyst particles at a high temperature of 1,800 DEG C or higher. However, this method also has a problem that expensive heat treatment equipment is required to perform high temperature heat treatment. Therefore, a new catalyst impurity removal method is required.

W. Huang et al. Carbon 41 (2003) 2585-2590

There is a problem that a device for removing impurities from carbon nanotube (CNT) fibers of the prior art is not economical. There is also a problem of environmental pollution.

Accordingly, it is an object of the present invention to provide an apparatus for manufacturing carbon nanotube fibers which can easily remove catalyst impurities and is simple and economical.

In order to achieve the above object, the present invention provides a method of manufacturing a carbon nanotube fiber, A voltage generator for applying a voltage to the guide to thermally heat the carbon nanotube fibers; And a spray furnace for spraying a chlorinated jet to the carbon nanotube fiber heated in a short time, wherein a catalyst impurity contained in the carbon nanotube fiber is reacted with the chlorinated jet to remove The present invention provides a carbon nanotube fiber manufacturing apparatus.

The present invention also provides a method for producing a carbon nanotube fiber, comprising the steps of: applying a voltage and a chlorine-based jet to a carbon nanotube fiber to convert the carbon nanotube fiber into a metal chloride; And passing the carbon nanotube fiber containing the metal chloride through a water bath to remove the metal chloride.

The present invention can provide a carbon nanotube fiber manufacturing apparatus capable of simply removing catalyst impurities by applying joule heating to carbon nanotube fibers and injecting chlorine-based jets to convert catalyst impurities into metal chlorides have. In addition, the apparatus for producing carbon nanotube fibers of the present invention simplifies the apparatus for removing catalyst impurities and is also economical.

By using the apparatus for producing carbon nanotube fibers according to the present invention, it is possible to obtain carbon nanotube fibers excellent in strength and elasticity from which catalyst impurities are removed. Accordingly, it is desired to provide a reinforcing material for a multifunctional composite material, a strain and damage sensor using a stable and repeated piezoresistive effect, a transmission line using high conductivity, a high specific surface area, an electrochemical device using excellent mechanical characteristics and electric conductivity, It is expected to be applicable to various fields such as microelectrode material, supercapacitor, actuator and the like.

1 shows a part of an apparatus for producing carbon nanotube fibers according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail. The following detailed description is merely an example of the present invention, and therefore, the present invention is not limited thereto.

In the drawings, like reference numerals are used for similar elements.

The term "and / or" includes any one or a combination of the plurality of listed items.

 It is to be understood that when an element is referred to as being "connected" or "connected" to another element, it is to be understood that other elements may be directly connected or connected, or intervening elements may be present.

 The singular expressions include plural expressions unless otherwise specified.

 The terms "comprises", "having", or "having" mean that there is a feature, a value, a step, an operation, an element, a component or a combination thereof described in the specification, Does not exclude the possibility that a number, a step, an operation, an element, a component, or a combination thereof may be present or added.

 The term "carbon nanotube fibers" in the present specification refers to both carbon nanotubes grown in a fiber form or formed by fusing a plurality of carbon nanotubes in a fiber form.

Techniques for producing carbon nanotube fibers include solution spinning, array spinning, aerogel spinning and / or film twisting or rolling. The present invention follows a process of directly spinning carbon nanotube fibers or ribbons from a carbon nanotube aerogel formed immediately after the introduction of a spinning material in a reactor by using chemical deposition (CD).

In the direct spinning, carbon nanotubes are synthesized in a heating furnace by injecting carbon nanotubes at a constant rate in a vertical furnace together with a carrier gas by adding a catalyst to the carbon nanotubes, and pure carbon nanotubes Carbon nanotube fibers are continuously produced.

The catalyst precursor of the present invention is a substance which is not contained in the catalyst cycle but is changed into an active catalyst (or produces an active catalyst) in the course of the catalytic reaction, and in the present invention, the catalyst precursor forms a catalyst Then, CNT is synthesized.

A conventional carbon nanotube (CNT) fiber manufacturing apparatus uses a strong acid to remove catalyst impurities contained in the carbon nanotube fibers. However, this method has a problem that a large amount of strong acid is generated as a waste liquid, which causes not only an environmental problem but also a high cost of disposal of waste water. Accordingly, the present inventors have made an effort to solve the problem by manufacturing an apparatus for manufacturing carbon nanotube fibers by simultaneously performing joule heating and chlorine jet spraying.

That is, in the apparatus for manufacturing a carbon nanotube fiber, a guide for feeding carbon nanotube fibers, a voltage generator for applying a voltage to the guide to heat the carbon nanotube fibers, A carbon nanotube fiber manufacturing apparatus comprising a catalyst impurity removal device including a spraying path for spraying a chlorine source, wherein the catalyst impurity contained in the carbon nanotube fiber is reacted with the chlorine sprayed product to remove the catalyst impurity. Lt; / RTI > The number of the guides is three or more, preferably three.

According to a preferred embodiment of the present invention, the carbon nanotube fiber manufacturing apparatus includes a cylindrical high-temperature reactor body having a reaction region, an inlet for injecting a spinning material and a carrier gas into a reaction region of the body, A heating means, a discharge port provided at a lower end of the main body for discharging the carbon nanotube fibers, and a winding means for collecting and collecting the discharged carbon nanotube fibers, wherein the catalyst impurity removal device comprises: May be provided between the means.

Hereinafter, the present invention will be described more specifically with reference to the drawings.

FIG. 1 shows a part of an apparatus for producing carbon nanotube fibers according to an embodiment of the present invention. The carbon nanotube fibers are provided with a voltage generator 12 for applying voltage to the guides 11a and 11b, And a jetting path 13 for jetting a chlorine source. Specifically, after the carbon nanotube fibers produced in the reactor are discharged, they pass through the catalyst impurity removal device 10 in the carbon nanotube fibers. That is, a voltage is applied to the two guides 11a and 11b, and carbon nanotube fibers generated by the line heating pass through the injection path. The length of the injection path may correspond to, or preferably correspond to, the two guide distances to which the voltage is applied. The carbon nanotube fibers are transported to another guide 14a located inside the water bath following the catalyst impurity removing device and then wound by the winding means 14b.

In the present invention, the inlet may include a spray nozzle for injecting the spinning material and a dispersing plate for injecting the carrier gas. The inlet may be an injection nozzle, but is not limited thereto.

The apparatus may further comprise a spinning material supply unit for supplying spinning material to the reactor body 11 at the inlet 10 and a carrier gas supply unit for supplying the carrier gas. In addition, the spinning material supply unit may include a mixer for dispersing the catalyst precursor in the gaseous or liquid carbon compound, and a transport pump for supplying the spinning material formed in the mixer to the spinneret spraying nozzle. The carrier gas introduced from the inlet may be introduced into the reaction zone at a linear velocity so as to form laminar flow, and a dispersion plate may be used for this purpose. The carrier gas may be introduced into the reactor body 11 through the inlet 10 from a carrier gas supply unit having a gas tank and flow control means. The flow regulating means regulates the gas flow rate so that the carrier gas is supplied at a linear velocity at which laminar flow can be formed. The heating means may be a heating furnace surrounding the reactor body, and the reaction region may be heated to 1,000 to 3,000 占 폚. The high temperature region of the reactor may preferably maintain a temperature of 1,000 to 2,000 DEG C, 1,000 to 1,500 DEG C or 1,000 to 1,300 DEG C, and more preferably 1,100 to 1,200 DEG C. [ The temperature in the high temperature region of the reactor influences the rate at which carbon is diffused into the catalyst to control the growth rate of the carbon nanotube. When synthesizing carbon nanotubes by chemical vapor deposition, generally, the higher the synthesis temperature, the higher the crystallinity and strength as the growth rate of carbon nanotubes increases.

In the present invention, the carrier gas injected into the reaction zone of the reactor body 11 may be injected at a linear velocity of 0.5 to 50 cm / min, preferably 0.5 to 40 cm / min or 0.5 to 30 cm / min or 0.5 to 20 cm / min or 1 to 10 cm / min. The carrier gas injection rate may vary depending on the type of carrier gas, the size of the reactor and / or the type of catalyst as described above.

In the present invention, the carrier gas controls the amount of the carbon nanotube to be injected into the reaction zone by diluting the carbon nanotube in the synthesis of the carbon nanotube. The purity of the carbon nanotube fiber produced by the reaction with the generated amorphous carbon or excess impurities is evacuated . The carrier gas may be a hydrocarbon-based gas, an inert gas, a reducing gas, or a mixed gas thereof. The inert gas, for example argon (Ar) may be a gas, a nitrogen (N 2) gas and / or their mixed gas, reducing gas, for example, hydrogen (H 2) gas, ammonia (NH 3) gas, and / Or a mixed gas thereof, but is not limited thereto.

In the present invention, the spinning material that is radiated in the high temperature region may be injected at a rate of 5 to 50 ml / hr, preferably at a rate of 5 to 40 ml / hr or 5 to 30 ml / hr or 5 to 20 ml / hr . The rate of injection of the spinning material may vary depending on the type of spinning material, the size of the reactor, and the like, as described above.

The reaction in the apparatus for producing carbon nanotube fibers of the present invention will be described in detail. The carbon nanotube fibers are introduced into the reactor through the inlet. When the catalyst precursor contained in the spinning material is supplied to the reactor, a catalyst is formed. The formed catalyst flows from the upper end to the lower end of the reactor to form carbon nanotubes and grow or fuse to form cylindrical carbon nanotube fibers. Then, the CNT-grown catalyst particles are moved to the lower end, and the formed CNT fibers are discharged through the discharge port. The unreacted catalyst, which is a catalyst impurity, is buried in the CNT, and the carbon nanotube fibers containing the catalyst impurities are passed through the catalyst impurity removing device.

Specifically, a voltage is applied to the two guides to generate joule heating on the carbon nanotube fibers themselves fed by the guide. The carbon nanotube fibers, which have been heated in a row, pass through a spray furnace that injects chlorine-based dispersions. Subsequently, when the chlorine-based jet is injected onto the carbon nanotube fibers through the injection port, the catalyst impurities contained in the carbon nanotube fibers are converted into metal chloride, which can be expressed by the following reaction formula (1).

[Reaction Scheme 1]

Figure pat00001

As shown in Reaction Scheme 1, when the converted carbon nanotube fibers containing the metal chloride are transferred to the water tank, the metal chloride contained in the carbon nanotube fibers is dissolved and removed by water, and the carbon nanotubes The tube fibers are wound by a winding means. On the other hand, the metal chloride such as FeCl 3 remaining in the carbon nanotube fiber after the conversion is dissolved in the water of the water tank and removed. That is, in the present invention, catalyst impurities such as iron (Fe), cobalt (Co), and nickel (Ni) converted into metal chloride can be dissolved and removed in water.

Meanwhile, in order to perform the reaction as shown in the reaction scheme 1, the catalyst impurities should be reacted with the chlorinated jet at a temperature of 450 to 900 ° C. Therefore, the voltage of the voltage generator may be 1 to 20 V, preferably 8 to 11 V. If the voltage of the voltage generator is less than 1 V, the reaction temperature may be too low to cause incomplete reaction. If the voltage exceeds 20 V, carbon nanotubes may burn up.

The spray furnace is provided with a chlorinated jetting nozzle, and may be an inert gas atmosphere in the spray furnace. Examples of the inert gas include nitrogen, argon and helium. In addition, a gas curtain may be formed at the inlet and the outlet of the injection path to prevent the reaction gas from flowing out to the outside, and to prevent the air from flowing into the reactor. The gas curtain can be made by a conventionally usable method. In addition, the chlorinated jetting nozzle may further include a chlorinated jetting unit for supplying a chlorinated jet. In addition, the chlorinated jet supply unit may include a mixing unit for mixing the chlorine compound and the solvent, and a transfer pump for supplying the chlorinated jet formed at the mixing unit to the chlorinated jetting nozzle. On the other hand, the chlorine-based jet is a liquid or gaseous chlorine compound such as Cl 2 (gas), CHCl 3 (liquid) and CH 2 Cl 2 (liquid) Further, the carrier gas and / or unreacted spinning material may be discharged through an exhaust port, and the exhaust port may be provided between the heating means and the discharge port or at a rear end of the CNT fiber outlet.

As the winding means, a spindle, a reel, a bobbin, a drum and a conveyor may be used, and a bobbin is most preferably used. However, the present invention is not limited thereto, May be used without limitation. The winding temperature and speed influence the orientation of the carbon nanotubes in the fiber in the fiber axis direction, thereby determining the thermal, electrical, and physical properties of the carbon nanotube fibers. Preferably, it can be wound at a temperature of 15 to 120 DEG C and a speed of 5 to 100 rpm. In addition, it is preferable that an inert gas is injected into the carbon nanotube fiber discharge port to form an inert gas curtain surrounding the continuous carbon nanotube fiber aggregate. The discharge port may include an outlet for discharging the generated carbon nanotube fibers and an exhaust line for discharging the carrier gas.

According to a preferred embodiment of the present invention, the emissive material may include a carbon compound in a gas form as well as a liquid form. The liquid or gaseous carbon compound diffuses as a carbon source as a catalyst and is synthesized into carbon nanotubes. The molecular weight distribution, concentration, viscosity, surface tension, dielectric constant and properties of the solvent to be used are taken into consideration.

According to a preferred embodiment of the present invention, the liquid or gaseous carbon compound is selected from the group consisting of methane, ethylene, acetylene, methyl acetylene, vinyl acetylene, ethanol, methanol, propanol, acetone, xylene, chloroform, ethyl acetic acid, And one or more selected from the group consisting of polyethylene glycol, ethyl formate, mesitylene, tetrahydrofuran (THF), dimethylformamide (DMF), dichloromethane, hexane, benzene, carbon tetrachloride and pentane. Specifically, the liquid carbon compound may be at least one selected from the group consisting of ethanol, methanol, propanol, acetone, xylene, chloroform, ethyl acetate, diethyl ether, polyethylene glycol, ethyl formate, mesitylene, tetrahydrofuran And may include one or more selected from the group consisting of formamide (DMF), dichloromethane, hexane, benzene, carbon tetrachloride, and pentane. (C 2 H 5 OH), xylene (C 8 H 10 ), diethyl ether [(C 2 H 5 ) 2 O ], polyethylene glycol [(CH 2 -CH 2 -O) 9 ] 1-propanol (CH 3 CH 2 CH 2 OH ), acetone (CH 3 OCH 3), ethyl formate (CH 3 CH 2 COOH), benzene (C 6 H 6), hexane (C 6 H 14) and mesitylene [C 6 H 3 (CH 3 ) 3 ]. The gas-phase carbon compound may include at least one selected from the group consisting of methane, ethylene, acetylene, methyl acetylene, and vinyl acetylene.

According to a preferred embodiment of the present invention, the spinning material may be a catalyst precursor dispersed in a liquid or gaseous carbon compound. The spinning material may be mixed with 0.5 to 5 wt%, preferably 1 to 5 wt%, or 1.5 to 4 wt% of the catalyst precursor to the liquid or gaseous carbon compound. If excess catalyst precursor is used in comparison with the liquid or gaseous carbon compound of the spinning material, the catalyst acts as an impurity and it is difficult to obtain high purity carbon nanotube fibers. It may also be a factor that hinders the thermal, electrical and / or physical properties of the carbon nanotube fibers. In the present invention, the catalyst precursor may include at least one selected from the group consisting of metallocene including ferrocene, iron, nickel, cobalt, platinum, ruthenium, molybdenum, vanadium and oxides thereof, no. The catalyst precursor may also be in the form of nanoparticles. And preferably in a metallocene form such as ferrocene, which is a compound containing iron, nickel, cobalt and the like; Iron such as iron chloride (FeCl 2 ); cobalt; And a nickel atom may be used as the catalyst precursor.

According to a preferred embodiment of the present invention, the spinning material may further include a catalytic activator. Generally, carbon nanotubes are synthesized by diffusion of carbon into the catalyst in the molten state of the catalyst, followed by precipitation of the carbon nanotubes. The catalyst activator is used as a promoter in the synthesis of carbon nanotubes to increase the carbon diffusion rate, Thereby synthesizing carbon nanotubes. As the catalytic activator, thiophene (C 4 H 4 S) may be used. Thiophene reduces the melting point of the catalyst and removes the amorphous carbon, allowing synthesis of high purity carbon nanotubes at low temperatures. The content of the catalytic activator may also affect the structure of the carbon nanotubes. For example, when 1 to 5% by weight of thiophene is mixed with ethanol as the carbon compound, multiwall carbon nanotube fibers are obtained And when the thiophene is mixed with ethanol in an amount of 0.5% by weight or less, single-walled carbon nanotube fibers can be obtained. According to a preferred embodiment of the present invention, the catalyst precursor and the catalytic activator may be liquid in the liquid carbon compound, and may be vapor in the vapor carbon compound. Therefore, the liquid carbon compound can be injected by dissolving the catalyst precursor or the catalytic activator, and vaporized into the gas-phase carbon compound to be injected into the gas form.

According to a preferred embodiment of the present invention, the carrier gas may be a hydrocarbon gas, an inert gas, a reducing gas or a mixture thereof. The inert gas may be argon, nitrogen, or a mixed gas thereof, and the reducing gas may be hydrogen, ammonia, or a mixed gas thereof.

Another aspect of the present invention provides a method for producing carbon nanotube fibers using the carbon nanotube fiber manufacturing apparatus of the present invention. That is, a method for producing a carbon nanotube fiber comprises the steps of: applying a voltage and a chlorine-based spray to carbon nanotube fibers to convert a catalyst substance contained in the carbon nanotube fibers into a metal chloride; Passing the nanotube fibers through a water bath to remove the metal chloride.

The carbon nanotube fibers can be shrunk as they pass through a water tank, and can be shaped like a thread. The carbon nanotube fibers may be prepared by reacting a spinning material with a carrier gas. Further, the carbon nanotube fibers from which the catalyst impurities are removed can be wound by a winding means. The other constitution is the same as that described in the carbon nanotube fiber production apparatus.

10: Catalytic impurity removal device
11a, 11b, 14a: Guide
12: voltage generator
13: Injection route
14b: winding means

Claims (18)

A guide for transporting the carbon nanotube fibers;
A voltage generator for applying a voltage to the guide to thermally heat the carbon nanotube fibers; And
And a spray furnace for spraying a chlorinated jet to the carbon nanotube fiber heated to a predetermined temperature,
Wherein the catalyst impurity contained in the carbon nanotube fibers is reacted with the chlorinated jetting material to remove the carbon nanotube fibers. The method according to claim 1,
The apparatus for manufacturing carbon nanotube fibers according to claim 1, wherein the number of the guides is three or more. The method according to claim 1,
Wherein the spray furnace is provided with a chlorinated jetting nozzle and an inert gas atmosphere is provided in the spray furnace. The method according to claim 1,
Wherein the voltage of the voltage unit is 1 to 20 V. The method according to claim 1,
Wherein the chlorine-based jet is a liquid or gaseous chlorine compound selected from the group consisting of Cl 2 , CHCl 3 and CH 2 Cl 2 . The method according to claim 1,
Wherein the catalyst impurity is selected from the group consisting of iron (Fe), cobalt (Co), and nickel (Ni). The method according to claim 1,
The carbon nanotube fiber manufacturing apparatus
A cylindrical high-temperature reactor body having a reaction zone;
An inlet for injecting a spinning material and carrier gas into the reaction zone of the body;
Heating means for heating the reaction region;
A discharge port installed at a lower end of the main body to discharge the carbon nanotube fibers; And
And winding means for collecting the discharged carbon nanotube fibers,
Wherein the catalyst impurity removing device is provided between the outlet and the winding means. The method of claim 7,
Wherein the winding means is selected from the group consisting of a spindle, a reel, a bobbin, a drum and a conveyor. The method of claim 7,
Wherein the heating means is a heating furnace enclosing the reactor main body, and the reaction region is heated to 1,000 to 3,000 占 폚. The method of claim 7,
Wherein the spinning material is characterized in that a catalyst precursor is dispersed in a liquid or gaseous carbon compound. The method of claim 10,
The liquid or gaseous carbon compound may be at least one selected from the group consisting of methane, ethylene, acetylene, methyl acetylene, vinyl acetylene, ethanol, methanol, propanol, acetone, xylene, chloroform, ethyl acetic acid, diethyl ether, polyethylene glycol, Wherein the carbon nanotube fiber is at least one selected from the group consisting of tetrahydrofuran (THF), dimethylformamide (DMF), dichloromethane, hexane, benzene, carbon tetrachloride and pentane. Claim 10
Wherein the catalyst precursor is at least one selected from the group consisting of metallocene including ferrocene, iron, nickel, cobalt, platinum, ruthenium, molybdenum, vanadium and oxides thereof. The method of claim 7,
Wherein the spinning material further comprises a catalytic activator. The method of claim 7,
Wherein the carrier gas is a hydrocarbon gas, an inert gas, a reducing gas, or a mixed gas thereof. Applying a voltage and a chlorine-based jet to the carbon nanotube fibers to convert the catalyst particles contained in the carbon nanotube fibers into metal chloride; And
And passing the carbon nanotube fiber containing the metal chloride through a water bath to remove the metal chloride. 16. The method of claim 15,
Wherein the voltage is between 1 and 20 volts. 16. The method of claim 15,
Wherein the chlorine-based jet is a liquid or gaseous chlorine compound selected from the group consisting of Cl 2 , CHCl 3 and CH 2 Cl 2 . 16. The method of claim 15,
Wherein the carbon nanotube fibers are produced by reacting a spinning material with a carrier gas.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003201630A (en) * 2001-12-26 2003-07-18 Nikkiso Co Ltd Method for post-treating carbon nanofiber and method for producing graphitized carbon nanofiber
KR20100033858A (en) * 2008-09-22 2010-03-31 삼성전자주식회사 Apparatus and method for surface treatment of carbon fiber using resistive heating
KR20140147004A (en) * 2013-06-18 2014-12-29 주식회사 엘지화학 Apparatus for preparing carbon nanotube fiber and process for preparing carbon nanotube fiber using same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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