METHOD FOR PREPARING CARBON NANOTUBE FIBER HAVING ENHANCED TENSILE STRENGTH

Abstract

The present invention relates to a method for preparing a carbon nanotube fiber which is a continuous array of carbon nanotube. The present invention enables minimization of rotational flow inside a tube reactor and thus can facilitate enhanced tensile strength of the prepared carbon nanotube fiber.

Claims

1. A method for manufacturing carbon nanotube fiber that is a continuous aggregate of carbon nanotubes, by feeding a reaction gas containing a carbon source into a reactor tube equipped with a heating furnace together with a catalyst or a catalyst precursor and a transfer gas, comprising: suppressing rotational flow within the reactor by providing a Gr/Re.sup.2 value, calculated from Grasshopper number Gr and Reynolds number Re in an area between an inlet of the reactor tube and an inlet of the heating furnace, of 0.12 or less.

2. The method for manufacturing carbon nanotube fiber according to claim 1, wherein a temperature gradient between the inlet of the reactor tube and the inlet of the heating furnace is adjusted so that the Grasshopper number Gr and the Reynolds number Re satisfy 0.007≤Gr/Re.sup.2≤0.12.

3. The method for manufacturing carbon nanotube fiber according to claim 1, wherein the reaction zone of the reactor tube is heated to 1,000 to 3,000° C., and a temperature difference between the inlet of the reactor tube and the inlet of the heating furnace is 510 to 1000° C.

4. The method for manufacturing carbon nanotube fiber according to claim 1, wherein the transfer gas comprises a reducing gas comprising hydrogen gas, ammonia gas, or a mixed gas thereof.

5. The method for manufacturing carbon nanotube fiber according to claim 1, wherein the transfer gas further comprises an inert gas.

6. The method for manufacturing carbon nanotube fiber according to claim 1, wherein the carbon source comprises at least one selected from the group consisting of methane, ethylene, acetylene, methyl acetylene, vinyl acetylene, ethanol, methanol, propanol, acetone, xylene, chloroform, ethyl acetate, diethyl ether, polyethylene glycol, ethyl formate, mesitylene, tetrahydrofuran (THF), dimethylformamide (DMF), dichloromethane, hexane, benzene, carbon tetrachloride and pentane.

7. The method for manufacturing carbon nanotube fiber according to claim 1, wherein the catalyst or the catalyst precursor comprises at least one selected from the group consisting of iron, nickel, cobalt, platinum, ruthenium, molybdenum, vanadium and oxides thereof.

8. The method for manufacturing carbon nanotube fiber according to claim 1, wherein a catalytic activator selected from element sulfur, a sulfur-containing compound, and combinations thereof is further fed together with the catalyst or the catalyst precursor.

9. The method for manufacturing carbon nanotube fiber according to claim 8, wherein the catalytic activator comprises a compound selected from methylthiol, methyl ethyl sulfide, dimethylthioketone, phenylthiol, diphenylsulfide, pyridine, quinoline, benzothiophene, thiophene, and combinations thereof.

10. The method for manufacturing carbon nanotube fiber according to claim 1, wherein the catalyst or the catalyst precursor is in a metallocene form.

11. The method for manufacturing carbon nanotube fiber according to claim 1, wherein Gas Hourly Space Velocity (GHSV) of the reaction gas is 0.12 to 6 hr.sup.−1, and the GHSV of the transfer gas is 1.2 to 60 hr.sup.−1.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0032] FIG. 1 schematically shows a method for producing carbon nanotube fibers by direct spinning.

[0033] FIG. 2 shows a schematic structure of a reactor for producing CNT aggregate fiber according to one embodiment of the present invention, and a CFD (computational fluid dynamics) simulation result for an airflow direction according to a Comparative Example and an Example.

DETAILED DESCRIPTION

[0034] Since various modifications and variations can be made in the present invention, particular embodiments are illustrated in the drawings and will be described in detail in the detailed description. It should be understood, however, that the invention is not intended to be limited to the particular embodiments, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention. In the following description of the present invention, detailed description of known functions will be omitted if it is determined that it may obscure the gist of the present invention.

[0035] The term “aggregate” as used herein may be described interchangeably with “agglomerate” and may be understood to mean a collection of singular individuals.

[0036] The term “feeding” as used herein may be described interchangeably with “inflow”, “injection”, and may be understood to mean flowing or putting liquid, gas or heat, etc. into the places in a need thereof.

[0037] The term “carbon nanotube fiber” in the present disclosure refers to both of carbon nanotubes grown in a fiber form and a plurality of carbon nanotubes fused in a fiber form.

[0038] Hereinafter, a method for producing carbon nanotube fibers according to an embodiment of the present invention will be described in detail.

[0039] A method for producing carbon nanotube fibers include coagulation spinning, liquid-crystalline spinning, array spinning, direct spinning, and the like. Among them, the present invention follows a process of directly spinning carbon nanotube fibers.

[0040] Direct spinning is a method of feeding a liquid carbon source and a catalyst together with a carrier gas into an inlet of a high-temperature heating furnace to synthesize carbon nanotubes, and winding up carbon nanotube aggregates discharged from an outlet of the heating furnace together with the carrier gas inside or outside the heating furnace to obtain fibers.

[0041] The present invention provides a method for manufacturing carbon nanotube fiber that is a continuous aggregate of carbon nanotubes by feeding a reaction gas containing a carbon source into a reactor tube together with a catalyst or a catalyst precursor and a transfer gas,

[0042] wherein a Gr/Re.sup.2 value calculated from the Grasshopper number Gr and the Reynolds number Re in the reactor tube is 0.12 or less, or satisfies 0.007≤Gr/Re.sup.2≤0.12, thereby suppressing a rotational flow.

[0043] The rotational flow refers to a vortex flow generated by a gas flowing in the direction opposite to the flow of a reaction gas containing a carbon source. As shown in FIG. 2, tensile strength of the resultant carbon nanotube fibers can be improved by suppressing a rotational flow.

[0044] Grasshopper number Gr and Reynolds number Re are as follows:

[0045] Reynolds number: Re=wd/ν

[0046] Grasshopper number: Gr=(d.sup.3gβΔθ)/(ν.sup.2)

[0047] wherein, w is the flow rate of the reaction gas containing the carbon source, ν is the kinetic viscosity of the reaction gas containing the carbon source, d is the inner diameter of the reactor tube, g is the gravitational acceleration, β is the thermal expansion coefficient of the reaction gas containing the carbon source, Δθ is the average temperature difference between the temperature of the reactor wall and the gas temperature inside the reactor.

[0048] According to the research by the present inventors, it was found that the rotational flow in the reactor tube was suppressed and tensile strength of the resultant CNT fiber was improved by 2 to 3 times, when the Grasshopper number Gr and the Reynolds number Re were controlled to 0.007≤Gr/Re.sup.2≤0.12 in the area of the reactor tube inlet, for example, in the area between the top of the reactor tube and the inlet of the furnace of the structure in which the furnace surrounds the reactor tube. According to one embodiment, Gr/Re.sup.2 may be 0.01 or more, or 0.02 or more, or 0.05 or more.

[0049] In order to ensure that the Grasshopper number Gr and the Reynolds number Re satisfy the above relationship, the temperature gradient inside the reactor tube, the gas flow rate, and the inside diameter of the reactor tube may be adjusted.

[0050] According to one embodiment, the catalyst or the catalyst precursor may be fed at 0.5 to 10 wt %, or 1 to 5 wt %, or 1.5 to 4 wt %, based on the carbon source. When the catalyst or the catalyst precursor is excessively used in comparison with the carbon source, the catalyst acts as an impurity, which makes it difficult to obtain high-purity carbon nanotube fibers. Rather, it may impair thermal, electrical, and physical properties of the carbon nanotube fibers.

[0051] The catalyst precursor is a substance that is not itself included in the catalytic cycle but changes to an active catalyst or produces an active catalyst in the system of the catalytic reaction. After the catalyst precursor forms a catalyst, CNT is synthesized.

[0052] The catalyst or the catalyst precursor may comprise at least one selected from the group consisting of iron, nickel, cobalt, platinum, ruthenium, molybdenum, vanadium and oxides thereof, but is not limited thereto. The catalyst may be in the form of nanoparticle. Preferably, it may be in a metallocene form such as ferrocene, which is a compound containing iron, nickel, cobalt, etc. According to a preferred embodiment, the ferrocene catalyst precursor can be fed at a rate of 0.05 to 0.2 g/hr or 0.05 to 0.1 g/hr.

[0053] In the present invention, the catalytic activator may be fed together with the catalyst or the catalyst precursor. In general, carbon nanotubes are synthesized by diffusion of carbons to the catalyst in a molten state, followed by precipitation of the carbon nanotubes. The catalytic activator increases a diffusion rate of carbon in the synthesis of carbon nanotubes, thereby allowing carbon nanotubes to be synthesized in a short time. In addition, the catalytic activator reduces a melting point of the catalyst and removes amorphous carbons to allow high purity carbon nanotubes to be synthesized at low temperature.

[0054] As the catalytic activator, for example, elemental sulfur, a sulfur-containing compound and a combination thereof can be used. Specific examples thereof include sulfur-containing aliphatic compounds such as methylthiol, methylethylsulfide, dimethylthioketone and the like; sulfur-containing aromatic compounds such as phenylthiol, diphenylsulfide and the like; sulfur-containing heterocyclic compounds such as pyridine, quinoline, benzothiophene, thiophene and the like; elemental sulfur, preferably sulfur or thiophene, and more preferably sulfur. According to a preferred embodiment, the catalytic activator may be fed at a rate of 0.01 to 0.3 g/hr, or 0.01 to 0.2 g/hr or 0.01 to 0.1 g/hr.

[0055] According to a preferred embodiment of the present invention, the catalyst precursor and the catalytic activator may be in a liquid phase for the liquid carbon compound, and may be in a gas phase for the gaseous carbon compound. Therefore, the catalyst precursor or the catalytic activator can be melted and then fed into the liquid carbon compound, or it can be vaporized and then fed in a gaseous state into the gaseous carbon compound.

[0056] In the present invention, the carbon source may be in a liquid or gas phase. The carbon source is diffused to a catalyst and thus synthesized into carbon nanotubes. It is used in consideration of molecular weight distribution, concentration, viscosity, surface tension, dielectric constant and properties of the solvent to be used.

[0057] The liquid or gaseous carbon source may comprise at least one selected from the group consisting of methane, ethylene, acetylene, methyl acetylene, vinyl acetylene, ethanol, methanol, propanol, acetone, xylene, chloroform, ethyl acetate, diethyl ether, polyethylene glycol, ethyl formate, mesitylene, tetrahydrofuran (THF), dimethylformamide (DMF), dichloromethane, hexane, benzene, carbon tetrachloride and pentane.

[0058] Specifically, the liquid carbon source may comprise 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 (THF) dimethylformamide (DMF), dichloromethane, hexane, benzene, carbon tetrachloride, and pentane. Preferably, it may comprise at least one selected from the group consisting of ethanol (C.sub.2H.sub.5OH), xylene (C.sub.8H.sub.10), diethyl ether [(C.sub.2H.sub.5).sub.2O], polyethylene glycol [—(CH.sub.2OH.sub.2O).sub.9], 1-propanol (CH.sub.3CH.sub.2CH.sub.2OH), acetone (CH.sub.3OCH.sub.3), ethyl formate (CH.sub.3CH.sub.2COOH), benzene (C.sub.6H.sub.6), hexane (C.sub.6H.sub.14), and mesitylene [C.sub.6H.sub.3(CH.sub.3).sub.3].

[0059] The gaseous carbon source may comprise at least one selected from the group consisting of methane, ethylene, acetylene, methyl acetylene, and vinyl acetylene.

[0060] In the present invention, the GHSV of the reaction gas to be supplied into the reaction zone may be 0.12 to 6.0 hr.sup.−1, preferably 0.6 to 3.6 hr.sup.−1, more preferably 0.84 to 2 hr.sup.−1, or 1 to 2 hr.sup.−1.

[0061] In addition, the GHSV of the transfer gas to be fed into the reaction zone, for example in the case of hydrogen gas, can be appropriately selected in the range of 1.2 to 60 hr.sup.−1, or 6 to 30 hr.sup.−1, or 12 to 30 hr.sup.−1.

[0062] According to another embodiment, the transfer gas may be fed 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 linear velocity of the transfer gas may vary depending on the kind of the transfer gas, the size of the reactor, the type of the catalyst, and the like.

[0063] According to one embodiment, the transfer gas (carrier gas) may comprise an inert gas, a reducing gas, or a combination thereof, preferably a reducing gas containing hydrogen atom. As the reducing gas, a gas containing hydrogen, ammonia, or a combination thereof may be used.

[0064] The inert gas may comprise a gas containing nitrogen, helium, neon, argon, krypton, xenon, radon or a mixture thereof. The inert gas is chemically very stable and has a nature of not exchanging or sharing electrons, and therefore it can serve to flow and migrate carbon nanotubes due to the gas inflow without reacting with carbon nanotube (CNT).

[0065] According to a preferred embodiment, the carbon nanotube fiber aggregate can be prepared by direct spinning, in which carbon nanotube fibers are directly spun by chemical vapor deposition. Direct spinning is a method of feeding a liquid carbon source and a catalyst together with a carrier gas into an inlet of a high-temperature heating furnace to synthesize carbon nanotubes, and winding up carbon nanotube aggregates discharged from an outlet of the heating furnace together with the carrier gas inside or outside the heating furnace to obtain fibers.

[0066] The temperature of the reaction zone may be 1,000 to 3,000° C. Preferably the temperature may be 1,000 to 2,000° C., or 1,000 to 1,500° C., or 1,000 to 1,300° C., and more preferably 1,150 to 1,300° C. If the temperature is less than 1,000° C., there may be a problem that carbon nanotube fibers are not formed. If the temperature exceeds 3,000° C., there may be a problem that carbon nanotubes are vaporized. Therefore, the above range is preferable.

[0067] The resulting carbon nanotube fibers may be collected by winding. The winding speed influences that the carbon nanotubes in the fiber are oriented in the fiber axis direction and determines the thermal, electrical and physical properties of the carbon nanotube fibers. Preferably it may be wound at a speed of 1 to 100 m/min

[0068] Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

EXAMPLES

Example 1: Synthesis of Carbon Nanotube Fiber

[0069] Ferrocene catalyst precursor and sulfur catalytic activator were vaporized and fed into a top of a vertical cylindrical reactor at a temperature of 1,170 to 1,250° C. at a rate of 0.06 to 0.08 g/hr and at a rate of 0.01 to 0.03 g/hr, respectively. And methane as a carbon compound and a transfer gas (hydrogen) were inflowed to the top of the reactor at a GHSV of 1 to 2 hr.sup.−1 and at a GHSV of 25 to 30 hr.sup.−1, respectively. The reaction was carried out by controlling the temperature gradient in the reactor such that 0.007≤Gr/Re.sup.2≤0.12 in the area between the inlet of the reactor tube and the inlet of the heating furnace. At this time, Gr=0.2 to 2.1 and Re=4.3 to 5.4, and the temperature gradient inside the reactor was adjusted so that the inlet temperature of the reactor tube was 250° C. and the temperature of the inlet of the heating furnace was 816° C. The carbon nanotube fibers discharged from the outlet at the bottom of the reactor were wound by a winding means comprising a bobbin.

Comparative Example 1: Synthesis of Carbon Nanotube Fiber

[0070] Carbon nanotube fibers were synthesized by direct spinning in the same manner as in Example 1, except that the temperature gradient at the upper portion of the reactor is adjusted to 250° C. at the inlet of the reactor tube and to 756° C. at the inlet of the heating furnace so that 0.12<Gr/Re.sup.2 in the area of the heating furnace inlet.

[0071] Specifically, the Reynolds number Re was calculated as follows.

Reynolds number: Re=W d/ν

[0072] W (flow rate of a reaction gas containing a carbon source): The gas flow rate is calculated considering the expansion of the gas according to the temperature. The gas flow rate is shown in Table 1 below.

[0073] ν (kinetic viscosity of a reaction gas containing a carbon source): The viscosity and the density according to the temperature are determined, and the viscosity is divided by the density to obtain a kinetic viscosity. The kinetic viscosity is shown in Table 1 below.

[0074] d (inner diameter of reactor tube)=0.065 m

TABLE-US-00001 TABLE 1 Location divided a distance Kinetic between reactor tube inlet and Viscosity Density Viscosity Gas Flow Rate heating furnace inlet by 10 (kg/m .Math. s) (kg/m3) (V) (W, m/s) Exam. 1 (Reactor tube inlet) 1 1.25.E−05 0.048 2.59.E−04 0.021 2 1.25.E−05 0.048 2.59.E−04 0.022 3 1.30.E−05 0.045 2.87.E−04 0.022 4 1.35.E−05 0.043 3.16.E−04 0.023 5 1.39.E−05 0.040 3.44.E−04 0.026 6 1.44.E−05 0.038 3.74.E−04 0.028 7 1.51.E−05 0.035 4.28.E−04 0.031 8 1.58.E−05 0.033 4.85.E−04 0.034 9 1.71.E−05 0.029 5.93.E−04 0.039 (Heating Furnace inlet) 10 1.82.E−05 0.026 7.07.E−04 0.044 Comp. (Reactor tube inlet) 1 1.25.E−05 0.048 2.59.E−04 0.021 Exam. 1 2  1.30E−05 0.045 2.87.E−04 0.022 3  1.33E−05 0.043 3.07.E−04 0.023 4  1.37E−05 0.042 3.28.E−04 0.024 5  1.41E−05 0.040 3.52.E−04 0.025 6  1.44E−05 0.038 3.77.E−04 0.026 7  1.51E−05 0.035 4.28.E−04 0.028 8  1.58E−05 0.033 4.81.E−04 0.030 9  1.75E−05 0.028 6.37.E−04 0.036 (Heating Furnace inlet) 10  1.91E−05 0.024 8.06.E−04 0.042

[0075] In addition, the Grasshopper number Gr was calculated as follows:

Grasshopper number: Gr=(d.sup.3gβΔθ)/(ν.sup.2)

[0076] wherein, g is the gravitational acceleration,

[0077] β is the thermal expansion coefficient of the reaction gas containing the carbon source,

[0078] d is the inner diameter of the reactor tube (0.065 m),

[0079] ν is the kinetic viscosity (see, Table 1),

[0080] Δθ=(the surface temperature of the reactor tube)−(the gas temperature inside the reactor).

[0081] Fluent CFD software (ver. 16, Ansys) was used to calculate the surface temperature of the reactor tube. The gas temperature inside the reactor was measured by placing a thermometer inside the reactor.

[0082] Table 2 shows the temperature and Gr/Re.sup.2 according to the distance from the inlet of the reactor tube to the inlet of the heating furnace for Example 1 and Comparative Example 1.

TABLE-US-00002 TABLE 2 Distance from the inlet of the reactor Temperature tube (m) (° C.) Gr Re Gr/Re.sup.2 Example 1 0.0 250 0.2 5.34 0.007 (reactor tube inlet) 0.2 816 1.97 4.05 0.12 (heating furnace inlet) Comparative 0.0 250 0.2 5.34 0.007 Example 1 (reactor tube inlet) 0.2 756 5.90 3.36 0.52 (heating furnace inlet)

[0083] It was found that in Comparative Example 1, since the temperature of the inlet of the heating furnace was low and a sudden change in temperature occurred, Gr/Re.sup.2 was increased, whereas in Example 1, since a relatively slow temperature change occurred around the inlet of the heating furnace, Gr/Re.sup.2 was decreased.

[0084] FIG. 2 shows CFD simulations about whether a rotational flow is formed or not, for Example 1 and Comparative Example 1. It is found that in the Comparative Example 1, the rotational flow was formed inside the reactor tube, whereas in the Example 1, the rotational flow was not formed and the airflow was stable.

[0085] The tensile strength of the carbon nanotube fibers of Example 1 and Comparative Example 1 was measured and the results are shown in Table 3. The tensile strength was measured at a speed of 2 mm/min using FAVIMAT+ instrument of Textechno (load cell range: 210 cN, gauge length: 2.0 cm).

TABLE-US-00003 TABLE 3 Formation of Relative tensile Gr/Re.sup.2 rotational flow strength Example 1 0.007 to 0.12 X 346.1 Comparative 0.12 or more to ◯ 100 (reference) Example 1 0.52

[0086] From the above results, it can be seen that the tensile strength is significantly improved by 3 times or more, when the Grasshopper number Gr and the Reynolds number Re satisfies 0.007≤Gr/Re.sup.2≤0.12 in the area between the inlet of the reactor tube and the inlet of the heating furnace. This is because the rotational flow in the reactor tube is minimized and the airflow is stabilized within the above range.

[0087] While the present invention has been particularly shown and described with reference to specific embodiments thereof, it will be apparent to those skilled in the art that this specific description is merely a preferred embodiment and that the scope of the invention is not limited thereby. It is therefore intended that the scope of the invention be defined by the claims appended hereto and their equivalents.