KR101773653B1 - Fluidized bed reactor and process for preparing carbon nanostructures using same - Google Patents

Abstract

A fluidized bed reactor and a method for producing a carbon nanostructure using the same are provided.
The fluidized bed reactor comprises a reactor body; A dispersion plate disposed inside the reactor body; A gas supply pipe for supplying the reaction gas in an upward flow manner from the lower part of the dispersion plate to the upper part; A first catalyst supply pipe disposed at a lower portion of the reactor body to supply a first catalyst; And an unreacted carbon source removing unit installed in the reactor body to remove unreacted carbon source, wherein the unreacted carbon source removing unit includes a catalyst housing accommodating a second catalyst, A second catalyst supply pipe for supplying a second catalyst from the outside of the reactor to the catalyst housing; And a second catalyst exhaust pipe for exhausting the second catalyst of the housing to the outside of the reactor.
The fluidized bed reactor according to the present invention can reduce the formation of carbon structures on the inner wall of the reactor by removing the unreacted carbon source, thereby enabling a continuous reaction for a long time in the fluidized bed reactor.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fluidized bed reactor, and more particularly, to a fluidized bed reactor and a carbon nanostructure using the same.

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fluidized bed reactor, and more particularly, to a fluidized bed reactor that can be used for producing carbon nanostructures such as carbon nanotubes and a method for producing carbon nanostructure using the same.

Fluidized bed reactors are reactor devices that can be used to perform a variety of multiphase chemical reactions. In a fluidized bed reactor, a fluid (gas or liquid) reacts with a solid material in a particulate state, typically the solid material is a catalyst having the shape of a small sphere and the fluid is flowed at a rate sufficient to float the solid material So that the solid material behaves like a fluid.

On the other hand, carbon nanostructures (CNS) refer to nano-sized carbon structures having various shapes such as nanotubes, nanofibers, fullerenes, nanocons, nanohorns, and nano-rods and have various excellent properties It is highly utilized in various technical fields. Carbon nanotubes (CNTs), which are typical carbon nanostructures, are formed by bonding three neighboring carbon atoms to each other in a hexagonal honeycomb structure to form a carbon plane, and the carbon plane is cylindrically shaped to have a tube shape. Carbon nanotubes have a characteristic of being a conductor or a semiconductor depending on the structure, that is, the diameter of the tube, and can be widely applied in various technical fields, and thus, they are popular as new materials. For example, the carbon nanotubes can be applied to an electrode of an electrochemical storage device such as a secondary cell, a fuel cell, or a super capacity, an electromagnetic wave shielding, a field emission display, or a gas sensor.

The carbon nanostructure can be produced, for example, by an arc discharge method, a laser evaporation method, or a chemical vapor deposition method. In the chemical vapor deposition method among the above-mentioned manufacturing methods, carbon nanostructures are produced by dispersing and reacting metal catalyst particles and hydrocarbon-based raw material gases in a fluidized bed reactor at a high temperature. That is, the metal catalyst reacts with the raw material gas while floating in the fluidized bed reactor by the raw material gas to grow the carbon nanostructure.

A method for manufacturing a carbon nanostructure using a fluidized bed reactor is disclosed in Patent Application Publication No. 10-2009-0073346, No. 10-2009-0013503, and the like. In the case of using a fluidized bed reactor, a dispersion plate is used so that the gas is uniformly distributed in the reactor and the powder such as catalyst existing on the dispersion plate can not pass downward.

When the activity of the catalyst is low or the residence time of the reaction gas is short in the reactor, unreacted carbon source gas remains in the reactor. Such an unreacted carbon source gas reacts with a metal such as iron or nickel constituting the reactor main body Thereby forming a carbon structure on the inner wall. Such a carbon structure inhibits the reaction of the fluidized bed reactor and may cause a continuous reaction over a long period of time.

A problem to be solved by the present invention is to provide a fluidized bed reactor having unreacted carbon source removing means for removing an unreacted carbon source.

Another object of the present invention is to provide a method for producing carbon nanostructure using the fluidized bed reactor.

According to an aspect of the present invention,

A reactor body;

A dispersion plate disposed inside the reactor body;

A gas supply pipe for supplying the reaction gas in an upward flow manner from the lower part of the dispersion plate to the upper part;

A first catalyst supply pipe disposed at a lower portion of the reactor body to supply a first catalyst; And

And an unreacted carbon source removing means installed in the reactor body for removing unreacted carbon source,

The unreacted carbon source removing means may comprise:

A catalyst housing capable of gas entry and exit and containing a second catalyst;

A second catalyst supply pipe for supplying a second catalyst from the outside of the reactor to the catalyst housing; And

And a second catalyst outlet pipe for discharging the second catalyst of the catalyst housing to the outside of the reactor.

According to another aspect of the present invention,

Supplying a first catalyst to the fluidized bed reactor;

Supplying a reactant gas containing a carbon source into the reactor;

Contacting the first catalyst with a reactive gas to produce a carbon nanostructure; And

In the unreacted carbon source removing means, a gas containing an unreacted carbon source is contacted with a second catalyst contained in the catalyst housing to remove unreacted carbon sources.

The fluidized bed reactor according to the present invention can provide an unreacted carbon source removing means inside the reactor to remove unreacted carbon sources in the reactor to reduce their approach to the reactor inner wall. As a result, the formation of the carbon structure at the inner wall of the reactor is reduced, so that a long-term continuous reaction can be performed in the fluidized bed reactor.

FIG. 1 is a schematic view of an unreacted carbon source removing means and a fluidized bed reactor body having the unreacted carbon source removing means according to one embodiment.
FIG. 2 is a schematic view of a non-reacted carbon source removing means and a fluidized bed reactor main body having the unreacted carbon source removing means according to another embodiment.
Figure 3 shows a schematic block diagram of a fluidized bed reactor with unreacted hydrocarbon removal means according to one embodiment.

BRIEF DESCRIPTION OF THE DRAWINGS The invention will be described in more detail with reference to the embodiments of the invention shown in the accompanying drawings. It is to be understood, however, that the invention is not to be limited to the specific embodiments, but includes all modifications, equivalents, or alternatives falling within the spirit and scope of the present invention.

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

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.

It is to be understood that the terms "comprises", "includes", or "having", etc., as used herein are intended to mean that a feature, a numerical value, a step, an operation, an element, a component, Does not exclude the possibility that other features, numbers, steps, operations, components, parts, or combinations thereof may be present or added.

It is to be understood that the terms "comprises", "includes", or "having", etc., as used herein are intended to mean that a feature, a numerical value, a step, an operation, an element, a component, Does not exclude the possibility that other features, numbers, steps, operations, components, parts, or combinations thereof may be present or added.

FIGS. 1 and 2 are schematic views illustrating a means for removing unreacted carbon sources and a fluidized bed reactor body having the same according to an embodiment of the present invention.

1, the fluidized bed reactor comprises a reactor body 10; A dispersion plate disposed inside the reactor body; A gas supply pipe (not shown) for supplying the reaction gas in an upward flow manner from the lower part of the dispersion plate to the upper part; A first catalyst supply pipe 25 disposed at a lower portion of the reactor body to supply a first catalyst; And an unreacted carbon source removing unit installed in the reactor body to remove unreacted carbon source, wherein the unreacted carbon source removing unit includes a catalyst housing 2 in which a gas can be taken in and out and a second catalyst is accommodated; A second catalyst supply pipe (5) for supplying a second catalyst from the outside of the reactor to the catalyst housing; And a second catalyst exhaust pipe (6) for exhausting the second catalyst of the housing to the outside of the reactor.

In the fluidized bed reactor, the unreacted carbon source removing means may be installed in the reactor to remove unreacted carbon sources remaining in the reactor. Whereby the unreacted carbon source reacts with the inner wall to fundamentally suppress the formation of the carbon structure.

The second catalyst accommodated in the catalyst housing 2 may be contacted with a gas containing an unreacted carbon source to remove the carbon source to remove the unreacted carbon source in the reactor.

The catalyst housing 2 has an internal space for accommodating the catalyst, and the shape of the catalyst housing 2 is not limited. For example, it may be a cylindrical shape vertically installed in the reactor body or a disk shaped in a direction parallel to the reactor body, but is not limited thereto. One embodiment according to the form of the catalyst housing 2 is shown in Figs. 1 and 2. Fig.

The catalyst housing 2 accommodates the second catalyst and can be used without limitation as long as it has a structure capable of allowing gas to flow in and out of the second catalyst. For example, metal foams, perforated plates, nozzles, sieves and bubble caps, but are not limited thereto. The perforated plate may have a plurality of vent holes, and the diameter of the vent holes formed in the perforated plate may be smaller than the diameter of the second catalyst particles.

The catalytic metal of the second catalyst 4 is not particularly limited as long as it is a substance promoting the growth of the carbon structure. Examples of the catalyst metal include at least one kind of metal selected from the group consisting of Groups 3 to 12 of the 18-element type element periodic table recommended by IUPAC in 1990. Among them, at least one kind of metal selected from the group consisting of 3, 5, 6, 8, 9 and 10 is preferable and iron (Fe), nickel (Ni), cobalt (Co), chromium (Cr) At least one metal selected from the group consisting of Mo, W, V, Ti, Ru, Rh, Pd, Pt and rare- Particularly preferred. Preferred examples of the catalyst include an element selected from iron (Fe), cobalt (Co), and nickel (Ni), an element selected from titanium (Ti), vanadium (V), and chromium (Cr), molybdenum (Mo), and tungsten ), Or a combination thereof.

The second catalyst 4 may take the form of powders, pellets, granules, beads, extrudates or secondary particles into which they are bundled, but is not limited thereto.

1 and 2, the second catalyst is supplied to the second catalyst supply pipe 5 connected to the catalyst housing 2 of the unreacted hydrocarbon removing means, and is supplied to the catalyst housing 2 for a predetermined time And is recovered through the second catalyst exhaust pipe 6 after removing the unreacted carbon source. 1 and 2, the second catalyst 4 is supplied with the second catalyst 4a before the reaction into the second catalyst supply line 5, and the supplied second catalyst 4a is supplied with the catalyst The second catalyst 4b is discharged to the second catalyst exhaust pipe 6 after the reaction with the unreacted carbon source by remaining in the housing 2 so that the continuous unreacted carbon source removal process is possible, And the second catalyst 4b can be regenerated through a catalyst regeneration process.

The second catalyst feed pipe 5 and the second catalyst feed pipe 6 are not particularly limited as long as they can be used to supply a catalyst. For example, a hopper, a screw feeder, A rotary air lock valve, and the like, but the present invention is not limited thereto. The supply device may be capable of controlling the supply speed and the supply amount of the catalyst.

The second catalyst recovered into the second catalyst exhaust pipe 6 may contain a carbon component. The discharged second catalyst may be regenerated by a catalyst regeneration means (not shown). For example, the second catalyst discharged to the second catalyst exhaust pipe 6 may be a metal carbide, and the recovered second catalyst may be a metal carbide, and the regeneration including oxidation and reduction of the metal carbide It can be reused through the process.

FIG. 3 shows a schematic configuration diagram of an apparatus for manufacturing a carbon nanostructure having unreacted hydrocarbon removing means according to an embodiment.

1, 2 and 3, the fluidized bed reactor is a reactor 1 in which a carbon nanostructure is synthesized. The reactor 1 includes a main body 10 having an inner space, And unreacted hydrocarbon removing means (not shown) disposed in the reactor.

The lower portion of the reactor body 10 may be formed as a tapered region 10a. A heater 19 may be provided outside the reactor body 10. A raw material gas supply unit 12 is provided at the bottom of the reactor 1. The raw material gas is supplied to the reactor main body 10 through the raw gas supply pipe 21 and can be preheated in the preheater 17 before being supplied to the reactor main body 10.

According to one embodiment, the fluidized bed reactor comprises: i) an expansion unit 11 connected to the top of the reactor 1; ii) a separator (14) attached to the side surface of the reactor body (10) to separate the mixed gas from the carbon nanostructure discharged from the reactor body; iii) a filter (18) which partially or wholly removes one or more component gases from the mixed gas discharged from the extender (11); And iv) a conveyance pipe 23 for discharging the mixed gas filtered by the filter 18 to the outside.

According to one embodiment, the manufacturing apparatus may further comprise a recycle line (22, 26) for recirculating a portion of the mixed gas to the reactor.

A discharge tube 24 is disposed on the side surface of the reactor body 10 to transfer the generated carbon nanostructure. The discharge tube 24 is mixed with a carbon nanostructure formed in an outer region of the inner column 2, And may be installed at the lower end of the side of the reactor to transfer the gas to the collector 15.

The carbon nanostructure and the mixed gas are transferred to the separator 14 through the discharge pipe 24, and the carbon nanostructure and the mixed gas are separated. The separated carbon nanostructure is transferred to the recoverer 15 and recovered.

The reactor (1) used in the present invention is a chemical vapor deposition reactor, for example, a fluidized bed reactor.

In order to synthesize carbon nanostructures by chemical vapor deposition (CVD), the reaction time of the reaction gas and the catalyst is required to be at least 10 minutes, and the residence time of the carbon nanostructure and catalyst to be produced in the reactor is determined by the purity And yield.

In the fluidized bed reactor, the catalyst is distributed evenly inside the catalyst and the contact between the catalyst and the reaction gas is excellent, the heat is easily diffused during the exothermic reaction and the retention time of the catalyst and the target product carbon nanostructure can be secured in the reactor, The production rate of the carbon nanostructure can be made).

The reactor is supplied with a carbon source, a reducing gas, an inert gas and the like through the reaction gas supply pipe 21 from the lower part of the reactor to the upper part of the reactor, Thereby separating the nanostructures.

The reaction gas supply pipe 21 is not particularly limited as long as it can be used in a manufacturing apparatus of a fluidized bed reactor. Specifically, it may be a gas distributor or the like.

Between the reactor and the separator may include the interior of the reactor, and a filter for separating the fine particles may also be disposed in an expander above the fluidized bed reactor.

The catalyst supply pipe 25 is not particularly limited as long as it can be used for the production of carbon nanostructures. Specifically, the catalyst supply pipe 25 may be a hopper, a feeder, a screw feeder, a rotary air lock valve A catalytic feeder composed of a rotary airlock valve, or the like.

The catalyst may be a heterogeneous catalyst composed of a composite structure of an active metal and a support, which may be conventionally used in the production of carbon nanostructure, and more specifically, a supported catalyst, a coprecipitation catalyst, and the like. When the supported catalyst is used as the preferred catalyst, the bulk density of the catalyst itself is higher than that of the coprecipitation catalyst. Unlike the coprecipitation catalyst, unlike the coprecipitation catalyst, fine particles less than 10 microns are less agglomeration And it is possible to reduce the possibility of occurrence of fine particles due to attrition which may occur in the fluidization process, and the mechanical strength of the catalyst itself is also excellent, so that the operation of the reactor can be stabilized.

When a coprecipitation catalyst is used as a preferable catalyst form, there is a merit that the production method of the catalyst is simple, the preferable metal salts are low in the cost of the catalyst raw material, and there is a virtual favorable aspect of the production, and a large specific surface area and high catalytic activity.

The inert gas may be nitrogen (N ₂ ), argon (Ar), or the like.

The operation mode of the fluidized bed reactor forms a fluidized bed in the reactor, and the catalyst reacts with the reaction gas in the fluidized bed. As the reaction proceeds, the carbon nanotube structure grows on the active metal of the catalyst to increase the bulk density (collecting pipe) at the upper side of the reactor when the bulk density is lowered.

The bulk density may be 0.03 to 0.3 g / cm3, preferably 0.05 to 0.2 g / cm3.

The flow rate of the fluidized bed formed in the reactor 10 is preferably 0.03 to 100 cm / s, more preferably 0.1 to 70 cm / s.

The minimum fluidization velocity of the fluidized bed in the reactor 10 is preferably 0.03-15 cm / s, more preferably 0.1-10 cm / s.

The reactor (1) comprises a catalyst supply pipe (25) to which a catalyst is supplied; A reaction gas supply pipe 21 to which a carbon source, a reducing gas and an inert gas are supplied; And a product discharge pipe 24 through which the mixed gas containing the generated carbon nanotubes and the reaction by-product gas is discharged.

Examples of the carbon source include a carbon-containing gas which can be decomposed in a heated state, and specific examples thereof include aliphatic alkanes, aliphatic alkenes, aliphatic alkynes, and aromatic compounds. More specific examples thereof include methane, ethane, ethylene, acetylene, ethanol, , Carbon monoxide, propane, butane, benzene, cyclohexane, propylene, butene, isobutene, toluene, xylene, cumene, ethylbenzene, naphthalene, phenanthrene, anthracene, acetylene, formaldehyde, acetaldehyde, CH _4), ethane (C ₂ H _6), carbon monoxide (CO), acetylene (C ₂ H _2), ethylene (C ₂ H _4), propylene (C ₃ H _6), propane (C ₃ H _8), butane (C ₄ H ₁₀ ) and a mixture of liquefied petroleum gas (LPG).

The separator 14 is not particularly limited as long as it is a means, a device, or a device capable of separating the carbon nanostructure and the mixed gas, but it may be a cyclone.

The filter 18 comprises a material, an apparatus, a machine, a means or an apparatus for selectively separating or removing the mixed gas discharged from the elongating unit.

The filter may be a gas separation unit that separately separates the carbon source, the reducing gas, and the inert gas from the mixed gas discharged from the separator connected to one or more of the upper portion of the reactor, and selectively transfers the carbon source, the reducing gas and the inert gas to the recycling pipe.

The reducing gas may be hydrogen or ammonia.

The gas separation unit of the metal membrane type is capable of selectively separating hydrogen at a temperature of less than 600 ° C.

The metal membrane may be selected from the group consisting of Pd, Ir, Rh, Pd-Ni alloy, Pd-Ag alloy and Pd-Cu alloy. Among them, Pd and Pd alloy are preferably used. But is not limited thereto.

One or more metal membranes may be used, and a minimum area is required to obtain the separation efficiency of the gas to be separated. If a large-area metal membrane can be produced, a desired flux can be obtained with one membrane. However, since a densified membrane can not be manufactured at a size of 100 mm * 100 mm or more, a membrane having a maximum size can be laminated to secure a surface area It is possible. It is not necessary to laminate a metal membrane when a membrane having a large area can be manufactured. However, there is a limit to the production of a metal membrane of high efficiency exceeding 100 mm * 100 mm with the present technology, Or by connecting them in series. The metal membrane can be used in various shapes such as a rod shape and a sheet shape.

By separating the carbon nanostructure particles and the mixed gas from the carbon nanostructure particles produced in the reactor 10 and the mixed gas using the cyclone, the carbon nanostructure particles are recovered through the discharge pipe 24 disposed on the upper side of the reactor , The mixed gas may pass through the hydrogen separation unit and then recycled, thereby reducing the amount of the raw material input to the production amount of the carbon nanostructure without installing the heat exchanger.

Preferably, the hydrogen separation unit comprises at least one metal membrane, more preferably a metal membrane of a maximum size that can be manufactured is stacked, or connected in parallel or in series to secure a desired hydrogen permeation flux. In this case, it is possible to remove only the hydrogen gas produced in the reaction by changing the membrane injection pressure, which is advantageous in controlling the composition of the recycle feed. However, if the separation efficiency is high, it is possible to separate even one membrane, and separation is achieved by controlling the pressure and feed amount in the separation unit.

The specific gas may be fed to the recycle line as needed, particularly if some of the gas (eg, some H ₂ ) is lacking in the gas mixture that is filtered.

The unreacted carbon source included in the mixed gas is preferably controlled to 2 to 30%, more preferably 5 to 25%, of the carbon source supplied to the reactor.

The fluidized bed reactor is charged with only the carbon source consumed in the reactor and the catalyst, so that it is possible to perform an ideal process operation having substantially the same reactant composition ratio and amount.

The fluidized bed reactor may be a mixed gas containing an unreacted carbon source, an inert gas, and a by-product gas, which has been incinerated or discharged using a conventional flare stack or an incinerator, with a reducing gas (hydrogen H ₂ ) can be selectively removed and recycled to obtain a carbon source conversion rate of 98% or more without further injection of an inert gas. Thus, production cost of carbon nanostructure can be drastically reduced, incineration treatment is not necessary, It is an eco-friendly process.

In addition, the fluidized bed reactor can reduce the size of the reactor with respect to the capacity with a low energy consumption apparatus, and can greatly reduce the energy cost of the fluidized bed reactor operating at 600 to 1000 ° C.

Since the fluidized bed reactor does not require a heat exchanger, which is essentially required for cooling the reaction gas when separating the mixed gas using pressure swing adsorption (PSA) or polymer separator, it is possible to reduce the capital investment cost and the size of the reaction system Compact, fluidized bed reactor. In addition, it is possible to reduce the required calorific value and size of the preheater by recirculating the high-temperature reaction gas through the recirculation pipe without cooling.

Between the reactor and the separator may include the interior of the reactor, and a filter for separating the fine particles may also be disposed in an expander above the fluidized bed reactor.

When the carbon nanostructure synthesized in the reactor is designed to be recovered to the lower part of the reactor, the filter may be installed in the reactor for removal of fine particles contained in the mixed gas discharged to the upper part, and the catalyst, carbon nanostructure, A separator such as a cyclone separating the gaseous mixture may also be disposed within the reactor.

The component gas may be a byproduct gas generated in the reactor.

Preferably, the fluidized bed reactor further comprises control means for controlling the amount of reactive gas supplied to the reactor and the amount of the component gas removed from the filter.

The control means may be a control means for controlling the amount of the reducing gas supplied to the reactor and the amount of the reducing gas passing through the filter.

The fluidized bed reactor preferably further comprises a filter, a scrubber or both, between the separator and the filter.

The filter recovers the carbon nanostructure particles remaining in the mixed gas separated by the separator, and the scrubber can remove harmful substances such as halides present in the mixed gas separated by the separator.

Preferably, the fluidized bed reactor further comprises a preheater for preheating the reactant gas prior to introduction into the reactor.

In the fluidized bed reactor, as the reactor size increases, a large amount of inert gas is required, and a reducing gas is injected in an amount equal to or greater than that of the carbon source, so that the effect of reducing the production cost remarkably increases.

The fluidized bed reactor may not include a waste incinerator such as a flare stack or an incinerator.

The molar ratio of the carbon source to the reducing gas is preferably 1: 0.5 to 1:10, more preferably 1: 0.9 to 1: 6, most preferably 1: 1 to 1: 5, The sintering of the catalyst is suppressed by controlling the rate of formation of the carbon nanostructure within the range, the amorphous carbon formation is suppressed, and the graphitic carbon generation is increased.

In the step of producing the carbon nanostructure, at least one selected from the group consisting of water, ammonia, NO, NO _2, etc. may be further added.

The catalyst used in the step of producing the carbon nanostructure may be selected from the group consisting of Co (NO ₃ ) ₂ -6H ₂ O, (NH ₄ ) ₆ Mo ₇ O ₂₄ -4H ₂ O, Fe (NO ₃ ) ₂ 6H ₂ O or (Ni (NO ₃ ) ₂ -6H ₂ O) dissolved in distilled water and then wet impregnated with a carrier such as Al ₂ O ₃ , SiO ₂ or MgO have.

The catalyst may be a catalyst prepared by treating a catalytically active metal precursor with a support such as Al (OH) ₃ , Mg (NO ₃ ) ₂ or colloidal silica together with ultrasonic waves.

The catalyst may be prepared by a sol-gel method using a chelating agent such as citric acid or tartaric acid so that the catalytically active metal precursor can be dissolved in water, Or by co-precipitation of the active metal precursor.

The filtration can be carried out using a separation method, a separation means or a separation apparatus capable of selectively separating the mixed gas.

The metal membrane type gas separation unit may selectively remove hydrogen at a temperature of less than 600 ° C, and the metal membrane may include Pd, Ir, Rh, a Pd-Ni alloy, a Pd-Ag alloy, and a Pd- , But is not limited thereto.

The carbon nanostructure described in this specification can be interpreted as referring to a nano-sized carbon structure having various shapes such as carbon nanotubes, carbon nanofibers, fullerenes, carbon nanocones, carbon nanohorns, and carbon nanorods.

The fluidized bed reactor according to the present invention can be used to produce carbon nanostructures. For example, a method for preparing a carbon nanostructure according to the present invention includes: supplying a fluidized bed reactor first catalyst as described above; Supplying a reactant gas containing a carbon source into the reactor; Reacting the first catalyst with a reactive gas to produce a carbon nanostructure; In the unreacted carbon source removing means installed in the reactor, a gas containing an unreacted carbon source is contacted with a second catalyst contained in the catalyst housing to remove unreacted carbon source.

The unreacted carbon source is removed through the unreacted carbon source removing means to inhibit the unreacted carbon source from reacting with the inner wall of the reactor body to form a carbon structure.

The reducing gas and the inert gas contained in the mixed gas discharged to the outside through the gas discharge pipe of the reactor main body can be supplied to the reactor through the recycle pipe and reused for manufacturing the carbon nanostructure.

1, 2, and 3 depict only the apparatus necessary to illustrate the present invention and illustrate other self-evident devices required to carry out the method, such as pumps, additional valves, piping, Boosting equipment, etc. are omitted from the drawings.

1. Fluidized bed reactor 2. Catalyst housing 4. Second catalyst
4a. Second catalyst before reaction 4b. After the reaction,
5. Second catalyst feed pipe 6. Second catalyst feed pipe 10. Reactor body
13. Dispersion plate

Claims (18)

A reactor body;
A dispersion plate disposed inside the reactor body;
A gas supply pipe for supplying the reaction gas in an upward flow manner from the lower part of the dispersion plate to the upper part;
A first catalyst supply pipe disposed at a lower portion of the reactor body to supply a first catalyst; And
And an unreacted carbon source removing means installed in the reactor body for removing unreacted carbon source,
The unreacted carbon source removing means may comprise:
A catalyst housing capable of gas entry and exit and containing a second catalyst;
A second catalyst supply pipe for supplying a second catalyst from the outside of the reactor to the catalyst housing; And
And a second catalyst exhaust pipe for exhausting the second catalyst of the housing to the outside of the reactor,
The second catalyst of the unreacted carbon source removing means is contacted with the gas containing the unreacted carbon source through the unreacted carbon source removing means to remove the unreacted carbon source so that the unreacted carbon source contacts the inner wall of the reactor body to form a carbon structure Lt; / RTI &
Wherein the second catalyst of the unreacted carbon source removing means is selected from the group consisting of Fe, Ni, Co, Cr, Mo, W, V, Ti, , At least one metal selected from ruthenium (Ru), rhodium (Rh), palladium (Pd), platinum (Pt) and rare earth elements. The method according to claim 1,
Wherein the unreacted carbon source removing device is installed in an upper part of the reactor main body. The method according to claim 1,
Wherein the catalyst housing of the unreacted carbon source removing apparatus has a plurality of vent holes and the diameter of the vent holes is smaller than the diameter of the second catalyst. The method according to claim 1,
i) an extension connected to the top of the reactor;
ii) a separator attached to a side surface of the reactor to separate the carbon nanostructure and the mixed gas discharged from the reactor;
iii) a filter which partially or wholly removes one or more component gases from the mixed gas discharged from the extender; And
and iv) a transfer tube for discharging the mixed gas filtered by the filter to the outside. 5. The method of claim 4,
And iii) the filter is a gas separation unit for separating a certain amount of the reducing gas from the mixed gas discharged from the elongating unit. 5. The method of claim 4,
Further comprising a recycle line for recycling some or all of the components of the mixed gas to the reactor. The method according to claim 1,
Wherein the reactor is a chemical vapor deposition reactor. 5. The method of claim 4,
And ii) the separator comprises a cyclone. 5. The method of claim 4,
And iii) the filter comprises a metal membrane. 10. The method of claim 9,
Wherein the metal membrane selectively separates hydrogen at a temperature less than < RTI ID = 0.0 > 600 C. < / RTI > 10. The method of claim 9,
Wherein the metal membrane comprises at least one selected from the group consisting of Pd, Ir, Rh, a Pd-Ni alloy, a Pd-Ag alloy, and a Pd-Cu alloy. Supplying a first catalyst to the fluidized bed reactor according to claim 1;
Supplying a reactant gas containing a carbon source into the reactor;
Contacting the first catalyst with a reactive gas to produce a carbon nanostructure;
Contacting the gas containing the unreacted carbon source with a second catalyst contained in the catalyst housing to remove unreacted carbon sources in the unreacted carbon source removing means installed in the reactor. 13. The method of claim 12,
Wherein the unreacted carbon source is removed through the unreacted carbon source removing means to prevent the unreacted carbon source from contacting the inner wall of the reactor body to form a carbon structure. 13. The method of claim 12,
Wherein the reducing gas and the inert gas contained in the mixed gas discharged to the outside through the gas discharge pipe of the reactor main body are supplied to the reactor through the recycle pipe and reused for the production of the carbon nanostructure. 15. The method according to any one of claims 12 to 14,
Wherein the carbon nanostructure is a carbon nanotube. delete delete delete

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