KR20100131069A - Filter reaction apparatus for producing carbon nano tube and hydrogen gas and production method for carbon nano tube and hydrogen gas from methane gas using thereof - Google Patents

Abstract

PURPOSE: A filter reaction apparatus, and a production method of the carbon nanotubes and the hydrogen gas from methane using thereof are provided to reduce the heat energy consumption for producing hydrogen. CONSTITUTION: A filter reaction apparatus producing carbon nanotubes and hydrogen gas comprises the following: a hopper unit(21) formed on the lower side of the cylinder type apparatus; a heating unit(22) applying the heat to the inside of the apparatus; a partition wall(23) dividing the internal space; a reaction chamber(20) filtering gas with a filter(24); a storage chamber(30) storing solid particles from inserted from the reaction chamber; the filter supplying methane gas to the reaction chamber; and a catalyst/nano particle generator(50).

Description

Filter Reaction Apparatus for Producing Carbon Nano Tube and Hydrogen Gas and Production Method for Carbon Nano Tube and Hydrogen Gas from Methane Gas using Thereof}

The present invention relates to a filter reaction apparatus for producing carbon nanotubes and hydrogen gas, and a method for producing carbon nanotubes and hydrogen gas from methane using the same, and more specifically, to a reactor by mixing catalyst nanoparticles with methane gas. In the process of separating the carbon and hydrogen by applying heat in the reactor, the separated carbon components are adsorbed and grown on the catalyst to form nanotubes, and the separated hydrogen is collected by passing through a filter to receive hydrogen gas. In addition, carbon nanotubes can be received. In addition, the present invention can reduce the thermal energy required for the production of hydrogen as the metal catalyst to the reaction can lower the thermal decomposition temperature of methane, additionally can receive expensive carbon nanotubes to produce hydrogen gas produced simultaneously The present invention relates to a filter reactor and a method of producing the same, which can secure cost competitiveness by lowering costs and prevent environmental pollution because carbon dioxide is not produced in the production process.

About 90% of natural gas is composed of methane (CH ₄ ) gas, which can directly produce hydrogen and carbon by pyrolysis in a high temperature atmosphere.

As a method of producing hydrogen, there are a method of reforming using water vapor as a catalyst and a method of using plasma. The method of using water vapor as a catalyst is a proven commercialization process that currently occupies 40% of the world's hydrogen production process, but the process is very complicated and the cost of treating carbon dioxide is generated in the reaction process due to the use of water vapor. Since it is required as a hydrogen production cost increases.

Next, the high temperature pyrolysis process using plasma has the advantage that carbon dioxide is not generated during the methane pyrolysis process, but the hydrogen production cost is increased because a large amount of energy must be supplied to the pyrolysis of methane. Of course, the carbon black produced as a by-product during the reaction can reduce the final hydrogen production cost due to economic value.

Therefore, research has been conducted in the direction of reducing hydrogen production costs by receiving additional high value products generated in the reaction as well as pure hydrogen production as in the plasma-based method.

Although some of them produce hydrogen and produce carbon nanotubes at the same time, most processes synthesize carbon nanotubes through catalytic pyrolysis of hydrocarbon gas and stop the operation of the device and capture carbon nanotubes. It has a discontinuous batch method.

Therefore, while receiving carbon nanotubes in the process of producing hydrogen gas from the methane, it is necessary to research and development to maximize the production efficiency by receiving carbon nanotubes while continuously producing hydrogen gas.

Filter reaction apparatus for producing carbon nanotubes and hydrogen gas of the present invention for solving the above problems,

In the filter reaction apparatus for producing carbon nanotubes and hydrogen gas using methane gas, the lower end is a cylindrical body formed with a cone-shaped hopper part of the upper and lower subsoils, and the heating part is installed on the outer surface to heat the inside. A partition wall is installed to partition the inner space up and down, and the partition wall is equipped with a filter on a lower surface of the reaction chamber for filtering the gas in the lower space and supplying it to the upper side; A storage chamber located at a lower portion of the reaction chamber and communicating with the hopper portion, and having a valve installed at a connection portion to open and close the reaction chamber so as to receive and store the remaining solid powder in the reaction chamber; A supply pipe communicating with a side of the reaction chamber and supplying methane gas into the reaction chamber; A catalytic nanoparticle generator for supplying catalytic nanoparticles to the methane gas provided on the flow path of the supply pipe; A hydrogen gas discharge pipe communicating with a partitioned upper space of the reaction chamber to discharge filtered hydrogen gas; And a powder discharge pipe communicating with the storage chamber to discharge the stored solid powder.

In addition, a method of producing carbon nanotubes and hydrogen gas from methane using a filter reactor,

A method of producing carbon nanotubes and hydrogen gas from methane using a reaction apparatus provided with a reaction chamber equipped with a filter and a storage chamber in which valves are opened and closed, the method comprising: mixing catalyst nanoparticles with methane gas; A pyrolysis step of separating carbon and hydrogen by injecting methane gas containing the catalyst nanoparticles into the reaction chamber and applying heat; A hydrogen receiving step of filtering the separated hydrogen gas with a filter installed in the reaction chamber to receive hydrogen from which carbon is removed; A carbon nanotube growth step in which the carbon component separated in the pyrolysis step is adsorbed on the catalyst nanoparticles and attached to the filter surface of the reaction chamber, and the carbon nanotube synthesis and growth are performed using the attached catalytic nanoparticles as the catalytic activity point; And storing the carbon nanotubes stripped from the filter surface and storing them in a lower storage chamber.

As described in detail above, a filter reactor for producing carbon nanotubes and hydrogen gas of the present invention and a method for producing carbon nanotubes and hydrogen gas from methane using the same,

Catalytic nanoparticles are mixed with methane gas and introduced into the reactor, and heat is added to the reactor to separate carbon and hydrogen, and the separated carbon components are adsorbed and grown on the catalyst to form nanotubes, and the separated hydrogen is filtered. In addition, carbon nanotubes can be additionally collected in the process of collecting hydrogen gas by passing through. In addition, the present invention can reduce the thermal energy required for the production of hydrogen as the metal catalyst to the reaction can lower the thermal decomposition temperature of methane, additionally can receive expensive carbon nanotubes to produce hydrogen gas produced simultaneously The cost can be lowered to secure price competitiveness, and carbon dioxide is not produced in the production process, thereby providing a useful device and method for preventing environmental pollution.

Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings.

As shown in FIG. 1, the filter reaction apparatus 10 according to the present invention includes a reaction chamber 20 having a hopper 21 formed at a lower end thereof in a conical shape of a light beam. The reaction chamber is provided with a heating unit 22 on the outer surface to allow thermal energy to be transferred therein to separate carbon and hydrogen atoms constituting the incoming methane gas. The partition 23 is installed inside the reaction chamber 20 to partition the inner space up and down. A filter 24 is further mounted on the lower surface of the installed partition wall to filter the gas separated by the reaction so that only hydrogen gas flows into the upper space. The filter may be formed in various shapes, and in order to increase the contact area with the separation gas, the filter may be formed in a protruding shape such as a cylinder.

The storage chamber 30 is installed in communication with the lower portion of the reaction chamber 20. The storage chamber is in communication with the hopper portion of the reaction chamber, the valve 31 is provided in the connected portion to control the opening and closing of the flow path. Therefore, the carbon nanotubes 80 loaded on the hopper 21 of the reaction chamber 20 are introduced into the storage chamber 30 by opening and closing the valve 31. At this time, the valve 31 is a carbon nanotube (80) collected in the hopper 21 while minimizing the pressure loss of the reaction chamber by the operation of the rotary valve, without stopping the thermal decomposition reaction in the reaction chamber using a rotary valve ) May be supplied to the storage chamber 30.

Next, a filter 24 for supplying methane gas to the inside of the reaction chamber is connected to the side of the reaction chamber 20, and a catalyst nanoparticle generator 50 is provided on the flow path of the supply pipe to the methane gas supplied. The catalyst nanoparticles are mixed and supplied.

Therefore, the methane gas in which the catalyst nanoparticles are mixed is introduced into the reaction chamber 20 having a high temperature atmosphere by the heating unit, and a pyrolysis reaction is performed in which carbon and hydrogen are separated. The pyrolyzed components are filtered by the filter 24 so that the gas components move to the upper space of the partition wall, and the catalyst nanoparticles and carbon components are adsorbed on the filter. At this time, the catalytic nanoparticles are catalytically active and carbon is adsorbed, and the synthesis and growth of the carbon nanotubes 80 is performed.

The hydrogen gas passing through the filter 24 is transferred to an external reservoir or a place of use through the hydrogen gas discharge pipe 60 communicating with the upper space of the partition 23, and includes carbon nanotubes including catalyst nanoparticles adsorbed to the filter ( 80) The powder is collected into the lower hopper 21 of the reaction chamber by exhaustion. The collected carbon nanotubes are introduced into and stored in the storage chamber 30 communicated with the lower portion of the hopper by opening and closing of the valve 31, and the stored carbon nanotubes are discharged into the powder discharge pipe 70 and separately stored or otherwise processed. A process may be performed to make this happen.

In addition, the exhaust is made by the exhaust nozzle 25 installed in the reaction chamber. The exhaust nozzle is installed in the upper space separated by the partition wall of the reaction chamber, and preferably the spraying direction of the exhaust nozzle is directed toward the inside of the filter 24 installed in the partition wall. The dedusting nozzle 25 is supplied with the degassing gas from the degassing gas storage tank so that injection is performed, and an intermittent flow path is used for the degassing valve 27.

In addition, the exhaust valve 27 is driven in conjunction with the differential pressure gauge 26 for measuring the upper and lower spaces respectively partitioned by the partition wall. The differential pressure gauge 26 measures the pressure in the upper and lower spaces of the reaction chamber and stops the supply of methane gas when the load is above a certain level, and removes the carbon nanotubes 80 adsorbed to the filter 24 so as to perform exhaustion. Re-feed methane to allow pyrolysis. As shown in FIG. 1, the exhaust nozzle 25 is provided with a single nozzle to spray the air or the exhaust nozzle is inserted into the filter in the form of a pipe having a plurality of through holes formed on the outer circumferential surface of the exhaust nozzle. The filter may be formed in various forms according to the shape of the filter such that the filter is exhausted.

In another embodiment, the material of the filter is a metal filter using a metal filter to reduce and activate the surface of the metal filter without supplying catalyst nanoparticles, thereby separating carbon and hydrogen to produce hydrogen, and simultaneously from the surface of the catalytically active point. Carbon nanotubes can be synthesized. The filter includes a filter made of stainless steel.

On the other hand, the method for producing carbon nanotubes and hydrogen gas from methane according to the present invention, as shown in FIG. In the method for producing nanotubes and hydrogen gas, a step (S1) of mixing catalyst nanoparticles with methane gas is performed in advance. In this step, the catalyst nanoparticles are mixed in the gas by passing methane gas or natural gas through the catalyst nanoparticle generator.

After the mixing step, a pyrolysis step (S2) is performed. The pyrolysis step is a step in which the pyrolysis reaction is performed by forming the inside of the reaction chamber at a high temperature atmosphere to allow the mixed catalyst methane gas to flow into the methane gas. For example, methane gas mixed with catalyst nanoparticles introduced into the high-temperature reaction chamber absorbs heat and carbon and hydrogen are separated. Wherein the general reaction chamber is to maintain a high temperature atmosphere of 850 ~ 1700 ℃ to perform the pyrolysis reaction, the present invention lowers the heating temperature of the reaction chamber by lowering the reaction temperature to 600 ~ 900 ℃ by catalyst nanoparticles The amount of thermal energy used to produce hydrogen can be reduced.

Next, the hydrogen receiving step (S3) is made. The step is a step of filtering the carbon component with a filter installed in the reaction chamber by the gas separated by the pyrolysis step and receiving only hydrogen gas to be transferred to a separate storage or use.

In addition, the carbon component separated during the pyrolysis reaction is a carbon nanotube growth step (S4) of synthesizing carbon nanotubes using catalytic nanoparticles as an active point. In this step, the carbon component separated in the pyrolysis reaction is synthesized using the catalytic nanoparticles adsorbed on the outer surface of the filter as an active point to generate carbon nanotubes, and the carbon nanotubes are continuously grown as the reaction proceeds.

As shown in FIG. 3, the grown carbon nanotubes are separated from the filter by a dedusting step S6. The dedusting step is a step of separating the carbon nanotubes adsorbed on the filter surface by injecting the dedusting gas in the reverse direction of the suction direction for hydrogen reception. Whether or not to perform the dedusting step is determined by the difference in pressure by installing a differential pressure gauge in each of two spaces separated by a partition in which a filter is installed in the reaction chamber. By blocking the inflow of gas and opening the exhaust nozzle, injection is performed in the reverse direction of hydrogen gas intake.

Next, a storage step (S5) of collecting and storing the carbon nanotubes separated from the filter or excessively grown carbon nanotubes separated from the filter in the dedusting step is performed. In the storing step, the collecting is primarily performed at the lower part of the reaction chamber, and a process of transferring the carbon nanotubes collected to the storage chamber communicating with the lower part of the reaction chamber by the operation of the valve is performed. The carbon nanotubes are subjected to a simple purification process, for example, to remove catalyst nanoparticles, so that the pure carbon nanotubes are received and stored or transferred to a place of use.

By pyrolyzing methane gas (natural gas) by the above filter reaction apparatus and production method, hydrogen can be produced and carbon nanotubes can be produced at the same time. Provide productivity.

In addition, there is no carbon dioxide emission in the hydrogen production process, and hydrogen can be produced with much lower energy than thermal energy used in the high temperature pyrolysis process. In addition, since the catalyst nanoparticles can be continuously supplied, there is no need for a regeneration process to prevent the deterioration of the life of the catalyst, and the carbon nanotubes can be continuously received without stopping the pyrolysis process.

In addition, the above-mentioned example is only an example to demonstrate this invention. Therefore, it is obvious that the ordinary skilled in the art to which the present invention pertains uses the partial change with reference to the detailed description.

1 is a schematic diagram showing the overall configuration of a filter reactor for producing carbon nanotubes and hydrogen gas of the present invention.

2 and 3 is a flow chart illustrating a method for producing carbon nanotubes and hydrogen gas according to the present invention.

<Explanation of symbols for the main parts of the drawings>

10: filter reaction device

20: reaction chamber

21: hopper portion 22: heating portion 23: partition wall

24 filter 25 exhaust nozzle 26 differential pressure gauge

27: exhaust valve

30: storage chamber

31: valve

40: supply pipe

50: catalytic nanoparticle generator

60: hydrogen gas discharge pipe

70: powder discharge pipe

80: carbon nanotube

Claims (6)

In the filter reactor for producing carbon nanotubes and hydrogen gas using methane gas, The lower end is a cylindrical body having a cone-shaped hopper portion 21 of the upper and lower sides, and a heating part 22 is installed on the outer surface to apply heat to the inside, and a partition 23 is installed inside to partition the inner space up and down. In addition, the partition wall has a filter 24 mounted on the lower surface of the reaction chamber 20 for filtering the gas in the lower space and supply to the upper side; Located in the lower portion of the reaction chamber is in communication with the hopper portion 21 and the connecting portion is provided with a valve 31 to open and close the storage chamber 30 for receiving and storing the solid powder remaining after the reaction in the reaction chamber Wow; A filter 24 communicating with the side of the reaction chamber and supplying methane gas into the reaction chamber; A catalytic nanoparticle generator (50) for supplying catalytic nanoparticles to methane gas provided on a flow path of the supply pipe; A hydrogen gas discharge pipe 60 communicating with a partitioned upper space of the reaction chamber to discharge filtered hydrogen gas; And a powder discharge pipe (70) for discharging the solid powder stored in communication with the storage chamber. The filter reactor for producing carbon nanotubes and hydrogen gas, comprising: a powder discharge pipe (70). The method of claim 1, The reaction chamber 20 is a filter reactor for producing carbon nanotubes and hydrogen gas, characterized in that the exhaust nozzle 25 is installed in the upper space partitioned by the partition wall 23 to separate the solid powder adsorbed to the filter. . The method of claim 1, The filter 24 is a filter reactor for producing carbon nanotubes and hydrogen gas, characterized in that the cylindrical. In the method for producing carbon nanotubes and hydrogen gas from methane by using a reaction apparatus provided with a reaction chamber equipped with a filter and a storage chamber in which valves are opened and closed in a vertical direction, Mixing the catalytic nanoparticles with methane gas (S1); A pyrolysis step (S2) of injecting methane gas containing the catalyst nanoparticles into the reaction chamber and then applying heat to separate carbon and hydrogen; The separated hydrogen gas is filtered through a filter installed in a reaction chamber to receive hydrogen from which carbon is removed (S3); The carbon component separated in the pyrolysis step is adsorbed onto the catalyst nanoparticles and attached to the filter surface of the reaction chamber, and the carbon nanotube growth step is performed in which carbon nanotubes are synthesized and grown using the attached catalytic nanoparticles as the catalytic activity point. S4); And collecting carbon nanotubes stripped from the filter surface and storing the carbon nanotubes in a lower storage chamber (S5). The method of producing carbon nanotubes and hydrogen gas from methane, comprising: The method of claim 4, wherein The carbon nanotube growth step (S4) is followed by the carbon nanotube and hydrogen gas from methane characterized in that the dedusting step (S6) to remove the attached carbon nanotubes by discharging the dedusting gas from the inside to the outside of the filter is further performed. How to produce. The method of claim 4, wherein The decomposition reaction temperature applied in the pyrolysis step (S2) is a method for producing carbon nanotubes and hydrogen gas from methane, characterized in that consisting of 600 ~ 900 ℃.

Images