KR20240159713A - Chemical vapor deposition system of parallel structure for producing nano-carbon material and hydrogen from carbon dioxide, and production method using the same - Google Patents

Abstract

The present invention comprises a reaction module having a gas supply section, a hollow column-shaped hollow section having an internal space and connected to the gas supply section to receive gas and generate a primary reaction product from the gas, and a rear reaction section formed in a hollow column-shaped hollow section spaced apart in the transverse direction of the shear reaction section and arranged parallel to the shear reaction section and connected to the shear reaction section to receive the primary reaction product, a moisture collection section located below the shear reaction section and collecting moisture generated when the primary reaction product is generated in the shear reaction section, and a primary reaction product transport section connecting the shear reaction section and the rear reaction section to provide a path for transporting the primary reaction product, characterized in that the shear reaction section and the rear reaction section are arranged in parallel with each other with respect to the ground, so that the primary reaction product discharged from the shear reaction section flows to the primary reaction product transport section and the moisture discharged from the shear reaction section flows to the moisture collection section. Provides a chemical vapor deposition system.

Description

{Chemical vapor deposition system of parallel structure for producing nano-carbon material and hydrogen from carbon dioxide, and production method using the same}

The present invention relates to a parallel structure chemical vapor deposition system for producing nano-carbon materials and hydrogen from carbon dioxide, and a production method using the same. More specifically, the present invention relates to a parallel structure chemical vapor deposition system for producing nano-carbon materials and hydrogen from carbon dioxide, and a production method using the same, which comprises a two-step process of producing methane from carbon dioxide and a process of producing nano-carbon materials from methane, and in which reactors are arranged in parallel.

The rapid increase in carbon dioxide concentration due to the use of fossil fuels is causing various environmental problems due to global warming, and the treatment and reduction of carbon dioxide is an urgent national issue.

As a result, carbon neutrality policies are being implemented worldwide, and among them, the field that urgently requires technological development is carbon dioxide conversion.

Accordingly, R&D investment costs, papers, patents, etc. are gradually increasing worldwide every year, and according to the 'Carbon Capture/Utilization Technology Innovation Roadmap', among the carbon dioxide chemical conversion fields, carbon material conversion and secondary battery material utilization fields are specified as next-generation technologies.

Therefore, it is important to invent and develop improved methods to reduce carbon dioxide emissions into the atmosphere.

In addition, as the demand for secondary batteries expands, it is important to secure the price competitiveness of secondary batteries, so technology to lower the cost of expensive nano-carbon materials used as next-generation secondary battery materials is needed, and the development of technology and equipment can create high value-added markets both domestically and internationally.

Currently, research is actively being conducted on carbon dioxide reduction methods using photochemical, biochemical, electrochemical, and metal catalysts.

Meanwhile, this carbon dioxide reduction reaction can produce various nano-carbon materials, including carbon nanotubes (CNTs).

Here, carbon nanotubes are materials that have a structure in which graphene sheets are usually wound and have a one-dimensional structure with a very large aspect ratio.

Carbon nanotubes are known to have excellent mechanical strength and flexibility, semiconductor and metallic conductivity, and are also very chemically stable.

Methods for manufacturing carbon nanotubes have been reported, including arc discharge method, laser evaporation method, and chemical vapor deposition method (hereinafter referred to as CVD (Chemical Vapor Deposition) method).

In particular, the CVD method is a synthetic method that is attracting attention as a synthetic method suitable for mass synthesis, continuous synthesis, and high purification.

In particular, it has been confirmed that single-walled carbon nanotubes (hereinafter referred to as “SWCNTs”) exhibit metallic and semiconducting properties depending on the winding method or diameter.

Applications to electrical and electronic devices are expected. For the synthesis of SWCNTs, the catalytic CVD method for growing nanotubes is the mainstream.

This catalytic CVD method uses metal nanoparticles as a catalyst. Then, by supplying a gaseous carbon source, the carbon source is thermally decomposed at high temperature and nanotubes are grown from the catalytic metal nanoparticles.

Korean Patent Publication No. 10-2022-0111299 (Title: Single-walled carbon nanotube film and its manufacturing method and manufacturing device) discloses a method for manufacturing single-walled carbon nanotubes, comprising: supplying a carrier carbon monoxide and a catalyst precursor to a mixing zone through a first inlet at a temperature below a reaction temperature of the catalyst precursor; supplying heated carbon monoxide to the mixing zone through a second inlet such that the heated carbon monoxide is mixed with the carrier carbon monoxide and the catalyst to form an aerosol; reacting the aerosol in a reaction chamber to form a composite aerosol including single-walled carbon nanotubes (SWCNTs), carbon monoxide, and carbon dioxide; and exposing a substrate to the composite aerosol to deposit an SWCNT film on a surface of the substrate.

(Patent Document 1) Republic of Korea Publication Patent No. 10-2022-0111299 (August 9, 2022)

The purpose of the present invention to solve the above problems is to provide a parallel structure chemical vapor deposition system for producing nanocarbon materials and hydrogen from carbon dioxide, which comprises a front-end reaction unit for producing methane by receiving a gas mixed with carbon dioxide and hydrogen from a gas supply unit, and a rear-end reaction unit for producing nanocarbon materials by receiving methane from the front-end reaction unit, and which comprises a moisture collection unit and a moisture adsorbent to capture and adsorb moisture generated in the front-end reaction unit, and which subdivides the process steps into the front-end reaction unit and the rear-end reaction unit, thereby producing high-quality nanocarbon materials. The system also provides a production method using the same.

The technical problems to be achieved by the present invention are not limited to the technical problems mentioned above, and other technical problems not mentioned can be clearly understood by a person having ordinary skill in the technical field to which the present invention belongs from the description below.

In order to achieve the above-described purpose, the present invention comprises: a reaction module comprising: a gas supply unit; a front reaction unit formed in a hollow columnar shape having an internal space and connected to the gas supply unit to receive gas and generate a first reaction product from the gas; and a rear reaction unit formed in a hollow columnar shape spaced apart in the transverse direction of the shear reaction unit and arranged parallel to the shear reaction unit, the front reaction unit connected to the shear reaction unit to receive the first reaction product; a moisture collection unit located below the shear reaction unit and collecting moisture generated when the first reaction product is generated in the shear reaction unit; And a first reaction product transfer unit that connects the first reaction unit and the second reaction unit to provide a path for transferring the first reaction product; The first reaction product and the second reaction unit are arranged in parallel with respect to the ground, so that the first reaction product discharged from the first reaction product flows to the first reaction product transfer unit and the moisture discharged from the first reaction unit flows to the moisture collection unit. The present invention provides a parallel structure chemical vapor deposition system for producing nano-carbon materials and hydrogen from carbon dioxide.

In an embodiment of the present invention, the first reaction product transfer unit may include a first gas transfer pipe having one end connected to the front reaction unit and providing a path for the first reaction product; and a second gas transfer pipe having one end connected to the other end of the first gas transfer pipe and the other end connected to the rear reaction unit.

In an embodiment of the present invention, a valve may be further included that is connected to each of the shear reaction unit, the water collection unit, and the first gas transfer pipe, and controls the connection between the shear reaction unit and the first gas transfer pipe or the connection between the water collection unit and the shear reaction unit.

In an embodiment of the present invention, the first gas transport pipe may have a moisture absorbent formed inside.

In an embodiment of the present invention, a gas mixing unit may be further included that is positioned between the first gas transfer pipe and the second gas transfer pipe and is connected to the first gas transfer pipe and the second gas transfer pipe.

In an embodiment of the present invention, the gas mixing unit can stir the primary reaction product passing through the gas mixing unit.

In an embodiment of the present invention, a flow rate control unit may be further included that is coupled to at least a portion of the second gas transport pipe and controls the flow rate of the first reaction product passing through the second gas transport pipe.

In an embodiment of the present invention, the device may further include a shear heating unit formed to be thermally connected to an outer surface of the shear reaction unit and heat the shear reaction unit; and a post-heating unit formed to be thermally connected to an outer surface of the post-reaction unit and heat the post-reaction unit.

In an embodiment of the present invention, the shear heating unit can heat the temperature of the shear reaction unit to 300°C to 350°C.

In an embodiment of the present invention, the post-heating unit can heat the temperature of the post-reaction unit to 700°C to 1000°C.

In an embodiment of the present invention, a cooling unit may be further included, which is arranged to surround the water collection unit and cools the water collection unit.

In an embodiment of the present invention, the gas supply unit may include: a plurality of gas tanks in which gas is stored; a flow controller connected to the plurality of gas tanks to measure and control the flow rate of gas discharged from the plurality of gas tanks; and a gas supply pipe having one end connected to the flow controller and the other end connected to the shear reaction unit to provide a path for gas discharged from the gas tank.

In an embodiment of the present invention, the gas may be a gas mixed with carbon dioxide and hydrogen.

In an embodiment of the present invention, the method may further include a control unit that controls the type or amount of gas delivered from the gas supply unit to the shear reaction unit and controls the temperature of each of the shear heating unit and the rear heating unit.

In addition, the configuration of the present invention for achieving the above purpose comprises: a first step in which a gas mixed with carbon dioxide and hydrogen is injected into the front-end reaction unit by the gas supply unit; a second step in which the gas reacts with a first catalyst formed inside the front-end reaction unit to generate a first reaction product inside the front-end reaction unit; a third step in which a product gas which is a gas among the first reaction products is transferred to the gas mixing unit through the first gas transfer pipe, and a product liquid which is a liquid among the first reaction products is transferred to the water collection unit by a valve coupled to the first reaction product transfer unit; a fourth step in which each substance in the product gas is stirred in the gas mixing unit; a fifth step in which the first reaction product which has passed through the gas mixing unit is transferred to the rear-end reaction unit through the second gas transfer pipe; It includes a sixth step in which the secondary catalyst formed inside the above-described post-reaction section reacts with the above-described first reaction product to produce nano-carbon material and hydrogen; and a seventh step in which the above-described hydrogen is discharged to the top of the above-described post-reaction section.

The effect of the present invention according to the above configuration is that it comprises a front-end reaction unit which receives a gas mixed with carbon dioxide and hydrogen from a gas supply unit and produces methane, and a rear-end reaction unit which receives methane from the front-end reaction unit and produces nanocarbon materials, and has a moisture collection unit and a moisture adsorbent to capture and adsorb moisture generated in the front-end reaction unit, and by subdividing the process steps into the front-end reaction unit and the rear-end reaction unit, it is possible to produce high-quality nanocarbon materials, thereby contributing scientific and practical technologies to the carbon-neutral field of greenhouse gas reduction, which is an environmental issue, and making it possible to commercialize nanocarbon materials which are expensive among various chemical substances that can be converted from carbon dioxide.

The effects of the present invention are not limited to the effects described above, and should be understood to include all effects that can be inferred from the detailed description of the present invention or the composition of the invention described in the claims.

FIG. 1 is a schematic diagram of a parallel structure chemical vapor deposition system for producing nanocarbon materials and hydrogen from carbon dioxide according to one embodiment of the present invention.
FIG. 2 is an image showing reactions occurring in a front reaction unit and a rear reaction unit provided in a parallel structure chemical vapor deposition system for producing nanocarbon materials and hydrogen from carbon dioxide according to one embodiment of the present invention.
FIG. 3 is a SEM image magnified 100,000 times of carbon nanotubes produced in a parallel chemical vapor deposition system for producing nanocarbon materials and hydrogen from carbon dioxide according to an embodiment of the present invention.
FIG. 4 is a SEM image magnified 200,000 times of carbon nanotubes produced in a parallel chemical vapor deposition system for producing nanocarbon materials and hydrogen from carbon dioxide according to an embodiment of the present invention.
FIG. 5 is a TEM image at 640,000 times magnification of carbon nanotubes produced in a parallel chemical vapor deposition system for producing nanocarbon materials and hydrogen from carbon dioxide according to an embodiment of the present invention.
FIG. 6 is a TEM image at 800,000 times magnification of carbon nanotubes produced in a parallel chemical vapor deposition system for producing nanocarbon materials and hydrogen from carbon dioxide according to an embodiment of the present invention.
FIG. 7 is a Raman spectrum of carbon nanotubes produced in a parallel chemical vapor deposition system for producing nanocarbon materials and hydrogen from carbon dioxide according to an embodiment of the present invention.

Hereinafter, the present invention will be described with reference to the attached drawings. However, the present invention can be implemented in various different forms, and therefore is not limited to the embodiments described herein. In addition, in order to clearly describe the present invention in the drawings, parts that are not related to the description are omitted, and similar parts are assigned similar drawing reference numerals throughout the specification.

Throughout the specification, when a part is said to be "connected (connected, contacted, joined)" to another part, this includes not only the case where it is "directly connected" but also the case where it is "indirectly connected" with another member in between. Also, when a part is said to "include" a certain component, this does not mean that other components are excluded, unless otherwise specifically stated, but that other components can be included.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the present invention. The singular expression includes the plural expression unless the context clearly indicates otherwise. As used herein, the terms "comprises" or "has" and the like are intended to specify the presence of a feature, number, step, operation, component, part or combination thereof described in the specification, but should be understood to not exclude in advance the possibility of the presence or addition of one or more other features, numbers, steps, operations, components, parts or combinations thereof.

Hereinafter, an embodiment of the present invention will be described in detail with reference to the attached drawings.

FIG. 1 is a schematic diagram of a parallel structure chemical vapor deposition system for producing nanocarbon materials and hydrogen from carbon dioxide according to one embodiment of the present invention.

Referring to FIG. 1, the parallel structure chemical vapor deposition system for producing nanocarbon materials and hydrogen from carbon dioxide of the present invention includes a valve (10), a gas supply unit (100), a reaction module (200), a heating module (300), a water collection unit (400), a first reaction product transport unit (500), a cooling unit (600), a gas mixing unit (700), a flow rate control unit (800), a control unit (900), and a pump (1000).

The valve (10) is connected to each of the shear reaction unit (210), the water collection unit (400) and the first gas transfer pipe (520) described below, and can control the connection between the shear reaction unit (210) and the first gas transfer pipe (520) or the connection between the water collection unit (400) and the shear reaction unit (210).

Specifically, the valve (10) may be configured as a three-way valve formed in a T shape and provided with holes penetrating through respective locations where the valve upper portion (10a), valve side portion (10b), and valve lower portion (10c) are formed, and each of the valve upper portion (10a), valve side portion (10b), and valve lower portion (10c) in which holes are formed in the valve (10) may be combined with the fluid transport pipe (510), the first gas transport pipe (520), and the liquid transport pipe (540) described below, respectively.

More specifically, a fluid transport pipe (510) may be coupled to the upper part of the valve (10a), a first gas transport pipe (520) may be coupled to the valve side (10b), and a liquid transport pipe (540) may be coupled to the lower part of the valve (10c).

The gas supply unit (100) is equipped with a gas tank (110), a flow controller (120), and a gas supply pipe (130).

The gas tank (110) is composed of multiple units and gas can be stored.

The gas stored in each of the above-mentioned multiple gas tanks (110) may be a different gas.

Here, the gas stored in each of the plurality of gas tanks (110) may be composed of carbon dioxide, hydrogen, etc., but is not limited thereto, and may be composed of various carbonized gases such as carbon monoxide and acetylene.

The flow controller (120) is connected to a plurality of gas tanks (110) and can measure and control the flow rate of gas discharged from the plurality of gas tanks (110).

The above-described flow controller (120) can control the type or amount of gas discharged from multiple gas tanks (110) by the control unit (900) described below.

Due to this, the flow controller (120) can control the mixing ratio of each gas by differently controlling the amount of each gas discharged from the gas tank (110).

The gas supply pipe (130) has one end connected to a flow controller (120) and the other end connected to a shear reaction unit (210) described later, so as to provide a path for gas discharged from a gas tank (110).

Here, the other end of the gas supply pipe (130) can be connected to the gas inlet (211) formed at the upper end of the shear reaction unit (210).

Here, gas discharged from the gas tank (110) can be supplied into the shear reaction unit (210) through the gas supply pipe (130).

At this time, the gas discharged from the gas tank (110) may be a gas mixed with carbon dioxide and hydrogen.

The reaction module (200) has a front reaction section (210) and a rear reaction section (220).

The shear reaction unit (210) is formed in a hollow column shape with an internal space and is connected to the gas supply unit (100) to receive gas and generate a primary reaction product from the gas.

Specifically, a gas inlet (211) is formed at the top of the shear reaction unit (210), and the gas inlet (211) and the gas supply pipe (130) are connected, and a first reaction product discharge port (212) is formed at the bottom of the shear reaction unit (210), and the first reaction product discharge port (212) and the first reaction product transfer unit (500) described below are connected.

In addition, a support formed in a mesh structure is provided inside the shear reaction unit (210) so that the primary catalyst (a) can be applied, and the gas supplied to the shear reaction unit (210) reacts with the primary catalyst (a) to generate a primary reaction product.

More specifically, the gas discharged from the gas tank (110) passes through the gas supply pipe (130) and is supplied to the shear reaction unit (210) through the gas inlet (211), and the gas supplied to the shear reaction unit (210) reacts with the primary catalyst (a) formed inside the shear reaction unit (210), thereby generating the primary reaction products, i.e., the product gas and the product liquid.

At this time, the generated product gas and generated liquid are transferred to the first reaction product transfer unit (500) through the first reaction product discharge port (212). The generated gas passes through the first gas transfer pipe (520) provided in the first reaction product transfer unit (500), and the generated liquid passes through the liquid transfer pipe (540) provided in the first reaction product transfer unit (500).

Here, the generating gas may be a gas containing methane, and the generating liquid may be water (hereinafter referred to as moisture). The same applies hereinafter.

In the above process, when the temperature of the shear reaction section (210) is 300°C to 350°C, a nano-carbon material (c) with high crystallinity can be ultimately produced.

Accordingly, it is preferable that the temperature of the shear reaction section (210) be maintained at 300°C to 350°C.

FIG. 2 is an image showing a reaction occurring in a front reaction unit (210) and a rear reaction unit (220) provided in a parallel structure chemical vapor deposition system for producing nanocarbon materials and hydrogen from carbon dioxide according to one embodiment of the present invention.

Specifically, in Fig. 2, a represents a primary catalyst (a), b represents a secondary catalyst (b), and c represents a nanocarbon material (c).

And, referring to Fig. 2, the chemical reaction that occurs when gas and the primary catalyst (a) react in the shear reaction section (210) is as shown in [Formula 1] below.

[Formula 1]

CO ₂ + 4H ₂ → CH ₄ + 2H ₂ O

(Here, _CO2 : carbon dioxide, _H2 : hydrogen, _CH4 : methane, _H2O : moisture)

Meanwhile, the above-mentioned primary catalyst (a) utilizes a metal and metal oxide catalyst, and mainly uses a transition metal, and may be composed of one or more materials selected from the group consisting of iron, cobalt, nickel, and molybdenum, but is not limited thereto, and may be composed of various transition metals considering the efficiency of production of the reaction product.

In addition, the above-mentioned support may be composed of ceramics such as oxide-based, nitride-based, and silicon carbide-based ceramics containing at least one element selected from the group consisting of silicon, aluminum, zirconium, and magnesium, but is not limited thereto, and may be composed of a metal or alloy containing at least one element selected from tungsten, molybdenum, titanium, iron, cobalt, and nickel, taking into consideration heat resistance, corrosion resistance, chemical resistance, and mechanical strength characteristics. The same applies hereinafter.

Referring again to FIG. 1, the rear reaction section (220) is formed in a hollow column shape spaced apart in the transverse direction of the shear reaction section (210) and arranged parallel to the shear reaction section (210), and is connected to the shear reaction section (210) to receive the primary reaction product.

This rear reaction unit (220) generates secondary reaction products from the primary reaction products supplied from the front reaction unit (210).

The above-described rear reaction section (220) has a first reaction product inlet (221) formed at the bottom of the rear reaction section (220), and the first reaction product inlet (221) is connected to a second gas transfer pipe (530) described later, and a second reaction product discharge port (222) is formed at the top of the rear reaction section (220).

In addition, a support formed in a mesh structure is provided inside the rear reaction section (220) so that a secondary catalyst (b) can be applied, and the primary reaction product supplied to the rear reaction section (220) reacts with the secondary catalyst (b) to generate a secondary reaction product.

Specifically, among the primary reaction products generated in the front reaction unit (210), the generated liquid passes through the liquid transfer pipe (540) and is collected in the water collection unit (400) described later, and the generated gas passes through the first gas transfer pipe (520), the gas mixing unit (700), and the second gas transfer pipe (530) in sequence and is supplied to the rear reaction unit (220) through the primary reaction product inlet (221). The generated gas supplied to the rear reaction unit (220) reacts with the secondary catalyst (b) formed inside the rear reaction unit (220) to generate secondary reaction products, such as nano-carbon materials (c) and hydrogen.

Here, when the generated gas passes through the first gas transport pipe (520), moisture remaining in the generated gas can be absorbed and removed by the moisture absorbent (521) formed inside the first gas transport pipe (520).

And, the hydrogen generated in the rear reaction unit (220) is discharged to the outside of the rear reaction unit (220) through the secondary reaction product discharge port (222).

In the above process, when the temperature of the rear reaction section (220) is 700°C to 1000°C, a nano-carbon material (c) with high crystallinity can be ultimately produced.

Accordingly, it is preferable that the temperature of the rear reaction section (220) be maintained at 700°C to 1000°C.

In addition, the shear reaction unit (210) and the rear reaction unit (220) are arranged in parallel with each other based on the ground, so that the primary reaction product discharged from the shear reaction unit (210) can flow to the primary reaction product transfer unit (500), and the moisture discharged from the shear reaction unit (210) can flow to the moisture collection unit (400).

In addition, referring to Fig. 2, the chemical reaction that occurs when the generated gas and the secondary catalyst (b) react in the rear reaction section (220) is as shown in [Formula 2] below.

[Formula 2]

CH ₄ → C + 2H ₂

(Here, CH ₄ : methane, C: nanocarbon material, H ₂ : hydrogen)

Meanwhile, the above-mentioned secondary catalyst (b) utilizes a metal and metal oxide catalyst, and mainly uses a transition metal, and may be composed of one or more materials selected from the group consisting of iron, cobalt, nickel, and molybdenum, but is not limited thereto, and may be composed of various transition metals considering the efficiency of production of the reaction product.

Here, the nano-carbon material (c) generated in the post-reaction section (220) can produce various carbon isotopes of nanometer size, such as carbon nanotubes, graphene, and fullerene, depending on the type of secondary catalyst (b).

On the other hand, since carbon dioxide has a chemically stable structure, it is difficult to manufacture high-quality nanocarbon material (c) by directly converting carbon dioxide into nanocarbon material (c) in just one step.

In order to solve the above problem, the parallel structure chemical vapor deposition system for producing nanocarbon material and hydrogen from carbon dioxide of the present invention is composed of a front reaction unit (210) for producing methane from carbon dioxide and a rear reaction unit (220) for producing nanocarbon material (c) from methane, and is comprised of a two-stage process, so that high-quality nanocarbon material (c) can be manufactured by subdividing the process stages.

Referring to Figure 1, the heating module (300) has a front heating unit (310) and a rear heating unit (320).

The shear heating unit (310) is formed to be thermally connected to the outer surface of the shear reaction unit (210) and heats the shear reaction unit (210).

The above-mentioned shear heating unit (310) can heat the temperature of the shear reaction unit (210) to 300°C to 350°C.

The rear heating unit (320) is formed to be thermally connected to the outer surface of the rear reaction unit (220) and heats the rear reaction unit (220).

The above-mentioned rear heating unit (320) can heat the rear reaction unit (220) to a temperature of 700°C to 1000°C.

Each of the aforementioned pre-heating unit (310) and post-heating unit (320) can heat the pre-reaction unit (210) and post-reaction unit (220) by using at least one heating method selected from among heating by microwave irradiation, inductive heating, radiofrequency heating (RF heating), and heating using a laser.

The moisture collection unit (400) is located below the shear reaction unit (210) and captures moisture generated when the primary reaction product is generated in the shear reaction unit (210).

The above-described moisture collection unit (400) is formed to have an internal space and is connected to a liquid transport pipe (540) described later, so that moisture generated in the shear reaction unit (210) can be captured in the moisture collection unit (400) through the liquid transport pipe (540).

Here, if a large amount of moisture generated in the front reaction section (210) moves to the rear reaction section (220), it may hinder the growth of the nanocarbon material (c).

To solve the above problem, the moisture collection unit (400) can prevent a large amount of moisture from moving to the rear reaction unit (220) by capturing moisture generated in the front reaction unit (210).

The first reaction product transport unit (500) connects the front reaction unit (210) and the rear reaction unit (220) to provide a path for transporting the first reaction product.

This primary reaction product transfer unit (500) may be equipped with a fluid transfer pipe (510), a first gas transfer pipe (520), a second gas transfer pipe (530), and a liquid transfer pipe (540).

The fluid transport pipe (510) is formed parallel to the longitudinal axis of the shear reaction unit (210), one end is connected to the shear reaction unit (210), and the other end is connected to the valve (10).

Specifically, the fluid transport pipe (510) can be connected to the first gas transport pipe (520) or the liquid transport pipe (540) by having the other end joined to the valve top (10a).

Due to this, the shear reaction unit (210) and the first gas transfer pipe (520) can be connected, or the shear reaction unit (210) and the liquid transfer pipe (540) can be connected.

Accordingly, the primary reaction product generated in the shear reaction unit (210) passes through the fluid transfer pipe (510), and the gas generated among the primary reaction products that pass through the fluid transfer pipe (510) can be transferred to the first gas transfer pipe (520), and the liquid generated among the primary reaction products that pass through the fluid transfer pipe (510) can be transferred to the liquid transfer pipe (540).

The first gas transfer pipe (520) is formed perpendicular to the longitudinal axis of the shear reaction section (210).

The above-mentioned first gas transport pipe (520) is connected at one end to the shear reaction unit (210) and can provide a path for the first reaction product.

Specifically, the first gas transfer pipe (520) has one end connected to the valve side (10b) and is connected to the fluid transfer pipe (510) and the shear reaction section (210), and the other end is connected to the second gas transfer pipe (530).

Accordingly, among the primary reaction products generated in the shear reaction unit (210), the generated gas can be transferred to the second gas transfer pipe (530) through the fluid transfer pipe (510) and the first gas transfer pipe (520).

This first gas transport pipe (520) can have a moisture absorbent (521) formed inside.

The above-mentioned moisture absorbent (521) has an internal space and an adsorbent that absorbs moisture is formed on the inner surface, so that moisture remaining in the primary reaction product passing through the moisture absorbent (521) can be absorbed.

As described above, by the moisture adsorbent (521) adsorbing and removing the moisture remaining in the first reaction product, when the first reaction product reacts with the second catalyst in the subsequent reaction section (220), the influence of moisture on the production of the nanocarbon material (c) can be minimized.

Here, the adsorbent formed on the inner surface of the moisture absorbent (521) may be composed of one or more materials selected from silica gel, alumina gel, molecular resorbable gel, activated carbon, diatomaceous earth, zeolite, and bentonite, but is not limited thereto, and various moisture absorbents may be used considering moisture absorption capacity, period of use, and usage environment.

The second gas transfer pipe (530) is formed perpendicular to the longitudinal axis of the shear reaction section (210).

The above-mentioned second gas transfer pipe (530) can have one end connected to the other end of the first gas transfer pipe (520) and the other end connected to the rear reaction unit (220).

Here, the other end of the second gas transfer pipe (530) can be connected to the first reaction product inlet (221) formed at the bottom of the rear reaction section (220).

The liquid transport pipe (540) is formed parallel to the longitudinal axis of the shear reaction unit (210), one end is connected to the valve (10), and the other end is connected to the water collection unit (400).

Specifically, the liquid transport pipe (540) can be connected to the fluid transport pipe (510) and the shear reaction unit (210) by having one end connected to the valve lower part (10c).

Accordingly, moisture generated in the shear reaction unit (210) can pass through the fluid transport pipe (510) and the liquid transport pipe (540) and be captured in the moisture collection unit (400).

In addition, when the lower valve (10c) is closed after the moisture is transferred to the moisture collection unit (400), it is possible to prevent the moisture transferred to the moisture collection unit (400) from affecting the process of generating the first reaction product in the pre-reaction unit (210) and the process of generating the second reaction product in the post-reaction unit (220).

Meanwhile, the valve (10) described above can open or close the valve side (10b) coupled with the first gas transport pipe (520) or the valve lower part (10c) coupled with the liquid transport pipe (540).

When explaining the operation of the valve (10) at this time, when the valve (10) opens the valve side (10b), the lower part of the valve (10c) is closed, and when the valve (10) closes the valve side (10b), the lower part of the valve (10c) can be opened.

Accordingly, when the valve side (10b) is opened and the valve bottom (10c) is closed, the gaseous product among the primary reaction products generated in the shear reaction section (210) is transferred to the first gas transfer pipe (520), and when the valve side (10b) is closed and the valve bottom (10c) is opened, the liquid product among the primary reaction products generated in the shear reaction section (210) is transferred to the liquid transfer pipe (540).

The cooling unit (600) is arranged to surround the moisture collection unit (400) and can cool the moisture collection unit (400).

The above-mentioned cooling unit (600) cools the moisture collection unit (400), thereby preventing moisture existing inside the moisture collection unit (400) from evaporating and reaching the primary catalyst (a) and secondary catalyst (b), and preventing it from affecting the production of nano-carbon material (c).

The gas mixing unit (700) is located between the first gas transfer pipe (520) and the second gas transfer pipe (530) and is connected to the first gas transfer pipe (520) and the second gas transfer pipe (530).

The above-mentioned gas mixing unit (700) can stir the primary reaction product passing through the gas mixing unit (700).

Specifically, the gas mixing unit (700) has an impeller inside to uniformly mix the primary reaction products supplied into the gas mixing unit (700).

The above-mentioned gas mixing unit (700) may be configured as a stirring device, and may also be configured as a gas mixer equipped with a mechanical mixing valve or an electronic valve that mixes by controlling the gas supply flow rate through the interaction of an orifice plate and a piston inside the mixer.

When the first reaction product uniformly mixed by the aforementioned gas mixing unit (700) is transferred to the rear reaction unit (220) through the second gas transfer pipe (530) to produce a nano-carbon material (c), which is one of the second reaction products, a nano-carbon material (c) formed in a more uniform form can be produced than when the nano-carbon material (c) is produced using the unstirred first reaction product.

In the parallel structure chemical vapor deposition system of the present invention for producing nano-carbon materials and hydrogen from carbon dioxide, the gas mixing unit (700) is described as being composed of a gas mixer equipped with a stirring device having an impeller or a mechanical mixing valve or an electronic valve, but is not limited thereto, and may be composed of various stirring devices in consideration of stirring time, rotational speed, required power, etc.

The flow control unit (800) is coupled to at least a portion of the second gas transport pipe (530) and can control the flow rate of the primary reaction product passing through the second gas transport pipe (530).

Specifically, the flow control unit (800) controls the flow rate of the primary reaction product transferred to the secondary reaction unit (220) through the secondary gas transfer pipe (530), thereby allowing an appropriate amount of the primary reaction product to be supplied to the secondary reaction unit (220) by considering the time for the secondary reaction product to be generated in the secondary reaction unit (220) and the amount of secondary reaction product that can be generated in the secondary reaction unit (220).

This flow control unit (800) may be configured as a flow control valve or a gas flow meter, which is an automatic control valve that can control the flow rate by maintaining a constant pressure difference due to a change in the flow rate.

The control unit (900) controls the type or amount of gas delivered from the gas supply unit (100) to the pre-heating unit (210), and controls the temperature of each of the pre-heating unit (310) and the post-heating unit (320).

Specifically, when supplying gas from the gas supply unit (100) to the front reaction unit (210), the control unit (900) can control the flow controller (120) to control the type of gas discharged from the gas tank (110) or the amount of each gas discharged from the gas tank (110), and can also control the type of gas discharged from the gas tank (110) and the amount of gas simultaneously.

Accordingly, the control unit (900) can control the supply ratio of each gas to be supplied at a preset ratio.

For example, the control unit (800) can control the supply ratio of carbon dioxide and hydrogen to be supplied at a preset ratio when supplying gas from the gas supply unit (100).

Meanwhile, when the front reaction section (210) has a temperature of 300°C to 350°C and the rear reaction section (220) has a temperature of 700°C to 1000°C, a highly crystallizable nanocarbon material (c) can be easily produced.

For the above reasons, the control unit (900) controls the heating temperature of the shear heating unit (310) that affects the temperature of the shear reaction unit (210) to be maintained between 300°C and 350°C. When the heating temperature of the shear heating unit (310) is 300°C or lower, the heating temperature of the shear heating unit (310) is increased, and when the heating temperature of the shear heating unit (310) is 350°C or higher, the heating temperature of the shear heating unit (310) is decreased.

And, the control unit (900) controls the heating temperature of the rear heating unit (320) that affects the temperature of the rear reaction unit (220) to be maintained between 700°C and 1000°C. When the heating temperature of the rear heating unit (320) is 700°C or lower, the heating temperature of the rear heating unit (320) is increased, and when the heating temperature of the rear heating unit (320) is 1000°C or higher, the heating temperature of the rear heating unit (320) is decreased.

In addition, the control unit (900) can also control the flow rate control unit (800) so that the primary reaction product is transported at a preset flow rate.

Here, the control unit (900) can control the flow rate control unit (800) by considering the time at which the secondary reaction product is generated in the post-stage reaction unit (220) or the amount of secondary reaction product that can be generated in the post-stage reaction unit (220).

Specifically, the control unit (900) controls the flow rate control unit (800) to reduce the flow rate of the primary reaction product when the time for the secondary reaction product to be generated in the secondary reaction unit (220) is slow or the amount of the secondary reaction product that can be generated in the secondary reaction unit (220) is small, so that the supplied primary reaction product remains in the secondary reaction unit (220).

In addition, the control unit (900) can control the flow rate control unit (800) to increase the flow rate of the primary reaction product when the time for the secondary reaction product to be generated in the secondary reaction unit (220) is short or the amount of secondary reaction product that can be generated in the secondary reaction unit (220) is large and the primary reaction product supplied is insufficient.

The pump (1000) can be connected to the top of the rear reaction section (220).

Specifically, the pump (1000) is connected to the secondary reaction product discharge port (222) formed at the top of the rear reaction unit (220) and sucks in, thereby allowing the gas supplied from the gas supply unit (100) to be easily transferred to the front reaction unit (210) and allowing the primary reaction product generated in the front reaction unit (210) to be easily transferred to the rear reaction unit (220).

Hereinafter, a method for producing nanocarbon materials and hydrogen using a parallel structure chemical vapor deposition system that produces nanocarbon materials and hydrogen from carbon dioxide of the present invention will be described.

First, in the first stage, a gas mixed with carbon dioxide and hydrogen can be injected into the shear reaction unit (210) by the gas supply unit (100).

Here, the mixing ratio of carbon dioxide and hydrogen can be appropriately changed depending on the reaction temperature in the shear reaction unit (210), the reaction speed in the shear reaction unit (210), and the type of primary catalyst provided in the shear reaction unit (210).

After performing the above-described first step, in the second step, the primary catalyst (a) formed inside the shear reaction unit (210) and gas react to generate a primary reaction product inside the shear reaction unit (210).

After the above-mentioned second step is performed, in the third step, the gaseous product among the first reaction products is transferred to the gas mixing unit (700) through the first gas transfer pipe (520), and the liquid product among the first reaction products can be transferred to the water collection unit (400) by the valve (10) connected to the first reaction product transfer unit (500).

Here, the generated gas may be a gas containing methane, and the generated liquid may be water.

In addition, when the generated gas passes through the first gas transport pipe (520), moisture remaining in the generated gas can be absorbed and removed by the moisture absorbent (521) formed inside the first gas transport pipe (520).

In addition, the moisture collection unit (400) can be cooled by the cooling unit (600) to prevent the generated liquid collected in the moisture collection unit (400) from evaporating.

In the fourth step after performing the above-described third step, each substance in the generated gas can be stirred in the gas mixing unit (700).

After performing the above-described fourth step, in the fifth step, the first reaction product that has passed through the gas mixing unit (700) can be transferred to the subsequent reaction unit (220) by passing through the second gas transfer pipe (530).

Here, the flow rate of the primary reaction product passing through the second gas transport pipe (530) can be controlled by the flow rate control unit (800) coupled with the second gas transport pipe (530).

After performing the above-described fifth step, in the sixth step, the second catalyst (b) formed inside the rear reaction section (220) and the first reaction product can react to produce nano-carbon material (c) and hydrogen.

In the seventh step after performing the above-described sixth step, hydrogen can be discharged from the top of the rear reaction section (220).

FIG. 3 is a SEM image magnified 100,000 times of carbon nanotubes produced in a parallel chemical vapor deposition system for producing nanocarbon materials and hydrogen from carbon dioxide according to an embodiment of the present invention.

FIG. 4 is a SEM image magnified 200,000 times of carbon nanotubes produced in a parallel chemical vapor deposition system for producing nanocarbon materials and hydrogen from carbon dioxide according to an embodiment of the present invention.

FIG. 5 is a TEM image at 640,000 times magnification of carbon nanotubes produced in a parallel chemical vapor deposition system for producing nanocarbon materials and hydrogen from carbon dioxide according to an embodiment of the present invention.

FIG. 6 is a TEM image at 800,000 times magnification of carbon nanotubes produced in a parallel chemical vapor deposition system for producing nanocarbon materials and hydrogen from carbon dioxide according to an embodiment of the present invention.

Referring to FIGS. 3 to 6, one can see enlarged images at various magnifications of the form of carbon nanotubes, which are one of the various carbon isotopes that can be produced using the parallel structure chemical vapor deposition system for producing nanocarbon materials and hydrogen from carbon dioxide of the present invention.

FIG. 7 is a Raman spectrum of carbon nanotubes produced in a parallel chemical vapor deposition system for producing nanocarbon materials and hydrogen from carbon dioxide according to an embodiment of the present invention.

Referring to Figure 7, carbon nanotubes produced in the parallel structure chemical vapor deposition system for producing nanocarbon materials and hydrogen from carbon dioxide of the present invention are about 1600 You can see that the light intensity is the strongest at peak.

Here, the Raman spectrum refers to continuous data of scattered light caused by the Raman effect, a phenomenon in which the intensity of Raman lines significantly increases when the frequency of the incident light used approaches or matches the electronic absorption band of the material.

The above description of the present invention is for illustrative purposes, and those skilled in the art will understand that the present invention can be easily modified into other specific forms without changing the technical idea or essential characteristics of the present invention. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive. For example, each component described as a single component may be implemented in a distributed manner, and likewise, components described as distributed may be implemented in a combined form.

The scope of the present invention is indicated by the claims described below, and all changes or modifications derived from the meaning and scope of the claims and their equivalent concepts should be interpreted as being included in the scope of the present invention.

10: Valve
10a: Top of valve
10b: Valve side
10c: valve bottom
100: Gas supply section
110: Gas Tank
120: Flow controller
130: Gas supply pipe
200: Reaction module
210: Shear reaction section
211: Gas inlet
212: Primary reaction product discharge port
220: Rear reaction section
221: 1st reaction product inlet
222: Secondary reaction product discharge port
300: Heating module
310: Shear heating section
320: Rear heating section
400: Moisture collection unit
500: 1st reaction product transfer
510: Fluid transfer pipe
520: First gas transfer pipe
521: Moisture absorbent
530: Second gas transfer pipe
540: Liquid transport piping
600: Cooling section
700: Gas Mixing Unit
800: Flow control unit
900: Control Unit
1000: Pump
a: primary catalyst
b: secondary catalyst
c: nano carbon material

Claims (15)

gas supply department;
A reaction module comprising: a hollow column-shaped body having an internal space, a front reaction section connected to the gas supply section to receive gas and generate a primary reaction product from the gas; and a rear reaction section formed in a hollow column-shaped body spaced apart in the transverse direction of the front reaction section and arranged parallel to the front reaction section, the front reaction section connected to the front reaction section to receive the primary reaction product;
A moisture collection unit located at the lower part of the shear reaction unit and capturing moisture generated when the first reaction product is generated in the shear reaction unit; and
It includes a first reaction product transfer unit that connects the above-mentioned front reaction unit and the above-mentioned rear reaction unit to provide a path for transferring the first reaction product;
A parallel structure chemical vapor deposition system for producing nano-carbon materials and hydrogen from carbon dioxide, characterized in that the shear reaction unit and the rear reaction unit are arranged in parallel with respect to the ground, so that the primary reaction product discharged from the shear reaction unit flows to the primary reaction product transport unit and the moisture discharged from the shear reaction unit flows to the moisture collection unit.
In paragraph 1,
The above first reaction product transfer unit is,
A first gas transfer pipe connected to the above-mentioned shear reaction section and providing a path for the above-mentioned first reaction product; and
A parallel structure chemical vapor deposition system for producing nano-carbon materials and hydrogen from carbon dioxide, characterized by comprising a second gas transfer pipe, the first end of which is connected to the other end of the first gas transfer pipe and the other end of which is connected to the rear reaction unit.
In the second paragraph,
A parallel structure chemical vapor deposition system for producing nano-carbon materials and hydrogen from carbon dioxide, characterized in that it further includes a valve connected to each of the shear reaction unit, the water collection unit, and the first gas transfer pipe, and controlling the connection between the shear reaction unit and the first gas transfer pipe or the connection between the water collection unit and the shear reaction unit.
In the second paragraph,
The above first gas transport pipe is,
A parallel structure chemical vapor deposition system for producing nanocarbon materials and hydrogen from carbon dioxide, characterized in that a moisture absorbent is formed inside.
In the second paragraph,
A parallel structure chemical vapor deposition system for producing nano-carbon materials and hydrogen from carbon dioxide, characterized in that it further includes a gas mixing unit positioned between the first gas transport pipe and the second gas transport pipe and connected to the first gas transport pipe and the second gas transport pipe.
In paragraph 5,
A parallel structure chemical vapor deposition system for producing nano-carbon materials and hydrogen from carbon dioxide, characterized in that the gas mixing unit stirs the primary reaction product passing through the gas mixing unit.
In the second paragraph,
A parallel structure chemical vapor deposition system for producing nano-carbon materials and hydrogen from carbon dioxide, characterized in that it further includes a flow rate control unit that is connected to at least a portion of the second gas transport pipe and controls the flow rate of the first reaction product passing through the second gas transport pipe.
In paragraph 1,
A shear heating unit formed to be thermally connected to the outer surface of the shear reaction unit and heats the shear reaction unit; and
A parallel structure chemical vapor deposition system for producing nano-carbon materials and hydrogen from carbon dioxide, characterized in that it further includes a post-heating unit formed to be thermally connected to the outer surface of the post-reaction unit and heats the post-reaction unit.
In Article 8,
A parallel structure chemical vapor deposition system for producing nano-carbon materials and hydrogen from carbon dioxide, characterized in that the shear heating unit heats the temperature of the shear reaction unit to 300°C to 350°C.
In Article 8,
A parallel structure chemical vapor deposition system for producing nano-carbon materials and hydrogen from carbon dioxide, characterized in that the post-heating unit heats the temperature of the post-reaction unit to 700°C to 1000°C.
In paragraph 1,
A parallel structure chemical vapor deposition system for producing nano-carbon materials and hydrogen from carbon dioxide, characterized in that it further includes a cooling unit arranged to surround the water collection unit and cool the water collection unit.
In paragraph 1,
The above gas supply unit,
Multiple gas tanks where gas is stored;
A flow controller connected to the plurality of gas tanks and measuring and controlling the flow rate of gas discharged from the plurality of gas tanks; and
A parallel structure chemical vapor deposition system for producing nano-carbon materials and hydrogen from carbon dioxide, characterized by having a gas supply pipe having one end connected to the flow controller and the other end connected to the shear reaction unit to provide a path for gas discharged from the gas tank.
In paragraph 1,
A parallel structure chemical vapor deposition system for producing nanocarbon materials and hydrogen from carbon dioxide, characterized in that the gas is a mixed gas of carbon dioxide and hydrogen.
In Article 8,
A parallel structure chemical vapor deposition system for producing nano-carbon materials and hydrogen from carbon dioxide, characterized in that it further includes a control unit for controlling the type or amount of gas delivered from the gas supply unit to the pre-reaction unit and controlling the temperature of each of the pre-heating unit and the post-heating unit.
In the method for producing nanocarbon materials and hydrogen using a parallel structure chemical vapor deposition system for producing nanocarbon materials and hydrogen from carbon dioxide of Article 5,
A first step in which a gas mixed with carbon dioxide and hydrogen is injected into the shear reaction unit by the gas supply unit;
A second step in which the gas reacts with the primary catalyst formed inside the shear reaction section to generate a primary reaction product inside the shear reaction section;
A third step in which the gaseous product among the first reaction products is transferred to the gas mixing unit through the first gas transfer pipe, and the liquid product among the first reaction products is transferred to the water collection unit by a valve connected to the first reaction product transfer unit;
A fourth step in which each substance in the above generated gas is stirred in the gas mixing unit;
A fifth step in which the first reaction product passing through the gas mixing section is transferred to the subsequent reaction section through the second gas transfer pipe;
A sixth step in which the secondary catalyst formed inside the above-mentioned post-reaction section reacts with the above-mentioned primary reaction product to produce nano-carbon material and hydrogen; and
A nano-carbon material and hydrogen production method, characterized by including a seventh step in which the hydrogen is discharged to the top of the rear reaction section.