KR20180117951A - Apparatus and method for producing high purity hydrogen and carbon monoxide using methane pyrolysis with liquid metal - Google Patents

Abstract

The present invention relates to a device and a method for pyrolyzing methane and generating high purity hydrogen and carbon monoxide using liquid metals, and more specifically, to a device and a method for pyrolyzing methane and generating high purity hydrogen and carbon monoxide using liquid metals, which uses carbons generated in a pyrolysis of methane to generate carbon monoxide. For a device for pyrolyzing methane and generating high purity hydrogen and carbon monoxide using liquid metals, which is applied to a pyrolysis apparatus, a configuration of the present invention comprises: a methane pyrolysis furnace in which melted liquid metals are accommodated; a methane supplying unit which supplies methane (CH_4) to the methane pyrolysis furnace; a first oxygen injecting unit which supplies oxygen to the methane pyrolysis furnace; a carbon recovery passage which accommodates carbon generated when the liquid metals are reacted with methane; and an oxidizing agent injecting unit which supplies oxygen to the carbon recovery passage. According to the device for pyrolyzing methane and generating high purity hydrogen and carbon monoxide using liquid metals, the carbon and the oxygen are reacted in the carbon recovery passage and, therefore, carbon monoxide (CO) is extracted.

Description

FIELD OF THE INVENTION [0001] The present invention relates to an apparatus and a method for producing methane pyrolysis and high purity hydrogen and carbon monoxide using liquid metal,

The present invention relates to an apparatus and a method for producing methane pyrolysis and high purity hydrogen and carbon monoxide using liquid metal, and more particularly, to a method and apparatus for producing hydrogen by pyrolyzing methane by using a high temperature liquid metal, And a method and apparatus for producing high purity hydrogen and carbon monoxide using liquid metal for producing methane.

As the demand for high-efficiency fuel cells increases along with the solution of carbon dioxide emissions caused by the use of hydrocarbon fuels, it is becoming more important to secure economical hydrogen production technology. In addition, high purity carbon monoxide is a raw material for a variety of chemical substances including acetic acid, and the demand thereof is greatly increasing recently. In the meantime, hydrogen and carbon monoxide are produced by pyrolysis of natural gas or petroleum gas, or gasification of coal, biomass, etc. to produce high purity hydrogen or carbon monoxide from a plurality of gases including hydrogen and carbon monoxide It is common to utilize gas separation techniques, including membranes, adsorbents, and the like.

Recently, hydrogen production technology through direct pyrolysis of methane has been proposed. However, when the catalyst is used, there is difficulty in continuous operation due to deposition problem due to solid carbon generated during methane pyrolysis.

In order to solve this problem, it is possible to consider using liquid metal, molten salt, etc. having high fluidity at high temperature as a thermal decomposition medium. In this case, hydrogen generated in the pyrolysis process of methane is captured by the vapor without separate separation device, Hydrogen production can be achieved without the use of carbon, and the use of carbon generated in the solid phase can greatly improve the overall economy of the system.

Therefore, there is a need for methane pyrolysis and product utilization methods that can maximize the economic efficiency through the technology of producing hydrogen by reforming methane using liquid metal and producing high purity carbon monoxide using by-product carbon.

Korean Registered Patent No. 1165453 (July 6, 2012)

It is an object of the present invention to solve the above problems, and an object of the present invention is to provide a process for producing hydrogen from pyrolysis of methane, and a method for producing methane pyrolysis and high purity hydrogen / carbon monoxide using liquid metal for producing high purity carbon monoxide And a method thereof.

It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory and are not intended to limit the invention to the precise form disclosed. There will be.

According to an aspect of the present invention, there is provided a methane pyrolysis furnace in which molten liquid metal is accommodated; Methane supply section for supplying a methane (CH ₄₎ to said methane pyrolysis; A carbon recovery furnace for containing carbon and liquid metal produced by pyrolyzing methane by the liquid metal; And an oxidant injector for supplying oxygen (O ₂ ) or carbon dioxide (CO ₂ ) to the carbon recovery furnace, wherein carbon is reacted with oxygen in the carbon recovery furnace to extract carbon monoxide (CO) It provides pyrolysis methane and high purity hydrogen and carbon monoxide production equipment using liquid metal.

In the embodiment of the present invention, the methane pyrolysis furnace may be characterized in that the molten liquid metal is heated by heating to a melting point or more.

In an embodiment of the present invention, the hydrogen storage unit may further include a hydrogen storage unit provided in the methane thermal decomposition furnace, wherein the hydrogen storage unit stores high purity hydrogen (H ₂ ) produced by pyrolyzing the methane in the methane pyrolysis furnace .

In an embodiment of the present invention, the methane supply unit may further supply the methane pyrolysis furnace to the methane pyrolysis furnace by receiving a predetermined amount of the high-purity hydrogen (H2) transferred toward the hydrogen storage unit.

According to an embodiment of the present invention, the carbon recovery path includes a filter provided on the upper side of the oxidant injection unit, and the filter is provided so as to pass only the carbon-removed liquid metal in the carbon recovery path .

In an embodiment of the present invention, the apparatus may further include a carbon monoxide storage unit for storing extracted carbon monoxide by reacting the carbon with oxygen in the carbon recovery furnace.

In the embodiment of the present invention, the carbon recovery furnace is characterized in that oxygen is injected by the oxidant injector in a state in which the temperature of the liquid metal is controlled to the oxidation-free temperature of the liquid metal itself .

In an embodiment of the present invention, the apparatus may further comprise a transfer pipe for transferring the liquid metal in the methane thermal decomposition furnace and the carbon in the solid phase to the carbon recovery furnace.

In one embodiment of the present invention, the apparatus may further include a recovery unit for providing a metal oxide generated by the reaction of the liquid metal and oxygen in the carbon recovery furnace to the methane pyrolysis furnace, wherein the metal oxide is methane, And is reduced by carbon and hydrogen.

According to an aspect of the present invention, there is provided a method for producing methane pyrolysis and high purity hydrogen / carbon monoxide production equipment using liquid metal, which is applied to a pyrolysis apparatus, comprising the steps of: a) providing molten liquid metal in a methane pyrolysis furnace step; b) pyrolyzing the methane by supplying methane to the methane pyrolysis furnace; c) discharging carbon generated by the reaction of the liquid metal and the methane to a carbon recovery furnace; And d) injecting oxygen or carbon dioxide into the carbon recovery furnace to react the discharged carbon with the oxygen. In the step d), the carbon reacts with the oxygen to extract carbon monoxide. The present invention provides a method for producing methane pyrolysis and high purity hydrogen and carbon monoxide production equipment using liquid metal.

In the embodiment of the present invention, in the step a), the methane thermal decomposition furnace may be heated to a melting point or more to house the molten liquid metal.

In the embodiment of the present invention, in step b), the methane is thermally decomposed into high purity hydrogen and carbon, and the high purity hydrogen is stored in the hydrogen storage part.

In an embodiment of the present invention, the method further comprises: after step d), e) providing metal oxide produced by the reaction of oxygen with the liquid metal in the carbon recovery furnace to the methane pyrolysis furnace to reduce it . ≪ / RTI >

In the embodiment of the present invention, in the step (e), high purity hydrogen in an amount necessary for reducing the metal oxide in the high purity hydrogen transferred toward the hydrogen storage part is supplied to the methane thermal decomposition furnace .

According to an embodiment of the present invention, in the step d), the oxygen is injected into the carbon recovery furnace while the temperature of the liquid metal is controlled to the non-oxidizing temperature.

In order to achieve the above object, the present invention provides a pyrolysis apparatus using methane pyrolysis and high purity hydrogen / carbon monoxide production apparatus using liquid metal.

In order to achieve the above object, the present invention provides a pyrolysis apparatus using methane pyrolysis using liquid metal and a production method of high purity hydrogen / carbon monoxide production apparatus.

The effect of the present invention according to the above configuration can produce hydrogen and carbon monoxide of high purity. Specifically, the present invention can provide high purity carbon monoxide by forming a liquid metal having a large heat capacity and a large heat transfer coefficient as a heating medium and more effectively forming pyrolysis conditions at a relatively low temperature, and at the same time, Carbon monoxide can be produced. Accordingly, the present invention has higher energy efficiency, solves the problem of carbon deposition, and can produce high purity carbon monoxide without discharging carbon dioxide, compared with conventional hydrocarbon pyrolysis processes.

Further, the present invention is economical because the metal oxide is reduced and reused through the recovery unit.

It should be understood that the effects of the present invention are not limited to the above effects and include all effects that can be deduced from the detailed description of the present invention or the configuration of the invention described in the claims.

FIG. 1 is an exemplary view showing a configuration of a pyrolysis methane pyrolysis and high purity hydrogen / carbon monoxide production apparatus using liquid metal according to an embodiment of the present invention.
FIG. 2 is a flowchart of a method for producing methane pyrolysis and high purity hydrogen / carbon monoxide production apparatus using liquid metal according to an embodiment of the present invention.
3 is an illustration of an apparatus for flowing liquid metal for high temperature corrosion prevention according to an embodiment of the present invention.
FIG. 4 is an exemplary view showing the inside of a flow pipe of liquid metal for preventing high-temperature corrosion according to an embodiment of the present invention.
5 is a flow chart of a method of operating a liquid metal flow apparatus for high temperature corrosion prevention according to an embodiment of the present invention.
FIG. 6 is a flowchart of steps of controlling a heat exchanger of a method for operating a liquid metal flow apparatus for preventing high-temperature corrosion according to an embodiment of the present invention.
7 is an illustration of an apparatus for flowing liquid metal for high temperature corrosion prevention according to another embodiment of the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described with reference to the accompanying drawings. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. In order to clearly illustrate the present invention, parts not related to the description are omitted, and similar parts are denoted by like reference characters throughout the specification.

Throughout the specification, when a part is referred to as being "connected" (connected, connected, coupled) with another part, it is not only the case where it is "directly connected" "Is included. Also, when an element is referred to as "comprising ", it means that it can include other elements, not excluding other elements unless specifically stated otherwise.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In this specification, the terms "comprises" or "having" and the like refer to the presence of stated features, integers, steps, operations, elements, components, or combinations thereof, But do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, or combinations thereof.

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

FIG. 1 is a view showing a configuration of a carbon monoxide production device using a liquid metal M according to an embodiment of the present invention.

1, the carbon monoxide production apparatus 1 using the liquid metal M includes a heating furnace 10, a methane thermal decomposition furnace 20, a methane supply section 30, a hydrogen storage section 40, A carbon recovery chamber 60, an oxidant injection unit 70, a carbon monoxide storage unit 80, and a recovery unit 90.

The heating furnace 10 heats and melts more than the melting point of the metal to produce a liquid metal M, and receives the generated liquid metal M.

The methane pyrolysis furnace 20 can receive and receive the melted liquid metal M from the heating furnace 10. Here, the liquid metal M may be tin (Sn). However, the kind of the liquid metal (M) is not limited to the tin (Sn). The methane pyrolysis furnace 20 may be provided below the heating furnace 10.

The methane pyrolysis furnace 20 may be provided through the flow apparatus 100 of the liquid metal M for preventing high temperature corrosion when the liquid metal M is supplied from the heating furnace 10. The flow apparatus 100 of the liquid metal M for preventing high temperature corrosion includes a flow pipe 110 and a heat exchange unit 120. A detailed description of the apparatus 100 for flowing the liquid metal M for preventing the high temperature corrosion will be described later with reference to Figs. 3 to 7.

The methane supply unit 30 can supply methane (CH ₄ , 31) and high purity hydrogen to the methane pyrolysis furnace 20. At this time, the methane supply unit 30 can supply the high-purity hydrogen to the methane pyrolysis furnace 20 by receiving a predetermined amount of the high-purity hydrogen that is transported toward the hydrogen storage unit 40.

The methane 31 supplied to the methane pyrolysis furnace 20 by the methane supply unit 30 can be pyrolyzed by the heat of the molten liquid metal M. Specifically, the methane 31 is pyrolyzed by the liquid metal M and can be separated into high purity hydrogen (H ₂ ) and carbon (C 32). At this time, the carbon 32 may be in a solid state. That is, the main reaction occurring in the methane pyrolysis furnace 20 is as follows.

CH ₄ - > C + 2H ₂

The high purity hydrogen generated by pyrolysis can be stored in the hydrogen storage part 40 coupled to one side of the methane pyrolysis furnace 20. [ At this time, the hydrogen of high purity transferred toward the hydrogen storage part 40 can pass through the first moisture condenser 45. The first moisture condenser 45 can collect and remove water vapor so that the water vapor generated in the high temperature methane pyrolysis furnace 20 is not transferred to the hydrogen storage unit 40 together with the high purity hydrogen. That is, only the pure hydrogen of high purity can be stored in the hydrogen storage unit 40.

The carbon recovery passage 60 can receive the carbon 32 generated by pyrolyzing the methane 31 by the liquid metal M from the methane pyrolysis furnace 20. For this purpose, a transfer pipe 50 may be provided between the methane pyrolysis furnace 20 and the carbon recovery furnace 60.

The transfer pipe 50 may be provided to transfer the liquid metal M and the carbon 32 in a solid phase to the carbon recovery furnace 60. The carbon hydride May be connected at a position lower than the level of the liquid metal (M) contained in the furnace (20).

The oxidant injector 70 may supply oxygen to the carbon recovery furnace 60. More specifically, the oxidant injector 70 oxidizes the carbon 32 to oxygen (O2) Or carbon dioxide (CO ₂ ) to the carbon recovery furnace 60. The supplied oxygen may react with the carbon 32 to generate carbon monoxide.

The oxidizing agent injecting unit 70 injects oxygen by the oxidizing agent injecting unit 70 while the temperature in the carbon recovery furnace 60 is controlled to a temperature at which the liquid metal M is not oxidized May be provided. In one example, if the liquid metal (M) is tin, the tin is oxidized above 550 degrees. Accordingly, when the liquid metal M is tin, the oxygen can be injected while the temperature of the liquid metal M is controlled to be less than 550 degrees.

That is, when oxygen is injected into the oxidant injecting unit 70, the main reaction occurring in the carbon recovery furnace 60 is as follows.

C + O ₂ -> CO

In addition, when carbon dioxide is injected into the oxidizing agent injecting unit 70 to generate carbon monoxide, a Bouduard reaction for generating carbon monoxide through the reaction of carbon and carbon dioxide is used. At this time, since the carbon dioxide has a higher reaction with carbon than tin, the temperature of the liquid metal M may be higher than the oxidation-occurring temperature to promote the puddle reaction.

Particularly, in the case of a general char or carbon, the temperature, the diffusion of the reaction gas into the interior of the vehicle, and the diffusion of the generated carbon monoxide gas to the outside, in accordance with the size of the vehicle and the conditions of the pore during the carbon dioxide gasification reaction The reaction rate depends on the reaction rate. However, as in the present invention, in the case of the carbon 32 produced by pyrolysis of the methane 31 in the course of pyrolysis of the liquid metal, it has a surface area maximized with atomic fine carbon. Therefore, the carbon 32 is very small in size compared to a general char, and is free from the influence of diffusion, has excellent reactivity with oxygen and carbon monoxide, and has an advantage that the reactivity is greatly increased in proportion to the temperature. Therefore, in the case of generating carbon monoxide by using carbon dioxide, it is effective to heat the temperature of the liquid metal (M) to the oxidation-generation temperature or higher because there is almost no possibility of oxidation. For example, when the liquid metal M is tin, the temperature of the liquid metal M can be controlled to be higher than 1000 degrees because it has excellent reactivity at 1000 degrees or more.

That is, when carbon dioxide is injected into the oxidant injector 70, the main reaction occurring in the carbon recovery furnace 60 is as follows.

C + CO ₂ - > 2CO

Meanwhile, the carbon recovery furnace 60 includes a filter 65 provided on the oxidant injection unit 70. The filter 65 is provided to pass only the liquid metal M from which the carbon has been removed in the carbon recovery furnace 60. Here, the filter 65 may be made of a metal or a ceramic material, but the material of the filter 65 is not limited thereto.

The oxidant injector 70 and the filter 65 may be physically separated from each other by pressure generated when oxygen or carbon dioxide is injected into the solid carbon 32 flowing into the carbon recovery furnace 60 have. At the same time, the carbon 32 reacts with the oxygen or the carbon dioxide to generate carbon monoxide. The liquid metal M from which the carbon 32 has been removed at a position adjacent to the filter 65 can be moved toward the heating furnace 10 through the filter 65. [

The carbon monoxide storage unit 80 may be coupled to the carbon recovery channel 60 to store the extracted carbon monoxide by reacting the carbon 32 with oxygen in the carbon recovery channel 60. At this time, the high-purity carbon monoxide transported toward the carbon monoxide storage unit 80 can pass through the second moisture condenser 85. The second moisture condenser 85 can collect and remove water vapor so that water vapor generated in the high temperature carbon recovery furnace 60 is not transferred to the carbon monoxide storage unit 80 together with the high purity carbon monoxide. That is, only the carbon monoxide of pure high purity can be stored in the carbon monoxide storage unit 80.

Some of the high-purity carbon monoxide transferred to the carbon monoxide storage unit 80 is transferred to the oxidant injection unit 70 by a predetermined amount and is re-injected into the carbon recovery furnace 60 in the form of carbon dioxide It is possible.

The recovery unit 90 may provide the methane pyrolysis furnace 20 with a metal oxide generated by the reaction of the liquid metal M and oxygen in the carbon recovery furnace 60. The metal oxide may be reduced by methane, carbon, and hydrogen in the methane pyrolysis furnace 20.

For example, the carbon 32 can generate oxidant 1 tin (SnO 2) and oxidant 2 tin (SnO ₂ ) through the oxidation reaction of the liquid metal (M) and the oxygen. The recovery unit 90 may be coupled to one side of the carbon recovery path 60 to receive the tin oxidant and the tin oxidant 2 generated in the carbon recovery furnace 60. The recovering unit 90 may transfer the provided tin oxide and tin 2 oxidant to the methane pyrolysis furnace 20 so as to be reduced in the methane pyrolysis furnace 20.

Thus, the recovery unit 90 may provide the pure liquid metal M again to the heating furnace 10, and the metal oxide may be reduced in the methane pyrolysis furnace 20. As described above, the recovery unit 90 is economical because it is provided for recycling the liquid metal.

The apparatus 1 for producing methane pyrolysis and high-purity hydrogen and carbon monoxide using the liquid metal as described above is characterized in that the liquid metal (M) having a large heat capacity and a large heat transfer coefficient is used as a heating medium and more effective pyrolysis conditions To produce high purity carbon monoxide. At the same time, it is possible to produce high purity carbon monoxide by reacting carbon produced in the solid phase with oxygen. Accordingly, the present invention has the effect of producing energy-efficient, high-purity carbon monoxide without the emission of carbon dioxide as compared with conventional hydrocarbon pyrolysis processes.

Further, in the methane pyrolysis furnace 20 and the carbon recovery furnace 60 of the present invention, a solid catalyst may be used if necessary. At this time, since the present invention is accommodated in the liquid metal (M), there is an advantage that the carbon (32) is not deposited on the surface of the solid catalyst.

The carbon monoxide production apparatus 1 using the liquid metal M prepared as described above can be applied to a pyrolysis apparatus.

2 is a flowchart of a production method of a carbon monoxide production apparatus using a liquid metal (M) according to an embodiment of the present invention.

Hereinafter, a production method of the carbon monoxide production device using the liquid metal (M) will be described with reference to FIG. 1 and FIG.

The production method of the carbon monoxide production device using the liquid metal M may firstly perform the step S10 of providing the molten liquid metal M to the methane pyrolysis furnace 20.

The methane pyrolysis furnace 20 is heated to a temperature higher than the melting point of the methane pyrolysis furnace 10 in the step of providing molten liquid metal M to the methane pyrolysis furnace 20, (M). At this time, the melted liquid metal M may be molten tin, but is not limited thereto.

Next, the methane 31 may be supplied to the methane pyrolysis furnace 20 to perform pyrolysis (S20). The methane 31 is pyrolyzed into the high purity hydrogen and the solid carbon 32 in the step of supplying methane to the methane pyrolysis furnace 20 and pyrolyzing the pyrolysis step S20, ). ≪ / RTI >

Next, the carbon 32 generated by the reaction of the liquid metal M and the methane 31 may be discharged to the carbon recovery furnace 60 (S30). The methane 31 is pyrolyzed with hydrogen and carbon in a step S30 of discharging the carbon 32 generated by the reaction of the liquid metal M and the methane 31 to the carbon recovery furnace 60, The hydrogen is stored in the hydrogen storage part 40 and the carbon 32 and the liquid metal M are transferred to the carbon recovery path 60 by the transfer pipe 50. At this time, the transfer pipe 50 for discharging the carbon 32 toward the carbon recovery furnace 60 may be made of stainless steel or a ceramic material. However, the material of the transfer pipe 50 is not limited thereto, and includes all materials that do not cause corrosion even in a high temperature environment. For example, it may be made of molybdenum.

Next, oxygen or carbon dioxide may be injected into the carbon recovery furnace 60 to react the discharged carbon 32 with the oxygen (S40). Specifically, when oxygen or carbon dioxide is injected into the carbon recovery furnace 60 using the oxidant injector 70, the carbon 32 reacts with the oxygen to extract carbon monoxide. The extracted high-purity carbon monoxide can be stored in the carbon monoxide storage unit 80. At this time, in the step S40 of injecting oxygen or carbon dioxide into the carbon recovery furnace 60 and reacting the discharged carbon 32 with the oxygen, the oxygen oxidizes the temperature of the liquid metal M Can be injected into the carbon recovery furnace (60) while being controlled at an undeveloped temperature.

As described above, the produced carbon monoxide can also separate carbon through a reduction reaction. The high purity hydrogen produced in the hydrogen storage unit 40 and the high purity carbon monoxide stored in the carbon monoxide storage unit 80 can be utilized in a hydrogen-related industry such as a fuel cell, refinery and fuel reforming, and a chemical manufacturing industry. .

Next, the metal oxide produced by the reaction of the liquid metal M with oxygen in the carbon recovery furnace 60 may be provided to the methane pyrolysis furnace 20 and reduced (S50) . Specifically, the recovery unit 90 may receive the metal oxide generated by oxidation of some oxygen and liquid metal, and may transfer the metal oxide to the methane pyrolysis furnace 20.

The methane supply unit 30 supplies the high purity hydrogen required for reducing the metal oxide transferred to the methane pyrolysis furnace 20 from the hydrogen storage unit 40 to the methane pyrolysis furnace 20 have. The high-purity hydrogen supplied in this way can reduce the metal oxide as a reducing agent.

For example, the recovery unit 90 is provided with the tin oxidant and the tin oxidant produced in the carbon recovery furnace 60, and provides the provided tin oxidant and tin oxidant to the methane pyrolysis furnace 20 can do. In the methane pyrolysis furnace 20, the tin oxidant and the tin oxidant can be separated into tin and oxygen through a reduction reaction.

As described above, the recovery unit 90 is economical because it is provided for recycling the liquid metal.

The above-described production method of methane pyrolysis and high purity hydrogen and carbon monoxide production equipment using liquid metal can be applied to a pyrolysis apparatus.

3 is an illustration of an apparatus for flowing liquid metal M for high temperature corrosion prevention according to an embodiment of the present invention.

3, the apparatus 100 for flowing liquid metal M for high temperature corrosion prevention according to an embodiment of the present invention includes a flow pipe 110 and a heat exchanging unit 120. As shown in FIG.

The flow tube 110 may be provided in one or more of the hollow tubes 110, and may be hollowed to allow the hot liquid metal M to pass therethrough.

The flow tube 110 may be configured to transfer the molten liquid metal from the heating furnace 10 coupled to one side to the methane pyrolysis furnace 20 coupled to the other side. Here, the liquid metal may be tin (Sn) or molten salt, and may be heated to a temperature higher than the high temperature corrosion inducing temperature in the heating furnace 10. However, the liquid metal is not limited to tin (Sn).

The flow pipe 110 may be formed of stainless steel, ceramic, molybdenum, tungsten, or the like, which is coated with a ceramic, and is prevented from being corroded by the liquid metal at a high temperature . At this time, the material of the flow pipe 110 is not limited thereto, and any material that does not cause corrosion by the high temperature liquid metal may be included in one embodiment.

The flow tubes 110 according to one embodiment may have different diameters when they are provided in two or more. Although the number of the flow tubes 110 is three in FIG. 1, the number of the flow tubes 110 is not limited thereto.

The heat exchanger 120 is coupled to the flow pipe 110 and can control the flow rate of the liquid metal passing through the flow pipe 110. In detail, the heat exchanging unit 120 according to an embodiment may be provided in the same number as the number of the flow tubes 110 and may be coupled to each of the flow tubes 110, The flow rate of the liquid metal can be individually controlled.

The heat exchanging unit 120 may heat the liquid metal to a temperature higher than the melting point, or may quench to a temperature below the melting point to stop the flow to control the flow rate. For example, when the liquid metal is tin (Sn), the melting point is 232 ° C. Accordingly, the heat exchanging unit 120 may heat the liquid metal passing through the flow pipe 110 to a temperature of 232 ° C. or higher to pass through the flow pipe 110, and conversely, The liquid metal can be rapidly cooled to less than 232 DEG C so as not to pass through the flow pipe 110. [

Since the viscosity of the liquid metal changes with temperature, it is possible to control the flow rate by using it.

The heat exchanging unit 120 may be provided as a thermoelectric element that can heat and cool the liquid metal. However, the heat exchanging unit 120 is not limited to the thermoelectric elements, and includes both a structure capable of heating and quenching the liquid metal. For example, the heat exchanging part 120 may be provided with a structure for rapidly cooling by supplying hot oil at a high temperature of 300 ° C and liquid nitrogen.

In addition, the methane pyrolysis furnace 20 may be provided with a remaining amount measuring sensor (not shown) so as to confirm the remaining capacity in terms of volume or weight, and the heat exchanging unit 120 may further include a control unit.

The remaining amount measuring sensor measures the remaining capacity of the methane pyrolysis furnace 20 and provides the remaining capacity to the control unit. The control unit controls the flow rate of the flow pipe 110 based on the remaining capacity of the methane pyrolysis furnace 20 The flow rate of the liquid metal to be passed through can be set. The control unit may control the heat exchanging unit 120 to pass the flow rate of the liquid metal set through the flow pipe 110.

FIG. 4 is an exemplary view showing the inside of a flow pipe of liquid metal for preventing high-temperature corrosion according to an embodiment of the present invention. 4 (a) shows the flow tube provided with the first heat conductive fins, and Fig. 4 (b) shows the flow tube provided with the second heat conductive fins.

4 (a), the first heat transfer fin 114 is provided inside the flow pipe 110 and extends from the inner surface of the flow pipe 110 toward the center of the flow pipe 110 May be provided in the form of a baffle. The first heat conductive fins 114 may be provided in at least one circumferential direction of the inner surface of the flow pipe 110. In FIG. 4 (a), the number of the first heat conductive fins 114 is eight, but the present invention is not limited thereto.

When the diameter of the flow pipe 110 is large, the first heat transfer fin 114 may be more thermally transferred to the liquid metal located on the inner center side of the flow pipe 110. Specifically, since the distance from the heat exchanging unit 120 to the liquid metal located on the inner center side of the flow pipe 110 increases, the heat exchange can not be smoothly performed compared with the liquid metal adjacent to the inner side face of the flow pipe 110 have. Therefore, the first heat conductive fin 114 can heat-exchange smoothly to the liquid metal located on the center side of the flow tube 110, thereby improving the heat efficiency.

Next, referring to FIG. 4 (b), the second heat conductive fin 115 is provided inside the flow tube 110 and may be provided in a honeycomb form. The second heat transfer fin 115 can be heat exchanged smoothly to the inner center side of the flow pipe 110 even when the flow pipe 110 has a large diameter. The second heat conductive fins 115 may be used when the diameter of the flowtube 110 is large so that the first heat conductive fins 114 may be bent or deformed. Specifically, the length of the first heat conductive fins 115 becomes longer as the diameter of the flow tube becomes larger, and at this time, the slenderness ratio is increased, so that the first heat conductive fins 115 may be bent or deformed by the flow of the liquid metal. In this case, the second heat conductive fins 115 may be provided in the flow tube 110 to improve stability.

A concrete operation method of the liquid metal (M) flow apparatus 100 for preventing high temperature corrosion as described above will be described with reference to the following drawings.

5 is a flow chart of a method of operating a flow apparatus for liquid metal M for high temperature corrosion prevention according to an embodiment of the present invention.

3 to 5, a method of operating a liquid metal (M) flow apparatus 100 for preventing high temperature corrosion applied to a pyrolysis apparatus is characterized in that the flow rate of the liquid metal M to be passed through the flow pipe 110 (S120) of controlling the heat exchanging unit 120 to correspond to the set flow rate of the liquid metal M and controlling the liquid metal M (M) set by the controlled heat exchanging unit 120 Is transmitted through the flow pipe 110 (S130).

The step S110 of setting the flow rate of the liquid metal to be passed through the flow pipe 110 requires maintaining the amount of the liquid metal in the heating furnace 10 constant or the flow rate of the liquid transferred by the flow pipe 110 And is set in real time in order to make the methane pyrolysis furnace 20 in which the metal is accommodated to accommodate the remaining capacity that can be accommodated. Specifically, when the amount of the liquid metal that is larger than the capacity that can be accommodated in the methane pyrolysis furnace 20 is transferred, mechanical failure occurs in the methane pyrolysis furnace 20 due to unacceptability, Problems can arise. Therefore, it is preferable that the flow rate of the liquid metal is set according to the remaining capacity that the methane pyrolysis furnace 20 can accommodate.

A control unit is provided in the heat exchanging unit 120, and a residual amount measuring sensor may be provided in the methane pyrolysis furnace 20. The remaining amount measuring sensor may transmit the remaining capacity of the methane thermal decomposition furnace 20 to the control unit of the heat exchanging unit 120 in real time. The control unit receives the remaining capacity information of the methane pyrolysis furnace 20 and can calculate and set the flow rate of the liquid metal M to pass through the flow pipe 110.

The temperature information of the liquid metal to be controlled together with the remaining amount measuring sensor is also very important for the flow control. As the flow rate of the liquid metal passing through the flow tube 110 is controlled through the temperature of the liquid metal, temperature information of the liquid metal is provided to the control unit to control the desired flow rate. The control unit can control the flow rate by using the amount of liquid metal and the temperature information of the heating furnace 10. [

6 is a flowchart of steps of controlling the heat exchanger of the method of operating the flow apparatus of liquid metal M for high temperature corrosion prevention according to an embodiment of the present invention.

3 to 6, after the step S110 of setting the flow rate of the liquid metal M to be passed through the flow pipe 110, the flow rate of the liquid metal M, which corresponds to the set flow rate of the liquid metal M, (S120) of controlling the display unit 120 according to the present invention.

The step S120 of controlling the heat exchange unit 120 to correspond to the set flow rate of the liquid metal may include selecting the flow pipe 110 corresponding to the set flow rate of the liquid metal S121, (S122) heating the liquid metal passing through the flow tube (110) and cooling the liquid metal passing through the non-selected flow tube (110).

Before describing the step S121 of selecting the flow tube 110 to correspond to the set flow rate of the liquid metal, the flow tube 110 of FIG. 1 has a first flow tube 111, A second flow pipe 112 and a third flow pipe 113. The heat exchange unit 120 includes a first heat exchange unit 121, a second heat exchange unit 122, and a third heat exchange unit 123 .

The first heat exchanging unit 121 is coupled to the first flow tube 111. The second heat exchanging unit 122 is coupled to the second flow tube 112. The third heat exchanging unit 123, is the first combined with three flow tube 113 may be individually controllable, the flow rate of the flow rate of 1m ³ / sec, the second flow tube 112 of the first flow tube 111 is 2m ³ / sec and the third It is assumed that the flow rate of the flow tube 113 is ³ m ³ / sec.

When the flow rate set in the previous step is 6 m ³ / sec, the apparatus 100 for preventing liquid metal for high temperature corrosion is provided with the first flow pipe 111, the second flow pipe 112, (113) are all selected. In addition, when the flow rate set in the previous step is 5 m ³ / sec, the second flow pipe 112 and the third flow pipe 113 can be selected. The number and the flow rate of the flow tubes 110 and the number of the heat exchanging units 120 are not limited to those described in the above embodiments, but are for illustrative purposes only.

In the step S121 of selecting the flow pipe 110 to correspond to the set flow rate of the liquid metal, the flow pipe 110 through which the liquid metal will pass may be selected according to the flow rate set in the previous step.

After the step S121 of selecting the flow tube 110 to correspond to the set flow rate of the liquid metal, the liquid metal passing through the selected flow tube 110 is heated and passes through the non-selected flow tube 110 The liquid metal may be cooled (S122). Wherein the heat exchanging part (120) is configured to heat the liquid metal passing through the selected flow tube (110) and to cool the liquid metal passing through the non-selected flow pipe (110) The liquid metal passing through the non-selected flow pipe 110 is heated to a temperature not lower than the melting point, and the liquid metal passing through the non-selected flow pipe 110 is cooled to a temperature lower than the melting point.

For example, when the set flow rate is ³ m ³ / sec, the step S 121 of selecting the flow pipe 110 corresponding to the set flow rate of the liquid metal selects the first flow pipe 111 and the second flow pipe 112 . Accordingly, the step S122 of heating the liquid metal passing through the selected flow tube 110 and cooling the liquid metal passing through the non-selected flow tube 110 may be performed by the selected first flow tube 111 and / The liquid metal passing through the second flow tube 112 may be heated to a melting point or more so that the liquid metal can pass through the second flow tube 112.

Conversely, the liquid metal M passing through the unselected third flow tube 113 may be quenched below the melting point to prevent it from flowing. The liquid metal (M) flow device 100 for such controlled high temperature corrosion prevention is configured to allow the liquid metal (M) to pass through only the first flow tube (111) and the second flow tube The flow rate of ³ m ³ / sec can be transferred.

In addition, in the step S122 in which the liquid metal passing through the selected flow pipe 110 is heated and the liquid metal passing through the non-selected flow pipe 110 is cooled, the heat exchange unit 120, In order to adjust the flow rate of the liquid metal passing through the selected flow tube 110, the viscosity of the liquid metal may be controlled by changing the temperature of the liquid metal.

The flow rate of the liquid metal M set by the controlled heat exchanging unit 120 is controlled by the flow control unit 120 after the step S120 of controlling the heat exchange unit 120 to correspond to the set flow rate of the liquid metal M, (S130), which is transmitted through the wireless communication unit 110.

The operation method of the flow apparatus 100 of the liquid metal M for preventing the high temperature corrosion applied to the above-described pyrolysis apparatus can be sequentially and repeatedly performed in real time.

According to the present invention as described above, the plurality of flow tubes 110 can be simultaneously controlled by using the heat exchanging unit 120. Specifically, the conventional technique can not control the flow rate using the valve when the diameter of the pipe exceeds a certain size. Therefore, conventionally, a plurality of pipes are provided, valves are provided for each, and the flow rate is individually controlled. However, when such a valve is provided, there is a problem that it is impossible to open and close the valves of all the pipes at the same time. However, according to the present invention, it is possible to simultaneously control a plurality of the flow tubes 110 by using the heat exchanging unit 120.

In addition, the flow tube 110 of the present invention can be manufactured using a low-cost corrosion-resistant material such as a ceramic coating metal or a ceramic, and can be fabricated using a simple structure and at least a high-cost material having a high corrosion resistance such as molybdenum and tungsten And the flow of the liquid metal is economical because it is controlled by using the heat exchanging unit 120. [

In addition, the present invention includes the flow tubes 110 having different diameters, and selectively controls the passage of the liquid metal in each of the flow tubes 110 according to the set flow rate, so that the flow rate can be precisely controlled in real time have. Further, even in the case of a tube having the same diameter, the present invention can control the flow rate by using the change of the viscosity according to the temperature of the liquid metal, so that more accurate and continuous flow rate control is possible.

Further, the present invention is excellent in airtightness. Specifically, in the related art, the hermetic member is damaged by the high-temperature liquid metal (M) between the valve and the flow tube to degrade airtightness. However, the present invention is not provided with a hermetic member, (M) is cooled to a temperature less than the melting point so as to control the flow, thereby preventing leakage of water.

The flow apparatus 100 of the liquid metal M for preventing the high temperature corrosion and the method of operating the apparatus 100 may be applied to the pyrolysis apparatus.

7 is an illustration of an apparatus for flowing liquid metal M for high temperature corrosion prevention according to another embodiment of the present invention.

As shown in FIG. 7, a flow apparatus 200 for liquid metal M for high temperature corrosion prevention according to another embodiment includes a flow pipe 210 and a heat exchange unit 220.

In Fig. 7, the plurality of flow tubes 210 are shown to have the same diameter, but it is also possible to have different diameters.

The heat exchanging unit 220 may be configured to enclose at least one of the flow tubes 210 so as to simultaneously control the flow rate of the liquid metal M passing through the one or more flow tubes 210 . The heat exchanger 220 may control all of the flow tubes 210 in the same manner and may be applicable when precise flow control is not required by controlling the flow tubes 210 individually.

The apparatus 200 for the liquid metal M for preventing high temperature corrosion according to another embodiment comprises the apparatus 100 for the liquid metal M for preventing high temperature corrosion according to an embodiment and the heat exchanging unit 220 ) Is the same as the technical configuration except for the features of FIG. Therefore, overlapping description will be omitted below.

The flow apparatus 200 for liquid metal M for preventing high-temperature corrosion according to another embodiment may also be applied to the pyrolysis apparatus.

It will be understood by those skilled in the art that the foregoing description of the present invention is for illustrative purposes only and that those of ordinary skill in the art can readily understand that various changes and modifications may be made without departing from the spirit or essential characteristics of the present invention. will be. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive. For example, each component described as a single entity may be distributed and implemented, and components described as being distributed may also be implemented in a combined form.

The scope of the present invention is defined by the appended claims, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be construed as being included within the scope of the present invention.

1: Methane pyrolysis and high purity hydrogen and carbon monoxide production equipment using liquid metal
10: heating furnace 20: methane pyrolysis furnace
30: methane supply part 31: methane
32: carbon 45: first moisture condenser
40: hydrogen storage part 50: transfer pipe
60: Carbon recovery furnace 65: Filter
70: oxidant injection unit 80: carbon monoxide storage unit
85: second moisture condenser 90:
100, 200: Flow of liquid metal to prevent high temperature corrosion
110, 210: flow tube 111: first flow tube
112: second flow tube 113: third flow tube
120, 220: heat exchanger 121: first heat exchanger
122: second heat exchanger 123: third heat exchanger

Claims (17)

A methane pyrolysis furnace in which molten liquid metal is received;
Methane supply section for supplying a methane (CH ₄₎ to said methane pyrolysis;
A carbon recovery furnace for containing carbon and liquid metal produced by pyrolyzing methane by the liquid metal; And
And an oxidant injector for supplying oxygen (O ₂ ) or carbon dioxide (CO ₂ ) to the carbon recovery furnace,
Wherein carbon is reacted with oxygen in the carbon recovery furnace to extract carbon monoxide (CO). The method according to claim 1,
In the methane pyrolysis furnace,
Wherein the molten metal is heated by a temperature higher than a melting point of the molten metal to thereby obtain a molten liquid metal, and the pyrolysis methane pyrolysis and high purity hydrogen / carbon monoxide production apparatus using the liquid metal. The method according to claim 1,
Further comprising a hydrogen storage part provided in the methane pyrolysis furnace,
The hydrogen storage unit includes:
And the high-purity hydrogen (H2) produced by pyrolyzing the methane in the methane pyrolysis furnace is stored in the methane pyrolysis furnace. The method of claim 3,
The methane-
Wherein a predetermined amount of the hydrogen (H ₂ ) having a high purity transferred to the hydrogen storage unit is supplied to the methane pyrolysis furnace, and further supplied to the methane pyrolysis furnace, thereby producing methane pyrolysis and high purity hydrogen / carbon monoxide using the liquid metal. The method according to claim 1,
In the carbon recovery furnace,
And a filter provided on the upper side of the oxidant injection unit,
Wherein the filter is provided to pass only the liquid metal from which carbon has been removed in the carbon recovery furnace. The method according to claim 1,
Further comprising a carbon monoxide storage unit for storing the extracted carbon monoxide by reacting the carbon with oxygen in the carbon recovery furnace. The method according to claim 1,
In the carbon recovery furnace,
Wherein the oxygen is injected by the oxidant injecting part in a state where the temperature of the liquid metal is controlled to a non-oxidizing temperature. The method according to claim 1,
And a transfer pipe for transferring the liquid metal and the solid carbon in the methane pyrolysis furnace to the carbon recovery furnace. The apparatus for producing methane pyrolysis and high purity hydrogen / carbon monoxide using liquid metal. The method according to claim 1,
Further comprising a recovery unit for providing a metal oxide generated by the reaction of the liquid metal and oxygen in the carbon recovery furnace to the methane pyrolysis furnace,
Wherein the metal oxide is reduced by methane, carbon and hydrogen in the methane pyrolysis furnace. A production method of methane pyrolysis and high purity hydrogen and carbon monoxide production apparatus using liquid metal applied to a pyrolysis apparatus,
a) providing a molten liquid metal in a methane pyrolysis furnace;
b) pyrolyzing the methane by supplying methane to the methane pyrolysis furnace;
c) discharging carbon generated by the reaction of the liquid metal and the methane to a carbon recovery furnace; And
d) injecting oxygen or carbon dioxide into the carbon recovery furnace to react the discharged carbon with the oxygen,
The method for producing methane pyrolysis and high-purity hydrogen / carbon monoxide using the liquid metal according to claim 1, wherein in step (d), the carbon reacts with oxygen to extract carbon monoxide. 11. The method of claim 10,
In the step a)
In the methane pyrolysis furnace,
Wherein the molten metal is heated to a temperature higher than the melting point to contain the molten liquid metal, and a method for producing methane pyrolysis and high purity hydrogen / carbon monoxide production apparatus using the liquid metal. 11. The method of claim 10,
In the step b)
The methane is pyrolyzed to high purity hydrogen and carbon,
Wherein the high purity hydrogen is stored in a hydrogen storage part. The method for producing methane pyrolysis and high purity hydrogen / carbon monoxide using the liquid metal. 13. The method of claim 12,
After the step d)
and e) providing a metal oxide produced by the reaction of oxygen with the liquid metal in the carbon recovery furnace to the methane pyrolysis furnace, thereby reducing the methane pyrolysis and high purity hydrogen carbon monoxide Production method of production equipment. 14. The method of claim 13,
In the step e)
Wherein the high-purity hydrogen supplied to the methane thermal decomposition furnace is supplied to the methane thermal decomposition furnace in an amount necessary for reducing the metal oxide in the high purity hydrogen transported toward the hydrogen storage section. Production method. 11. The method of claim 10,
In the step d)
Wherein the oxygen is injected into the carbon recovery furnace while the temperature of the liquid metal is controlled to the non-oxidizing temperature. A pyrolysis apparatus using methane pyrolysis and high purity hydrogen / carbon monoxide production apparatus using liquid metal according to any one of claims 1 to 9. 15. A pyrolysis apparatus to which a production method of methane pyrolysis and high purity hydrogen / carbon monoxide production apparatus using liquid metal according to any one of claims 10 to 15 is applied.

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