WO2024075890A1 - Réacteur catalytique fonctionnel et dispositif de reformage de gaz combustible - Google Patents

Réacteur catalytique fonctionnel et dispositif de reformage de gaz combustible Download PDF

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Publication number
WO2024075890A1
WO2024075890A1 PCT/KR2022/016942 KR2022016942W WO2024075890A1 WO 2024075890 A1 WO2024075890 A1 WO 2024075890A1 KR 2022016942 W KR2022016942 W KR 2022016942W WO 2024075890 A1 WO2024075890 A1 WO 2024075890A1
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reactor
reformed
ventilation
reformed gas
ventilation portion
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PCT/KR2022/016942
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English (en)
Korean (ko)
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김환
송형운
엄성현
황상연
이동규
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고등기술연구원연구조합
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
    • C01B3/24—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
    • C01B3/26—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons using catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/40—Carbon monoxide

Definitions

  • the present invention relates to a functional catalytic reactor and fuel gas reforming device.
  • Hydrogen is generally produced by reforming hydrogen-containing fuels such as alcohol-based fuels (methanol, ethanol, etc.), hydrocarbon-based fuels (methane, butane, propane, etc.), natural gas-based fuels (liquefied natural gas, etc.), and biogas by a fuel reformer. obtained.
  • fuel reformers mainly use the steam reforming method.
  • hydrogen-containing fuel is supplied into the reformer along with water, and reacts with a catalyst within the reformer to produce hydrogen through a hydrogen production reaction. At this time, heat suitable for the reaction can be supplied by the burner.
  • this steam reforming method involves a strong endothermic reaction, requires a high heat source, and has problems with slow start-up characteristics.
  • there are various technical limitations such as catalyst poisoning from trace amounts of sulfur compounds, and as the size of the reformer increases, there is a problem of increased operation and maintenance costs.
  • a fuel reformer that uses plasma to reform hydrogen-containing fuel is in progress.
  • plasma-inducing gas is discharged by direct current power converted from alternating current power to generate high-temperature plasma, and the fuel is reformed using the generated high-temperature plasma.
  • the conventional plasma reforming type fuel reformer has the problem of incurring additional costs because alternating current power must be converted back to direct current power.
  • the present applicant has proposed a composite fuel reforming system that combines two reforming methods.
  • the composite fuel reforming system produces reformed gas by first reforming fuel through a first reforming reaction unit using plasma, and produces hydrogen by reforming the primary reformed gas again through a second reforming reaction unit using a catalyst.
  • the plasma reforming reactor which is the first reforming reaction unit of the composite fuel reforming system
  • the plasma reforming reactor has a problem in that the reforming efficiency of the catalytic reforming reactor, which is the second reforming reaction unit, is reduced due to low methane (CH 4 ) conversion rate and high carbon dioxide (CO 2 ) production. .
  • Patent Document 1 Korean Patent Publication No. 2390611
  • Embodiments of the present invention were invented in the above background, and are a functional catalyst reactor capable of improving the production performance of hydrogen and carbon monoxide by reducing carbon dioxide by reacting unreacted gas generated in the first reactor with a functional catalyst. We would like to provide.
  • the functional catalytic reactor includes an electrode, a first reactor for reforming fuel to generate reformed gas, and a second reactor for reforming the reformed gas again by the first reactor.
  • a functional catalytic reactor installed in a fuel gas reforming device, comprising: a ventilation portion through which the reformed gas reformed by the first reactor passes and a receiving space is formed therein; and a functional catalyst accommodated in the accommodation space of the ventilation unit and reacting with the reformed gas passing through the ventilation unit. It guides the reformed gas reformed by the first reactor to the second reactor and includes a hollow vent supporter supporting the vent so that the vertical position of the vent can be adjusted.
  • the ventilation portion support is formed to surround the electrode, and the electrode may communicate with the outside through the ventilation portion.
  • the ventilation unit may include: a first ventilation unit installed at an end of the ventilation unit support at the second reactor side and having a plurality of ventilation holes for the reformed gas reformed by the first reactor to pass through; and is installed on the inside of the ventilation portion support so as to be spaced apart from the first ventilation portion to create the receiving space between the first ventilation portion and the reformed gas reformed by the electrode of the first reactor passes through. It may include; a second ventilation portion in which a plurality of ventilation holes are formed to
  • the first reactor is configured to generate plasma for use as a reforming means, and the ventilation portion passes through the reformed gas reformed by the first reactor at a temperature of 600°C to 900°C. It can be installed at any point.
  • the functional catalyst is Ni/BaZrO 3 having a perovskite structure. It can be.
  • a fuel gas reforming device includes a first reactor including an electrode and reforming fuel to generate reformed gas; a second reactor that re-reforms the reformed gas reformed by the first reactor; and a functional catalytic reactor that reacts the unreacted gas generated in the first reactor, wherein the functional catalytic reactor passes the reformed gas reformed by the first reactor, and a ventilation portion in which a receiving space is formed. ; and a functional catalyst accommodated in the accommodation space of the ventilation unit and reacting with the reformed gas passing through the ventilation unit. It guides the reformed gas reformed by the first reactor to the second reactor and includes a hollow vent supporter supporting the vent so that the vertical position of the vent can be adjusted.
  • Figure 1 is a schematic diagram showing a fuel gas reforming device in which a functional catalytic reactor is installed according to an embodiment of the present invention.
  • Figure 2 is a cross-sectional view showing a fuel gas reforming device in which a functional catalytic reactor is installed according to an embodiment of the present invention.
  • Figure 3 is a diagram showing a functional catalytic reactor according to an embodiment of the present invention.
  • a component when a component is mentioned as being 'connected', 'supported', 'connected', 'supplied', 'delivered', or 'contacted' with another component, it is directly connected, supported, connected, or connected to that other component. It may be supplied, delivered, or contacted, but it should be understood that other components may exist in the middle.
  • the fuel gas reforming device 1 may include a reactor 10, a burner unit 20, a first reactor 30, a heat exchange unit 40, and a second reactor 50.
  • the reactor 10 may provide an internal space in which the burner unit 20, the first reactor 30, the heat exchange unit 40, and the second reactor 50 can be placed.
  • the reactor 10 includes a first reaction body 11 and a first reactor 11 in which at least one of the burner unit 20, the first reactor 30, the heat exchange unit 40, and the second reactor 50 is disposed. It is coupled to the reaction body 11 and may include a second reaction body 12 in which the remainder of the burner unit 20, the first reactor 30, the heat exchange unit 40, and the second reactor 50 are disposed. there is.
  • the first reactor 30 is disposed in the first reaction body 11, and the burner unit 20, the heat exchanger 40, and the second reactor ( 50) is placed as an example.
  • the first reaction body 11 has a first reactor 30 disposed therein, a first reaction body side accommodating portion 111 having an open top, and an opening of the first reaction body side accommodating portion 111. It may include a first reaction body-side coupling portion 112 connected to the upper part of the body, and a guide member 113 connected to the inner surface of the first reaction body-side coupling portion 112. At this time, the first reaction body-side accommodating portion 111, the first reaction body-side coupling portion 112, and the guide member 113 may be formed integrally, and the first reaction body-side accommodating portion 111 and the first reaction body-side accommodating portion 111 1 The reaction body side coupling portion 112 and the guide member 113 may be manufactured separately and then coupled to each other.
  • an inlet 1111 may be connected to the bottom of the first reaction body side receiving portion 111. Fluids to be reformed, such as fuel or plasma-inducing gas, may flow through this inlet 1111, and the introduced fluids may be supplied between electrodes 31 of the first reactor 30, which will be described later.
  • the guide member 113 may guide the reformed gas flowing out of the first reactor 30 to the second reactor 50.
  • the guide member 113 extends from the lower surface of the first reaction body side coupling portion 112 toward the bottom surface of the first reaction body side receiving portion 111, thereby forming a predetermined space therein. At least a portion of the first reactor 30 may be placed in the inner space of the guide member 113 formed in this way and covered by the guide member 113.
  • the second reaction body 12 has a burner unit 20, a heat exchanger 40, and a second reactor 50 disposed therein, and includes a second reaction body side receiving portion 121 having an open bottom shape, and It may include a second reaction body side coupling portion 122 connected to the open lower portion of the second reaction body side receiving portion 121.
  • the second reaction main body side accommodating part 121 and the second reaction main body side coupling part 122 may be formed integrally, and the second reaction main body side accommodating part 121 and the second reaction main body side coupling part ( 122) may be manufactured separately and then combined together.
  • a connection member 1211 may be provided on the inner surface of the second reaction body side receiving portion 121. At least one of the heat exchanger 41, the burner unit 20, and the second reactor 50 may be connected to this connection member 1211.
  • first reaction body side coupling portion 112 of the first reaction body 11 and the second reaction main body side coupling portion 122 of the second reaction body 12 are connected by separate fastening means (not shown). can be mutually concluded.
  • first through hole 1121 formed in the first reaction body side coupling portion 112 of the first reaction body 11 and the second reaction body side coupling portion 122 of the second reaction body 12 The second through-holes 1221 previously formed may be in communication with each other.
  • the first through-holes 1121 and the second through-holes 1221 communicated with each other in this way are used to supply the first reformed gas generated in the first reactor 30 to the heat exchanger 41 of the heat exchanger 40. It can be used as a passage.
  • the end of the heat exchanger 41 of the heat exchanger 40 may be connected to a position corresponding to the first through hole 1121 and the second through hole 1221.
  • the burner unit 20 transfers heat to the heat exchange unit 40 to preheat the first reformed gas to a first temperature, and transfers heat to the second reactor 50 to preheat the first reformed gas to the first temperature.
  • the gas may be heated to a second temperature that is higher than the first temperature.
  • the first reformed gas supplied to the heat exchange unit 40 is preheated to the first temperature by the heat of the burner unit 20, and the burner unit 20
  • the preheated first reformed gas supplied to the second reactor 50 may be heated to the second temperature.
  • the first reformed gas refers to a gas produced by reforming fuel by the first reactor 30.
  • the first reformed gas heated to the second temperature may be reformed by the second reactor 50, which will be described later, and converted into the second reformed gas.
  • the first temperature may be about 650°C to about 700°C
  • the second temperature may be about 800°C to about 850°C.
  • the burner unit 20 may be provided inside the reactor 10, for example, inside the second reaction body 12. This burner unit 20 may be inserted into a hole previously formed in the second reaction body 12 and may be supported by a connection member 1211 coupled to the inner surface of the second reaction body 12. For this purpose, support pieces 21 may be formed to protrude along the circumference of the burner unit 20, and these support pieces 21 may be in surface contact with the connection member 1211.
  • the burner unit 20 may, for example, be provided as a cylindrical structure with a predetermined space formed therein to correspond to the shape of the inner peripheral surface of the second reaction body 12.
  • the burner unit 20 in order to uniformly supply the heat of the burner unit 20 to the heat exchange unit 40 and the second reactor 50, the burner unit 20 has an internal cylindrical off gas to which metal fiber is applied, for example. It may be provided with a burner. Accordingly, the amount of heat required to preheat the first reformed gas in the heat exchanger 40 through the burner unit 20 and the amount of heat required to reform the first reformed gas preheated in the second reactor 50 will be supplied uniformly at the same time. You can.
  • the first reactor 30 may convert fuel into a first reformed gas.
  • the first reactor 30 may be provided inside the reactor 10, for example, inside the first reaction body 11, and may include a first reforming means capable of reforming fuel supplied from the outside. Can be created optionally.
  • the fuel may be a hydrogen-containing fuel such as alcohol-based fuel, hydrocarbon-based fuel, natural gas-based fuel, or biogas, and the first reforming means may be gliding arc plasma.
  • This first reactor 30 may include an electrode 31, an electrode support 32, and a power supply (not shown).
  • the electrode support 32 extends upward from the bottom of the first reaction body side accommodating portion 111, and the electrode 31 may be coupled to and supported at the top.
  • the electrode 31 may be supported by being coupled to an electrode support 32 that is coupled to the first reaction body side receiving portion 111.
  • the electrode 31 may be provided in a fan-shaped shape including a curved line.
  • a plurality of electrodes 31 can be provided to increase the plasma discharge area.
  • the plurality of electrodes 31 may be arranged to be spaced apart at a predetermined interval so that the gap between the electrodes 31 widens toward the top.
  • the electrode 31 is electrically connected to the power supply device and can receive alternating current power from the power supply device.
  • the heat exchange unit 40 may receive the first reformed gas from the first reactor 30, and transfer heat from the burner unit 20 to the first reformed gas supplied from the first reactor 30 to perform the first reformed gas.
  • the gas may be preheated to a first temperature.
  • the heat exchange unit 40 may be disposed inside the reactor 10, for example, inside the second reaction body 12.
  • at least some of the plurality of heat exchangers 41 are arranged to be offset from at least some of the plurality of second reforming reactors 51 of the second reforming reaction unit 50, which will be described later, so that the radiant heat of the burner unit 20 It can be easily transferred to a plurality of heat exchangers 41.
  • This heat exchange unit 40 may include a plurality of heat exchangers 41.
  • the plurality of heat exchangers 41 may be arranged to be spaced apart along an imaginary circle with a certain radius based on the center of the burner unit 20.
  • the heat exchanger 41 may have a passage inside through which the first reformed gas can flow.
  • one end of the heat exchanger 41 may be coupled to the inner surface of the second reaction body side coupling portion 122 of the second reaction body 12.
  • one end of the heat exchanger 41 has a first through hole 1121 formed in the first reaction body side coupling portion 112 of the first reaction body 11 and a second through hole 1121 of the second reaction body 12. It may be in communication with the second through hole 1221 already formed in the reaction body side coupling portion 122.
  • the passage provided inside the heat exchanger 41 communicates with the internal space of the first reaction body 11, so that the first reformed gas of the first reaction body 11 is supplied to the heat exchanger 41.
  • the other end of the heat exchanger 41 may be coupled through a hole already formed in the connection member 1211 coupled to the inner surface of the second reaction body side receiving portion 121.
  • an extension piece may be formed extending from one surface of the connecting member 1211 corresponding to the outer circumference of the hole. This extension piece can cover a hole already formed in the connecting member 1211.
  • the first reformed gas discharged through the other end of the heat exchanger 41 can be supplied to the second reactor 50 through the connection pipe.
  • the second reactor 50 may convert the first reformed gas that has passed through the heat exchanger 40 into a second reformed gas.
  • the second reactor 50 may be equipped with a second reforming means that is different from the first reforming means.
  • the second reactor 50 may be disposed inside the reactor 10, for example, inside the second reaction body 12.
  • at least a portion of the plurality of second reaction units 51 is arranged to be offset from at least a portion of the plurality of heat exchangers 41, so that the radiant heat of the burner unit 20 is easily transferred to the plurality of second reaction units 51. can be conveyed.
  • This second reactor 50 may include a plurality of second reaction units 51.
  • the plurality of second reaction units 51 may be spaced apart from each other along an imaginary circle with a certain radius based on the center of the burner unit 20.
  • the second reactor 50 is disposed closer to the burner unit 20 than the heat exchange unit 40, so that the plurality of second reaction units 51 form a circle based on the center of the burner unit 20.
  • the size may be smaller than the size of the circle formed by the plurality of heat exchangers 41 based on the center of the burner unit 20.
  • the second reactor 50 may include an exterior 511 and an inner tube 512 disposed inside the exterior 511. At this time, the lower end of the outer tube 511 may be closed, and the lower end of the inner tube 512 may be provided in an open structure.
  • a second reforming means for example, a reforming catalyst, may be provided between the outer tube 511 and the inner tube 512.
  • the second reactor 50 is provided in the form of a double tube including an outer tube 511 and an inner tube 512, the residence time of the first reformed gas can be increased.
  • the outer pipe 511 is provided with a first passage 5112 through which the first reformed gas flows, and the inner pipe 512 is in communication with the first passage 5112, and at least one of the first reformed gas and the second reformed gas is provided.
  • a flowing second passage 5122 may be provided.
  • a reforming reaction proceeds as the first reforming gas passes through a second reforming means, for example, a reforming catalyst, provided between the outer tube 511 and the inner tube 512.
  • the temperature of the first reformed gas moved to the bottom of the outer tube 511 is higher than the temperature of the first reformed gas supplied to the top of the outer tube 511, and the raised first reformed gas rises through the inner tube 512, which is a riser tube. After being converted to the second reformed gas, it is discharged through the outlet 5121 connected to the top of the inner tube 512.
  • fuel is first reformed in the first reactor 30, preheated to a temperature at which a reforming reaction can occur through the heat exchanger 40, and then secondarily reformed in the second reactor 50. Reforming improves reforming efficiency.
  • the primary reformed gas primary reformed by the first reactor 30 has a low conversion rate of methane (CH 4 ) and a high amount of carbon dioxide (CO 2 ) generated in the second reactor 50. ) There is a problem that the reforming efficiency of is reduced.
  • a functional catalytic reactor 60 is formed between the first reactor 30 and the second reactor 50, and unreacted methane and carbon dioxide of the primary reformed gas reformed by the first reactor 30 are formed.
  • the reforming efficiency of the second reactor 50 can be increased by producing more hydrogen by performing a methane reforming reaction (DRM, Dry Reforming of Methane) using the functional catalytic reactor 60.
  • the functional catalytic reactor 60 according to an embodiment of the present invention extends from the bottom of the first reaction body side receiving portion 111 to the upper side, that is, toward the second reactor 50, and is used by the first reactor 30.
  • It is installed at the end of the second reactor 50 side of the ventilation portion support 61 that guides the reformed reformed gas toward the second reactor 50, and allows the reformed gas reformed by the first reactor 30 to pass through and is accommodated therein. It includes a ventilation portion 62 in which a space is formed and a functional catalyst 63 that is accommodated in the internal accommodation space of the ventilation portion 62 and reacts with the reformed gas passing through the ventilation portion 62.
  • the ventilation portion support 61 has a hollow cylindrical shape, and a space is formed therein, so that the first reactor 30 can be placed in this inner space.
  • the ventilation portion support 61 may extend upward from the bottom of the first reaction body side receiving portion 111 to provide a space in which the fuel to be reformed and the plasma inducing gas for inducing the gliding arc plasma flow.
  • a plasma reforming reaction may be performed in the internal space formed in the ventilation portion support 61.
  • the ventilation portion support 61 may be made of a material that can be electrically insulated from the electrode 31.
  • the lower part of the ventilation portion support 61 extends upward from the bottom of the first reaction body side receiving portion 111, and the upper part of the ventilation portion support 61 (upper part in FIG. 2) is open.
  • a ventilation portion 62 may be installed on one open side. That is, the ventilation portion support 61 surrounds the first reactor 30 so that the portion excluding the upper open side of the ventilation portion support 61 where the ventilation portion 62 is formed blocks the first reactor 30 from the outside. It can be formed as follows. Because of this, all of the reformed gas reformed through the first reactor 30 passes through the ventilation portion 62.
  • the ventilation portion support 61 may be disposed radially inside the guide member 113.
  • the horizontal separation distance between the ventilation unit support 61 and the guide member 113 may be smaller than the horizontal separation distance between the ventilation unit support 61 and the side wall of the first reaction body side receiving portion 111. You can.
  • the separation distance between the upper end of the electrode 31 and the upper end of the ventilation support 61 can be formed to be larger than the separation distance between the lower end of the electrode 31 and the bottom of the first reaction body side accommodating portion 111. there is.
  • the ventilation unit 62 may be installed on the upper part of the ventilation unit support 61 and may be formed of a mesh member having a plurality of ventilation holes for the reformed gas reformed by the first reactor 30 to pass through, and the ventilation unit ( It may include a first ventilation portion 621 and a second ventilation portion 622 spaced apart at a predetermined interval along the thickness direction of 62).
  • the first vent 621 and the second vent 622 may be installed inside the vent support 61.
  • the first ventilation portion 621 and the second ventilation portion 622 are formed to have an area corresponding to the cross-sectional area of the internal space formed by the ventilation portion support 61 to close one open side of the ventilation portion support 61. Can be installed.
  • first ventilation part 621 and the second ventilation part 622 may be spaced apart at a certain interval to create an accommodation space therebetween.
  • One open side of the vent supporter 61 is closed by the first vent 621 and the second vent 622, but the first vent 621 and the second vent 622 have a plurality of vents. Pores are formed so that the reformed gas guided through the ventilation portion supporter 61 passes through the first ventilation portion 621 and the second ventilation portion 622.
  • the reformed gas generated from the first reactor 30 passes through the ventilation portion 62 and then flows downward along the space formed between the guide member 113 and the ventilation portion support 61, and flows downward toward the first reaction body. After rising through the space formed between the side wall of the receiving part 111 and the guide member 113, it may flow into the heat exchange part 40. According to this flow path, the reformed gas generated in the first reactor 30 may flow into the heat exchange unit 40 without remaining inside the first reaction body 11.
  • the functional catalyst 63 is accommodated in the receiving space formed between the first ventilation portion 621 and the second ventilation portion 622 and reacts with the reformed gas passing through the ventilation portion 62.
  • the reforming gas and the functional catalyst 63 undergo methane reforming reaction (DRM), and reaction heat of 600°C to 900°C is required for the metal reforming reaction to occur.
  • DRM methane reforming reaction
  • the first reactor 30 reforms fuel by plasma, the reformed gas reformed by the first reactor 30 is maintained at a high temperature.
  • the ventilation portion 62 must be installed at a location where the reformed gas maintains a high temperature, that is, a point through which the reformed gas can pass while its temperature is between 600°C and 900°C. Since the ventilation portion 62 is installed at one open end of the ventilation portion support 61, the length of the ventilation portion support 61 is adjusted to adjust the ventilation portion 62 so that the temperature of the reformed gas is 600°C to 900°C. It can be installed at a point where it passes through at °C.
  • the length of the ventilation portion support 61 is formed to be long, and predetermined fastening means, such as a rack and pinion gear, are provided on the inner surface of the ventilation portion support 61 and the outer surface of the ventilating portion, respectively, to secure the ventilation portion.
  • (62) can be installed inside the ventilation portion support 61 so that the ventilation portion 62 is installed at a point where the reformed gas passes through at a temperature of 600°C to 900°C. In this case, the ventilation portion 62 can be installed at the corresponding location regardless of the total length of the ventilation portion support 61.
  • the ventilation portion support 61 adjusts its overall length or adjusts the vertical position of the ventilation portion 62 disposed inside the ventilation portion 62 so that the temperature of the reformed gas is maintained at 600°C to 900°C. It can be installed at a point where it passes through at °C.
  • the vertical separation distance between the ventilation portion 62 and the first reaction body side coupling portion 112 is greater than the separation distance between the lower end of the guide member 113 and the bottom of the first reaction body side receiving portion 111. You can.
  • the functional catalyst 63 may be Ni/BaZrO 3 having a perovskite structure.
  • the functional catalyst 63 uses BaZrO 3 as a support, and is a catalyst coated with nickel on BaZrO 3 powder prepared by a solid-phase method and a pellet-shaped BaZrO 3 structure manufactured by extrusion molding. Looking at the method of manufacturing the functional catalyst 63, first, the precursors are barium carbonate (BaCO 3 , 99.9%), zirconium oxide (ZrO 2 , 99.9%), yttrium oxide (Y 2 O 3 , 99.9%), and acetone. Mix and homogenize.
  • the mixed materials as described above are dried and ground at 110°C, then heat-treated in air at 1200°C for 5 hours, and the heat-treated material is ground into uniform powder using an attrition milling.
  • the BaZrO 3 powder prepared in this way may be a structure having a specific surface area of 10 m 2 /g to 20 m 2 /g.
  • the metal precursor is coated on BaZrO 3 powder through temperature-controlled chemical vapor deposition.
  • Ni(Cp) 2 may be used as the metal precursor, and the metal precursor is injected at 1 wt% to 30 wt% based on the weight of the BaZrO 3 carrier (BaZrO 3 powder or BaZrO 3 gear-type pellets) to form a surface of the BaZrO 3 carrier.
  • the content of nickel (Ni) coated on can be controlled.
  • nickel vapor in the form of an organic metal compound sublimated at a temperature of 250 °C reacts with oxygen in the air on the surface of the BaZrO 3 carrier to coat it in the form of NiO, and is coated in the form of NiO at 800 °C (reducing atmosphere) for 2 to 4 hours.
  • a functional catalyst (63) made of Ni/BaZrO 3 is prepared by heat treatment.
  • the functional catalyst (63), Ni/BaZrO 3 has high performance in methane reforming reaction (DRM) and a structurally stabilized perovskite structure, enabling steam It has high stability in (steam) atmosphere. Accordingly, the unreacted methane (CH 4 ), carbon dioxide (CO 2 ), and CxHx series gases generated in the first reactor 30 are supplied to the functional catalytic reactor 60 and are combined with the plasma heat source of the first reactor 30.
  • the reforming efficiency of fuel can be increased by increasing the production of hydrogen (H 2 ) and carbon monoxide (CO) through methane reforming reaction (DRM).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • General Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Toxicology (AREA)
  • Physics & Mathematics (AREA)
  • Hydrogen, Water And Hydrids (AREA)
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Abstract

L'invention concerne un réacteur catalytique fonctionnel qui est installé dans un dispositif de reformage de gaz combustible comprenant : un premier réacteur qui comprend une électrode et reforme du combustible afin de produire un gaz reformé; et un second réacteur qui reforme à nouveau le gaz reformé reformé par le premier réacteur. Le réacteur catalytique fonctionnel comprend : une unité de ventilation qui comporte un espace de logement formé à l'intérieur de celle-ci et à travers laquelle passe le gaz reformé reformé par le premier réacteur; un catalyseur fonctionnel qui est logé dans l'espace de logement de l'unité de ventilation et réagit avec le gaz reformé passant à travers l'unité de ventilation; et un support de ventilation creux qui guide le gaz reformé reformé par le premier réacteur vers le second réacteur et soutient l'unité de ventilation de sorte que la position verticale de l'unité de ventilation puisse être ajustée.
PCT/KR2022/016942 2022-10-06 2022-11-01 Réacteur catalytique fonctionnel et dispositif de reformage de gaz combustible WO2024075890A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011076850A (ja) * 2009-09-30 2011-04-14 Jx Nippon Oil & Energy Corp 燃料電池用燃料処理装置
KR20190076367A (ko) * 2017-12-22 2019-07-02 고등기술연구원연구조합 건식 개질 촉매 및 건식 개질 촉매의 제조 방법
WO2020012687A1 (fr) * 2018-07-09 2020-01-16 株式会社村田製作所 Catalyseur de reformage d'hydrocarbures et appareil de reformage d'hydrocarbures
CN112723308A (zh) * 2021-01-18 2021-04-30 浙江华电器材检测研究所有限公司 一种碳烃燃料等离子体催化链式制氢的方法
KR102390611B1 (ko) * 2021-10-21 2022-04-25 고등기술연구원연구조합 복합 연료 개질 시스템 및 이를 이용한 복합 연료 개질 방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011076850A (ja) * 2009-09-30 2011-04-14 Jx Nippon Oil & Energy Corp 燃料電池用燃料処理装置
KR20190076367A (ko) * 2017-12-22 2019-07-02 고등기술연구원연구조합 건식 개질 촉매 및 건식 개질 촉매의 제조 방법
WO2020012687A1 (fr) * 2018-07-09 2020-01-16 株式会社村田製作所 Catalyseur de reformage d'hydrocarbures et appareil de reformage d'hydrocarbures
CN112723308A (zh) * 2021-01-18 2021-04-30 浙江华电器材检测研究所有限公司 一种碳烃燃料等离子体催化链式制氢的方法
KR102390611B1 (ko) * 2021-10-21 2022-04-25 고등기술연구원연구조합 복합 연료 개질 시스템 및 이를 이용한 복합 연료 개질 방법

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