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WO2023054753A1 - Système de génération d'hydrogène et de carbone utilisant une pyrolyse de méthane au moyen d'un échange de chaleur indirect en lit fluidisé - Google Patents

Système de génération d'hydrogène et de carbone utilisant une pyrolyse de méthane au moyen d'un échange de chaleur indirect en lit fluidisé Download PDF

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Publication number
WO2023054753A1
WO2023054753A1 PCT/KR2021/013390 KR2021013390W WO2023054753A1 WO 2023054753 A1 WO2023054753 A1 WO 2023054753A1 KR 2021013390 W KR2021013390 W KR 2021013390W WO 2023054753 A1 WO2023054753 A1 WO 2023054753A1
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methane
carbon
combustor
supplied
hydrogen
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Korean (ko)
Inventor
이은도
양창원
방병열
정수화
가야트리인그래
권현민
조천현
오승진
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Korea Institute of Industrial Technology KITECH
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    • 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
    • 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
    • B01J6/00—Heat treatments such as Calcining; Fusing ; Pyrolysis
    • 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
    • B01J6/00—Heat treatments such as Calcining; Fusing ; Pyrolysis
    • B01J6/008—Pyrolysis reactions
    • 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
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • 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
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/1836—Heating and cooling the reactor
    • 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
    • C01B3/28—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons using moving solid particles
    • C01B3/30—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons using moving solid particles using the fluidised bed technique
    • 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
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • 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
    • C01B32/50—Carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0833—Heating by indirect heat exchange with hot fluids, other than combustion gases, product gases or non-combustive exothermic reaction product gases
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • C01B2203/1241—Natural gas or methane

Definitions

  • the present invention relates to a system for producing hydrogen and carbon through methane pyrolysis using a fluidized bed indirect heat exchange method, and more particularly, to a fluidized bed technology having excellent effects on heat and mass transfer in a multi-phase flow (gas-solid) reaction.
  • Fluidized bed indirect heat exchange method methane pyrolysis that uses gas as a medium to supply the reaction heat necessary for methane pyrolysis and generates reaction heat necessary for the entire reaction process through pure oxy-combustion using a part of the carbon produced through methane pyrolysis as fuel It relates to a system for producing hydrogen and carbon through
  • the thermal decomposition reaction of methane which is a typical endothermic reaction, is activated between 900 ° C and 1200 ° C, and the higher the temperature, the higher the conversion rate of methane approaches 100%.
  • Related methane pyrolysis technologies include technologies using liquid metal and molten salt, technologies using plasma, and technologies using solid catalysts.
  • liquid metal and molten salt has limitations in heating the liquid medium to a high temperature, and a separate process is required to improve the purity of the carbon because the liquid metal or molten salt is smeared on solid carbon.
  • the technology using plasma requires a huge amount of regenerative power and requires a technology for collecting carbon generated in atomic units.
  • the technology using a solid catalyst has a problem in that the activity of the catalyst is rapidly reduced due to a coking phenomenon in which carbon generated in the thermal decomposition process adheres to the surface of the catalyst.
  • liquid catalysts such as liquid metals or molten salts are used, plasmas are used, iron oxide, nickel, carbon-based Technologies utilizing solid catalysts have been proposed, but the technology level is low, so additional technology development is required for commercialization.
  • Patent Document 1 Patent Publication No. 10-2004-0004799 (2004.01.16.)
  • Patent Document 2 Patent Registration No. 10-2211017 (2021.01.27.)
  • An object of the present invention to solve the above problem is to produce a high-temperature gas composed of 100% carbon dioxide (CO 2 ) through pure oxy-combustion using a portion of solid carbon produced by methane pyrolysis as fuel to produce beads such as alumina
  • an object of the present invention for solving the above problems is to use the fuel when the carbon adhered to the bead is supplied to the combustor, and in this process, the bead is automatically regenerated, so that the coking of the floating yarn that occurred in the prior art It is to provide a hydrogen and carbon production system through methane pyrolysis of a fluidized bed indirect heat exchange method that solves the problem.
  • the object of the present invention for solving the above problems is that a separate catalyst such as a liquid catalyst, a molten salt, or a solid catalyst is not required, and the incorporation of foreign substances into the produced solid carbon is fundamentally blocked to obtain high-purity carbon. It is to provide a hydrogen and carbon production system through methane pyrolysis of a fluidized bed indirect heat exchange method that solves the quality problem of solid carbon products that have occurred in the technology.
  • the object of the present invention for solving the above problem is that, unlike the existing process such as SMR, which requires a separation process of hydrogen and carbon dioxide, hydrogen and carbon dioxide (CO 2 ) are separated and discharged from the pyrolysis machine, so separate separation It is to provide a hydrogen and carbon production system through methane pyrolysis of a fluidized bed indirect heat exchange method that does not require a process and thus minimizes the cost of a hydrogen-carbon dioxide separation process.
  • an object of the present invention for solving the above problem is to react high-temperature carbon produced by pyrolysis with high-temperature carbon dioxide (CO 2 ) produced by pure oxygen combustion to obtain high-purity carbon monoxide (Boudouard reaction) CO) can be easily produced, and both carbon and carbon dioxide (CO 2 ) generated in the methane pyrolysis process are over 1000 °C, so the above reaction can be easily implemented without adding a separate heat transfer process.
  • CO 2 carbon dioxide
  • the composition of the present invention for achieving the above object is a combustor for generating carbon dioxide by burning the fuel in a circulating fluidized bed with pure oxygen; a methane passage disposed inside the combustor and circulating methane supplied from the outside; a thermal decomposer communicating with the methane flow path and producing hydrogen and carbon through thermal decomposition of methane supplied along the methane flow path using heat transferred from beads supplied from the combustor; a separator for separating the hydrogen and the carbon transported from the pyrolysis unit, generating at least a portion of the carbon into solid carbon, and supplying another portion of the carbon to the combustor; A first heat exchanger for exchanging heat between oxygen supplied from the outside and the hydrogen supplied from the separator and a second heat exchanger disposed to surround at least a portion of the methane flow path and exchanging heat between the methane supplied from the combustor and the carbon dioxide heat exchanger; a carbon dioxide tank for storing carbon dioxide heat-exchanged through the second heat
  • the composition of the present invention for achieving the above object is a combustor for generating carbon dioxide by burning the fuel in a pure oxygen circulation fluidized bed; a methane passage disposed inside the combustor and circulating methane supplied from the outside; a thermal decomposer communicating with the methane flow path and producing hydrogen and carbon through thermal decomposition of the methane supplied along the methane flow path; a separator for separating the hydrogen and the carbon transported from the pyrolysis unit, generating at least a portion of the carbon into solid carbon, and supplying another portion of the carbon to the combustor; A first heat exchanger for exchanging heat between oxygen supplied from the outside and the hydrogen supplied from the separator and a second heat exchanger disposed to surround at least a portion of the methane flow path and exchanging heat between the methane supplied from the combustor and the carbon dioxide heat exchanger; a carbon dioxide tank for storing carbon dioxide heat-exchanged through the second heat exchanger; and a blower including an oxygen
  • the group is a ceramic reactor located inside the combustor, and hydrogen and carbon production through methane pyrolysis of a fluidized bed indirect heat exchange method, characterized in that the methane is decomposed using heat transferred from the bead to the outer surface of the pyrolysis machine provide the system.
  • the composition of the present invention for achieving the above object is a combustor for generating carbon dioxide by burning the fuel in a pure oxygen circulation fluidized bed; a methane passage disposed inside the combustor and circulating methane supplied from the outside; a thermal decomposer communicating with the methane flow path and producing hydrogen and carbon through thermal decomposition of methane supplied along the methane flow path; a bead separator including a first bead separator and a second bead separator for separating beads from the oxy-circulating fluidized bed while being adjacent to the methane passage and positioned inside the combustor; a separator for separating the hydrogen and the carbon transported from the pyrolysis unit and generating at least a part of the carbon as solid carbon; and a heat exchanger arranged to surround at least a portion of the methane passage and exchanging heat between the beads supplied from the first and second bead separators and the methane supplied from the combustor, wherein the thermal decom
  • a system for producing hydrogen and carbon through methane pyrolysis of a fluidized bed indirect heat exchange method characterized in that the ceramic reactor is located in, and the methane is decomposed using heat transferred from the beads to the outer surface of the pyrolysis device.
  • a first connection pipe communicating between the combustor and the thermal decomposer and transporting the bead inside the combustor to the thermal decomposer; and a second connection pipe positioned below the first connection pipe to communicate between the combustor and the thermal decomposer and transfer the bead supplying heat to the thermal decomposer to the combustor.
  • the methane passage may be formed along an inner surface of the combustor.
  • the first heat exchanger exchanges heat so that the heat contained in the hydrogen is transferred to the oxygen
  • the second heat exchanger exchanges heat so that the heat contained in the carbon dioxide is transferred to the methane. Characterized in that can do.
  • it may be characterized in that it further comprises a control unit for adjusting the amount of at least a portion of the carbon supplied from the separator.
  • the heat exchanger may be characterized in that heat is exchanged so that heat contained in carbon dioxide supplied from the combustor is transferred to the methane.
  • the first bead separator is located on one lower side of the combustor while being adjacent to the methane flow passage, and the second bead separator is located on the other upper side of the combustor while being adjacent to the pyrolysis device can be characterized.
  • the bead separator supplies the beads to the methane passage to adhere to the inner surface of the methane passage when some of the carbon generated in the pyrolysis reaction is attached to the inner surface of the methane passage It can be characterized by separating the carbon product produced.
  • the bead may be characterized in that it serves as a catalyst to promote the thermal decomposition reaction of the methane.
  • an oxidation reaction in which the fuel is combusted in the oxy-circulating fluidized bed occurs in the combustor, and a reduction reaction in which methane is thermally decomposed in the thermal decomposer may occur.
  • CO 2 carbon dioxide
  • the effect of the present invention according to the configuration as described above is that when the carbon adhered to the bead is supplied to the combustor, it is used as fuel, and in this process, the bead is automatically regenerated, thereby causing the coking problem of the floating yarn that occurred in the prior art. can solve
  • the effects of the present invention according to the configuration as described above do not require a separate catalyst such as a liquid catalyst, a molten salt, or a solid catalyst, and the incorporation of foreign substances into the produced solid carbon is fundamentally blocked to obtain high-purity carbon. It is possible to solve the quality problem of solid carbon products that occurred in
  • FIG. 1 is a conceptual diagram illustrating a system for producing hydrogen and carbon through methane pyrolysis using a fluidized bed indirect heat exchange method according to a first embodiment of the present invention.
  • FIG. 2 is a conceptual diagram illustrating a system for producing hydrogen and carbon through methane pyrolysis using a fluidized bed indirect heat exchange method according to a second embodiment of the present invention.
  • FIG. 3 is a conceptual diagram illustrating a system for producing hydrogen and carbon through methane pyrolysis using a fluidized bed indirect heat exchange method according to a third embodiment of the present invention.
  • the combustor for generating carbon dioxide by the pure oxygen circulation fluidized bed combustion of the fuel; a methane passage disposed inside the combustor and circulating methane supplied from the outside; a thermal decomposer communicating with the methane flow path and producing hydrogen and carbon through thermal decomposition of methane supplied along the methane flow path using heat transferred from beads supplied from the combustor; a separator for separating the hydrogen and the carbon transported from the pyrolysis unit, generating at least a portion of the carbon into solid carbon, and supplying another portion of the carbon to the combustor; A first heat exchanger for exchanging heat between oxygen supplied from the outside and the hydrogen supplied from the separator and a second heat exchanger disposed to surround at least a portion of the methane flow path and exchanging heat between the methane supplied from the combustor and the carbon dioxide heat exchanger; a carbon dioxide tank for storing carbon dioxide heat-exchanged through the second heat exchanger; and
  • a fluidized bed reactor including a combustor 100 and a pyrolysis decomposer 200 decomposes methane using an indirect heat exchange method.
  • a process it is characterized in that the combustor 100 and the thermal decomposer 200 are operated separately.
  • FIG. 1 is a conceptual diagram illustrating a system for producing hydrogen and carbon through methane pyrolysis using a fluidized bed indirect heat exchange method according to a first embodiment of the present invention.
  • a system for producing hydrogen and carbon through methane pyrolysis using a fluidized bed indirect heat exchange method includes a combustor 100, a thermal cracker 200, a methane flow path 300, a heat exchanger 400, and a separator 500 ), a carbon dioxide tank 600 and a blower 700.
  • the combustor 100 uses a fast fluidized bed, combusts the fuel in the oxy-circulating fluidized bed, and generates carbon dioxide, which is a by-product produced during the combustion process.
  • the oxy-circulating fluidized bed technology is a future development technology capable of reducing greenhouse gases as well as desulfurization and denitrification by combining oxy-combustion and circulating fluidized bed combustion technologies.
  • pure oxygen combustion of carbon is implemented by the following ⁇ Chemical Reaction Formula 1>.
  • combustion gas generated through pure oxy-combustion of carbon is carbon dioxide (CO 2 ) with a purity of 100%, it can be linked to CCUS without a separate separation/collection process.
  • Pure carbon dioxide (CO 2 ) can be used to control the temperature of oxy-combustion of carbon.
  • the operating temperature of the entire reactor is 1000 degrees, it is preferable to use a material having a high melting point such as alumina as a solid bead used as a heat exchange medium.
  • the present invention communicates between the combustor 100 and the thermal decomposer 200 and transfers the beads inside the combustor 100 to the thermal decomposer 200. It may further include a second connection pipe positioned at a lower portion of the connection pipe to communicate between the combustor 100 and the thermal decomposer 200 and transfer the beads supplying heat to the thermal decomposer 200 to the combustor 100. .
  • the combustor 100 supplies beads flowing inside the combustor 100 to the first connection pipe, and the beads supplied to the first connection pipe are supplied to the thermal decomposer 200 . At this time, the beads are heated in the combustor 100 and the temperature is raised.
  • the beads perform a function similar to the fluidized sand mainly used in a general fluidized bed reactor, and may be alumina beads.
  • the beads promote combustion in the process of combustion of the fuel in the pure oxygen circulating fluidized bed inside the combustor 100, and after being heated inside the combustor 100, pass through the first connection pipe to the inside of the thermal decomposer 200. After being introduced into the methane, heat is transferred to the methane, thereby providing the reaction heat necessary for methane to be thermally decomposed.
  • the beads introduced into the thermal decomposer 200 transfer heat to methane flowing into the thermal decomposer 200 through the methane flow path 300, and the thermal decomposer 200 transfers the heat to the lowered beads to the second
  • the heated bead supplied through the connection pipe and supplied through the second connection pipe is again supplied into the combustor 100 and then heated by the combustor 100.
  • the thermal decomposer 200 supplies carbon dioxide generated by combustion of the pure oxygen circulating fluidized bed to the second heat exchanger 420 .
  • the carbon dioxide at this time is carbon dioxide that has been heated.
  • the thermal cracker 200 uses a bubbling fluidized bed, communicates with the methane flow path 300, and uses heat transferred from beads supplied from the combustor 100 to generate methane supplied along the methane flow path 300. Hydrogen and carbon are produced through thermal decomposition of , and at this time, a reduction reaction in which methane is thermally decomposed occurs in the thermal decomposer 200 .
  • the combustor 100 uses a high-speed fluidized bed and the thermal cracker 200 uses a bubble fluidized bed, but they may be used interchangeably.
  • thermal cracker 200 supplies the produced hydrogen and carbon to the separator 500.
  • hydrogen and carbon are discharged through the upper outlet of the thermal cracker 200 and separated into carbon and hydrogen in the separator 500.
  • Some of the carbon is used as a solid carbon material, and the other part is supplied to the combustor and used as fuel .
  • Beads supplied with heat from the pyrolysis reactor are transported to the combustor 100 through an outlet at the bottom of the reactor, heated and continuously circulated, and serve to transfer heat from the combustor 100 to the pyrolysis unit 200.
  • Some of the carbon produced in the thermal decomposer 200 may adhere to the beads.
  • the adhered carbon is burned with pure oxygen as fuel again. participate in the process
  • the methane passage 300 is disposed inside the combustor 100 and methane is supplied from the outside and circulated. At this time, methane may be supplied from a methane supply unit (not shown).
  • the yellow line shown in FIG. 1 represents the methane passage 300 in which methane circulates and the section preheated by heat exchange, and the gray dotted line shown in FIG. It means the section where the thermal decomposition reaction takes place.
  • the methane passage 300 extends to pass through the second heat exchanger 420 and is formed along the inner surface of the combustor 100 while communicating with the combustor 100 .
  • the methane flow passage 300 communicates with the thermal decomposer 200 .
  • the methane passages 300 located inside the combustor 100 receive heat generated from the combustor 100 and preheat the methane flowing into the methane passage 300,
  • the methane passage 300 is also a preheating section for preheating methane.
  • the above methane flow path 300 supplies methane (CH 4 ) supplied from the outside to the thermal decomposer 200 .
  • the heat exchanger 400 includes a first heat exchanger 410 and a second heat exchanger 420 .
  • the first heat exchanger 410 exchanges heat between oxygen supplied from the outside and hydrogen supplied from the separator 500 .
  • oxygen may be supplied from an oxygen supply unit (not shown).
  • the first heat exchanger 410 exchanges heat so that the heat contained in hydrogen is transferred to oxygen, and after the heat exchange, the heated hydrogen is supplied to a fuel cell or a hydrogen station and used.
  • the second heat exchanger 420 is disposed to surround at least a portion of the methane flow path 300 and exchanges heat between methane and carbon dioxide supplied from the combustor 100 .
  • the second heat exchanger 420 exchanges heat so that heat contained in carbon dioxide is transferred to methane.
  • the separator 500 separates hydrogen and carbon transported from the thermal decomposer 200, converts at least a portion of the carbon into solid carbon, and supplies another portion of the carbon to the combustor 100.
  • the separator 500 generates at least a portion (C, solid) of carbon as solid carbon (Carbon CB, CNT), and supplies another portion (C) of the carbon to the combustor 100 do.
  • the separator 500 supplies the separated hydrogen to the first heat exchanger 410 .
  • the carbon dioxide tank 600 stores carbon dioxide heat-exchanged through the second heat exchanger 420 .
  • the carbon dioxide tank 600 supplies and utilizes at least a portion of the carbon dioxide where carbon dioxide is needed, and supplies another portion of the carbon dioxide to the carbon dioxide blower 720 .
  • the blower 700 includes an oxygen blower 710 and a carbon dioxide blower 720 .
  • the oxygen blower 710 supplies oxygen supplied through the first heat exchanger 410 to the combustor.
  • the oxygen blower 710 for this is located between the combustor 100 and the first heat exchanger 410, and communicates the combustor 100 and the first heat exchanger 410 through the first heat exchanger 410.
  • the supplied oxygen is supplied to the combustor 100.
  • the carbon dioxide blower 720 supplies at least a portion of the carbon dioxide supplied from the carbon dioxide tank 600 to the combustor 100 .
  • the present invention may further include a controller (not shown) for adjusting the amount of at least a portion of the carbon supplied from the separator 500 .
  • the control unit turns on/off the separator 500 to control the amount of carbon supplied to the burner 100 by the separator 500. It is possible to control off and the blowing strength of the blower 720 .
  • control unit may control the heat source by controlling the separator 500 to reduce the amount of carbon supplied to the combustor 100 .
  • the heat source is controlled by reducing the amount of carbon separately supplied to the combustor 100 .
  • carbon monoxide may be produced and utilized by reacting a part of the produced high-temperature carbon with high-temperature carbon dioxide (CO 2 ).
  • low-temperature carbon dioxide (CO 2 ) may be recycled and utilized.
  • CO 2 low-temperature carbon dioxide
  • Second Embodiment Hydrogen and carbon production system through methane pyrolysis using fluidized bed indirect heat exchange
  • FIG. 2 is a conceptual diagram illustrating a system for producing hydrogen and carbon through methane pyrolysis using a fluidized bed indirect heat exchange method according to a second embodiment of the present invention.
  • the combustor and the pyrolysis unit are not separated, but the pyrolysis unit is located inside the combustor to pyrolyze methane inside the combustor happens.
  • a system for producing hydrogen and carbon through methane pyrolysis using a fluidized bed indirect heat exchange method includes a combustor 100', a pyrolysis machine 200', a methane flow path 300', and a heat exchanger 400' , a separator 500', a carbon dioxide tank 600' and a blower 700'.
  • the combustor 100' generates carbon dioxide as a by-product by combusting the fuel in a pure oxygen circulation fluidized bed.
  • pure oxy-pulverized coal combustion Oxy-PC
  • pressurized oxy combustion Poxy, pressurized oxy combustion
  • mild poxy Poxy under mild combustion conditions
  • mild combustion means that it is performed under mild combustion conditions, and the above-mentioned mild combustion maintains the temperature of the reactant and oxidant above the ignition temperature of the fuel and is very uniform under normal flameless conditions. It is a combustion technology that forms a temperature control field.
  • the thermal cracker 200' communicates with the methane flow path 300 and produces hydrogen and carbon through thermal decomposition of methane supplied along the methane flow path 300.
  • the thermal decomposer 200' is a ceramic reactor located inside the combustor 100', and may be, for example, a ceramic pipe.
  • thermal decomposer 200' decomposes methane using heat transferred from beads to the outer surface of the thermal decomposer 200'.
  • the yellow line shown in FIG. 2 represents the methane passage 300' in which methane circulates and the section preheated by heat exchange, and the gray dotted line shown in FIG. It means the section where heat is transferred to and the thermal decomposition reaction takes place.
  • the methane passage 300' is disposed inside the combustor 100', and methane is supplied from the outside and circulated.
  • the yellow line shown in FIG. 2 is the methane flow path 300 'and means a section in which methane circulated inside the methane flow path 300' is preheated, and the gray dotted line shown in FIG. 2 is a thermal decomposer such as a ceramic pipe ( 200) and simulates a process in which methane circulating inside the pyrolyzer 200 is directly pyrolyzed by heat indirectly transferred from the high-temperature combustion gas outside (through the outer surface of the pyrolyzer).
  • a thermal decomposer such as a ceramic pipe ( 200)
  • a ceramic pipe of the pyrolysis unit 200 may be used in the yellow preheating section, but a metal material having good heat transfer may be used in a heat exchange region of 700 ° C or less.
  • the pyrolysis reactor 200 which is a gray viscous ceramic reactor, serves to increase methane conversion by maintaining the temperature at 1000° C. or higher.
  • the methane passage 300' extends from the second heat exchanger 420 to the inside of the combustor 100'.
  • at least a portion of the methane passage 300' may be formed along an inner surface of the combustor 100' and communicates with the thermal decomposer 200'.
  • the aforementioned methane passage 300' is also a preheating section for preheating methane.
  • the heat exchanger 400' includes a first heat exchanger 410' and a second heat exchanger 420'.
  • the first heat exchanger 410' exchanges heat between oxygen supplied from the outside and the hydrogen supplied from the separator 500.
  • the above-described first heat exchanger 410' exchanges heat so that the heat contained in hydrogen is transferred to oxygen, and since this first heat exchanger 410' is the same as the first heat exchanger 410 of the first embodiment, detailed description refer to the foregoing.
  • the second heat exchanger 420' is disposed to surround at least a portion of the methane flow path 300' and exchanges heat between methane and carbon dioxide supplied from the combustor 100'.
  • the separator 500' separates hydrogen and carbon transferred from the pyrolysis machine 200', converts at least a portion of the carbon into solid carbon, and supplies another portion of the carbon to the combustor 100'.
  • the carbon dioxide tank 600' stores carbon dioxide heat-exchanged through the second heat exchanger 420'.
  • the blower 700' includes an oxygen blower 710' and a carbon dioxide blower 720'.
  • the oxygen blower 710' supplies oxygen supplied through the first heat exchanger 410' to the combustor 100', and since this oxygen blower 710' is the same as the oxygen blower 710 of the first embodiment, For a detailed description, refer to the foregoing.
  • the carbon dioxide blower 720' supplies at least a portion of the carbon dioxide supplied from the carbon dioxide tank 600' to the burner 100', and the carbon dioxide blower 720' is the same as the carbon dioxide blower 720 of the first embodiment.
  • the carbon dioxide blower 720' is the same as the carbon dioxide blower 720 of the first embodiment.
  • the present invention may further include a control unit for adjusting the amount of at least a portion of the carbon supplied from the separator 500 'as in the first embodiment, and since the control unit is the same as the control unit in the first embodiment, For explanation, refer to the foregoing.
  • FIG. 3 is a conceptual diagram illustrating a system for producing hydrogen and carbon through methane pyrolysis using a fluidized bed indirect heat exchange method according to a third embodiment of the present invention.
  • the hydrogen and carbon production system through methane pyrolysis of the fluidized bed indirect heat exchange method according to the third embodiment is an applied form of the first and second embodiments, and a bead separator is installed inside the single pulverized coal combustor and the methane passage through which methane flows Methane is pyrolyzed through indirect heat exchange that promotes heat transfer to methane on the outer surface of the methane flow channel by inserting ceramic beads into the inside.
  • a system for producing hydrogen and carbon through methane pyrolysis of a fluidized bed indirect heat exchange method includes a combustor (100′′), a pyrolysis device (200′′), a methane flow path (300′′), a heat exchanger ( 400′′), a separator 500′′ and a bead separator 800′′.
  • the combustor 100'' generates carbon dioxide as a by-product by combusting the fuel in a pure oxygen circulation fluidized bed.
  • the thermal cracker 200'' communicates with the methane flow path 300'' and produces hydrogen and carbon through thermal decomposition of methane supplied along the methane flow path 300''.
  • the thermal decomposer 200 ′′ is a ceramic reactor located inside the combustor 100 ′′, and may be illustratively a ceramic pipe.
  • thermal decomposer 200'' decomposes methane using heat transferred from beads to the outer surface of the thermal decomposer 200''.
  • the thermal cracker 200 ′′ supplies carbon and hydrogen obtained by thermally decomposing methane to the separator 500 .
  • the yellow line shown in FIG. 3 indicates the methane passage 300′′ in which methane circulates and the section preheated by heat exchange, and the gray dotted line shown in FIG. It refers to the section where heat is directly transferred to meet and a thermal decomposition reaction occurs.
  • the methane passage 300'' is disposed inside the combustor 100'', and methane is supplied from the outside and circulated.
  • the methane flow path 300'' extends from the heat exchanger 400'' to the inside of the combustor 100'', and in particular, at least a portion of the methane flow path 300'' is part of the combustor 100''. It is arranged so as to be adjacent to the inner surface.
  • the methane passage 300'' is also a preheating section for preheating methane.
  • the heat exchanger 400'' is arranged to surround at least a portion of the methane flow path 300'', and the beads supplied from the first and second bead separators 810'' and 820'' and the combustor 100'' Methane supplied from the heat exchanger.
  • the high-temperature beads returned to the methane supply unit for supplying methane to the methane flow path 300'' pass through the methane flow path 300'' along with methane through the methane flow path 300''. While circulating, heat exchange is performed so that the heat of the beads is transferred to methane.
  • the heat exchanger 200'' exchanges heat so that the heat contained in the carbon dioxide supplied from the combustor 100'' is transferred to methane.
  • the separator 500'' separates hydrogen and carbon transported from the thermal cracker 200'' and produces at least a portion of the carbon as solid carbon, and this separator 500'' is the separator of the first and second embodiments ( 500) and the separator 500', so the detailed description is referred to the above.
  • the bead separator 800'' functions to separate gas and solids inside the combustor using a cyclone, etc., and the separated high-temperature beads are reintroduced to the methane supply unit to increase the temperature of methane inside the reactor. .
  • the bead separator 800 ′′ prevents carbon from adhering inside the combustor by separating it from the wall when some of the carbon generated in the pyrolysis reaction adheres to the inner surface of the combustor.
  • the bead separator 800'' is a bead, and when granular carbon is used instead of ceramic beads, it serves as a catalyst to promote the pyrolysis reaction of methane and at the same time prevents carbon from adhering to the reactor wall.
  • the bead is used only inside the methane passage 300 ′′ to which methane is supplied.
  • the bead separator 800'' described above includes a first bead separator 810'' and a second bead separator 820''.
  • the first bead separator 810'' is adjacent to the methane passage 300'' and is located inside the combustor 100'' to separate the beads from the pure oxygen circulation fluidized bed.
  • the first bead separator 810'' is located on one side of the lower part of the combustor 100'' while adjacent to the methane flow path 300'', so as to remove beads from gases and solids inside the combustor 100''. After separation, it is supplied to the methane supply unit.
  • the second bead separator 820'' is adjacent to the methane passage 300'' and is located inside the combustor 100'' to separate the beads from the pure oxygen circulation fluidized bed.
  • the second bead separator 820'' is located on the other side of the upper part of the burner 100'' while adjacent to the thermal decomposer 200'' to separate the beads from gas and solids inside the combustor 100''. After separation, it is supplied to the methane supply unit.
  • CO 2 carbon dioxide
  • beads such as alumina
  • the present invention does not require a separate catalyst such as a liquid catalyst, molten salt, or a solid catalyst, and can obtain high-purity carbon by fundamentally blocking the incorporation of foreign substances into the produced solid carbon, which is a problem in the quality of solid carbon products that occurred in the prior art. can solve
  • the present invention does not require a separate separation process because hydrogen and carbon dioxide (CO 2 ) are separated and discharged from the thermal decomposer, and accordingly, hydrogen-carbon dioxide The cost of the separation process can be minimized.
  • the present invention can easily produce high-purity carbon monoxide (CO) through the Boudouard reaction by reacting the high-temperature carbon produced in pyrolysis with the high-temperature carbon dioxide (CO 2 ) produced by pure oxygen combustion, methane pyrolysis
  • CO 2 carbon dioxide
  • Both carbon and carbon dioxide (CO 2 ) generated in the process are above 1000 degrees, so the above reaction can be easily implemented without adding a separate heat transfer process.
  • the present invention has an advantage in linking CCUS technology because the purity of the produced carbon dioxide (CO 2 ) is 100%.

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

Abstract

La présente invention concerne un système de génération d'hydrogène et de carbone utilisant une pyrolyse de méthane au moyen d'un échange de chaleur indirect en lit fluidisé, le système comprenant : une chambre de combustion pour générer du dioxyde de carbone par oxy-combustion en lit fluidisé circulant de combustible ; un trajet d'écoulement de méthane qui est disposé à l'intérieur de la chambre de combustion et à travers lequel du méthane est fourni depuis l'extérieur et circule ; un pyrolyseur communiquant avec le trajet d'écoulement de méthane et générant de l'hydrogène et du carbone par pyrolyse du méthane fourni par l'intermédiaire du trajet d'écoulement de méthane au moyen de la chaleur transférée à partir de billes fournies par la chambre de combustion ; un séparateur pour séparer l'hydrogène et le carbone transférés du pyrolyseur, générer au moins une partie du carbone en carbone solide, et fournir le reste du carbone à la chambre de combustion ; des échangeurs de chaleur comprenant un premier échangeur de chaleur, pour échanger de la chaleur entre l'oxygène fourni à partir de l'extérieur et l'hydrogène fourni par le séparateur, et un second échangeur de chaleur disposé de façon à entourer au moins une partie du trajet d'écoulement de méthane et à échanger de la chaleur entre le méthane et le dioxyde de carbone fournis par la chambre de combustion ; un réservoir de dioxyde de carbone pour stocker le dioxyde de carbone qui a été échangé thermiquement par le second échangeur de chaleur ; et des ventilateurs comprenant un ventilateur d'oxygène, pour fournir l'oxygène fourni par l'intermédiaire du premier échangeur de chaleur à la chambre de combustion, et un ventilateur de dioxyde de carbone pour fournir au moins une partie du dioxyde de carbone fourni par le réservoir de dioxyde de carbone à la chambre de combustion.
PCT/KR2021/013390 2021-09-29 2021-09-29 Système de génération d'hydrogène et de carbone utilisant une pyrolyse de méthane au moyen d'un échange de chaleur indirect en lit fluidisé Ceased WO2023054753A1 (fr)

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KR102870858B1 (ko) * 2023-10-20 2025-10-17 주식회사 삼천리 청록수소를 활용한 에너지 최적 관리 시스템

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