WO2013115316A1 - Dispositif ainsi que procédé de pyrolyse aqueuse mettant en œuvre une couche d'écoulement par circulation interne - Google Patents

Dispositif ainsi que procédé de pyrolyse aqueuse mettant en œuvre une couche d'écoulement par circulation interne Download PDF

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WO2013115316A1
WO2013115316A1 PCT/JP2013/052211 JP2013052211W WO2013115316A1 WO 2013115316 A1 WO2013115316 A1 WO 2013115316A1 JP 2013052211 W JP2013052211 W JP 2013052211W WO 2013115316 A1 WO2013115316 A1 WO 2013115316A1
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reactor
hydrothermal decomposition
fluidized bed
thermal reduction
communication port
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PCT/JP2013/052211
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English (en)
Japanese (ja)
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児玉　竜也
展之 郷右近
篤 櫻井
幸治 松原
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国立大学法人新潟大学
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Priority to JP2013556494A priority Critical patent/JP5986589B2/ja
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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
    • C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
    • C01B3/042—Decomposition of water
    • C01B3/045—Decomposition of water in gaseous phase
    • 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
    • B01J8/1845—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with particles moving upwards while fluidised
    • B01J8/1854—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with particles moving upwards while fluidised followed by a downward movement inside the reactor to form a loop
    • 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
    • B01J8/1845—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with particles moving upwards while fluidised
    • B01J8/1863—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with particles moving upwards while fluidised followed by a downward movement outside the reactor and subsequently re-entering it
    • 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
    • B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
    • B01J8/36—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique with fluidised bed through which there is an essentially horizontal flow of 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
    • B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
    • B01J8/38—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique with fluidised bed containing a rotatable device or being subject to rotation or to a circulatory movement, i.e. leaving a vessel and subsequently re-entering it
    • B01J8/382—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique with fluidised bed containing a rotatable device or being subject to rotation or to a circulatory movement, i.e. leaving a vessel and subsequently re-entering it with a rotatable device only
    • 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
    • B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
    • B01J8/42—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique with fluidised bed subjected to electric current or to radiations this sub-group includes the fluidised bed subjected to electric or magnetic fields
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/02—Preparation of oxygen
    • C01B13/0203—Preparation of oxygen from inorganic compounds
    • C01B13/0207—Water
    • 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
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/00433—Controlling the temperature using electromagnetic heating
    • B01J2208/00451—Sunlight; Visible light
    • 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
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00743—Feeding or discharging of solids
    • B01J2208/00752—Feeding
    • 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
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00796—Details of the reactor or of the particulate material
    • B01J2208/00893—Feeding means for the reactants
    • B01J2208/00929—Provided with baffles
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/133—Renewable energy sources, e.g. sunlight

Definitions

  • the present invention relates to a hydrothermal decomposition apparatus and a hydrothermal decomposition method using an internal circulating fluidized bed.
  • a two-stage hydrothermal decomposition cycle with metal oxides such as iron oxide and cerium oxide is promising as a method for producing hydrogen by hydrothermal decomposition using heat of 1000 ° C or higher obtained by concentrating sunlight.
  • the development of reactors for this purpose is being conducted by research institutions in each country.
  • the present inventors have developed a fluidized bed solar reactor in which metal oxide particles are circulated internally, and using this fluidized bed solar reactor, hydrogen that is two reactions of a two-stage hydrothermal decomposition cycle is developed.
  • a method of simultaneously producing hydrogen and oxygen by developing a production reaction and an oxygen production reaction simultaneously in a reactor in which metal oxide particles flow in an internal circulation was developed (Patent Document 1).
  • this fluidized bed type solar reactor includes a reactor 101 made of a stainless alloy and an inconel alloy, and this reactor 101 contains a fluidized bed 102 made of metal oxide particles. Yes. Inside the reactor 101, a cylindrical draft tube 103 opened in the vertical direction is provided. The draft tube 103 is buried in the fluidized bed 102 and disposed at the center of the fluidized bed 102. Further, at the bottom of the reactor 101, dispersion plates 104 and 105 are provided at the center and the periphery, respectively. Dispersion plates 104 and 105 are formed of a porous material so that particles of metal oxide constituting fluidized bed 102 can be held in reactor 101 and gas can be introduced from the bottom of reactor 101. ing.
  • a quartz window 106 is provided on the ceiling of the reactor 101 so that sunlight can pass therethrough.
  • a gas separator having a truncated cone shape is provided above the draft pipe 103 in order to divert the gas released upward from the inside of the draft pipe 103 and the gas released upward from the outside of the draft pipe 103.
  • 107 is provided.
  • take-out ports 108 and 109 for taking out the gas diverted by the gas separator 107 are provided.
  • 201 is a ground reflector called a heliostat
  • 202 is a tower reflector.
  • the ground reflector 201 and the tower reflector 202 constitute a beam-down type condensing system.
  • the beam-down type condensing system collects the sunlight S and irradiates the central portion of the upper surface of the fluidized bed 102 accommodated in the reactor 101.
  • the fluidized bed 102 is circulated inside and outside the draft tube 103 by making the flow rate of nitrogen inside the draft tube 103 larger than the flow rate of water vapor outside the draft tube 103. That is, the fluidized bed 103 rises in a region inside the draft pipe 103, and an internal circulation flow is generated in which the fluidized bed 103 descends in a region between the outside of the draft pipe 103 and the reactor 101.
  • the sunlight S collected by the ground reflecting mirror 201 and the tower reflecting mirror 202 is irradiated to the center of the upper surface of the fluidized bed 102 through the window 106 to heat the fluidized bed 102.
  • a high temperature portion H of 1400 ° C. or higher is formed, and a thermal reduction reaction proceeds at this high temperature portion H, and oxygen is released from the metal oxide particles.
  • the released oxygen passes through above the gas separator 107 and is collected from the outlet 108.
  • the reduced metal oxide particles are sent to the lower part of the reactor 101 through the region between the outside of the draft tube 103 and the reactor 101 by the internal circulation flow.
  • the temperature of the metal oxide particles decreases while being sent to the lower part of the reactor 101, and as a result, a low temperature part L of 1400 ° C. or lower is formed in the lower part of the fluidized bed 102.
  • the hydrothermal decomposition reaction proceeds in the low temperature portion L, and the metal oxide particles reduced by the thermal reduction reaction become the original metal oxide even when oxidized, and hydrogen is generated at the same time.
  • the generated hydrogen passes through the lower side of the gas separator 107 and is collected from the take-out port 109.
  • the above-described conventional method is characterized by focusing on the temperature distribution of the fluidized bed 103 formed by the irradiation of sunlight S, and causing the oxygen generation reaction and the hydrogen generation reaction to proceed simultaneously in the upper part and the lower part of the fluidized bed 103, respectively.
  • this method has the following problems. 1 Due to the structure of the reactor, oxygen and hydrogen are mixed through the gap between the surface of the fluidized bed 102 and the gas separator 107 and a part of oxygen and hydrogen are recombined, so that the amount of hydrogen recovered decreases.
  • the hydrogen generation reaction that proceeds in the lower part of the fluidized bed 102 is an exothermic reaction
  • the oxygen generation reaction that proceeds in the upper part of the fluidized bed 102 is an endothermic reaction, but the reaction time and reaction rate of each reaction are arbitrarily controlled. Therefore, it is difficult to sufficiently utilize the reaction heat (heat radiation amount) generated in the hydrogen generation reaction for the endothermic reaction in the oxygen generation, and it is difficult to improve the solar heat ⁇ hydrogen conversion efficiency.
  • a high-temperature portion H of 1400 ° C. or higher is formed in the vicinity of the center of the upper surface of the fluidized bed 102 irradiated with the sunlight S. However, due to the reactor structure, a part of the condensed sunlight S is a gas separator.
  • the region between the outside of the draft tube 103 and the reactor 101 cannot be heated, and the utilization efficiency of solar energy is lowered. 6 Because of the structure of the reactor, a part of the vicinity of the center of the upper surface of the fluidized bed 102 is blocked by the gas separator 107, so it is difficult to widen the region of the high temperature portion H of 1400 ° C. or higher and increase the amount of oxygen produced. is there. 7 Due to the structure of the reactor, the region of the low temperature part L of 1400 ° C. or lower is limited to the lower part of the fluidized bed 102, and it is difficult to widen the region of the low temperature part L and increase the amount of hydrogen generation.
  • the metal oxide particles in the high temperature portion H formed in the vicinity of the center of the upper surface of the fluidized bed 102 quickly move to the region between the outside of the draft tube 103 and the reactor 101. It is difficult to recover and reuse the high-temperature sensible heat of 1400 ° C. or higher possessed by the metal oxide particles in the high-temperature portion H as exhaust heat.
  • the present invention can reliably separate and recover the generated oxygen and hydrogen, and can arbitrarily set the reaction temperature, reaction rate, reaction time, and reaction region of the reaction that proceeds simultaneously in the fluidized bed. It is also possible to provide a hydrothermal decomposition apparatus and hydrothermal decomposition method using an internal circulating fluidized bed that can be controlled to high temperature, and can recover and reuse high-temperature heat as exhaust heat with high efficiency. And
  • the hydrothermal decomposition apparatus using the internal circulation fluidized bed according to the present invention condenses sunlight into a reactor containing a fluidized bed made of metal oxide particles and the fluidized bed contained in the reactor.
  • the solar light collecting means for irradiating, the reactor comprising: a thermal reduction reactor for performing a thermal reduction reaction; a hydrothermal decomposition reactor for performing a hydrothermal decomposition reaction; and a low oxygen content from below to the thermal reduction reactor.
  • Low oxygen partial pressure gas introducing means for introducing pressurized gas, steam introducing means for introducing water vapor into the hydrothermal decomposition reactor from below, and oxygen recovery for recovering gas containing oxygen generated from the thermal reduction reactor
  • a hydrogen recovery means for recovering a gas containing hydrogen generated from the hydrothermal decomposition reactor, wherein the interior of the thermal reduction reactor and the interior of the hydrothermal decomposition reactor are in communication with the upper communication port and the lower communication port.
  • the upper communication port and the lower communication port The fluidized bed is buried in the fluidized bed so that the fluidized bed can flow between the thermal reduction reactor and the hydrothermal decomposition reactor through the upper communication port and the lower communication port, Sunlight is irradiated to the upper surface of the fluidized bed accommodated in the thermal reduction reactor by a light collecting means.
  • the thermal reduction reactor and the hydrothermal decomposition reactor are partitioned by a partition plate, and the interior of the thermal reduction reactor and the interior of the hydrothermal decomposition reactor are upper communication ports formed in the partition plate. And the lower communication port, the upper communication port and the lower communication port are buried in the fluidized bed, and through the upper communication port and the lower communication port, the thermal reduction reactor The fluidized bed is configured to flow directly between the hydrothermal decomposition reactors.
  • the upper communication port and the lower communication port are provided with screw conveyors for conveying the fluidized bed between the thermal reduction reactor and the hydrothermal decomposition reactor.
  • an enlarged portion that expands the horizontal cross-sectional area of the thermal reduction reactor upward is formed in the upper portion of the thermal reduction reactor, and a quartz window through which sunlight passes is formed in the upper portion of the enlarged portion. It is characterized by having.
  • thermal reduction reactor and the hydrothermal decomposition reactor are configured separately from each other.
  • a moving means for moving the fluidized bed in the thermal reduction reactor is provided inside the thermal reduction reactor.
  • the hydrothermal decomposition method using the inner circulating fluidized bed according to the present invention uses the hydrothermal decomposition apparatus using the inner circulating fluidized bed according to the present invention, and converts the fluidized bed into the thermal reduction reactor and the hydrothermal decomposition reactor.
  • the oxygen generation reaction in which a part of the fluidized bed is heated by sunlight in a low oxygen partial pressure gas atmosphere while releasing the oxygen from the metal oxide, and the metal after releasing the oxygen. It is characterized in that two reactions of a hydrogen generation reaction in which water vapor is brought into contact with the oxide to generate hydrogen simultaneously proceed.
  • the oxygen generation reaction proceeds at 1400 ° C. or higher, and the hydrogen generation reaction proceeds at 1400 ° C. or lower.
  • the metal oxide is characterized by being ferrite or zirconia supporting ferrite.
  • the zirconia is any of monoclinic zirconia, cubic zirconia, and tetragonal zirconia, and the cubic zirconia contains any of yttria, calcia, and magnesia as a stabilizer.
  • the metal oxide is characterized by nickel ferrite or monoclinic zirconia supporting nickel ferrite.
  • the metal oxide is cerium oxide or zirconia supporting cerium oxide.
  • the particle size of the metal oxide particles is 100 to 750 ⁇ m.
  • the low oxygen partial pressure gas is nitrogen or argon.
  • the thermal reduction reactor and the hydrothermal decomposition reactor are partitioned by the partition plate, and the interior of the thermal reduction reactor and the water are separated.
  • the interior of the pyrolysis reactor communicates directly with the upper communication port and the lower communication port formed in the partition plate, and the upper communication port and the lower communication port are buried in the fluidized bed, Since the fluidized bed can flow directly between the thermal reduction reactor and hydrothermal decomposition reactor through the lower communication port, oxygen generated in the thermal reduction reactor and generated in the hydrothermal decomposition reactor.
  • the reaction temperature, reaction rate, reaction time and reaction region of the two reactions that proceed simultaneously in the fluidized bed of the thermal reduction reactor and the fluidized bed of the hydrothermal decomposition reactor Each can be controlled easily Can, furthermore, it is possible to recover the heat of reaction at a high efficiency occurring in the hydrothermal decomposition reactor for reuse in the heat reduction reactor. Furthermore, the high-temperature heat generated in the thermal reduction reactor and the hydrothermal decomposition reactor can be recovered and reused as waste heat with high efficiency.
  • the present invention can solve the problems of the conventional methods as follows. 1 Since oxygen and hydrogen are generated separately in the thermal reduction reactor and hydrothermal decomposition reactor, respectively, there is no need for gas separation of oxygen and hydrogen by a gas separator or the like, and the purity of recovered oxygen and hydrogen is reduced. Will improve. 2 Since the thermal reduction reaction and hydrothermal decomposition reaction proceed in the thermal reduction reactor and hydrothermal decomposition reactor, respectively, it becomes easy to arbitrarily control the reaction temperatures of the two reactions having different reaction temperatures. Oxygen generation and hydrogen generation from the reactor are improved.
  • Concentrated sunlight is widely irradiated in the vicinity of the upper surface of the fluidized bed in the thermal reduction reactor without being blocked by the gas separator, and can contribute to the formation of a high-temperature part of 1400 ° C or higher. In addition, it can be used for heating metal oxide particles, and the utilization efficiency of solar energy is increased. 6 Since the collected sunlight can be widely irradiated in the vicinity of the upper surface of the fluidized bed in the thermal reduction reactor without being blocked by the gas separator, it can contribute to the formation of a high temperature portion of 1400 ° C. or higher. The region of the high temperature part can be expanded, and the amount of oxygen produced can be increased.
  • the size of the hydrothermal cracking reactor can be changed arbitrarily, so that the region of the low temperature part below 1400 ° C formed in the hydrothermal cracking reactor can be expanded, and the amount of hydrogen produced Can be increased.
  • the metal oxide particles in the high temperature part formed in the vicinity of the upper surface of the fluidized bed in the thermal reduction reactor have an upper communication port located below the upper surface of the fluidized bed. Since some of them stay around the high temperature part H and are heated to a higher temperature, the thermal reduction reaction is more likely to proceed, and the amount of oxygen generated is improved.
  • the metal oxide particles in the high temperature part formed in the vicinity of the upper surface of the fluidized bed in the thermal reduction reactor have an upper communication port located below the upper surface of the fluidized bed. A part of the stagnation stays around the high-temperature part H, and the high-temperature sensible heat of 1400 ° C. or higher possessed by the metal oxide particles of the high-temperature part H can be recovered and reused as exhaust heat with high efficiency.
  • FIG. 6 is a graph showing a change over time in the hydrogen production rate produced from the hydrothermal decomposition reactor 4 in Example 3.
  • FIG. 6 is a graph obtained by measuring changes with time in oxygen generation rate generated from the thermal reduction reactor 3 in Example 3 and hydrogen flowing in from the hydrothermal decomposition reactor 4.
  • FIG. 6 is a graph obtained by measuring changes over time in the hydrogen production rate produced from the hydrothermal decomposition reactor 4 in Example 4 and oxygen flowing in from the thermal reduction reactor 3.
  • FIG. 6 is a graph obtained by measuring changes with time in the oxygen generation rate generated from the thermal reduction reactor 3 in Example 4 and hydrogen flowing in from the hydrothermal decomposition reactor 4.
  • FIG. 6 is a graph showing a change over time in a hydrogen / oxygen generation rate ratio, which is a value obtained by dividing the hydrogen generation rate generated from the hydrothermal decomposition reactor 4 in Example 4 by the oxygen generation rate generated from the thermal reduction reactor 3.
  • It is a schematic diagram which shows another Example of the hydrothermal decomposition apparatus using the internal circulation fluidized bed of this invention.
  • hydrothermal decomposition apparatus and hydrothermal decomposition method using the inner circulating fluidized bed of the present invention will be described with reference to the accompanying drawings.
  • the hydrothermal decomposition apparatus and hydrothermal decomposition method using the internal circulation fluidized bed of this invention are suitably implemented in the sun belt area whose solar radiation is 1800 kWh / m ⁇ 2 > or more per year.
  • FIG. 1 showing an embodiment of a hydrothermal decomposition apparatus using an internal circulating fluidized bed of the present invention
  • 1 is a reactor made of a stainless alloy and an Inconel alloy, and this reactor 1 contains metal oxide particles.
  • a fluidized bed 2 as an inner circulating fluidized bed is housed.
  • the metal oxide examples include iron oxides such as Fe 3 O 4 , NiFe 2 O 4 , and CoFe 2 O 4 , iron oxides containing multiple metals, and these iron oxides supported on a carrier such as zirconia.
  • Cerium oxide (CeO 2 ) cerium oxide supported on a carrier such as zirconia, or iron ions or cerium ions dissolved in zirconia can be used.
  • zirconia any of monoclinic zirconia, cubic zirconia, and tetragonal zirconia can be used.
  • cubic zirconia is stabilized zirconia or partially stabilized zirconia containing a stabilizer such as yttria, calcia, and magnesia, and includes zirconia containing at least cubic crystals as a crystal layer.
  • the fine powder of yttria-stabilized cubic zirconia carrying the ferrite represented by More preferably, fine powders of NiFe 2 O 4 and NiFe 2 O 4 / m-ZrO 2 are used.
  • a fine powder of cerium oxide and a fine powder of zirconia supporting cerium oxide are also preferably used.
  • the size of the metal oxide particles is preferably 30 to 1000 ⁇ m, more preferably 100 to 750 ⁇ m, in order to maintain the fluidity of the fluidized bed 2.
  • zirconia supporting ferrite for example, disperses zirconia fine powder in an aqueous solution of Fe (II) salt and adds an alkaline aqueous solution such as an aqueous solution of sodium hydroxide to form a colloid of Fe (II) hydroxide.
  • an alkaline aqueous solution such as an aqueous solution of sodium hydroxide
  • This is oxidized by bubbling air, and after the colloid of Fe (II) hydroxide is dissolved in the aqueous solution, the dissolution precipitation reaction that precipitates as Fe 3 O 4 proceeds to disperse fine zirconia powder It can be obtained by growing Fe 3 O 4 on the body.
  • a fine powder of zirconia is dispersed in an aqueous solution of Fe (II) salt, this is evaporated to dryness, and then fired to convert the Fe (II) salt on zirconia into a metal oxide. It can also be obtained by baking at a temperature of 0 ° C. or higher.
  • the reactor 1 includes a thermal reduction reactor 3 that performs a thermal reduction reaction and a hydrothermal decomposition reactor 4 that performs a hydrothermal decomposition reaction.
  • the thermal reduction reactor 3 and the hydrothermal decomposition reactor 4 are partitioned by a single partition plate 5, and the interior of the thermal reduction reactor 3 and the interior of the hydrothermal decomposition reactor 4 are located above the partition plate 5.
  • An upper communication port 6 that directly communicates with each other is formed, and a lower communication port 7 that directly communicates the interior of the thermal reduction reactor 3 and the interior of the hydrothermal decomposition reactor 4 is formed at the lower portion of the partition plate 5.
  • the upper communication port 6 and the lower communication port 7 are buried in the fluidized bed 2.
  • the fluidized bed 2 can flow directly between the thermal reduction reactor 3 and the hydrothermal decomposition reactor 4 through the upper communication port 6 and the lower communication port 7.
  • a dispersion plate 9 for introducing water vapor into 4 is provided.
  • the dispersion plates 8 and 9 are connected to the lowermost part 7 ′ of the lower communication port 7 so as not to hinder the flow of the fluidized bed 2 at the lower communication port 7.
  • the surface of the dispersion plate 8 substantially coincides with the height of the lowermost part 7 ′ of the lower communication port 7, and the dispersion plate 9 is provided inclined with the lowermost part 7 ′ of the lower communication port 7 as the lowest part. .
  • the dispersion plates 8 and 9 are made of a porous material so that the metal oxide particles constituting the fluidized bed 2 can be held in the reactor 1 and gas can be introduced from the bottom of the reactor 1. Is formed.
  • An introduction pipe 10 for introducing a low oxygen partial pressure gas is provided at the bottom of the thermal reduction reactor 3, and an introduction pipe 11 for introducing water vapor is provided at the bottom of the hydrothermal decomposition reactor 4.
  • the upper part of the thermal reduction reactor 3 is connected to the side wall of the thermal reduction reactor 3 and the partition plate 5 above the uppermost part 6 ′ of the upper communication port 6, and the horizontal side of the thermal reduction reactor 3 upwards.
  • An enlarged portion 12 that enlarges the cross-sectional area is formed.
  • the enlarged portion 12 allows sunlight S to be irradiated to the fluidized bed 2 without being blocked by the wall of the thermal reduction reactor 3.
  • a quartz window 13 is provided on the ceiling above the enlarged portion 12 of the thermal reduction reactor 3 so that sunlight can pass therethrough.
  • a gas outlet 14 for containing oxygen generated by the thermal reduction reaction.
  • An outlet 15 for extracting gas containing hydrogen generated by the decomposition reaction is provided on the side of the upper part of the enlarged portion 12 of the thermal reduction reactor 3.
  • 201 is a ground reflector called a heliostat
  • 202 is a tower reflector installed in a tower (not shown)
  • the ground reflector 201 and the tower reflector 202 constitute a beam-down type condensing system.
  • the beam-down type condensing system collects sunlight S and irradiates the upper surface of the fluidized bed 2 accommodated in the thermal reduction reactor 3.
  • a low oxygen partial pressure gas is introduced from the dispersion plate 8 into the thermal reduction reactor 3, and at the same time, water vapor is introduced from the dispersion plate 9 into the hydrothermal decomposition reactor 4.
  • the low oxygen partial pressure gas for example, nitrogen having a purity of 99.999% is used.
  • the low oxygen partial pressure gas introduced into the thermal reduction reactor 3 may be a gas having a low oxygen partial pressure, and is not limited to nitrogen, and may be, for example, argon.
  • transduced into the hydrothermal decomposition reactor 4 should just contain water vapor
  • the fluidized bed 2 is circulated between the thermal reduction reactor 3 and the hydrothermal decomposition reactor 4 by making the flow rate of nitrogen larger than the flow rate of water vapor. That is, the fluidized bed 2 rises in the thermal reduction reactor 3, and an internal circulation flow in which the fluidized bed 2 descends in the hydrothermal decomposition reactor 4 is generated.
  • the fluidized bed 2 is heated by irradiating the fluidized bed 2 with the sunlight S collected by the ground reflector 201 and the tower reflector 202 through the window 13.
  • a high-temperature portion H of 1400 ° C. or higher is formed, and the thermal reduction reaction proceeds at the high-temperature portion H to form metal oxide particles. Releases oxygen. The released oxygen is collected from the outlet 14.
  • the reaction formula of the thermal reduction reaction is as follows. NiFe 2 O 4 ⁇ 3Ni 1/3 Fe 2/3 O + (1/2) O 2
  • the reaction formula of the thermal reduction reaction is as follows. CeO 2 ⁇ CeO 2 ⁇ x + (x / 2) O 2 (0 ⁇ x ⁇ 0.5)
  • the reduced metal oxide particles are sent to the hydrothermal decomposition reactor 4 through the upper communication port 6 by internal circulation flow.
  • the temperature of the metal oxide particles decreases while flowing in the hydrothermal decomposition reactor 4, and as a result, the fluidized bed 2 in the hydrothermal decomposition reactor 4 has a temperature of 1400 ° C or less, preferably 1200 ° C or less. More preferably, a low temperature portion L of 1000 ° C. or lower is formed.
  • the hydrothermal decomposition reaction proceeds in the low temperature portion L, and the metal oxide particles reduced by the thermal reduction reaction become the original metal oxide even when oxidized, and hydrogen is generated at the same time. The generated hydrogen is recovered from the extraction port 15.
  • the reaction formula of the hydrothermal decomposition reaction is as follows. 3Ni 1/3 Fe 2/3 O + H 2 O ⁇ NiFe 2 O 4 + H 2
  • the reaction formula of the hydrothermal decomposition reaction is as follows. CeO 2-x + xH 2 O ⁇ CeO 2 + xH 2 (0 ⁇ x ⁇ 0.5)
  • the temperature of the fluidized bed 2 at the lower part of the thermal reduction reactor 3 is lower than the temperature of the fluidized bed 2 of the hydrothermal decomposition reactor 4, and a sufficient temperature difference is required.
  • nitrogen is introduced into the thermal reduction reactor 3 and water vapor is simultaneously introduced into the hydrothermal decomposition reactor 4, and the flow rate of nitrogen is made larger than the flow rate of water vapor to make the fluidized bed 2 into the reactor.
  • the hydrothermal decomposition apparatus using the inner circulation fluidized bed of the present embodiment includes the reactor 1 that contains the fluidized bed 2 made of metal oxide particles, and the fluid that is contained in the reactor 1.
  • the ground reflecting mirror 201 and the tower reflecting mirror 202 as sunlight collecting means for collecting and irradiating the sunlight S on the layer 2 are provided, and the reactor 1 includes a thermal reduction reactor 3 that performs a thermal reduction reaction,
  • Dispersion plate 9 and introduction pipe 11 as water vapor introduction means for introducing water vapor into hydrothermal decomposition reactor 4 from below, and oxygen recovery means for recovering the gas containing oxygen generated from thermal reduction reactor 3 Collects hydrogen-containing gas generated from the outlet 14 and the hydrothermal decomposition reactor 4
  • the inside of the decomposition reactor 4 is directly communicated with an upper communication port 6 and a lower communication port 7 formed in the partition plate 5, and the upper communication port 6 and the lower communication port 7 are connected to the fluidized bed 2.
  • the fluidized bed 2 can be directly flowed between the thermal reduction reactor 3 and the hydrothermal decomposition reactor 4 through the upper communication port 6 and the lower communication port 7.
  • the solar reflecting light is applied to the upper surface of the fluidized bed 2 accommodated in the thermal reduction reactor 3 by the ground reflecting mirror 201 and the tower reflecting mirror 202 as the sunlight collecting means. is there.
  • an enlarged portion 12 that expands the horizontal cross-sectional area of the thermal reduction reactor 3 upward is formed in the upper portion of the thermal reduction reactor 3, and sunlight S is transmitted through the upper portion of the enlarged portion 12.
  • a quartz window 13 is provided.
  • the hydrothermal decomposition method using the inner circulation fluidized bed of this embodiment uses the hydrothermal decomposition apparatus using the inner circulation fluidized bed of this embodiment, and the dispersion plate 8 as the low oxygen partial pressure gas introduction means and By making the flow rate of the low oxygen partial pressure gas introduced from the introduction pipe 10 larger than the flow rate of the water vapor introduced from the dispersion plate 9 and the introduction pipe 11 as the steam introduction means, the fluidized bed 2 is subjected to the thermal reduction reaction. While partly circulating between the vessel 3 and the hydrothermal decomposition reactor 4, a part of the fluidized bed 2 is heated by sunlight S in a low oxygen partial pressure gas atmosphere to release oxygen from the metal oxide. Two reactions of an oxygen generation reaction and a hydrogen generation reaction in which water vapor is brought into contact with the metal oxide after releasing oxygen to generate hydrogen are simultaneously advanced.
  • the oxygen generation reaction in the thermal reduction reactor 3 and the hydrogen generation reaction in the hydrothermal decomposition reactor 4 proceed simultaneously. Therefore, the recovery of oxygen and hydrogen can be performed continuously. Further, the thermal reduction reactor 3 and the hydrothermal decomposition reactor 4 are clearly partitioned by a partition plate 5 and are generated because oxygen is generated in the thermal reduction reactor 3 and hydrogen is generated in the hydrothermal decomposition reactor 4. There is no mixing of oxygen and hydrogen. Therefore, the generated oxygen and hydrogen can be reliably separated and recovered. As a result, the purity of the recovered hydrogen can be improved and the production cost of hydrogen can be reduced.
  • Example 1 For the hydrothermal decomposition apparatus using the inner circulating fluidized bed of Example 1, under the calculation conditions shown in FIG. FLUENT ver.13) was used to conduct a fluidization simulation on the behavior of fluidized particles and circulating gas in the reactor 1. In this simulation, the compressible Navier-Stokes equation was adopted as a physical model for solid-gas multiphase flow, and the Euler-granular model was applied to the interaction between particles and gas. Furthermore, in the heat transfer analysis of the fluidized bed 2, the energy equation and the radiation transport equation were combined, and the amount of radiant heat transfer was analyzed by the spherical harmonic function method. The fluidized bed 2 was filled with CeO 2 particles having a diameter of 450 ⁇ m in the reactor 1.
  • FIGS. FIG. 3 shows the volume fraction of the solid phase, which progresses in time from the upper left to the lower right. From this result, it was found that bubbles were generated from the lower inlet. From the particle flow velocity distribution (left side of FIG. 4), it was found that the flowing particles flow in an internal circulation between the thermal reduction reactor 3 and the hydrothermal decomposition reactor 4. Further, from the gas flow velocity distribution (right in FIG. 4), the oxygen produced in the thermal reduction reactor 3 and the hydrogen produced in the hydrothermal decomposition reactor 4 are not mixed with each other, and the reactor is separated from oxygen and hydrogen. It was found that it could be taken out of 1.
  • nitrogen having a purity of 99.999% is flowed to the thermal reduction reactor 3 at a flow rate of 8 L / min and a linear flow velocity of 2.22 m / min, and the hydrothermal decomposition reactor 4 is a mixed gas of water vapor and nitrogen. At a flow rate of 4 L / min and a linear flow rate of 1.77 m / min.
  • the types of gas produced from the thermal reduction reactor 3 and the hydrothermal decomposition reactor 4 and their production rates were quantitatively analyzed with a mass spectrometer and a gas chromatograph.
  • FIG. 5 shows the change over time in the amount of hydrogen generated from the hydrothermal decomposition reactor 4 at this time.
  • the total amount of hydrogen generated from the hydrothermal decomposition reactor 4 was 554 ml (1 atm, 25 ° C.).
  • generation of oxygen was not seen from the gas exhaust port connected to the hydrothermal decomposition reactor 4.
  • FIG. 6 shows the change over time in the amount of oxygen generated from the thermal reduction reactor 3.
  • the total amount of oxygen generated from the thermal reduction reactor 3 was 318 ml (1 atm, 25 ° C.). No hydrogen was produced from the gas outlet connected to the thermal reduction reactor 3. From this result, it can be seen that the hydrogen generated in the hydrothermal decomposition reactor 4 does not enter the thermal reduction reactor 3.
  • the fluidized bed 2 after the reaction did not sinter and agglomerate and had a powder form. Therefore, when CeO 2 fine powder was used for the fluidized bed 2, it was confirmed that the oxygen generation amount and the hydrogen generation amount can be increased by further extending the reaction time.
  • FIG. 7 shows the change over time in the amount of hydrogen generated from the hydrothermal decomposition reactor 4 at this time.
  • the total amount of hydrogen generated from the hydrothermal decomposition reactor 4 was 847 ml (1 atm, 25 ° C.). Also, almost no oxygen was generated from the gas outlet connected to the hydrothermal decomposition reactor 4. From this result, it can be seen that oxygen generated from the thermal reduction reactor 3 is not mixed into the hydrothermal decomposition reactor 4.
  • FIG. 8 shows the change over time in the amount of oxygen generated from the thermal reduction reactor 3.
  • the total amount of oxygen generated from the thermal reduction reactor 3 was 1319 ml (1 atm, 25 ° C.). Almost no hydrogen was generated from the gas outlet connected to the thermal reduction reactor 3. From this result, it can be seen that hydrogen produced in the hydrothermal decomposition reactor 4 does not enter the thermal reduction reactor 3.
  • the fluidized bed 2 after the reaction did not sinter and agglomerate and had a powder form. Therefore, when CeO 2 fine powder was used for the fluidized bed 2, it was confirmed that the oxygen generation amount and the hydrogen generation amount can be increased by further extending the reaction time.
  • FIG. 9 shows the change over time in the hydrogen / oxygen generation rate ratio, which is a value obtained by dividing the hydrogen generation rate generated from the hydrothermal decomposition reactor 4 by the oxygen generation rate generated from the thermal reduction reactor 3. It can be seen that the hydrogen / oxygen ratio produced over time approaches 2 which is the stoichiometric ratio of water molecules (H 2 O). Therefore, it can be seen that the two-stage hydrothermal decomposition reaction in the reactor proceeds according to the stoichiometric ratio.
  • the thermal reduction reactor 3 and the hydrothermal decomposition reactor 4 are configured separately from each other.
  • Upper communication ports 6a and 6b communicating the inside of the thermal reduction reactor 3 and the inside of the hydrothermal decomposition reactor 4 are formed at the upper parts of the thermal reduction reactor 3 and the hydrothermal decomposition reactor 4, respectively.
  • Lower communication ports 7 a and 7 b that communicate the inside of the thermal reduction reactor 3 and the inside of the hydrothermal decomposition reactor 4 are formed in the lower part of the vessel 3 and the hydrothermal decomposition reactor 4, respectively.
  • the upper communication ports 6 a and 6 b and the lower communication ports 7 a and 7 b are buried in the fluidized bed 2.
  • a screw conveyor 21 is provided between the upper communication ports 6a and 6b, and the fluidized bed 2 is transported from the thermal reduction reactor 3 to the hydrothermal decomposition reactor 4.
  • a screw conveyor 22 is provided between the lower communication ports 7 a and 7 b so that the fluidized bed 2 is transported from the hydrothermal decomposition reactor 4 to the thermal reduction reactor 3.
  • the screw conveyors 21 and 22 are driven by motors 23 and 24, respectively, and the rotational speeds of the screw conveyors 21 and 22 are configured to be controllable.
  • the fluidized bed 2 can flow between the thermal reduction reactor 3 and the hydrothermal decomposition reactor 4 through the upper communication ports 6a and 6b and the lower communication ports 7a and 7b.
  • a dispersion plate 9 for introducing water vapor into 4 is provided.
  • the dispersion plates 8 and 9 are provided so as to be connected to the lowermost portions 7a 'and 7b' of the lower communication ports 7a and 7b so as not to disturb the flow of the fluidized bed 2 at the lower communication port 7.
  • the surface of the dispersion plate 8 substantially coincides with the height of the lowermost portion 7a ′ of the lower communication port 7a, and the distribution plate 9 is provided inclined with the lowermost portion 7b ′ of the lower communication port 7b as the lowest portion. .
  • the two screw conveyors 21 and 22 may be located on the line which connects the center of the thermal reduction reactor 3, and the center of the hydrothermal decomposition reactor 4, FIG.
  • the two screw conveyors 21 and 22 may be located on the same line connecting a portion away from the center of the thermal reduction reactor 3 and a portion away from the center of the hydrothermal decomposition reactor 4.
  • the two screw conveyors 21 and 22 are located on separate lines connecting a portion away from the center of the thermal reduction reactor 3 and a portion away from the center of the hydrothermal decomposition reactor 4.
  • a plurality of upper and lower screw conveyors may be arranged or may be inclined.
  • the screws constituting the screw conveyors 21 and 22 may be uniaxial or biaxial, and one of the screw conveyors 21 and 22 may be omitted.
  • a low oxygen partial pressure gas is introduced from the dispersion plate 8 to the thermal reduction reactor 3, and at the same time, water vapor is introduced from the dispersion plate 9 to the hydrothermal decomposition reactor 4.
  • the screw conveyors 21 and 22 are driven by the motors 23 and 24, and the fluidized bed 2 is transported from the thermal reduction reactor 3 to the hydrothermal decomposition reactor 4 through the upper communication ports 6a and 6b.
  • the fluidized bed 2 is circulated between the thermal reduction reactor 3 and the hydrothermal decomposition reactor 4 by transporting the fluidized bed 2 from the hydrothermal decomposition reactor 4 to the thermal reduction reactor 3 through 7b. That is, the fluidized bed 2 rises in the thermal reduction reactor 3 and the fluidized bed 2 descends in the hydrothermal decomposition reactor 4 through the upper communication ports 6a and 6b and the lower communication ports 7a and 7b.
  • the fluidized bed 2 is irradiated with sunlight S through the window 13 to heat the fluidized bed 2.
  • a high-temperature portion H of 1400 ° C. or higher is formed, and the thermal reduction reaction proceeds at the high-temperature portion H to form metal oxide particles. Releases oxygen.
  • the reduced metal oxide particles are sent to the hydrothermal decomposition reactor 4 through the upper communication ports 6a and 6b by the internal circulation flow.
  • the temperature of the metal oxide particles decreases while flowing in the hydrothermal decomposition reactor 4, and as a result, the fluidized bed 2 in the hydrothermal decomposition reactor 4 has a temperature of 1400 ° C or less, preferably 1200 ° C or less. More preferably, a low temperature portion L of 1000 ° C. or lower is formed.
  • the hydrothermal decomposition reaction proceeds in the low temperature portion L, and the metal oxide particles reduced by the thermal reduction reaction become the original metal oxide even when oxidized, and hydrogen is generated at the same time.
  • the hydrothermal decomposition apparatus using the inner circulation fluidized bed of the present embodiment includes the reactor 1 that contains the fluidized bed 2 made of metal oxide particles, and the fluid that is contained in the reactor 1.
  • the solar light collecting means for condensing and irradiating sunlight S to the layer 2 is provided, and the reactor 1 includes a thermal reduction reactor 3 that performs a thermal reduction reaction, and a hydrothermal decomposition reactor that performs a hydrothermal decomposition reaction.
  • a dispersion plate 8 as low oxygen partial pressure gas introduction means for introducing a low oxygen partial pressure gas into the thermal reduction reactor 3 from below, and steam introduction for introducing water vapor into the hydrothermal decomposition reactor 4 from below Dispersion plate 9 as means, oxygen recovery means for recovering gas containing oxygen generated from thermal reduction reactor 3, and hydrogen recovery for recovering gas containing hydrogen generated from hydrothermal decomposition reactor 4 Means, and the inside of the thermal reduction reactor 3 and the inside of the hydrothermal decomposition reactor 4
  • the upper communication ports 6a and 6b and the lower communication ports 7a and 7b communicate with each other, and the upper communication ports 6a and 6b and the lower communication ports 7a and 7b are buried in the fluidized bed 2 and the upper communication ports
  • the fluidized bed 2 is configured to flow between the thermal reduction reactor 3 and the hydrothermal decomposition reactor 4 through the ports 6a and 6b and the lower communication ports 7a and 7b.
  • the solar light S is irradiated to the upper surface of the fluidized bed 2 accommodated in the
  • a screw conveyor 21 as a conveying means for conveying the fluidized bed 2 between the thermal reduction reactor 3 and the hydrothermal decomposition reactor 4 to the upper communication ports 6a and 6b and the lower communication ports 7a and 7b. , 22 is provided.
  • thermal reduction reactor 3 and the hydrothermal decomposition reactor 4 are configured separately from each other.
  • the fluidized bed 2 is formed as in the configuration of the first embodiment by installing the screw conveyors 21 and 22. Therefore, it is not necessary to adjust the gas flow rate, and the metal oxide particles forming the fluidized bed 2 can be forcibly moved between the thermal reduction reactor 3 and the hydrothermal decomposition reactor 4. Further, the generated oxygen and hydrogen can be reliably separated and recovered by the gas sealing action by the metal oxide particles in the screw conveyors 21 and 22.
  • Oxygen and hydrogen are generated separately in the thermal reduction reactor 3 and the hydrothermal decomposition reactor 4, respectively. Therefore, there is no need for gas separation of oxygen and hydrogen by a gas separator or the like as in the prior art. Improves purity.
  • 2 In the thermal reduction reactor 3 and the hydrothermal decomposition reactor 4, in order to advance the thermal reduction reaction and hydrothermal decomposition reaction, respectively, it becomes easy to arbitrarily control the reaction temperatures of two reactions having different reaction temperatures, Oxygen generation amount and hydrogen generation amount from each reactor are improved.
  • the generation amount and the hydrogen generation amount are improved, and the generation concentrations of recovered oxygen and hydrogen are improved.
  • the reaction heat (heat release amount) generated in the generation reaction can be fully utilized for the endothermic reaction in oxygen generation, and the solar heat ⁇ hydrogen conversion efficiency is improved.
  • the collected sunlight can be widely irradiated in the vicinity of the upper surface of the fluidized bed in the thermal reduction reactor 3 without being blocked by the gas separator, it can contribute to the formation of a high temperature portion of 1400 ° C. or higher.
  • Condensed sunlight is widely irradiated in the vicinity of the upper surface of the fluidized bed in the thermal reduction reactor 3 without being blocked by the gas separator, and can contribute to the formation of the high temperature portion H of 1400 ° C. or higher.
  • the region of the high temperature part H can be expanded, and the amount of oxygen generated can be increased.
  • the size of the hydrothermal decomposition reactor 4 can be arbitrarily changed due to the structure of the reactor, the region of the low temperature portion L of 1400 ° C. or less formed in the hydrothermal decomposition reactor 4 can be expanded, Hydrogen production can be increased.
  • the metal oxide particles of the high temperature portion H formed near the upper surface of the fluidized bed in the thermal reduction reactor 3 have the upper communication port 6a positioned below the upper surface of the fluidized bed 2. Therefore, a part of the stagnation stays in the vicinity of the high temperature portion H and is heated to a higher temperature, so that the thermal reduction reaction is more likely to proceed and the amount of oxygen generated is improved.
  • the metal oxide particles in the high temperature part H formed in the vicinity of the upper surface of the fluidized bed 2 in the thermal reduction reactor 3 have the upper communication port 6a positioned below the upper surface of the fluidized bed 2 Therefore, a part of the stagnation stays around the high temperature part H, and the high-temperature sensible heat of 1400 ° C. or higher possessed by the metal oxide particles in the high temperature part H can be efficiently recovered and reused as exhaust heat.
  • This embodiment is a modification of the fifth embodiment.
  • the same parts as those in the fifth embodiment are denoted by the same reference numerals, and the description thereof is omitted.
  • the outlets of the screw conveyors 21 and 22 are reduced. That is, the opening amount of the upper communication port 6 b in the hydrothermal decomposition reactor 4 is smaller than the opening amount of the upper communication port 6 a in the thermal reduction reactor 3. Further, the opening amount of the lower communication port 7 a in the thermal reduction reactor 3 is smaller than the opening amount of the lower communication port 7 b in the hydrothermal decomposition reactor 4.
  • the gas in the thermal reduction reactor 3 and the gas in the hydrothermal decomposition reactor 4 are mixed.
  • the packing density of the metal oxide particles at the upper communication port 6b and the lower communication port 7a is increased by reducing the outlets of the screw conveyors 21 and 22 as described above. Therefore, mixing of the gas in the thermal reduction reactor 3 and the gas in the hydrothermal decomposition reactor 4 can be drastically reduced. As a result, the hydrogen generation efficiency can be improved.
  • This embodiment is another modification of the fifth embodiment.
  • the same parts as those in the fifth embodiment are denoted by the same reference numerals, and the description thereof is omitted.
  • a screw conveyor 27 for promoting the rise of metal oxide particles is arranged in the thermal reduction reactor 3.
  • the vertical movement of the screw conveyor 27 can promote the upward movement of the metal oxide particles.
  • the screw conveyor 27 may be one axis, two axes, or multiple axes. According to the present embodiment, the supply amount of the low oxygen partial pressure gas supplied for increasing the metal oxide particles can be greatly reduced. For this reason, the apparatus which manufactures low oxygen partial pressure gas, such as nitrogen, can be reduced in size, and the operating cost of the apparatus which manufactures low oxygen partial pressure gas can be reduced. As a result, the cost of hydrogen production can be reduced.
  • FIG. 14 which shows the hydrothermal decomposition apparatus using the internal circulation fluidized bed of a present Example
  • the inside of the thermal reduction reactor 3 and hydrothermal decomposition reaction are carried out.
  • Upper communication ports 6 a and 6 b communicating with the interior of the reactor 4 are formed, respectively, and the interior of the thermal reduction reactor 3 and the hydrothermal decomposition reactor 4 are provided below the thermal reduction reactor 3 and the hydrothermal decomposition reactor 4.
  • Lower communication ports 7a and 7b communicating with each other are formed. Further, the lower communication ports 7 a and 7 b are buried in the fluidized bed 2.
  • a belt conveyor 25 is provided between the upper communication port 6a and the lower communication port 7b, and the fluidized bed 2 is transported from the hydrothermal decomposition reactor 4 to the thermal reduction reactor 3.
  • a screw conveyor 26 is provided inside the thermal reduction reactor 3, and the fluidized bed 2 in the thermal reduction reactor 3 is connected to the other end side where the lower communication port 7a is provided from one end side where the upper communication port 6a is provided. It is comprised so that it may be conveyed toward.
  • the lower communication port 7 a of the thermal reduction reactor 3 communicates directly with the upper communication port 6 b of the water splitting reactor 4.
  • the fluidized bed 2 can flow between the thermal reduction reactor 3 and the hydrothermal decomposition reactor 4 through the upper communication ports 6a and 6b and the lower communication ports 7a and 7b.
  • a dispersion plate 9 for introducing water vapor into 4 is provided.
  • the dispersion plates 8 and 9 are provided so as to be connected to the lowermost portions 7a 'and 7b' of the lower communication ports 7a and 7b so as not to disturb the flow of the fluidized bed 2 at the lower communication port 7.
  • the surface of the dispersion plate 8 is inclined with the lowest part 7a 'of the lower communication port 7a as the lowest part, and the dispersion plate 9 substantially coincides with the height of the lowermost part 7b' of the lower communication port 7b.
  • a low oxygen partial pressure gas is introduced from the dispersion plate 8 to the thermal reduction reactor 3, and at the same time, water vapor is introduced from the dispersion plate 9 to the hydrothermal decomposition reactor 4.
  • the belt conveyor 25 and the screw conveyor 26 are driven to transport the fluidized bed 2 from the thermal reduction reactor 3 to the hydrothermal decomposition reactor 4 through the lower communication port 7a and the upper communication port 6b, and the lower communication port 7b
  • the fluidized bed 2 is circulated between the thermal reduction reactor 3 and the hydrothermal decomposition reactor 4 by transporting the fluidized bed 2 from the hydrothermal decomposition reactor 4 to the thermal reduction reactor 3 through the upper communication port 6a. That is, an internal circulation flow is generated through the upper communication ports 6a and 6b and the lower communication ports 7a and 7b.
  • the fluidized bed 2 is irradiated with sunlight S through the window 13 to heat the fluidized bed 2.
  • a high-temperature portion H of 1400 ° C. or higher is formed, and the thermal reduction reaction proceeds at the high-temperature portion H to form metal oxide particles. Releases oxygen.
  • the reduced metal oxide particles are sent to the hydrothermal decomposition reactor 4 through the lower communication port 7a and the upper communication port 6b.
  • the temperature of the metal oxide particles decreases while flowing in the hydrothermal decomposition reactor 4, and as a result, the fluidized bed 2 in the hydrothermal decomposition reactor 4 has a temperature of 1400 ° C or less, preferably 1200 ° C or less. More preferably, a low temperature portion L of 1000 ° C. or lower is formed.
  • the hydrothermal decomposition reaction proceeds in the low temperature portion L, and the metal oxide particles reduced by the thermal reduction reaction become the original metal oxide even when oxidized, and hydrogen is generated at the same time.
  • the fluidized bed 2 can be moved in the thermal reduction reactor 3 by introducing a low oxygen partial pressure gas from the inclined dispersion plate 8, and the screw conveyor 26 can be omitted. Further, the fluidized bed 2 may be moved by applying vibration to the thermal reduction reactor 3, and introduction of the low oxygen partial pressure gas from the inclined dispersion plate 8 may be omitted.
  • the hydrothermal decomposition apparatus using the inner circulation fluidized bed of the present embodiment includes the reactor 1 that contains the fluidized bed 2 made of metal oxide particles, and the fluid that is contained in the reactor 1.
  • the solar light collecting means for condensing and irradiating sunlight S to the layer 2 is provided, and the reactor 1 includes a thermal reduction reactor 3 that performs a thermal reduction reaction, and a hydrothermal decomposition reactor that performs a hydrothermal decomposition reaction.
  • a dispersion plate 8 as low oxygen partial pressure gas introduction means for introducing a low oxygen partial pressure gas into the thermal reduction reactor 3 from below, and steam introduction for introducing water vapor into the hydrothermal decomposition reactor 4 from below Dispersion plate 9 as means, oxygen recovery means for recovering gas containing oxygen generated from thermal reduction reactor 3, and hydrogen recovery for recovering gas containing hydrogen generated from hydrothermal decomposition reactor 4 Means, and the inside of the thermal reduction reactor 3 and the inside of the hydrothermal decomposition reactor 4 Is communicated with the upper communication ports 6a and 6b and the lower communication ports 7a and 7b.
  • the lower communication ports 7a and 7b are buried in the fluidized bed 2 so as to communicate with the upper communication ports 6a and 6b and the lower communication ports.
  • the fluidized bed 2 is configured to flow between the thermal reduction reactor 3 and the hydrothermal decomposition reactor 4 through the ports 7a and 7b, and is accommodated in the thermal reduction reactor 3 by the sunlight collecting means. It is comprised so that sunlight S may be irradiated to the upper surface of the said fluidized bed 2. As shown in FIG.
  • a belt conveyor 25 as a conveying means for conveying the fluidized bed 2 between the thermal reduction reactor 3 and the hydrothermal decomposition reactor 4 is provided at the upper communication port 6a and the lower communication port 7b. Is.
  • the fluidized bed is formed between the thermal reduction reactor 3 and the hydrothermal decomposition reactor 4 between the upper communication port 6 a of the thermal reduction reactor 3 and the lower communication port 7 b of the hydrothermal decomposition reactor 4.
  • a belt conveyor 25 is provided as a transport means for transporting 2, and the lower communication port 7 a of the thermal reduction reactor 3 and the upper communication port 6 b of the hydrothermal decomposition reactor 4 are in direct communication. .
  • a screw conveyor 26 is provided as a moving means for moving the fluidized bed 2 in the thermal reduction reactor 3 inside the thermal reduction reactor 3.
  • the hydrothermal decomposition apparatus and hydrothermal decomposition method using the inner circulating fluidized bed of the present embodiment as described above by installing the belt conveyor 25 or the screw conveyor 26 in addition to this, the configuration of the first embodiment is obtained. Therefore, it is not necessary to adjust the gas flow rate to form the fluidized bed 2, and the metal oxide particles forming the fluidized bed 2 are forcibly moved between the thermal reduction reactor 3 and the hydrothermal decomposition reactor 4. It becomes possible.
  • This embodiment is a modification of the eighth embodiment.
  • the same portions as those in the eighth embodiment are denoted by the same reference numerals, and the description thereof is omitted.
  • FIG. 15 which shows the hydrothermal decomposition apparatus using the internal circulation fluidized bed of the present embodiment
  • the metal oxide particles are held in a storage tank 28 connected to the thermal reduction reactor 3 and are contained in the thermal reduction reactor 3. It is transported and moved by the screw conveyor 29. Further, a screw conveyor 26 is disposed in order to cause the metal oxide particles to flow in the thermal reduction reactor 3.
  • the screw conveyor 26 may be arranged in the vertical direction and the tanning direction in addition to the horizontal direction. In this embodiment, three screw conveyors 26 are arranged in the horizontal direction, the vertical direction, and the tanning direction.
  • a screw conveyor 30 is arranged to flow the metal oxide particles in the hydrothermal decomposition reactor 4.
  • the screw conveyor 30 is not limited to the configuration arranged in the vertical direction as in the present embodiment, but may be arranged in the horizontal direction and the licking direction.
  • a storage tank 31 for storing the metal oxide particles after the hydrothermal decomposition reaction is provided at the lower part of the hydrothermal decomposition reactor 4.
  • a screw conveyor 32 for moving and transporting the metal oxide particles from the hydrothermal decomposition reactor 4 to the storage tank 31 is disposed.
  • a belt conveyor 25 is provided between the storage tank 31 and the storage tank 28 for moving and transporting the metal oxide particles after the hydrothermal decomposition reaction.
  • the storage tanks 28 and 31 are provided, whereby the metal oxide particles after the hydrothermal decomposition reaction can be temporarily stored. For this reason, the metal oxide particles can be moved by the belt conveyor 25 at night.
  • the shape of the thermal reduction reactor or hydrothermal decomposition reactor is not limited to a vertically long rectangular parallelepiped, but also a horizontally long rectangular parallelepiped, a cube, a vertically long cylindrical shape, a horizontally long cylindrical shape, a vertically long elliptical cylinder, or a horizontally long elliptical cylindrical shape.
  • the bottom shape of the thermal reduction reactor or hydrothermal decomposition reactor may be horizontal or inclined.
  • a container such as a bucket, or vibration generated by applying an external force may be used.

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Abstract

L'invention fournit un dispositif ainsi qu'un procédé de pyrolyse aqueuse mettant en œuvre une couche d'écoulement par circulation interne, et permet de séparer de manière sûre et récupérer un oxygène et un hydrogène générés, de commander de manière arbitraire et individuelle la température, la vitesse, la durée et la région de réactions se déroulant simultanément sur la couche d'écoulement, et de récupérer et réutiliser selon un haut rendement une chaleur réactionnelle. Le dispositif de l'invention est équipé : d'un réacteur de réduction thermique (3) dans lequel est effectuée une réaction de réduction thermique ; d'un réacteur de pyrolyse aqueuse (4) dans lequel est effectuée une réaction de pyrolyse aqueuse ; d'une plaque de dispersion (8) ainsi que d'une plaque de dispersion (9) acheminant respectivement un gaz de faible pression partielle d'oxygène jusqu'au réacteur de réduction thermique (3), et une vapeur d'eau jusqu'au réacteur de pyrolyse aqueuse (4) ; d'une ouverture d'extraction (14) pour récupérer un gaz contenant un oxygène généré par le réacteur de réduction thermique (3) ; et d'une ouverture d'extraction (15) pour récupérer un gaz contenant un hydrogène généré par le réacteur de pyrolyse aqueuse (4). Un ouverture de communication partie supérieure (6) et une ouverture de communication partie inférieure (7) qui sont formées sur une plaque de cloisonnement (5) cloisonnant le réacteur de réduction thermique (3) et le réacteur de pyrolyse aqueuse (4), sont immergées à l'intérieur de la couche d'écoulement (2), et la couche d'écoulement (2) configurée de sorte qu'elle peut s'écouler directement entre le réacteur de réduction thermique (3) et le réacteur de pyrolyse aqueuse (4) en passant par l'ouverture de communication partie supérieure (6) et l'ouverture de communication partie inférieure (7).
PCT/JP2013/052211 2012-01-31 2013-01-31 Dispositif ainsi que procédé de pyrolyse aqueuse mettant en œuvre une couche d'écoulement par circulation interne WO2013115316A1 (fr)

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