WO2012090865A1 - Dispositif de désulfuration et système de piles à combustible - Google Patents

Dispositif de désulfuration et système de piles à combustible Download PDF

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Publication number
WO2012090865A1
WO2012090865A1 PCT/JP2011/079839 JP2011079839W WO2012090865A1 WO 2012090865 A1 WO2012090865 A1 WO 2012090865A1 JP 2011079839 W JP2011079839 W JP 2011079839W WO 2012090865 A1 WO2012090865 A1 WO 2012090865A1
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Prior art keywords
desulfurization
flow path
hydrogen
heat
fluid
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PCT/JP2011/079839
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English (en)
Japanese (ja)
Inventor
修平 咲間
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Ｊｘ日鉱日石エネルギー株式会社
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Priority to JP2012550902A priority Critical patent/JP5738318B2/ja
Publication of WO2012090865A1 publication Critical patent/WO2012090865A1/fr

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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
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0662—Treatment of gaseous reactants or gaseous residues, e.g. cleaning
    • H01M8/0675—Removal of sulfur
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/16—Hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8603—Removing sulfur compounds
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/19—Details relating to the geometry of the reactor
    • B01J2219/194—Details relating to the geometry of the reactor round
    • B01J2219/1941—Details relating to the geometry of the reactor round circular or disk-shaped
    • B01J2219/1944—Details relating to the geometry of the reactor round circular or disk-shaped spiral
    • 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
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/066—Integration with other chemical processes with fuel cells
    • 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
    • C01B2203/1258—Pre-treatment of the feed
    • C01B2203/1264—Catalytic pre-treatment of the feed
    • C01B2203/127—Catalytic desulfurisation
    • 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
    • Y02E60/50—Fuel cells
    • 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
    • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

Definitions

  • Various aspects and embodiments of the present invention relate to a desulfurization apparatus employed in a fuel cell system.
  • a desulfurization apparatus employed in a fuel cell system an apparatus having a desulfurization unit that desulfurizes a hydrogen-containing fuel is known.
  • a desulfurization part what is heated so that it may become the reaction temperature of a desulfurization catalyst is disclosed (for example, refer patent documents 1-3).
  • the desulfurization section described in Patent Document 1 is heated by the heated reformed gas after flowing through the reformer being guided into the desulfurization section.
  • the desulfurization part of patent document 2 is arrange
  • the desulfurization part described in Patent Document 3 is heated using water supplied to the reforming catalyst and received heat.
  • the desulfurization apparatus is used in a fuel cell system that generates power by a cell stack using a hydrogen-containing fuel and recovers exhaust heat of the cell stack using a heat medium.
  • the desulfurization apparatus includes a desulfurization unit and a desulfurization system heat exchange unit.
  • the desulfurization section has a desulfurization flow path containing a desulfurization catalyst, and desulfurizes the hydrogen-containing fuel by flowing through the desulfurization flow path.
  • the desulfurization system heat exchange unit is a spiral flow channel that is accommodated in the desulfurization flow channel and causes the heat medium after the exhaust heat of the cell stack is collected to flow and heat exchange between the heat medium and the desulfurization unit.
  • the fluid circulation direction of the desulfurization heat exchange section and the fluid circulation direction of the desulfurization flow path are formed so as to face each other.
  • the heat medium that recovers the exhaust heat of the cell stack exchanges heat with the desulfurization unit. Since the heat medium is heated by the exhaust heat of the cell stack, the temperature becomes lower than the temperature of the reformed gas, the temperature of the water supplied to the reforming catalyst and receiving heat, and the reaction temperature of the combustion catalyst. For this reason, the desulfurization part which should be kept at a comparatively low temperature can be warmed efficiently. Moreover, since the desulfurization type heat exchange part is formed in a spiral shape, the heat medium can be circulated for a longer distance than the flow path formed in a straight line. Therefore, it is possible to keep the desulfurization part warm with energy efficiency. Furthermore, in the desulfurization apparatus according to one aspect of the present invention, the flow direction of the hydrogen-containing fuel and the flow direction of the heat medium are formed so as to face each other. For this reason, a desulfurization part can be heat-retained efficiently.
  • the desulfurization flow path is formed with a folded portion that circulates the hydrogen-containing fuel flowing from the fluid inlet to one side to the other side opposite to the one side, and the desulfurization flow channel from the fluid inlet to the folded portion
  • a desulfurization heat exchange section is housed inside, so that the fluid flow direction of the desulfurization flow path from the fluid inlet to the turn-up section and the fluid flow direction of the desulfurization flow path from the turn-up section to the fluid outlet are opposite flows. It may be formed.
  • the hydrogen-containing fuel that flows through the desulfurization flow path from the fluid inlet to the turned-up portion and the hydrogen-containing fuel that flows through the heat medium and the desulfurization flow path from the turned-up portion to the fluid outlet flow counter-currently. It is said. That is, the hydrogen-containing fuel that flows through the desulfurization flow path from the fluid inlet to the turn-up portion is heated from the heat medium and is also heated by the hydrogen-containing fuel that flows through the desulfurization flow path from the turn-up portion to the fluid outlet.
  • the thermal efficiency can be improved by setting the flow direction of the fluid to be heated and the flow direction of the heating source fluid to be opposite flows, it is possible to keep the desulfurization section warm with high energy efficiency.
  • a baffle plate for changing the flow of fluid may be provided at the fluid inlet inside the desulfurization flow path.
  • a baffle plate that changes the flow of fluid may be provided in the folded portion inside the desulfurization flow path.
  • the desulfurization flow path from the fluid inlet to the turn-up portion is defined by an inner wall provided inside the desulfurization portion, and the desulfurization flow path from the turn-up portion to the fluid outlet is defined by the outer peripheral wall and the inner wall of the desulfurization portion.
  • the inner wall may be provided such that the desulfurization flow path from the fluid inlet to the turn-up portion and the desulfurization flow path from the turn-up portion to the fluid outlet have the same volume.
  • the desulfurization part has a cylindrical shape, and has a radius set so that the surface area obtained based on the radius of the desulfurization part and a predetermined amount of catalyst accommodated in the desulfurization part becomes a minimum value. Good. By comprising in this way, the thermal radiation of the desulfurization apparatus 90 can be suppressed appropriately.
  • a fuel cell system includes the above-described desulfurization apparatus and is configured to generate power using the hydrogen-containing fuel after desulfurization. Since the fuel cell system includes the above-described desulfurization apparatus, the temperature of the desulfurization unit can be maintained with high energy efficiency.
  • FIG. 4 is a sectional view taken along line IV-IV of the desulfurization apparatus shown in FIG. 3. It is a schematic diagram for demonstrating the internal structure of the upper part of the desulfurization apparatus which concerns on a modification. It is a schematic diagram for demonstrating the internal structure of the lower part of the desulfurization apparatus which concerns on a modification.
  • FIG. 6 is a cross-sectional view of the desulfurization apparatus shown in FIG. 5 taken along line VII-VII.
  • FIG. 1 is a block diagram showing the configuration of the fuel cell system according to the present embodiment.
  • the fuel cell system 1 includes a desulfurization unit 2, a water vaporization unit 3, a hydrogen generation unit 4, a cell stack 5, an off-gas combustion unit 6, a hydrogen-containing fuel supply unit 7, The water supply part 8, the oxidizing agent supply part 9, the power conditioner 10, and the control part 11 are provided.
  • the fuel cell system 1 generates power in the cell stack 5 using a hydrogen-containing fuel and an oxidant.
  • the type of the cell stack 5 in the fuel cell system 1 is not particularly limited, and examples thereof include a polymer electrolyte fuel cell (PEFC), a solid oxide fuel cell (SOFC), and phosphoric acid.
  • PEFC polymer electrolyte fuel cell
  • SOFC solid oxide fuel cell
  • phosphoric acid a fuel cell
  • PAFC Phosphoric Acid Fuel Cell
  • MCFC molten carbonate Fuel Cell
  • 1 may be appropriately omitted depending on the type of cell stack 5, the type of hydrogen-containing fuel, the reforming method, and the like.
  • hydrocarbon fuel a compound containing carbon and hydrogen in the molecule (may contain other elements such as oxygen) or a mixture thereof is used.
  • hydrocarbon fuels include hydrocarbons, alcohols, ethers, and biofuels. These hydrocarbon fuels are derived from conventional fossil fuels such as petroleum and coal, and synthetic systems such as synthesis gas. Those derived from fuel and those derived from biomass can be used as appropriate. Specific examples of hydrocarbons include methane, ethane, propane, butane, natural gas, LPG (liquefied petroleum gas), city gas, town gas, gasoline, naphtha, kerosene, and light oil. Examples of alcohols include methanol and ethanol. Examples of ethers include dimethyl ether. Examples of biofuels include biogas, bioethanol, biodiesel, and biojet.
  • oxygen-enriched air for example, air, pure oxygen gas (which may contain impurities that are difficult to remove by a normal removal method), or oxygen-enriched air is used.
  • the desulfurization unit 2 desulfurizes the hydrogen-containing fuel supplied to the hydrogen generation unit 4.
  • the desulfurization part 2 has a desulfurization catalyst for removing sulfur compounds contained in the hydrogen-containing fuel.
  • a desulfurization method of the desulfurization unit 2 for example, an adsorptive desulfurization method that adsorbs and removes sulfur compounds and a hydrodesulfurization method that removes sulfur compounds by reacting with hydrogen are employed.
  • the desulfurization unit 2 supplies the desulfurized hydrogen-containing fuel to the hydrogen generation unit 4.
  • the water vaporization unit 3 generates water vapor supplied to the hydrogen generation unit 4 by heating and vaporizing water.
  • heat generated in the fuel cell system 1 such as recovering the heat of the hydrogen generation unit 4, the heat of the off-gas combustion unit 6, or the heat of the exhaust gas may be used.
  • FIG. 1 only heat supplied from the off-gas combustion unit 6 to the hydrogen generation unit 4 is described as an example, but the present invention is not limited to this.
  • the water vaporization unit 3 supplies the generated water vapor to the hydrogen generation unit 4.
  • the hydrogen generation unit 4 generates a hydrogen rich gas (hydrogen-containing gas) using the hydrogen-containing fuel from the desulfurization unit 2.
  • the hydrogen generator 4 has a reformer that reforms the hydrogen-containing fuel with a reforming catalyst.
  • the reforming method in the hydrogen generating unit 4 is not particularly limited, and for example, steam reforming, partial oxidation reforming, autothermal reforming, and other reforming methods can be employed.
  • the hydrogen generator 4 may have a configuration for adjusting the properties in addition to the reformer reformed by the reforming catalyst depending on the properties of the hydrogen rich gas required for the cell stack 5.
  • the hydrogen generation unit 4 is configured to remove carbon monoxide in the hydrogen-rich gas. (For example, a shift reaction part and a selective oxidation reaction part).
  • the hydrogen generation unit 4 supplies a hydrogen rich gas to the anode 12 of the cell stack 5.
  • the cell stack 5 generates power using the hydrogen rich gas from the hydrogen generation unit 4 and the oxidant from the oxidant supply unit 9.
  • the cell stack 5 includes an anode 12 to which a hydrogen-rich gas is supplied, a cathode 13 to which an oxidant is supplied, and an electrolyte 14 disposed between the anode 12 and the cathode 13.
  • the cell stack 5 supplies power to the outside via the power conditioner 10.
  • the cell stack 5 supplies the hydrogen rich gas and the oxidant, which have not been used for power generation, to the off gas combustion unit 6 as off gas.
  • a combustion section for example, a combustor that heats the reformer
  • the hydrogen generation section 4 may be shared with the off-gas combustion section 6.
  • the off gas combustion unit 6 burns off gas supplied from the cell stack 5.
  • the heat generated by the off-gas combustion unit 6 is supplied to the hydrogen generation unit 4 and used for generation of a hydrogen rich gas in the hydrogen generation unit 4.
  • the hydrogen-containing fuel supply unit 7 supplies hydrogen-containing fuel to the desulfurization unit 2.
  • the water supply unit 8 supplies water to the water vaporization unit 3.
  • the oxidant supply unit 9 supplies an oxidant to the cathode 13 of the cell stack 5.
  • the hydrogen-containing fuel supply unit 7, the water supply unit 8, and the oxidant supply unit 9 are configured by a pump, for example, and are driven based on a control signal from the control unit 11.
  • the power conditioner 10 adjusts the power from the cell stack 5 according to the external power usage state. For example, the power conditioner 10 performs a process of converting a voltage and a process of converting DC power into AC power.
  • the control unit 11 performs control processing for the entire fuel cell system 1.
  • the control unit 11 is configured by a device including a CPU (Central Processing Unit), a ROM (Read Only Memory), a RAM (Random Access Memory), and an input / output interface, for example.
  • the control unit 11 is electrically connected to a hydrogen-containing fuel supply unit 7, a water supply unit 8, an oxidant supply unit 9, a power conditioner 10, and other sensors and auxiliary equipment not shown.
  • the control unit 11 acquires various signals generated in the fuel cell system 1 and outputs a control signal to each device in the fuel cell system 1.
  • the fuel cell system 1 is provided with a heat recovery system that uses the heat generated by the cell stack 5 to change the water into hot water and stores the hot water in a hot water tank. That is, the fuel cell system 1 includes a so-called cogeneration system.
  • the heat recovery system in the fuel cell system 1 will be outlined.
  • FIG. 2 is a block diagram showing the configuration of the fuel cell system according to the present embodiment. In FIG. 2, parts not related to the heat recovery system are partially omitted.
  • the heat recovery system of the fuel cell system 1 recovers the exhaust heat of the cell stack 5, and includes a hot water storage tank 81, a heat exchanger 80, a desulfurization system heat exchange unit 82, and a circulating flow.
  • a path 83 is provided.
  • the hot water storage tank 81, the heat exchanger 80, and the desulfurization system heat exchange unit 82 are sequentially connected by a circulation channel 83.
  • the desulfurization unit 2 includes the desulfurization unit 2 and the desulfurization system heat exchange unit 82.
  • the hot water tank 81 is a unit that stores water or hot water.
  • water is water that is in a liquid state regardless of its temperature, and warm water is obtained by adding heat to “water”.
  • the stored water in the hot water storage tank 81 is supplied to the heat exchanger 80 as a heat medium.
  • the heat medium may be cooled by a radiator or the like before being supplied to the heat exchanger 80.
  • the heat exchanger 80 is connected to the hot water storage tank 81 via the circulation channel 83 and is connected to the output side of the cell stack 5.
  • the heat exchanger 80 exchanges heat between the off gas (exhaust gas) of the cell stack 5 and the heat medium. That is, the heat medium is heated by the heat exchanger 80 using off-gas as a heating source. The heat medium is heated to about 60 ° C. to 80 ° C.
  • the heat medium after the heat exchange is supplied to the desulfurization system heat exchange unit 82 of the desulfurization unit 2 through the circulation flow path 83.
  • the desulfurization heat exchange unit 82 is connected to the heat exchanger 80 via the circulation channel 83 and is in thermal contact with the desulfurization unit 2.
  • the desulfurization heat exchange unit 82 exchanges heat between the heat medium and the desulfurization unit 2. That is, the desulfurization unit 2 is heated by the desulfurization heat exchange unit 82 using the heat medium as a heating source.
  • the heat medium after the heat exchange is returned to the hot water storage tank 81 through the circulation flow path 83.
  • the low-temperature heat medium is supplied from the hot water storage tank 81 to the heat exchanger 80 and heated, and the heated heat medium is supplied to the desulfurization system heat exchange unit 82 of the desulfurization apparatus.
  • the desulfurization part 2 is heated.
  • the reformed gas of the fuel cell system 1 is produced by the hydrogen generator 4 and is said to have a temperature of about 600 ° C. to 700 ° C.
  • the reforming water supplied to the reforming catalyst is also superheated and is in a steam state, and therefore has a considerably high temperature.
  • the catalytic combustion temperature of a normal combustion catalyst is about 600 ° C.
  • the reformed gas, the reformed water, or the combustion catalyst has a very high temperature, so that an energy loss is large even if the temperature of the desulfurization section 2 that should be kept at a relatively low temperature is kept.
  • An example of such a low-temperature desulfurization section 2 is a zeolite-based adsorptive desulfurization section (heat retention temperature 60 ° C. to 80 ° C.). Since the fuel cell system 1 uses a heat medium, when the low-temperature desulfurization unit 2 is employed, it is possible to keep warm with little energy loss.
  • FIG. 3 is a perspective view of the desulfurization apparatus according to the present embodiment
  • FIG. 4 is a cross-sectional view taken along the line IV-IV of the desulfurization apparatus shown in FIG.
  • the desulfurization apparatus 90 has a substantially cylindrical shape, and includes a desulfurization unit 2 and a desulfurization system heat exchange unit 82.
  • a fluid inlet 20a for introducing the hydrogen-containing fuel before the desulfurization treatment into the desulfurization section 2 is formed on the upper side portion of the desulfurization apparatus 90.
  • a fluid outlet 20 b through which the hydrogen-containing fuel after the desulfurization treatment is led out from the desulfurization unit 2 is formed on the upper side portion of the desulfurization apparatus 90.
  • a fluid inlet 21a for introducing the heat medium after recovering the exhaust heat of the cell stack 5 into the desulfurization system heat exchange unit 82 is formed on the lower side of the desulfurization apparatus 90.
  • a fluid outlet 21b for leading the exchanged heat medium from the desulfurization heat exchange unit 82 is formed on the lower side of the desulfurization apparatus 90.
  • the desulfurization part 2 is formed in a substantially cylindrical shape with the outer peripheral wall 2a as a side wall.
  • the desulfurization catalyst 21 is accommodated in the inside.
  • an inner peripheral wall (inner wall) 2 b is erected on the upper inner wall of the desulfurization part 2 toward the lower inner wall of the desulfurization part 2.
  • the inner peripheral wall 2b extends along the outer peripheral wall 2a while being separated from the outer peripheral wall 2a.
  • a gap (folded portion 25) is provided between the front end side of the inner peripheral wall 2 b and the lower inner wall of the desulfurization portion 2.
  • a desulfurization flow path 22 is defined inside the inner peripheral wall 2b inside the desulfurization section 2, and a desulfurization flow path 23 is defined by the outer peripheral wall 2a and the inner peripheral wall 2b.
  • the desulfurization flow path is arranged in order of the desulfurization flow path 22 and the desulfurization flow path 23 from the inner side to the outer side of the desulfurization part 2, and the desulfurization flow path 23 is configured to cover the side of the desulfurization flow path 22.
  • the fluid inlet 20a of the desulfurization part 2 is connected to the desulfurization flow path 22 defined inside the inner peripheral wall 2b.
  • the fluid outlet 20b of the desulfurization part 2 is connected to a desulfurization flow path 23 defined by the outer peripheral wall 2a and the inner peripheral wall 2b.
  • the hydrogen-containing fuel introduced from the fluid inlet 20a to the desulfurization section 2 flows from the upper side to the lower side (one side) through the desulfurization flow path 22 defined in the inner peripheral wall 2b, and turns back. 25, and flows through the desulfurization flow path 23 defined by the outer peripheral wall 2 a and the inner peripheral wall 2 b to the upper side (the other side) opposite to the one side, and as a hydrogen-containing fuel after desulfurization, the fluid outlet 20b.
  • a desulfurization heat exchange section 82 is disposed in the desulfurization flow path 22 of the desulfurization section 2.
  • the desulfurization heat exchange unit 82 is a tube wound in a spiral shape, and allows a heat medium to flow through the tube.
  • the heat medium introduced from the fluid inlet 21a to the desulfurization heat exchange unit 82 flows through the inside of the desulfurization heat exchange unit 82 from the lower side to the upper side and is led out from the fluid outlet 21b.
  • the desulfurization flow path 22 from the fluid inlet 20a to the turn-up portion 25 is disposed so as to be in thermal contact with the desulfurization system heat exchange unit 82, and the fluid flow direction and desulfurization of the desulfurization system heat exchange unit 82 are arranged. It is formed so that the fluid flow direction of the flow path 22 is a counter flow. For this reason, heat can be efficiently given to the hydrogen-containing fuel flowing through the desulfurization flow path 22 or the desulfurization flow path 22 from the heat medium flowing through the desulfurization heat exchange section 82. Moreover, since the desulfurization type heat exchange part 82 is formed in a spiral shape, the heat medium can be circulated for a longer distance than the flow path formed in a linear shape. Therefore, it is possible to keep the desulfurization part 2 warm with energy efficiency.
  • the fluid flow direction of the desulfurization flow path 22 from the fluid inlet 20a to the folded portion 25 and the fluid flow direction of the desulfurization flow path 23 from the folded portion 25 to the fluid outlet 20b are formed so as to face each other. .
  • heat can be efficiently given from the hydrogen-containing fuel flowing through the desulfurization flow path 23 to the hydrogen-containing fuel flowing through the desulfurization flow path 22.
  • heat can be efficiently applied from the already heated hydrogen-containing fuel to the hydrogen-containing fuel to be heated.
  • it is set as the structure by which self-heat recovery is carried out, the uniformization of the heat
  • the heat medium recovered from the exhaust heat of the cell stack 5 exchanges heat with the desulfurization unit 2. Since the heat medium is heated by the exhaust heat of the cell stack 5, the temperature is lower than the temperature of the reformed gas, the temperature of the water supplied to the reforming catalyst and receiving heat, and the reaction temperature of the combustion catalyst. . For this reason, the desulfurization part 2 which should be heat-retained at a comparatively low temperature can be heat-retained efficiently. Moreover, since the heater for heating the desulfurization part 2 etc. becomes unnecessary, cost is also excellent.
  • the desulfurization type heat exchanging portion 82 is formed in a spiral shape, the heat medium can be circulated for a longer distance than the flow path formed in a straight line. Therefore, it is possible to keep the desulfurization part 2 warm with energy efficiency.
  • the flow direction of the hydrogen-containing fuel and the flow direction of the heat medium are formed so as to face each other. It can keep warm efficiently.
  • the hydrogen-containing fuel flowing through the desulfurization flow path 23 is counterflowed. That is, the hydrogen-containing fuel that flows through the desulfurization passage 22 from the fluid inlet 20a to the turn-up portion 25 is heated from the heat medium, and the hydrogen-containing fuel that flows through the desulfurization passage 23 from the turn-up portion 25 to the fluid outlet 20b. Is also heated.
  • the thermal efficiency can be improved by setting the flow direction of the fluid to be heated and the flow direction of the heating source fluid to be opposite flows, it is possible to keep the desulfurization unit 2 warm with high energy efficiency.
  • embodiment mentioned above shows an example of the desulfurization apparatus and fuel cell system which concern on this invention.
  • the desulfurization apparatus and the fuel cell system according to the present invention are not limited to the desulfurization apparatus 90 and the fuel cell system 1 according to the embodiment, and the desulfurization apparatus according to the embodiment is within a range not changing the gist described in each claim. 90 and the fuel cell system 1 may be modified or applied to others.
  • the example in which the exhaust heat is recovered from the off gas of the cell stack 5 has been described.
  • the heat generated from the cell stack 5 may be directly recovered.
  • the turn-back portion 25 is provided in the desulfurization flow path of the desulfurization portion 2 has been described.
  • the turn-back portion 25 may be omitted.
  • the fluid inlet and the fluid outlet of the heat medium and the hydrogen-containing fuel have been described, but the present invention is not limited to the attachment position and the attachment direction shown in the above-described embodiment.
  • the fluid inlet and the fluid outlet may be in opposite directions, and the fluid inlet and the fluid outlet of the heat medium may be provided at the lower part and the upper part instead of the side of the desulfurization apparatus 90.
  • FIG. 5 is a schematic diagram for explaining an internal structure of an upper part of a desulfurization apparatus according to a modification.
  • FIG. 6 is a schematic diagram for explaining the internal structure of the lower part of the desulfurization apparatus according to the modification.
  • FIG. 7 is a cross-sectional view taken along line VII-VII of the desulfurization apparatus shown in FIG.
  • the description which overlaps with the said embodiment is abbreviate
  • a baffle plate 91 is provided on the downstream side of the fluid inlet 20a for introducing the hydrogen-containing fuel before the desulfurization treatment into the desulfurization section 2.
  • the baffle plate 91 is provided inside the desulfurization flow path 22 on the upstream side of the desulfurization flow path 22 (a position separated from the fluid inlet 20a by a predetermined distance).
  • the baffle plate 91 is a circular plate member.
  • a through-hole 91 a that penetrates in the thickness direction is formed at the center of the baffle plate 91.
  • the shape of the baffle plate 91 is not limited to a circle, and may be a rectangle.
  • the baffle plate 91 is provided so as to change the flow of the hydrogen-containing fuel flowing from the fluid inlet 20a.
  • the baffle plate 91 is provided so that the flow direction of the hydrogen-containing fuel and the main surface of the baffle plate 91 are orthogonal to each other.
  • the baffle plate 91 is arranged so that its main surface is orthogonal to the axial direction of the desulfurization apparatus 90 (that is, approximately). Placed horizontally).
  • the baffle plate 91 By providing the baffle plate 91, the hydrogen-containing fuel that has flowed into the desulfurization flow path 22 collides with the baffle plate 91 and diffuses inside the desulfurization flow path 22 in the radial direction of the desulfurization apparatus 90. Therefore, uneven flow generated in the vicinity of the fluid inlet 20 a can be suppressed, and the hydrogen-containing fuel can be circulated uniformly in the desulfurization flow path 22. Furthermore, by providing the through hole 91 a, a part of the hydrogen-containing fuel is introduced into the desulfurization device 90 without hitting the baffle plate 91. Therefore, the degree of suppression of drift can be adjusted by providing the through hole 91a.
  • a baffle plate 93 may be provided in the folded portion 25.
  • the baffle plate 93 is provided at the lower end portion of the inner peripheral wall 2 b erected from the upper inner wall of the desulfurization unit 2 toward the lower inner wall of the desulfurization unit 2.
  • the baffle plate 93 is disposed at the end of the inner peripheral wall 2b so as to protrude inward in the radial direction of the inner peripheral wall 2b.
  • the baffle plate 93 is a ring-shaped member having an opening 93a at the center thereof.
  • the outer diameter of the baffle plate 93 is substantially the same as the outer diameter or inner diameter of the inner peripheral wall 2b, and the inner diameter of the baffle plate 93 is smaller than the inner diameter of the inner peripheral wall 2b.
  • the baffle plate 93 is provided so as to change the flow of the hydrogen-containing fuel in the folded portion 25.
  • the baffle plate 93 is disposed so that the main surface thereof is orthogonal to the axial direction of the desulfurization apparatus 90 (that is, substantially horizontal).
  • the hydrogen-containing fuel that circulates in the folded portion 25 circulates around the baffle plate 93 and flows into the desulfurization flow path 23 from the opening 93 a having a diameter smaller than the diameter of the desulfurization flow path 22.
  • the hydrogen-containing fuel can be uniformly circulated in the desulfurization flow path 23 by flowing into the desulfurization flow path 23 from the center side in the vicinity of the turning portion 25.
  • the first catalyst tank and the second catalyst are suppressed in order to suppress the drift of the hydrogen-containing fuel inside the desulfurization apparatus 90.
  • the circular radius of the columnar desulfurization apparatus 90 may be set so that the surface area of the desulfurization apparatus 90 becomes a minimum value.
  • the radius of the first catalyst tank is r 1
  • the length from the center to the outer diameter of the second catalyst tank is r 2
  • the catalyst amount (volume V) is constant (predetermined value).
  • the surface area (namely, the surface area of the desulfurization part 2) S of the desulfurization apparatus 90 can be expressed by the following equation.
  • r 2 is set so that the surface area S is the minimum value.
  • SYMBOLS 1 Fuel cell system, 2 ... Desulfurization part (desulfurization apparatus), 2a ... Outer wall, 2b ... Inner wall, 5 ... Cell stack, 20a ... Fluid inlet, 20b ... Fluid outlet, 21 ... Desulfurization catalyst, 21a ... Fluid inlet, 21b ... Fluid outlet, 22, 23 ... Desulfurization flow path, 25 ... Folding part, 82 ... Desulfurization system heat exchange part (desulfurization device).

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Electrochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Fuel Cell (AREA)

Abstract

L'invention concerne un dispositif de désulfuration utilisé dans un système de piles à combustible, qui récupère la chaleur perdue d'un empilement de piles par l'intermédiaire d'un milieu chauffant, et qui produit de l'électricité au moyen de l'empilement de piles en utilisant un combustible contenant de l'hydrogène. Le dispositif de désulfuration comprend: une unité désulfuration, qui comporte une conduite de désulfuration contenant un catalyseur de désulfuration, et désulfure le combustible contenant de l'hydrogène par l'écoulement dudit combustible dans la conduite de désulfuration; et un échangeur de chaleur de système de désulfuration, qui est contenu dans la conduite de désulfuration et forme une conduite hélicoïdale produisant un échange de chaleur entre le milieu chauffant et l'unité de désulfuration, par l'écoulement du milieu chauffant, après que le milieu chauffant a récupéré la chaleur perdue de l'empilement de piles. Le dispositif de désulfuration est conçu de sorte que la direction d'écoulement du fluide de l'échangeur de chaleur du système de désulfuration et la direction d'écoulement du fluide de la conduite de désulfuration forment un contre-courant.
PCT/JP2011/079839 2010-12-27 2011-12-22 Dispositif de désulfuration et système de piles à combustible WO2012090865A1 (fr)

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Cited By (2)

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JP2015018758A (ja) * 2013-07-12 2015-01-29 東京瓦斯株式会社 硫黄化合物含有ガスの処理方法、燃料電池システム及びその運転方法
GB2604803B (en) * 2019-11-19 2024-02-28 Ceres Ip Co Ltd Desulfurization unit, SOFC system and vehicle

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JPH04298228A (ja) * 1991-03-27 1992-10-22 Tokyo Gas Co Ltd 脱硫反応器
JP2004051865A (ja) * 2002-07-23 2004-02-19 Idemitsu Kosan Co Ltd 脱硫器及び脱硫方法。
JP2010024402A (ja) * 2008-07-23 2010-02-04 Toshiba Fuel Cell Power Systems Corp 燃料電池発電システムおよびそれに用いる脱硫器

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JP2630543B2 (ja) * 1992-11-27 1997-07-16 川崎重工業株式会社 遠心流動層脱塵・脱硫・脱硝装置
JP4298398B2 (ja) * 2002-06-28 2009-07-15 出光興産株式会社 燃焼装置におけるｎ２ｏ及びｎｏｘの排出抑制方法
JP2007218108A (ja) * 2006-02-14 2007-08-30 Hino Motors Ltd 排気浄化装置
JP2009079155A (ja) * 2007-09-26 2009-04-16 Toshiba Fuel Cell Power Systems Corp 液体燃料脱硫装置及び液体燃料脱硫システム
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JPH04298228A (ja) * 1991-03-27 1992-10-22 Tokyo Gas Co Ltd 脱硫反応器
JP2004051865A (ja) * 2002-07-23 2004-02-19 Idemitsu Kosan Co Ltd 脱硫器及び脱硫方法。
JP2010024402A (ja) * 2008-07-23 2010-02-04 Toshiba Fuel Cell Power Systems Corp 燃料電池発電システムおよびそれに用いる脱硫器

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015018758A (ja) * 2013-07-12 2015-01-29 東京瓦斯株式会社 硫黄化合物含有ガスの処理方法、燃料電池システム及びその運転方法
GB2604803B (en) * 2019-11-19 2024-02-28 Ceres Ip Co Ltd Desulfurization unit, SOFC system and vehicle

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JP5738318B2 (ja) 2015-06-24

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