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WO2008068156A1 - Appareil pour générer de l'hydrogène, en particulier pour alimenter les piles à combustible - Google Patents

Appareil pour générer de l'hydrogène, en particulier pour alimenter les piles à combustible Download PDF

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Publication number
WO2008068156A1
WO2008068156A1 PCT/EP2007/062847 EP2007062847W WO2008068156A1 WO 2008068156 A1 WO2008068156 A1 WO 2008068156A1 EP 2007062847 W EP2007062847 W EP 2007062847W WO 2008068156 A1 WO2008068156 A1 WO 2008068156A1
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Prior art keywords
reaction
duct
reaction duct
containment chamber
heat exchange
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English (en)
Inventor
Giovanni Pisani
Gabriele Malaspina
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Ici Caldaie SpA
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Ici Caldaie SpA
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/008—Details of the reactor or of the particulate material; Processes to increase or to retard the rate of reaction
    • 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
    • B01J12/00—Chemical processes in general for reacting gaseous media with gaseous media; Apparatus specially adapted therefor
    • B01J12/007—Chemical processes in general for reacting gaseous media with gaseous media; Apparatus specially adapted therefor in the presence of catalytically active bodies, e.g. porous plates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/2415—Tubular reactors
    • B01J19/243—Tubular reactors spirally, concentrically or zigzag wound
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/0207—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid flow within the bed being predominantly horizontal
    • B01J8/0235—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid flow within the bed being predominantly horizontal in a spiral shaped bed
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/0285—Heating or cooling the reactor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
    • B01J8/067—Heating or cooling the reactor
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    • 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
    • C01B3/384—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 the catalyst being continuously externally heated
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    • 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
    • C01B3/48—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 followed by reaction of water vapour with carbon monoxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/00106—Controlling the temperature by indirect heat exchange
    • B01J2208/00309—Controlling the temperature by indirect heat exchange with two or more reactions in heat exchange with each other, such as an endothermic reaction in heat exchange with an exothermic reaction
    • 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
    • B01J2208/00504—Controlling the temperature by means of a burner
    • 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
    • B01J2208/0053—Controlling multiple zones along the direction of flow, e.g. pre-heating and after-cooling
    • 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
    • B01J2208/00884—Means for supporting the bed of particles, e.g. grids, bars, perforated plates
    • 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
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
    • B01J2219/00087—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
    • B01J2219/00099—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor the reactor being immersed in the heat exchange medium
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    • 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
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0435—Catalytic purification
    • C01B2203/044—Selective oxidation of carbon monoxide
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    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/047—Composition of the impurity the impurity being carbon monoxide
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    • 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
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
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    • 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
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1052—Nickel or cobalt catalysts
    • C01B2203/1058—Nickel catalysts
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1064—Platinum group metal catalysts
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
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    • C01B2203/107—Platinum catalysts
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • C01B2203/1241—Natural gas or methane
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/16—Controlling the process
    • C01B2203/1642—Controlling the product
    • C01B2203/1647—Controlling the amount of the product

Definitions

  • the present invention relates to an apparatus for generating hydrogen, particularly for supplying fuel cells or the like.
  • hydrogen intended in particular to supply fuel cells or other similar devices is generated by using apparatuses which allow to provide a so-called "steam reforming" process, which substantially consists in reacting, in the presence of a catalyst and by applying heat, methane and water vapor to obtain hydrogen (H 2 ), carbon dioxide (CO 2 ) and, in small amounts, carbon monoxide (CO) as reaction products.
  • steam reforming substantially consists in reacting, in the presence of a catalyst and by applying heat, methane and water vapor to obtain hydrogen (H 2 ), carbon dioxide (CO 2 ) and, in small amounts, carbon monoxide (CO) as reaction products.
  • the products obtained from the steam reforming process are then further processed to reduce the amount of CO, which is harmful for fuel cells, possibly obtaining higher quantities of hydrogen.
  • the gases obtained from the steam reforming reaction are generally sent to a first apparatus, which performs an exothermic process known as "water gas shift", which consists in practice in introducing water vapor into the gases to be treated, keeping the temperature at a preset value by means of a cooling fluid which is fed to the water gas shift apparatus, and then to a second apparatus, which in turn allows to perform an additional exothermic process which is known in technical jargon as "prox” and consists instead in introducing oxygen in the gases being processed at a preset temperature, which is also kept constant by means of a suitable cooling fluid.
  • water gas shift an exothermic process known as "water gas shift”
  • prox additional exothermic process which is known in technical jargon as "prox” and consists instead in introducing oxygen in the gases being processed at a preset temperature, which is also kept constant by means of a suitable cooling fluid.
  • tubular elements arranged inside the heat exchange region are in fact fixed at their opposite ends to respective supporting tube plates by means of a butt weld which is difficult to perform due to the flattened shape of the passage section of such tubular elements.
  • the aim of the present invention is to provide a valid solution to the drawbacks cited above by providing an apparatus for generating hydrogen particularly for supplying fuel cells or the like which has an extremely simplified structure, so that it can be manufactured at very low cost.
  • an object of the invention is to provide an apparatus which, thanks to its particular constructive characteristics, is capable of offering the greatest assurances of reliability and safety in operation.
  • Another object of the invention is to provide an apparatus which can be used to perform a steam reforming process or a water gas shift process or a prox process.
  • Another object of the present invention is to provide an apparatus for generating hydrogen which allows to modify easily its operating conditions to adapt, it to the different contingent requirements, by acting very simply only on some of its constructive characteristics.
  • Still another object of the present invention is to provide an apparatus for generating hydrogen which is structurally very compact and has small dimensions.
  • an apparatus for generating hydrogen particularly for supplying fuel cells or the like, according to the invention, comprising an enclosure which defines a heat exchange region which can be supplied with a heat exchange fluid and is crossed by at least one reaction duct which accommodates a catalyst and has an inlet for the inflow of the reagents and an outlet for the discharge of the reaction products and is characterized in that said at least one reaction duct has a cylindrical spiral shape.
  • Figure 1 is a schematic longitudinal sectional view of the apparatus according to the invention in an embodiment adapted to perform a steam reforming process
  • Figure 2 is a schematic longitudinal sectional view, taken to illustrate the interior, of a reaction duct of the apparatus according to the invention, the duct being shown, for the sake of simplicity in illustration, as if it were straight, and being further shown in the specific case of the first embodiment of the invention of Figure 1 ;
  • Figure 3 is a schematic longitudinal sectional view of three apparatuses according to the invention arranged in series to each other, each designed to perform a different process for obtaining hydrogen. Ways of carrying out the Invention
  • the apparatus according to the invention designated by the reference numerals Ia, Ib and Ic in the different embodiments, generally comprises an enclosure 2, which defines a heat exchange region 3 which is crossed by at least one reaction duct 4 inside which a catalyst agent 5 is arranged.
  • the reaction duct 4 has in particular an inlet 4a for the inflow of the reagents and an outlet 4b for the discharge of the reaction products.
  • the heat exchange region 3 is supplied with a heat exchange fluid, which is designed to exchange heat with the products which flow inside the reaction duct 4.
  • the peculiar aspect of the invention consists in that the reaction duct. 4 has, along at least one of its portions arranged inside the heat exchange region 3, a preferably cylindrical spiral shape, so as to provide in practice a coil.
  • the heat exchange region 3 is conveniently provided by a substantially cylindrical containment chamber 6 inside which the reaction duct 4 is positioned.
  • the containment chamber 6 can be obtained for example by providing the enclosure 2 by means of a cylindrical side wall 2a, which is closed at its opposite ends by two opposite end walls 2b.
  • the reaction duct 4 lies, with its cylindrical spiral portion, substantially coaxially with respect to the containment chamber 6.
  • the catalyst 5 is provided by means of at least one elongated plate-like element 7 which is arranged along at least one portion of the longitudinal extension of the reaction duct 4 and supports a catalyst agent, which can vary as a function of the type of reaction to be performed inside the reaction duct 4.
  • the plate-like element 7 conveniently comprises at least one grid-like portion 7a, preferably made of a material which is inert with respect to the reaction that occurs inside the reaction duct 4 and more preferably is made of a heat-resistant metallic material, such as for example an AISI 316 L, AISI 309 S, AISI 304, AISI 430, AISI 310 S steel and the like or an unalloyed carbon steel.
  • a heat-resistant metallic material such as for example an AISI 316 L, AISI 309 S, AISI 304, AISI 430, AISI 310 S steel and the like or an unalloyed carbon steel.
  • the catalyst agent is deposited onto at least one face of the grid-like portion 7a by means of a process which depends on the materials used.
  • the plate-like element 7 is folded in a helix along its longitudinal extension, so as to define inside the reaction duct 4 at least one substantially helical path for the reagents which forces such reagents to affect the surfaces of the plate-like element 7.
  • the plate-like element 7 can have a helix with a constant pitch or advantageously with a pitch which varies along its longitudinal extension.
  • the catalyst 5 is optionally also possible for the catalyst 5 to be constituted by a plurality of small bodies, such as for example spheroidal elements or pellets, on the outer surface of which the catalyst agent is applied.
  • such bodies provide, inside the reaction duct 4, a loose system which is permeable to the flow of the reagents, so as to create a large surface of contact between the catalyst agent and the reagents. It should be noted that it is also possible to provide for the combined use of the different types of catalysts 5 described above.
  • the apparatus Ia allows to perform a steam reforming process.
  • the reagents introduced in the reaction duct 4 at its inlet 4a comprise water vapor and at least, one hydrocarbon preferably in gaseous form, such as for example methane or other natural gas, whereas at the outlet 4b of the reaction duct 4 it is possible to obtain a mixture of gases containing hydrogen and carbon dioxide with the optional presence of carbon monoxide.
  • the auxiliary inlets 4c which may be present along the reaction duct 4 additional amounts of water vapor and/or methane to control the quantities of the various reaction products obtained.
  • the heat exchange fluid fed to the heat exchange region 3 is constituted by the hot combustion flue gases generated by a burner 8 which is functionally associated with said heat exchange region 3.
  • the burner 8 is conveniently arranged coaxially with respect to the spiral formed by the reaction duct 4 and is advantageously arranged at a first axial end 6a of the containment chamber 6, which at its axial end 6b which lies opposite the first end 6a is connected to a port 10 for the discharge of the combustion flue gases, in order to allow their evacuation into the external environment.
  • the containment chamber 6 In order to ensure effective transfer of the heat from the combustion flue gases to the reagents which transit in the heat exchange region 3 through the reaction duct 4, conveniently inside the containment chamber 6 there is at least one baffle for the combustion flue gases which allows to create a convoluted path for the combustion flue gases which pass through the containment chamber 6.
  • the baffle can be provided by means of at least one disk 1 1 made of heat resistant material, which is arranged coaxially to the spiral formed by the reaction duct 4 and is arranged in practice between the inlet 4a and the outlet 4b of the reaction duct 4.
  • the inlet 4a of the reaction duct 4 is advantageously positioned proximate to the first end 6a of the containment chamber 6 and therefore of the burner 8, while its outlet 4b is arranged proximate to the opposite end 6b of the containment chamber 6 and therefore proximate to the combustion flue gas discharge port 10.
  • the catalyst agent can be constituted by a layer of platinum which is applied by electrolytic deposition to the grid-like portion 7a of the plate-like element 7, conveniently made of AISI 304, AISI 316, AISI 310 S or AISI 309 S steel.
  • the second embodiment of the invention allows to provide a water gas shift process, particularly on the reaction products obtained in output from the apparatus Ia, in order to eliminate or at least reduce the amount of carbon monoxide generated by the steam reforming reaction performed by the apparatus 1 a.
  • reaction duct 4 of the apparatus Ib is connected, by means of its inlet 4a, to the outlet 4b of the reaction duct of the apparatus Ia and to a water vapor source, so as to receive in input, as reagents, a mixture in gaseous form which contains hydrogen, carbon dioxide and carbon monoxide, and a preset quantity of water vapor.
  • the catalyst agent is constituted for example by platinum, palladium, rhodium, chromium, nickel, iron oxides and noble metals. Since the water gas shift reaction is exothermic, the heat exchange region 3, and more particularly the chamber 6 for containing the apparatus Ib, is fed with a cooling fluid, which is constituted in particular by a diathermic fluid, such as for example water, in order to maintain the temperature inside the reaction duct 4 at a substantially constant value which is adapted to ensure activation of the catalyst 5.
  • a cooling fluid which is constituted in particular by a diathermic fluid, such as for example water, in order to maintain the temperature inside the reaction duct 4 at a substantially constant value which is adapted to ensure activation of the catalyst 5.
  • the temperature inside the reaction duct 4 of the apparatus Ib is generally kept from 300 to 500 0 C.
  • the cooling fluid is introduced in the containment chamber 6 of the apparatus Ib by means of an inlet 12, which is connected to a line 12a for delivering the cooling fluid and is discharged from the containment chamber 6 by means of an outlet 13 which leads to a line 13a for drawing the cooling fluid.
  • the delivery line 12a and the withdrawal line 13a of the cooling fluid are preferably both connected, respectively through the inlet 12 and the outlet 13, to the same end 6a of the containment chamber 6, in the proximity to which the inlet 4a of the reaction duct 4 is conveniently positioned.
  • the apparatus I c allows to perform a prox process, which allows to further reduce the amount of carbon monoxide which may be present as a residue after the steam reforming and water gas shift process.
  • reaction products obtained in output from the apparatus Ib are introduced through the inlet 4a into the reaction duct 4 of the apparatus 1 c and receive the addition of a preset amount of air or oxygen which is dispensed by an appropriately provided source, not shown, which is also connected to the inlet 4a of the reaction duct 4.
  • the apparatus Ic has a structure which is substantially similar to the structure of the apparatus Ib.
  • the heat exchange region 3 of the apparatus Ic also is supplied with a cooling fluid, which allows to keep the temperature in the reaction duct 4 at a substantially constant level, preferably ranging from 100 to 300 0 C.
  • the cooling fluid is preferably introduced in the containment chamber 6 by means of an inlet 12 which is connected to a line 12a for the delivery of the cooling fluid and is arranged at the same end 6a of the containment chamber 6 at which an outlet 13 is opened which reaches a line 13a for drawing the cooling fluid.
  • the delivery line 12a and the withdrawal line 13a connected to the apparatus I c may be the same ones that feed the heat exchange region of the apparatus Ib or may also be different.
  • the inlet 4a of the reaction duct 4 is positioned proximate to the end 6a of the containment chamber 6.
  • the catalyst agent used in the apparatus I c can be constituted for example by platinum, palladium, rhodium, chromium, nickel, iron oxides and noble metals, copper, silver.
  • the apparatuses Ia, Ib and Ic may be arranged so that their corresponding reaction ducts 4 are connected in series to each other, so as to provide a complete hydrogen generation process.
  • reaction region even two or more reaction ducts 4, each of which has, along at least one portion, a cylindrical spiral shape.
  • reaction ducts 4 are preferably arranged substantially coaxially to each other and so that the turns of one of the reaction ducts 4 are interleaved between the turns of the others. It should also be specified that in all the embodiments each reaction duct 4 is preferably made of stainless steel.
  • a mixture of water vapor and methane preferably at a temperature substantially ranging from 0 to 200 0 C, is introduced through the inlet 4a into the reaction duct 4, ] 1 inside which it comes into contact with the catalyst 5, which allows the activation of the steam reforming reaction.
  • the burner 8 is operated so as to generate inside the containment chamber 6 combustion flue gases at a temperature which ranges substantially from 300 to 1000 0 C, in order to transmit to the reagents which transit through the reaction duct 4 the heat required to perform the steam reforming reaction.
  • the flow of the combustion flue gases is diverted, with the aid of the disk 1 1, toward the coils of the reaction duct 4, through which it flows, striking externally the reaction duct 4, until it reaches the end 6b of the containment chamber 6, from which it exits by means of the discharge port 10.
  • reaction products constituted by hydrogen, carbon dioxide and optionally carbon monoxide, obtained from the steam reforming reaction exit from the reaction duct 4 at its outlet 4b and are drawn in order to be sent directly to a fuel cell or optionally to an additional treatment step.
  • reaction products extracted from the apparatus Ia are sent to the apparatus Ib, in which they undergo a water gas shift process and more specifically are introduced in the reaction duct 4 of the apparatus 1 b by means of the corresponding inlet 4a, to which a stream of water vapor is also fed which, by reacting with the carbon monoxide, allows to obtain additional quantities of hydrogen and carbon dioxide.
  • the optimum temperature conditions for performing this reaction are maintained by introducing in the heat exchange region 3 of the apparatus Ib the cooling fluid dispensed by the delivery line 12a through the inlet 12 and making it exit toward the withdrawal line 13a by means of the outlet 13.
  • reaction products obtained in output from the reaction duct 4 of the apparatus Ib can be used to supply a fuel cell or, if there are still unwanted residues of carbon monoxide, they can be sent to the apparatus Ic, in which they are treated with a prox process.
  • the inlet 4a of the reaction duct 4 of the apparatus I c can thus be connected to the outlet 4b of the reaction duct 4 of the apparatus Ib and to a source of oxygen or air. Due to the circulation of the cooling fluid inside the heat exchange region 3 of the apparatus Ic, performed by introducing it through the inlet 12 and extracting it through the outlet 13, the reagents which transit along the reaction duct 4 of the apparatus Ic are kept at a substantially constant temperature, preferably ranging from 100 to 300 0 C. With these temperature conditions and by means of the action of the catalyst 5, the reaction between the carbon monoxide and the oxygen introduced in input occurs in the reaction duct 4 of the apparatus Ic, consequently obtaining carbon dioxide.
  • invention achieves, in all of its embodiments, the intended aim and objects and in particular the fact is stressed that the cylindrical spiral structure of the reaction duct allows to achieve extremely uniform temperatures along the entire reaction duct itself, so as to ensure the optimum reaction conditions for the reagents along its entire extension. Moreover, in the particular case of the first embodiment, the spiral structure of the reaction duct allows to bring the reagents that transit inside it to extremely high temperatures, so as to achieve ideal conditions for triggering the steam reforming reaction on the part of the catalyst.
  • Another advantage of the invention consists in that by using the reaction duct arranged in a spiral, the welds exposed to contact with the combustion flue gases are eliminated, overcoming the limitations that occur in the background art.
  • Another advantage of the invention resides in that due to its spiral shape the time for which the reaction duct is crossed by the reagents can be very long, allowing the complete development of the reactions which lead to the formation of hydrogen.
  • the apparatus according to the invention structured in the manner described above, is capable of having an extremely low thermal inertia, which makes it very flexible to the variable load required by fuel cells.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
  • Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
  • Hydrogen, Water And Hydrids (AREA)

Abstract

La présente invention concerne un appareil (1a) destiné à générer de l'hydrogène, en particulier pour alimenter des piles à combustible ou analogues, comprenant une enveloppe (2) qui définit une région d'échange thermique (3) dans laquelle on peut introduire un fluide d'échange thermique et qui est traversée par au moins un conduit de réaction (4), ce dernier (4) contenant un catalyseur (5) et comportant un orifice d'admission (4a) pour l'introduction des réactifs et un orifice d'évacuation (4b) pour la décharge des produits réactionnels, ledit conduit (4) ayant une forme en spirale sur au moins une de ses parties.
PCT/EP2007/062847 2006-12-04 2007-11-27 Appareil pour générer de l'hydrogène, en particulier pour alimenter les piles à combustible Ceased WO2008068156A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ITVR2006A000186 2006-12-04
ITVR20060186 ITVR20060186A1 (it) 2006-12-04 2006-12-04 Apparecchiatura per la produzione di idrogeno particolarmente per l'alimentazione di celle a combustibile o simili

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WO2008068156A1 true WO2008068156A1 (fr) 2008-06-12

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IT (1) ITVR20060186A1 (fr)
WO (1) WO2008068156A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104203397A (zh) * 2011-12-06 2014-12-10 Hy9公司 催化剂容纳反应器系统以及相关方法
WO2015041555A1 (fr) * 2013-09-23 2015-03-26 Celac Vasile Procédé et système pour la production de gaz de synthèse
WO2018154063A1 (fr) * 2017-02-24 2018-08-30 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e. V. Échangeur thermique et réacteur
WO2021044318A1 (fr) * 2019-09-02 2021-03-11 Araya Matteo Julio Cesar Système et procédé pour l'obtention d'énergie à travers l'utilisation d'hydrocarbures de qualité réduite et d'hydrogène produit à partir de l'eau dans la production d'énergie de combustion
US11667728B1 (en) 2022-03-02 2023-06-06 David T. Camp Reactor and processes for endothermic reactions at high temperatures
WO2024133627A3 (fr) * 2022-12-22 2024-08-15 Napop As Système de génération d'énergie doté d'un brûleur catalytique

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2190903A1 (fr) * 1972-06-30 1974-02-01 Foster Wheeler Corp
US4737161A (en) * 1987-01-27 1988-04-12 International Fuel Cells Corporation Compact hydrogen generator
FR2780316A1 (fr) * 1998-06-24 1999-12-31 Inst Francais Du Petrole Regeneration de catalyseurs de reformage ou d'isomerisation ou de deshydrogenation des paraffines par passage en mode descendant sur un transporteur helicoidal vibrant
US6221117B1 (en) * 1996-10-30 2001-04-24 Idatech, Llc Hydrogen producing fuel processing system
EP1584603A2 (fr) * 1999-05-27 2005-10-12 Haldor Topsoe A/S Réacteur de reformage à la vapeur d'eau pour la production de gaz de synthèse
US20060045828A1 (en) * 2004-09-01 2006-03-02 Aaron Timothy M Catalytic reactor

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2190903A1 (fr) * 1972-06-30 1974-02-01 Foster Wheeler Corp
US4737161A (en) * 1987-01-27 1988-04-12 International Fuel Cells Corporation Compact hydrogen generator
US6221117B1 (en) * 1996-10-30 2001-04-24 Idatech, Llc Hydrogen producing fuel processing system
FR2780316A1 (fr) * 1998-06-24 1999-12-31 Inst Francais Du Petrole Regeneration de catalyseurs de reformage ou d'isomerisation ou de deshydrogenation des paraffines par passage en mode descendant sur un transporteur helicoidal vibrant
EP1584603A2 (fr) * 1999-05-27 2005-10-12 Haldor Topsoe A/S Réacteur de reformage à la vapeur d'eau pour la production de gaz de synthèse
US20060045828A1 (en) * 2004-09-01 2006-03-02 Aaron Timothy M Catalytic reactor

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104203397A (zh) * 2011-12-06 2014-12-10 Hy9公司 催化剂容纳反应器系统以及相关方法
WO2015041555A1 (fr) * 2013-09-23 2015-03-26 Celac Vasile Procédé et système pour la production de gaz de synthèse
WO2018154063A1 (fr) * 2017-02-24 2018-08-30 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e. V. Échangeur thermique et réacteur
US10737232B2 (en) 2017-02-24 2020-08-11 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Heat exchanger and reactor
WO2021044318A1 (fr) * 2019-09-02 2021-03-11 Araya Matteo Julio Cesar Système et procédé pour l'obtention d'énergie à travers l'utilisation d'hydrocarbures de qualité réduite et d'hydrogène produit à partir de l'eau dans la production d'énergie de combustion
US11719135B2 (en) 2019-09-02 2023-08-08 Julio Cesar ARAYA MATTEO System and method for obtaining power by the use of low-quality hydrocarbons and hydrogen produced from the water in the generation of combustion energy
US11667728B1 (en) 2022-03-02 2023-06-06 David T. Camp Reactor and processes for endothermic reactions at high temperatures
WO2024133627A3 (fr) * 2022-12-22 2024-08-15 Napop As Système de génération d'énergie doté d'un brûleur catalytique

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