EP2220712A1 - Système à base de pile à combustible de génération de puissance électrique - Google Patents

Système à base de pile à combustible de génération de puissance électrique

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Publication number
EP2220712A1
EP2220712A1 EP08862643A EP08862643A EP2220712A1 EP 2220712 A1 EP2220712 A1 EP 2220712A1 EP 08862643 A EP08862643 A EP 08862643A EP 08862643 A EP08862643 A EP 08862643A EP 2220712 A1 EP2220712 A1 EP 2220712A1
Authority
EP
European Patent Office
Prior art keywords
reforming
hydrogen
reforming reactor
fuel cell
anode
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP08862643A
Other languages
German (de)
English (en)
Inventor
Jingyu Cui
Erik Edwin Engwall
Mahendra Ladharam Joshi
Scott Lee Wellington
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shell Internationale Research Maatschappij BV
Original Assignee
Shell Internationale Research Maatschappij BV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shell Internationale Research Maatschappij BV filed Critical Shell Internationale Research Maatschappij BV
Publication of EP2220712A1 publication Critical patent/EP2220712A1/fr
Withdrawn legal-status Critical Current

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    • 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
    • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
    • 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
    • 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
    • C01B3/382—Multi-step processes
    • 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
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04007—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids related to heat exchange
    • 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
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04089—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
    • H01M8/04097—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants with recycling of the reactants
    • 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
    • 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
    • C01B2203/02—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
    • 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
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/025—Processes for making hydrogen or synthesis gas containing a partial oxidation step
    • C01B2203/0261—Processes for making hydrogen or synthesis gas containing a partial oxidation step containing a catalytic partial oxidation step [CPO]
    • 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
    • C01B2203/02—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
    • 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
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0405—Purification by membrane separation
    • C01B2203/041—In-situ membrane purification during hydrogen production
    • 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
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/042—Purification by adsorption on solids
    • C01B2203/043—Regenerative adsorption process in two or more beds, one for adsorption, the other for regeneration
    • C—CHEMISTRY; METALLURGY
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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
    • C01B2203/04—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
    • C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06—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
    • C01B2203/08—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
    • C01B2203/0827—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel at least part of the fuel being a recycle stream
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0833—Heating by indirect heat exchange with hot fluids, other than combustion gases, product gases or non-combustive exothermic reaction product gases
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—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
    • 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
    • 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
    • C01B2203/14—Details of the flowsheet
    • C01B2203/142—At least two reforming, decomposition or partial oxidation steps in series
    • 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
    • C01B2203/14—Details of the flowsheet
    • C01B2203/148—Details of the flowsheet involving a recycle stream to the feed of the process for making hydrogen or synthesis gas
    • 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
    • C01B2203/16—Controlling the process
    • C01B2203/1604—Starting up the process
    • 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
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M2008/1293—Fuel cells with solid oxide electrolytes
    • 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

Definitions

  • Solid oxide fuel cells are formed of an anode, a cathode, and a solid electrolyte sandwiched between the anode and cathode.
  • An oxidizable fuel gas, or a gas that may be reformed in the fuel cell to an oxidizable fuel gas, is fed to the anode, and an oxygen containing gas, typically air, is fed to the cathode to provide the chemical reactants.
  • the oxidizable fuel gas fed to the anode is typically syngas — a mixture of hydrogen and carbon monoxide.
  • the fuel cell is operated at a high temperature, typically from 800 0 C to 1100 0 C, to convert oxygen in the oxygen containing gas to ionic oxygen that may cross the electrolyte to interact with hydrogen and/or carbon monoxide from the fuel gas at the anode.
  • Electrical power is generated by the conversion of oxygen to ionic oxygen at the cathode and the chemical reaction of the ionic oxygen with hydrogen and/or carbon monoxide at the anode.
  • the following reactions describe the electrical power generating chemical reactions in the cell: Cathode charge transfer: O 2 + 4e ⁇ ⁇ 20 "
  • An electrical load or storage device may be connected between the anode and the cathode so an electrical current may flow between the anode and cathode, powering the electrical load or providing electrical power to the storage device.
  • Fuel gas is typically supplied to the anode of the fuel cell by a steam reforming reactor that reforms a low molecular weight hydrocarbon and steam into hydrogen and carbon oxides.
  • Methane for example as natural gas, is a preferred low molecular weight hydrocarbon used to produce fuel gas for the fuel cell.
  • the fuel cell anode may be designed to internally effect a steam reforming reaction on a low molecular weight hydrocarbon such as methane and steam supplied to the anode of the fuel cell.
  • a methane feed and/or other low molecular weight hydrocarbon feed used in the steam reforming reactor may be produced from a liquid fuel such as gasoline, diesel, or kerosene.
  • the liquid fuel may be converted to a feed for the steam reforming reactor in a pre-reforming reactor.
  • the liquid fuel may be converted to a feed for the steam reforming reactor by mixing the fuel with steam and reacting the fuel and steam at a temperature of 55O 0 C or greater, often 700 0 C or greater.
  • Methane steam reforming provides a fuel gas containing hydrogen and carbon monoxide according to the following reaction: CH 4 + H 2 O * * ⁇ CO + 3H 2 .
  • Heat must be supplied to effect the steam reforming reaction since the reaction to form hydrogen and carbon monoxide is quite endothermic.
  • the reaction is typically conducted at a temperature in the range of 75O 0 C to HOO 0 C to convert a substantial amount of methane or other hydrocarbon and steam to hydrogen and carbon monoxide.
  • Heat for 1) inducing the methane steam reforming reaction in a steam reforming reactor and, if desired, 2) for converting liquid fuel into feed for the steam reforming reactor has been conventionally provided by a burner that combusts an oxygen containing gas with a fuel, typically a hydrocarbon fuel such as natural gas, to provide the required heat.
  • Flameless combustion has also been utilized to provide the heat for driving the steam reforming reaction, where the flameless combustion is also driven by providing a hydrocarbon fuel and a oxygen containing gas to a flameless combustor in relative amounts that avoid inducing flammable combustion.
  • U.S. Patent Application No. 2005/0164051 discloses a system and a process in which reforming reactor and a pre-reforming reactor may be thermally integrated with a fuel cell. Heat produced by the fuel cell is used to provide heat to drive the endothermic reaction of the reforming reactor.
  • the reforming reactor is thermally integrated with the fuel cell by placing the reforming reactor in the same hot box as the fuel cell and/or by placing the fuel cell and the reformer in thermal contact with each other.
  • the fuel cell and the reformer may be placed in thermal contact with each other by placing the reformer in close proximity to the fuel cell, where the cathode exhaust conduit of the fuel cell may be in direct contact with the reformer (e.g. by wrapping the cathode exhaust conduit around the reformer, or by one or more walls of the reformer comprising a wall of the cathode exhaust conduit) so that the cathode exhaust from the fuel cell provides conductive heat transfer to the reformer.
  • Supplemental heat is provided from a combustor to the reformer, where the thermal contact of the fuel cell and the reformer lowers the combustion heat requirement of the reformer to effect the reforming reaction.
  • the process is still relatively thermally inefficient since 1) the heat from the fuel cell is insufficient to completely drive the reforming reaction because the heat of the exhaust from the fuel cell has a temperature at or near the temperature required to drive the reforming reaction (75O 0 C-1100 0 C), and, unless near perfect heat exchange occurs, the heat from the fuel cell will not be sufficient to drive the reforming reaction without additional heat from another source such as a combustor; and 2) significant amounts of heat from the fuel cell exhaust will be convectively transferred away from the reforming reactor as well as towards the reactor.
  • the pre-reforming reactor also does not convert a liquid hydrocarbon feedstock to a lower molecular weight feed for the steam reforming reactor, and insufficient heat is likely provided from the fuel cell to do so.
  • solid oxide fuel cells coupled with pre-reforming and reforming reactors are typically run in a manner that is not electrochemically efficient and does not produce a high electrical power density.
  • Solid oxide fuel cells are typically operated commercially in a "hydrogen-lean" mode, where the conditions of the production of the fuel gas, for example by steam reforming, are selected to limit the amount of hydrogen exiting the fuel cell in the fuel cell exhaust. This is done to balance the electrical energy potential of the hydrogen in the fuel gas with the potential (thermal + electrochemical) energy lost by hydrogen leaving the cell without being converted to electrical energy.
  • Hydrogen is a very expensive gas to use to fire a burner, therefore, conventionally, the amount of hydrogen used in the solid oxide fuel cell is adjusted to utilize most of the hydrogen provided to the fuel cell to produce electrical power and minimize the amount of hydrogen exiting the fuel cell in the fuel cell exhaust.
  • U.S. Patent Application Publication No. 2007/0017369 (the '369 publication) provides a method of operating a fuel cell system in which a feed is provided to a fuel inlet of the fuel cell.
  • the feed may include a mixture of hydrogen and carbon monoxide provided from an external steam reformer or, alternatively may include a hydrocarbon feed that is reformed to hydrogen and carbon monoxide internally in the fuel cell stack.
  • the fuel cell stack is operated to generate electricity and a fuel exhaust stream that contains hydrogen and carbon monoxide, where the hydrogen and carbon monoxide in the fuel exhaust stream are separated from the fuel exhaust stream and fed back to the fuel inlet as a portion of the feed.
  • the fuel gas for the fuel cell therefore, is a mixture of hydrogen and carbon monoxide derived by reforming a hydrocarbon fuel source and hydrogen and carbon monoxide separated from the fuel exhaust system. Recycling at least a portion of the hydrogen from the fuel exhaust through the fuel cell enables a high operation efficiency to be achieved.
  • the system further provides high fuel utilization in the fuel cell by utilizing about 75% of the fuel during each pass through the stack.
  • the 2005/0164051 provides a method of operating a fuel cell system in which a fuel is provided to a fuel inlet of the fuel cell.
  • the fuel may be a hydrocarbon fuel such as methane; natural gas containing methane with hydrogen and other gases; propane; biogas; an unreformed hydrocarbon fuel mixed with a hydrogen fuel from a reformer; or a mixture of a non-hydrocarbon carbon containing gas such as carbon monoxide, carbon dioxide, oxygenated carbon containing gas such as methanol, or other carbon containing gas with a hydrogen containing gas such as water vapor or syngas.
  • the fuel cell stack is operated to generate electricity and a fuel exhaust stream that contains hydrogen.
  • a hydrogen separator is utilized to separate non-utilized hydrogen from the fuel side exhaust stream of the fuel cell.
  • the hydrogen separated by the hydrogen separator may be re-circulated back to the fuel cell or may be directed to a subsystem for other uses having a hydrogen demand.
  • the amount of hydrogen re- circulated back to the fuel cell may be selected according to electrical demand or hydrogen demand, where more hydrogen is re-circulated back to the fuel cell when electrical demand is high.
  • the fuel cell stack may be operated at a fuel utilization rate of from 0 to 100%, depending on electrical demand. When the electrical demand is high, the fuel cell is operated at a high fuel utilization rate to increase electricity production — a preferred rate is from 50 to 80%.
  • pre-reforming reactor feed precursor inlets coupled in gas/fluid communication with the pre-reforming region through which a feed precursor may be introduced into the pre-reforming region;
  • a hydrogen gas outlet located in gaseous communication with the member, the member being interposed between the reforming region of the reforming reactor and the hydrogen gas outlet to permit selective flow of hydrogen from the reforming region to the hydrogen gas outlet through the member, wherein the hydrogen gas outlet is operatively coupled in gaseous communication with the anode inlet of the fuel cell to permit the flow of a hydrogen gas stream from the hydrogen separation apparatus to the anode of the fuel cell.
  • a pre-re forming region adapted to crack one or more hydrocarbons in a feed precursor to form a feed, said pre-reforming region containing a cracking catalyst therein positioned to contact a vaporized mixture of steam and one or more hydrocarbons of a feed precursor;
  • one or more pre-reforming reactor anode exhaust inlets coupled in gaseous communication with the pre-reforming region and operatively coupled in gaseous communication with the anode exhaust outlet, through which an anode exhaust stream from the fuel cell may be introduced into the pre-reforming region;
  • a reforming region adapted to reform a vaporized mixture of steam and a feed comprising one or more gaseous hydrocarbons, said reforming region containing a reforming catalyst therein positioned to contact the vaporized mixture of steam and feed in the reforming region;
  • Fig. 1 is a schematic of a system of the present invention for conducting a process of the present invention including a pre-reforming reactor, a reforming reactor with a hydrogen separation apparatus located therein, and a solid oxide fuel cell.
  • Fig. 2 is a schematic of a system of the present invention for conducting a process of the present invention including a pre-reforming reactor, a reforming reactor, a hydrogen separation device operatively connected to the reforming reactor, and a solid oxide fuel cell.
  • Fig. 3 is a schematic of a basic system of the present invention including a pre- reforming reactor, a reforming reactor with a hydrogen separation apparatus located therein, and a solid oxide fuel cell.
  • the present invention provides a highly efficient process for generating electricity from a liquid hydrocarbon fuel at a high electrical power density in a system utilizing a solid oxide fuel cell.
  • the process of the present invention is more thermally energetically efficient than processes disclosed in the art. Thermal energy from a fuel cell exhaust is transferred directly into a pre-reforming reactor, and a portion of this thermal energy is then transferred from the pre-reforming reactor into a reforming reactor. Optionally, thermal energy may also be transferred directly from the fuel cell into the reforming reactor.
  • the transfer of thermal energy directly from the anode exhaust of the fuel cell to the pre-reforming reactor is highly efficient since the transfer is effected by molecularly mixing a hot anode exhaust stream from the fuel cell directly with a feed precursor and steam in the pre-reforming reactor, producing a feed that is then fed to the reforming reactor.
  • the transfer of thermal energy from the pre-reforming reactor to the reforming reactor is also highly efficient, since the thermal energy is contained in the feed fed from the pre-reforming reactor to the reforming reactor.
  • the optional transfer of thermal energy from the fuel cell to the reforming reactor via the fuel cell cathode exhaust is also thermally efficient since the heat transfer may take place directly within the reforming reactor.
  • the process of the present invention is also more thermally efficient than processes disclosed in the art since the reforming reactor may effect the production of hydrogen at lower temperatures than typical steam reforming processes.
  • hydrogen may be separated from the reformed product gases as the reforming reaction occurs in the reforming reactor, driving the equilibrium toward the production of hydrogen and lowering the temperature required to effect the production of hydrogen. Further, more hydrogen may be produced at the lower reforming reactor temperatures since the equilibrium of the water-gas shift reaction H 2 O + CO ** ⁇ CO 2 + H 2 favors the production of hydrogen at the lower reforming reactor temperatures, whereas it is not favored at conventional reforming reaction temperatures.
  • the reforming reactor is designed to produce hydrogen at much lower temperatures than typical reforming reactors so the heat from the feed supplied from the pre-reforming reactor, or from the feed in combination with heat from the fuel cell cathode exhaust, is sufficient to drive the lower temperature reforming reaction with no extraneous heat source.
  • the process of the present invention also may produce a higher electrical power density in a solid oxide fuel cell system than processes disclosed in the art by utilizing a hydrogen-rich fuel. This is achieved by recycling the anode exhaust stream, which contains hydrogen and steam, through the pre-reforming reactor and the reforming reactor. Hydrogen not utilized to produce electricity in the fuel cell is recycled continuously into the pre-reforming reactor, and, ultimately, back to the fuel cell. This enables production of a high electrical power density relative to the lowest heating value of the fuel by eliminating the problem associated with losing potential energy by hydrogen leaving the cell without being converted to electrical energy.
  • the anode of a solid oxide fuel cell is flooded with hydrogen over the entire path length of the anode so that the concentration of hydrogen at the anode electrode available for electrochemical reaction is maintained at a high level over the entire anode path length, thereby maximizing the electrical power density of the fuel cell.
  • Use of a hydrogen-rich fuel that is primarily, and preferably almost all, hydrogen in the process maximizes the electrical power density of the fuel cell system since hydrogen has a significantly greater electrochemical potential than other oxidizable compounds typically used in solid oxide fuel cell systems such as carbon monoxide.
  • the concentration of the oxidation products is equivalent to the concentration of hydrogen in the fuel exhaust, and the concentration of oxidation products in the fuel cell decreases the electrical power the fuel cell provides.
  • a high electrical power density is provided by the fuel cell since an excess of hydrogen is present for electrochemical reaction at the anode electrode along the entire anode path length of the fuel cell.
  • the present invention is directed to a system for generating electricity at a high electrical power density in a highly efficient manner.
  • hydrogen refers to molecular hydrogen unless specified otherwise.
  • operatively connected when two or more elements are described as “operatively connected” or “operatively coupled”, the elements are defined to be directly or indirectly connected to allow direct or indirect fluid flow between the elements.
  • fluid flow refers to the flow of a gas or a fluid.
  • direct fluid flow means that the flow of a fluid or a gas between two defined elements may be directed through one or more additional elements to change one or more aspects of the fluid or gas as the fluid or gas flows between the two defined elements.
  • aspects of a fluid or a gas that may be changed in indirect fluid flow include physical characteristics, such as the temperature or the pressure of a gas or a fluid, and/or the composition of the gas or fluid, e.g. by separating a component of the gas or fluid, for example, by condensing water from a gas stream containing steam.
  • Indirect fluid flow excludes changing the composition of the gas or fluid between the two defined elements by chemical reaction, for example, oxidation or reduction of one or more elements of the fluid or gas.
  • the term "selectively permeable to hydrogen” is defined as permeable to molecular hydrogen or elemental hydrogen and impermeable to other elements or compounds such that at most 10%, or at most 5%, or at most 1% of the non- hydrogen elements or compounds may permeate what is permeable to molecular or elemental hydrogen.
  • high temperature hydrogen-separation device is defined as a device or apparatus effective for separating hydrogen, in molecular or elemental form, from a gas stream at a temperature of at least 25O 0 C, typically at temperatures of from 300 0 C to 65O 0 C.
  • per pass hydrogen utilization as referring to the utilization of hydrogen in a fuel in a solid oxide fuel cell, is defined as the amount of hydrogen in a fuel utilized to generate electricity in one pass through the solid oxide fuel cell relative to the total amount of hydrogen in a fuel input into the fuel cell for that pass.
  • the per pass hydrogen utilization may be calculated by measuring the amount of hydrogen in a fuel fed to the anode of a fuel cell, measuring the amount of hydrogen in the anode exhaust of the fuel cell, subtracting the measured amount of hydrogen in the anode exhaust of the fuel cell from the measured amount of hydrogen in the fuel fed to the fuel cell to determine the amount of hydrogen used in the fuel cell, and dividing the calculated amount of hydrogen used in the fuel cell by the measured amount of hydrogen in the fuel fed to the fuel cell.
  • the per pass hydrogen utilization may be expressed as a percent by multiplying the calculated per pass hydrogen utilization by 100.
  • pre-reforming reactor refers to a reactor in which a cracking reaction, and optionally, other reactions such as a reforming reaction, and optionally, physical transformations of a material such as vaporization may take place.
  • Cracking reactions that may take place in the pre-reforming reactor break hydrocarbon molecules into simpler molecules. Cracking may involve the reduction of the molecular chain length of hydrocarbon compounds and/or the reduction of the molecular weight of hydrocarbon compounds in the pre-reforming reactor.
  • cracking reactions that may take place in the pre-reforming reactor may reduce the molecular chain length of hydrocarbon compounds having at least four carbon atoms to hydrocarbon compounds having at most 3 carbon atoms.
  • the cracking reactions that may take place in the pre- reforming reactor may be thermal cracking reactions or hydrocracking reactions.
  • a feed precursor that contains a liquid hydrocarbon from which hydrogen may be derived may be fed to the pre-reforming reactor 101 via line 109.
  • the feed precursor may contain one or more of any vaporizable hydrocarbon that is liquid at 2O 0 C at atmospheric pressure (optionally oxygenated) that is vaporizable at temperatures up to 400 0 C at atmospheric pressure.
  • Such feed precursors may include, but are not limited to, light petroleum fractions such as naphtha, diesel, and kerosene, having a boiling point range of 50-205 0 C.
  • Such feed precursors may also include oxygenated hydrocarbons, including, but not limited to, methanol, ethanol, propanol, isopropanol, and butanol.
  • the feed precursor may optionally contain some hydrocarbons that are gaseous at 2O 0 C such as methane, ethane, propane, or other compounds containing from one to four carbon atoms that are gaseous at 2O 0 C (atmospheric pressure).
  • the feed precursor may contain at least 0.5, or at least 0.6, or at least 0.7, or at least 0.8 mole fraction of hydrocarbons containing at least five, or at least six, or at least seven carbon atoms.
  • the feed precursor may be decane.
  • the feed precursor may be diesel fuel.
  • the feed precursor may be optionally heated further in heat exchanger 117 by exchanging heat with a cathode exhaust stream from the fuel cell 105 prior to being fed to the pre-reforming reactor 101.
  • the feed precursor may be desulfurized in desulfurizer 111 after being heated in heat exchanger 117 (as shown) or prior to being heated in the heat exchanger 117 (not shown), but before being fed to the pre-reforming reactor 101.
  • the feed precursor may be desulfurized in the desulfurizer 111 by contact with a conventional hydrodesulfurizing catalyst under conventional desulfurizing conditions.
  • the feed precursor is fed into the pre-reforming region 119 of the pre-re forming reactor 101.
  • the pre-reforming region 119 may, and preferably does, contain a pre- reforming catalyst therein.
  • the pre-reforming catalyst may be a conventional pre- reforming catalyst, and may be any known in the art.
  • Typical pre-reforming catalysts which can be used include, but are not limited to, Group VIII transition metals, particularly nickel and a support or substrate that is inert under high temperature reaction conditions.
  • Suitable inert compounds for use as a support for the high temperature pre- reforming/hydrocracking catalyst include, but are not limited to, ⁇ -alumina and zirconia.
  • An anode exhaust stream separated from the anode 121 of the solid oxide fuel cell 105 is also fed into the pre-reforming region 119 of the pre-reforming reactor 101.
  • the anode exhaust may be fed directly from the anode exhaust outlet 123 to the pre-reforming reactor 101 through line 125.
  • Providing a molar ratio of at least 2: 1 , or at least 3 : 1 , or at least 4:1 steam to carbon in the feed precursor in the pre-re forming reactor 101 may be useful to inhibit coke formation in the pre-reforming region 119 of the pre -reforming reactor 101.
  • Metering valve 129 may be used to control the rate that steam is fed to the pre-reforming reactor 101 through line 127.
  • the high pressure steam may then be fed to line 127 via line 135.
  • the high pressure steam may be depressurized to the desired pressure by expanding the high pressure steam through an expander, then feeding to it to the pre-reforming reactor.
  • steam may be generated for use in the pre-reforming reactor by feeding low pressure water through the one or more heat exchangers 133 and passing the resulting steam into the pre-reforming reactor 101.
  • the feed precursor, optional steam, and the anode exhaust stream are mixed and contacted with the pre-reforming catalyst in the pre-reforming region 119 of the pre- reforming reactor 103 at a temperature effective to vaporize any feed precursor not in vapor form and to crack the feed precursor to form the feed.
  • the feed precursor, optional steam, and anode exhaust stream are mixed and contacted with the pre-reforming catalyst at a temperature of at least 600 0 C, or from 75O 0 C to 1050 0 C, or from 800 0 C to 900 0 C.
  • the anode exhaust stream fed from the exothermic solid oxide fuel cell 105 to the pre-reforming reactor 101 supplies heat to drive the endothermic cracking reactions in the pre -reforming reactor 101.
  • the anode exhaust stream fed from the solid oxide fuel cell 105 to the pre-reforming reactor 101 is very hot, having a temperature of at least 800 0 C, typically having a temperature of from 85O 0 C to HOO 0 C, or from 900 0 C to 1050 0 C.
  • the transfer of thermal energy from the solid oxide fuel cell 105 to the pre-reforming reactor 101 is extremely efficient since thermal energy from the solid oxide fuel cell 105 is contained in the anode exhaust stream, and is transferred to the mixture of feed precursor, optional steam, and anode exhaust stream in the pre-reforming region 119 of the pre- reforming reactor 101 by directly mixing the anode exhaust stream with the feed precursor and steam.
  • the anode exhaust stream provides at least 99%, or substantially all, of the heat required to produce the feed from the mixture of feed precursor, optional steam, and anode exhaust stream.
  • no heat source other than the anode exhaust stream is provided to the pre-reforming reactor to convert the feed precursor to the feed.
  • the relative rates at which the feed precursor, optional steam, and anode exhaust stream are fed to the pre-reforming reactor 101 may be selected and controlled such that the heat provided by the anode exhaust stream is sufficient to provide at least 99%, or substantially all, of the heat required to produce the feed in the pre-reforming reactor 101.
  • the rate at which the feed precursor is fed to the pre-reforming reactor 101 may be controlled by adjusting metering valve 137, which controls the rate that the feed precursor is fed to the system 100.
  • the rate at which steam, other than steam in the anode exhaust stream, is fed to the pre-reforming reactor 101 may be controlled by adjusting metering valve 139, which controls the rate water is fed to the system 100, or by adjusting metering valves 143 and 141, which control the rates at which steam is fed to the pre-reforming reactor 101 and the reforming reactor 103, or by adjusting metering valves 129 and 145, which control the rates at which steam is fed to the pre-reforming reactor and to a turbine 147, or by adjusting metering valves 161 and 163 which control the rates at which steam is fed to the reforming reactor 103 and the pre-reforming reactor 101.
  • the pressure at which the anode exhaust stream, the feed precursor, and the optional steam are contacted with the pre-reforming catalyst in the pre- reforming region 119 of the pre-reforming reactor 101 may range from 0.07 MPa to 3.0 MPa. If the high pressure steam is not fed to the pre-reforming reactor, the anode exhaust stream, the feed precursor, and optional low pressure steam may be contacted with the pre-reforming catalyst in the pre-reforming region 119 of the pre-reforming reactor 101 at a pressure at the low end of this range, typically from 0.07 MPa to 0.5 MPa, or from 0.1 MPa to 0.3 MPa.
  • the feed precursor may comprise hydrocarbons containing at least 5, or at least 6, or at least 7 carbon atoms that are converted to hydrocarbons useful as feed to the reforming reactor 103 containing at most 4, or at most 3, or at most 2 carbon atoms.
  • the feed precursor may comprise at least 0.5, or at least 0.6, or at least 0.7 mole fraction of hydrocarbons having containing at least 5, or at least 6, or at least 7 carbon atoms, and the hydrocarbon portion of the resulting feed may be comprised at least 0.5, or at least 0.6, or at least 0.7, or at least 0.8 mole fraction of hydrocarbons containing at most 4 carbon atoms, or at most 3, or at most 2 carbon atoms.
  • the feed precursor may be reacted in the pre-reforming reactor 101 such that the feed produced in the pre- reforming reactor 101 may be comprised of not more than 0.1, or not more than 0.05, or not more than 0.01 mole fraction of hydrocarbons with four carbon atoms or more.
  • feed precursor may be cracked such that at least 0.7, or at least 0.8, or at least 0.9, or at least 0.95 mole fraction of the hydrocarbons in the feed produced from the feed precursor is methane.
  • contacting the feed precursor, steam and anode exhaust with the pre-reforming catalyst in the pre-reforming reactor 101 at a temperature of at least 600 0 C, or from 75O 0 C to 1050 0 C, or from 800 0 C to 900 0 C may also effect at least some reforming of the hydrocarbons in the feed precursor and feed produced within the pre- reforming reactor 101 to produce hydrogen and carbon oxides, particularly carbon monoxide.
  • the amount of reforming may be substantial, where the feed resulting from both cracking and reforming in the pre-reforming reactor may contain at least 0.05, or at least 0.1, or at least 0.15 mole fraction carbon monoxide.
  • the temperature and pressure conditions in the pre-reforming region 119 of the pre-reforming reactor 101 may be selected so the feed produced in the pre-reforming reactor 101 comprises light hydrocarbons that are gaseous at 2O 0 C, typically containing 1 to 4 carbon atoms.
  • the hydrocarbons in the feed are comprised of at least 0.6, or at least 0.7, or at least 0.8, or at least 0.9 mole fraction methane.
  • the feed also comprises hydrogen from the anode exhaust stream and, if reforming is effected in the pre-reforming reaction, from reformed feed precursor compounds.
  • the feed also comprises steam from the anode exhaust stream and, optionally, from the pre -reformer steam feed. If substantial reforming is effected in the pre-reforming reactor 101 the feed produced in the pre-reforming reactor 101 that is fed to the reforming reactor 103 may also comprise carbon monoxide.
  • the feed is fed from the pre-reforming reactor 101 to the reforming reactor 103, which is operatively connected to the pre-reforming reactor 101 through line 153.
  • the feed may be optionally cooled in one or more heat exchangers 133 prior to being fed to the reforming reactor 103.
  • the feed may also optionally be compressed in a compressor 155 prior to being fed to the reforming reactor 103.
  • the feed may be cooled to a temperature of from 15O 0 C to 65O 0 C, or from 15O 0 C to 300 0 C, or from 400 0 C to 65O 0 C, or from 45O 0 C to 55O 0 C.
  • the cooled feed may be fed from the one or more heat exchangers 133 to the compressor 155, or, in another embodiment, may be fed directly to the reforming reactor 103.
  • the feed exiting the pre-reforming reactor 101 may be fed to the compressor 155 or the reforming reactor 103 without cooling.
  • the feed may be compressed by compressor 155 to a pressure of at least 0.5 MPa, or at least 1.0 MPa, or at least 1.5 MPa, or at least 2 MPa, or at least 2.5 MPa, or at least 3 MPa to maintain sufficient pressure in the reforming region 157 of the reforming reactor 103 to drive the hydrogen present in the feed and produced from the feed in the reforming reactor 103 through the hydrogen-separation device 107 in the reforming reactor 103.
  • the compressor 155 is a compressor capable of operating at high temperatures, and preferably is a commercially available StarRotor compressor.
  • high pressure water may be injected into the feed by mixing the high pressure water and feed in one or more of the heat exchangers 133.
  • high pressure water may be injected into the feed in line 153 either before or after passing the feed to the one or more heat exchangers 133 or before or after passing the feed to the compressor 155.
  • high pressure water may be injected into line 153, or into compressor 155, or in the one or more heat exchangers 133, where either the compressor 155 or the one or more heat exchangers 133 is not included in the system 100.
  • the high pressure water is heated to form steam by mixing with the feed, and the feed is cooled by mixing with the water.
  • the cooling provided to the feed by the water injected therein may eliminate or reduce the need for the one or more heat exchangers 133, preferably limiting the number of heat exchangers 133 used to cool the feed to at most one.
  • high pressure steam may be injected into the reforming region 157 of the reforming reactor 103 or the line 153 to the reforming reactor 103 to be mixed with the feed.
  • the high pressure steam may be steam produced by heating high pressure water injected into the system 100 through water inlet line 131 in the one or more heat exchangers 133 by exchanging heat with the feed exiting the pre- reforming reactor 101.
  • the high pressure steam may be fed to the reforming reactor 101 through line 159.
  • Metering valves 161 and 163 may be used to control the flow of steam to the reforming reactor 103.
  • the high pressure steam may have a pressure similar to that of the feed being fed to the reforming reactor 103.
  • the high pressure steam may be fed to line 153 to be mixed with the feed prior to the feed being fed to compressor 155 so the mixture of steam and feed may be compressed together to a selected pressure.
  • the high pressure steam may have a temperature of from 200 0 C to 500 0 C.
  • the rate the high pressure water or high pressure steam is injected into the feed may be selected to provide an amount of steam to the reforming reactor 103 effective to optimize reforming and water gas shift reactions to produce hydrogen in the reforming reactor 103. If high pressure water is injected into the feed, metering valves 139, 141, and 143 may be adjusted to control the rate the water is injected into the feed through line 165. If high pressure steam is injected into the reforming reactor 103 or into line 153, metering valves 139, 143, 161, and 163 may be adjusted to control the rate the steam is injected into the reforming reactor 103 or into line 153.
  • the feed and, optionally, additional steam are fed into the reforming region 157 of the reforming reactor 103.
  • the reforming region may, and preferably does, contain a reforming catalyst therein.
  • the reforming catalyst may be a conventional steam reforming catalyst, and may be known in the art. Typical steam reforming catalysts which can be used include, but are not limited to, Group VIII transition metals, particularly nickel. It is often desirable to support the reforming catalysts on a refractory substrate (or support).
  • the support if used, is preferably an inert compound. Suitable inert compounds for use as a support contain elements of Group III and IV of the Periodic Table, such as, for example the oxides or carbides of Al, Si, Ti, Mg, Ce, and Zr.
  • the feed and, optionally additional steam, are mixed and contacted with the reforming catalyst in the reforming region 157 at a temperature effective to form a reformed product gas containing hydrogen and carbon oxides.
  • the reformed product gas may be formed by steam reforming the hydrocarbons in the feed.
  • the reformed product gas may also be formed by water-gas shift reacting steam and carbon monoxide in the feed and/or produced by steam reforming the feed.
  • the reforming reactor 103 may act more as a water-gas shift reactor if a substantial amount of reforming was effected in the pre -reforming reactor and the feed contains substantial amounts of carbon monoxide.
  • the reformed product gas may contain hydrogen and at least one carbon oxide. Carbon oxides that may be in the reformed product gas include carbon monoxide and carbon dioxide.
  • One or more high temperature tubular hydrogen-separation membranes 107 may be located in the reforming region 157 of the reforming reactor 103 positioned so that the feed and the reformed product gas may contact the hydrogen separation membrane(s) 107 and hydrogen may pass through membrane wall 167 of the membrane(s) 107 to a hydrogen conduit 169 located within the tubular membrane(s) 107.
  • the membrane wall 167 of each respective hydrogen separation membrane 107 separates the hydrogen conduit 169 of the membrane 107 from gaseous communication with non-hydrogen compounds of the reformed product gas, feed, and steam in the reforming region 157 of the reforming reactor 103.
  • the membrane wall 167 is selectively permeable to hydrogen, elemental and/or molecular, so that hydrogen in the reforming region 157 may pass through the membrane wall 167 of a membrane 107 to the hydrogen conduit 169 while other gases in the reforming region 157 are prevented from passing to the hydrogen conduit 169 by the membrane wall 167.
  • the high temperature tubular hydrogen-separation membrane(s) 107 in the reforming region may comprise a support coated with a thin layer of a metal or alloy that is selectively permeable to hydrogen.
  • the support may be formed of a ceramic or metallic material that is porous to hydrogen. Porous stainless steel or porous alumina are preferred materials for the support of the membrane 107.
  • the hydrogen selective metal or alloy coated on the support may be selected from metals of Group VIII, including, but not limited to Pd, Pt, Ni, Ag, Ta, V, Y, Nb, Ce, In, Ho, La, Au, and Ru, particularly in the form of alloys. Palladium and platinum alloys are preferred.
  • a particularly preferred membrane 107 used in the present process has a very thin film of a palladium alloy having a high surface area coating a porous stainless steel support.
  • Membranes of this type can be prepared using the methods disclosed in U.S. Pat. No. 6,152,987. Thin films of platinum or platinum alloys having a high surface area would also be suitable as the hydrogen selective material.
  • the pressure within the reforming region 157 of the reforming reactor 103 is maintained at a level significantly above the pressure within the hydrogen conduit 169 of the tubular membrane 107 so that hydrogen is forced through the membrane wall 167 from the reforming region 157 of the reforming reactor into the hydrogen conduit 169.
  • the hydrogen conduit 169 is maintained at or near atmospheric pressure
  • the reforming region 157 is maintained at a pressure of at least 0.5 MPa, or at least 1.0 MPa, or at least 2 MPa, or at least 3 MPa.
  • the reforming region 157 may be maintained at such elevated pressures by compressing the feed from the pre- re forming reactor 101 with compressor 155 and injecting the mixture of feed at high pressure into the reforming region 157.
  • the reforming region 157 may be maintained at such high pressures by mixing high pressure steam with the feed as described above and injecting the high pressure mixture into the reforming region 157 of the reforming reactor 103.
  • the reforming region 157 may be maintained at such high pressures by mixing high pressure steam with the feed precursor in the pre- reforming reactor 101 and injecting a high pressure feed produced in the pre -reforming reactor 101 into the reforming reactor 103 either directly or through one or more heat exchangers 133.
  • the reforming region 157 of the reforming reactor 103 may be maintained at a pressure of at least 0.5 MPa, or at least 1.0 MPa, or at least 2.0 MPa, or at least 3.0 MPa.
  • the temperature at which the feed, and optionally additional steam, is/are mixed and contacted with the reforming catalyst in the reforming region 157 of the reforming reactor 103 is at least 400 0 C, and preferably may range from 400 0 C to 65O 0 C, most preferably in a range of from 45O 0 C to 55O 0 C.
  • the equilibrium of the reforming reaction in the present process is driven towards the production of hydrogen in the reforming reactor operating temperature range of 400 0 C to 65O 0 C since hydrogen is removed from the reforming region 157 into the hydrogen conduit 169 of the hydrogen separation membrane(s) 107 and thence removed from the reforming reactor 103.
  • An operating temperature of 400 0 C to 65O 0 C favors the shift reaction as well, converting carbon monoxide and steam to more hydrogen, which is then removed from the reforming region 103 into the hydrogen conduit 169 of the hydrogen separation membrane(s) 107 through the membrane wall 167 of the membrane(s) 107.
  • Nearly complete conversion of hydrocarbons and carbon monoxide to hydrogen and carbon dioxide by the reforming and water gas shift reactions is achieved in the reforming reactor 103 since equilibrium is never reached due to the continuous removal of hydrogen from the reforming reactor 103.
  • the feed fed from the pre-re forming reactor 101 to the reforming reactor 103 supplies heat to drive the reactions in the reforming reactor 103.
  • the feed fed from the pre-reforming reactor 101 to the reforming reactor 103 may contain sufficient thermal energy to drive the reactions in the reforming reactor 103, and may have a temperature of from 600 0 C to 1000 0 C.
  • the thermal energy of the feed from the pre-reforming reactor 101 may be in excess of the thermal energy needed to drive the reactions in the reforming reactor 103, and, as described above, the feed may be cooled to a temperature of from 400 0 C to less than 600 0 C in the one or more heat exchangers 133 and/or by injecting water into the feed prior to the feed being fed to the reforming reactor 103.
  • Cooling the feed prior to feeding the feed to the reforming reactor 103 may be preferable so that 1) the temperature within the reforming reactor 103 may be adjusted to favor the production of hydrogen in the water-gas shift reaction; 2) the membrane 107 life-span may be extended; and 3) to improve compressor 155 performance.
  • the transfer of thermal energy from the pre -re forming reactor 101 to the reforming reactor 103 is extremely efficient since thermal energy from the pre-reforming reactor 101 is contained in the feed, which is intimately involved in the reactions within the reforming reactor 103.
  • additional heat may be supplied to the reforming reactor 103 from a hot cathode exhaust stream from the solid oxide fuel cell 105.
  • a hot cathode exhaust stream having a temperature of from 800 0 C to HOO 0 C exits the cathode 171 of the fuel cell 105 from cathode exhaust outlet 173 and may be fed through line 175 to one or more cathode exhaust conduit(s) 177 that may be located within the reforming region 157 of the reforming reactor 103.
  • Heat from the hot cathode exhaust stream may be exchanged between the cathode exhaust stream and the feed and, optionally, the additional steam, in the reforming region 157 of the reforming reactor 103 as the cathode exhaust stream passes through the cathode exhaust conduit(s) 177.
  • the heat exchange, if any, from the cathode exhaust stream from the fuel cell 105 to the endothermic reforming reactor 101 is efficient.
  • the cathode exhaust conduit(s) 177 within the reforming region 157 of the reforming reactor 103 permits exchange of heat between the hot cathode exhaust stream and the feed and, if present, the additional steam, within the reactor 103, transferring heat to the feed and, if present, additional steam, at the location that the reforming and shift reactions take place.
  • cathode exhaust conduit(s) 177 within the reforming region 157 permits the hot cathode exhaust stream to heat the reforming catalyst in the reforming region 157 as a result of the close proximity of the conduit(s) 177 to the catalyst bed. Provision of heat from the cathode exhaust stream to the reforming reactor 103 may be controlled by selecting and controlling the rate the cathode exhaust stream is fed to the cathode exhaust conduit(s) 177 in the reforming reactor 103, which is controlled by operation of metering valves 179 and 181.
  • heat exchanger 117 may be supplied to heat exchanger 117 to heat the feed precursor by feeding a cooled cathode exhaust stream exiting the cathode exhaust conduit(s) 177 in the reforming reactor 103 to heat exchanger 117 through line 180, where the cooled cathode exhaust stream has sufficient thermal energy to provide heat to the feed precursor.
  • a hydrogen-depleted reformed product gas stream may be removed from the reforming region 157 via line 183, where the hydrogen-depleted reformed product gas stream may include unreacted feed and gaseous non-hydrogen reformed products in the reformed product gas.
  • the non-hydrogen reformed products and unreacted feed may include carbon dioxide, water (as steam), and small amounts of carbon monoxide and unreacted hydrocarbons. Small amounts of hydrogen may be contained in the hydrogen- depleted reformed product gas stream as well.
  • the hydrogen-depleted reformed product gas stream separated from the reforming region 157 may be a carbon dioxide gas stream containing at least 0.8, or at least 0.9, or at least 0.95, or at least 0.98 mole fraction carbon dioxide on a dry basis.
  • the carbon dioxide gas stream is a high pressure gas stream, having a pressure of at least 0.5 MPa, or at least 1 MPa, or at least 2 MPa, or at least 2.5 MPa.
  • the hydrogen-depleted reformed product gas stream will be referred to as the carbon dioxide gas stream.
  • the high pressure carbon dioxide gas stream may exit the reforming reactor 103 and be utilized to heat the feed precursor in heat exchanger 115 and/or be utilized to heat an oxygen containing gas stream that is fed to the cathode 171 of the fuel cell 105 in heat exchanger 185.
  • the high pressure carbon dioxide gas stream may be utilized to heat the feed precursor by passing the carbon dioxide gas stream through line 187 to heat exchanger 115 while feeding the feed precursor into the heat exchanger 115 through the feed precursor inlet line 113.
  • the resulting cooled high pressure carbon dioxide stream may then be fed to the heat exchanger 185 through line 189 to heat the oxygen containing gas stream being fed to the cathode 171 of the fuel cell 105.
  • the cooled high pressure carbon dioxide stream may be expanded through a turbine 147.
  • the high pressure carbon dioxide gas stream exiting the pre- reforming reactor may be used to heat the oxygen containing gas stream being fed to the cathode 171 of the fuel cell 105 without heating the feed precursor.
  • the high pressure carbon dioxide gas stream may be fed from the reforming reactor 103 through line 183 to the heat exchanger 185 to heat the oxygen containing gas stream and cool the carbon dioxide gas stream.
  • the cooled carbon dioxide gas stream may then be expanded through turbine 147.
  • the oxygen containing gas may be heated to a temperature such that the cathode exhaust stream exiting the fuel cell has a temperature of from 75O 0 C to HOO 0 C, where the oxygen containing gas may be heated to a temperature of from 15O 0 C to 45O 0 C.
  • the metering valves 193 and 195 may be adjusted automatically by a feedback mechanism, where the feedback mechanism may measure the temperature of the cathode exhaust stream exiting the fuel cell 105 and/or the temperature of the feed precursor entering the pre -reforming reactor 101 and adjust the metering valves 193 and 195 to maintain the temperature of the cathode exhaust stream and/or the feed precursor entering the pre-reforming reactor 101 within set limits while maintaining the internal pressure within the reforming reactor 103 at a desired level.
  • the high pressure carbon dioxide gas stream may contain significant amounts of water as steam as it exits the reforming reactor 103.
  • the steam may be removed from the high pressure carbon dioxide gas stream by cooling the high pressure carbon dioxide gas stream in heat exchanger 115 and/or in heat exchanger 185 and, if necessary, one or more additional heat exchangers (not shown) and condensing water from the stream. This may be useful if a relatively pure carbon dioxide stream is desired, for example, for use in enhancing oil recovery from an oil formation, or for use in carbonating beverages.
  • the high pressure carbon dioxide stream may be expanded through turbine 147 to drive the turbine 147 and produce a low pressure carbon dioxide stream.
  • high pressure steam that is not utilized in the pre-reforming reactor 101 or the reforming reactor 103 may be passed through line 191 to be expanded through the turbine 147 together with the high pressure carbon dioxide stream, or, optionally, without the high pressure carbon dioxide stream.
  • the turbine 147 may be used to generate electricity in addition to electricity generated by the fuel cell 105.
  • the turbine 147 may be used to drive one or more compressors, such as compressors 155 and 197.
  • a gas stream containing hydrogen hereinafter the hydrogen gas stream, may be separated from the reformed product gas in the reforming reactor 103 by selectively passing hydrogen through the membrane wall 167 of the hydrogen separation membrane(s) 107 into the hydrogen conduit 169 of the hydrogen separation membrane(s) 107.
  • the hydrogen gas stream may contain a very high concentration of hydrogen, and may contain at least 0.9, or at least 0.95, or at least 0.98 mole fraction hydrogen.
  • the hydrogen gas stream may be separated from the reformed product gas at a relatively high rate due to the high flux of hydrogen through the hydrogen separation membrane 107.
  • Hydrogen is passed at a high flux rate through the hydrogen separation membrane 107 since hydrogen is present in the reforming reactor 103 at a high partial pressure.
  • the high partial pressure of hydrogen in the reforming reactor 103 is due to 1) significant quantities of hydrogen in the anode exhaust stream fed to the pre-reforming reactor 101 and passed to the reforming reactor 103 in the feed; 2) hydrogen produced in the pre-reforming reactor 101 and fed to the reforming reactor 103; and 3) hydrogen produced in the reforming reactor 103 by the reforming and shift reactions.
  • the solid oxide fuel cell 105 is operated at a temperature effective to enable ionic oxygen to traverse the electrolyte 235 from the cathode 171 to the anode 121 of the fuel cell 105.
  • the solid oxide fuel cell 105 may be operated at a temperature of from 700 0 C to HOO 0 C, or from 800 0 C to 1000 0 C.
  • the oxidation of hydrogen with ionic oxygen at the one or more anode electrodes is a very exothermic reaction, and the heat of reaction generates the heat required to operate the solid oxide fuel cell 105.
  • the temperature at which the solid oxide fuel cell 105 is operated may be controlled by independently controlling the temperature of the hydrogen gas stream and the oxygen containing gas stream, and the flow rates of these streams to the fuel cell 105.
  • valve 253 may be closed to prevent flow of the oxygen containing feed to the catalytic partial oxidation reforming reactor 237 during operation of the fuel cell 105. Continuous operation of the fuel cell may then conducted according to the process of the invention.
  • the hydrogen gas stream and the oxidant are preferably mixed at the one or more anode electrodes of the fuel cell 105 to generate electricity at an electrical power density of at least 0.4 W/cm 2 , more preferably at least 0.5 W/cm 2 , or at least 0.75 W/cm 2 , or at least 1 W/cm 2 , or at least 1.25 W/cm 2 , or at least 1.5 W/cm 2 .
  • Electricity may be generated at such electrical power densities by selecting and controlling the rate that the hydrogen gas stream is fed to the anode 121 of the fuel cell 105 and the rate that the oxygen containing gas stream is fed to the cathode 171 of the fuel cell 105.
  • the flow rate of the oxygen containing gas stream to the cathode 171 of the fuel cell 105 may be selected and controlled by adjusting the oxygen gas inlet valve 259.
  • mixing the hydrogen gas stream and the oxidant at the one or more anode electrodes generates water (as steam) by the oxidation of a portion of hydrogen present in the hydrogen gas stream fed to the fuel cell 105 with the oxidant.
  • Water generated by the oxidation of hydrogen with an oxidant is swept through the anode 121 of the fuel cell 105 by the unreacted portion of the hydrogen gas stream to exit the anode 121 as part of the anode exhaust stream.
  • the flow rate of the oxygen containing gas stream provided to the cathode 171 of the solid oxide fuel cell 105 should be selected to provide sufficient oxidant to the anode to generate electricity at an electrical power density of at least 0.4 W/cm , or at least 0.5 W/cm 2 , or at least 0.75 W/cm 2 , or at least 1 W/cm 2 , or at least 1.25 W/cm 2 , or at least 1.5 W/cm when combined with the fuel from the hydrogen gas stream at the one or more anode electrodes.
  • the flow rate of the oxygen containing gas stream to the cathode 171 may be selected and controlled by adjusting the oxygen gas inlet valve 259.
  • recycling the anode exhaust stream through the system 100 and provision of a hydrogen-rich first gas stream to the fuel cell 105 by separating the hydrogen-rich first gas stream from the reformed gas product then feeding the first gas stream to the fuel cell 105 reduces the amount of hydrogen required to be produced by the reforming reactor 301 and increases the electrical efficiency of the process, thereby reducing attendant carbon dioxide by-product production.
  • the process of the present invention utilizes a system including a thermally integrated steam reformer, a hydrogen-separating device located exterior to the steam reformer, and a solid oxide fuel cell.
  • a system including a thermally integrated steam reformer, a hydrogen-separating device located exterior to the steam reformer, and a solid oxide fuel cell.
  • the system 200 for practicing the process of this embodiment is similar to the system 100 shown in Fig. 1 , and the system components are generally numbered the same, excepting the reforming reactor 303, the hydrogen-separation device 301 and its components, and certain lines connecting the hydrogen-separation device 301 into the system 200.
  • the reformed product gas, steam, and unreacted feed may be cooled in one or more heat exchangers (not shown), operatively connected between the reforming reactor 303 and the hydrogen separation device 301 and connected by line 305, to a temperature at which the pressure swing adsorption apparatus may be utilized to separate the hydrogen gas stream from other compounds in the mixture of reformed product gas, steam and unreacted feed — typically a temperature of below 15O 0 C, or below 100 0 C, or below 75 0 C.
  • Gaseous non-hydrogen reformed products and unreacted feed may be separated as a gaseous stream from the hydrogen separation device 301 via line 313.
  • the non- hydrogen reformed products and unreacted feed may include carbon dioxide, water (as steam), and small amounts of carbon monoxide and unreacted hydrocarbons.
  • the non- hydrogen reformed products and unreacted feed may be fed to either heat exchanger 185 or heat exchanger 115 for cooling and to heat the oxygen containing gas fed to the cathode 171 of the fuel cell 105 or the feed precursor, respectively, via line 187.
  • Valves 195 and 315 may be used to control the flow of the non-hydrogen reformed products and unreacted feed to heat exchanger 185 and/or heat exchanger 115.
  • the present invention is directed to a system of generating electricity.
  • the system 400 includes a pre -reforming reactor 401, a reforming reactor 403, a solid oxide fuel cell 405, and a hydrogen separation apparatus 407.
  • the solid oxide fuel cell 405 of the system 400 includes an anode 409 having an anode inlet 411 and an anode exhaust outlet 413, a cathode 415 having a cathode inlet 417 and a cathode exhaust outlet 419, and an electrolyte 421 positioned between contacting and separating the anode 409 and the cathode 415.
  • Solid oxide fuel cells useful in the system of the present invention, their anodes, cathodes, and electrolytes are described in further detail above.
  • the one or more pre-reforming reactor anode exhaust inlets 427 are coupled in gaseous communication with the pre-reforming region 423 of the pre-reforming reactor 401 and operatively coupled in gaseous communication with the anode exhaust outlet 413 of the fuel cell 405 so that an anode exhaust stream exiting the fuel cell 405 from the anode exhaust outlet 413 may be introduced into the pre-reforming region 423 of the pre- reforming reactor 401 through the one or more pre-reforming reactor anode exhaust inlets 427.
  • the anode exhaust outlet 413 is directly coupled in gaseous communication with the one or more pre-reforming reactor anode exhaust inlets 427.
  • the one or more pre-reforming reactor outlets 429 are in gaseous communication with the pre-reforming region 423 of the pre-reforming reactor 401.
  • the reforming reactor 403 of the system 400 includes a reforming region 433 and one or more reforming region inlets 435.
  • the reforming region 433 of the reforming reactor 403 is adapted to reform a vaporized mixture of steam and a feed comprising one or more hydrocarbons to form a reformed product gas containing hydrogen.
  • the reforming region 433 contains a reforming catalyst 437 therein positioned to contact a vaporized mixture of steam and a feed comprising one or more hydrocarbons in the reforming region 433.
  • the reforming catalyst may be a reforming catalyst as described in further detail above.
  • the hydrogen separation apparatus 407 of the system 400 includes a member 439 that is selectively permeable to hydrogen and a hydrogen gas outlet 441.
  • the hydrogen permeable member 439 of the hydrogen separation apparatus 407 may be located in the reforming region 433 of the reforming reactor 403 in gaseous communication with the reforming region 433 of the reforming reactor 403 so the hydrogen permeable member 439 may contact vaporized gases in the reforming region 433 of the reforming reactor 403.
  • the hydrogen gas outlet 441 is coupled in gaseous communication with the hydrogen permeable member 439, where the hydrogen permeable member 439 is interposed between the reforming region 433 of the reforming reactor 403 and the hydrogen gas outlet 441 to permit selective flow of hydrogen from the reforming region 433 to the hydrogen gas outlet 441 through the hydrogen permeable member 439.
  • the hydrogen gas outlet is also operatively coupled in gaseous communication with the anode inlet 411 of the fuel cell 405 to permit the flow of a hydrogen gas stream from the hydrogen separation apparatus 407 to the anode 409 of the fuel cell 405.
  • the system 400 may include a first heat exchanger 443.
  • the first heat exchanger may be operatively coupled in gaseous communication with the one or more pre-reforming reactor outlets 429 of the pre-reforming reactor 401 and operatively coupled in gaseous communication with the one or more reforming region inlets 435 of the reforming reactor 403 so the first heat exchanger may cool a feed passing from the pre-reforming reactor 401 to the reforming reactor 403.
  • the system 400 may include a condenser 449.
  • the condenser 449 may be operatively connected to the hydrogen gas outlet 441 of the hydrogen separation apparatus 407 and may be operatively connected to the anode inlet 411 of the anode 409 of the fuel cell 405 so the condenser 449 may condense water from a hydrogen gas stream passing from the hydrogen separation apparatus 407 to the anode 409 of the fuel cell 405 when a steam sweep gas is utilized to sweep hydrogen out of the hydrogen separation apparatus 407.
  • the system 500 may comprise a pre- reforming reactor 501, a reforming reactor 503, a solid oxide fuel cell 505, and a hydrogen separation apparatus 507 as described above with respect to system 400, except the hydrogen separation apparatus 507 is located outside the reforming reactor 503 and is operatively connected in gaseous communication with the reforming region 533 of the reforming reactor 503.
  • the hydrogen-permeable, hydrogen-selective member 539 is operatively coupled in gaseous communication with the reforming region 533 of the reforming reactor 503 so the reformed gas products produced in the reforming region 533 may pass from the reforming region 533 to the member 539 so hydrogen may be separated from the reformed product gas by the member 539.
  • the member 539 may be a high-temperature hydrogen- permeable, hydrogen-selective membrane, as described above.
  • the member 539 may be a pressure swing adsorber.
  • one or more heat exchangers 553 may be coupled in gaseous communication between the reforming region 533 of the reforming reactor 503 and the member 539 to cool the reformed product gas prior to separating hydrogen from the reformed product gas with the member 539.
  • the hydrogen gas outlet 541 of the hydrogen separation apparatus 507 is located in gaseous communication with the selectively hydrogen permeable member 539 of the hydrogen separation apparatus 507.
  • the selectively hydrogen permeable member 539 is interposed between the reforming region 533 of the reforming reactor 503 and the hydrogen gas outlet 541 to permit selective flow of hydrogen from the reforming region 533 through the hydrogen permeable member 539 and out of the hydrogen separation apparatus 507 through hydrogen gas outlet 541.
  • the hydrogen gas outlet 541 is operatively coupled in gaseous communication with the anode inlet 511 of the fuel cell 505 so that hydrogen produced in the reforming reactor 503 and separated from a reformed product gas by the hydrogen separation apparatus 507 may be fed to the anode 509 of the fuel cell 505.
  • one or more heat exchangers 547 and a condenser 549 may be operatively coupled in gaseous communication between the hydrogen gas outlet 541 and the anode inlet 511 to cool the hydrogen gas stream exiting the hydrogen gas outlet 541 and condense water from the hydrogen gas stream prior to the hydrogen gas stream entering the anode 509 of the fuel cell 505.
  • system of the present invention may be a system as depicted in Fig. 2 and described above in the description of a process of the present invention.

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Abstract

La présente invention concerne un système de pile à combustible à oxyde solide. Ce système comprend un réacteur de préreformage, un réacteur de reformage, un appareil de séparation d'hydrogène et une pile à combustible à oxyde solide. La sortie d'évacuation d'anode de la pile à combustible à oxyde solide est connectée de manière opérationnelle à l'entrée du réacteur de préreformage de sorte que l'évacuation d'anode de la pile à combustible puisse entrer dans le réacteur de préreformage. Ce réacteur de préreformage possède aussi une entrée pour un précurseur de charge hydrocarbure. Le réacteur de reformage est couplé de manière opérationnelle au réacteur de préreformage de sorte qu'une charge produite dans le réacteur de préreformage à partir du précurseur de charge puisse être alimentée vers le réacteur de reformage. Le réacteur de reformage est connecté de manière opérationnelle à l'appareil de séparation d'hydrogène de sorte que l'hydrogène produit dans le réacteur de reformage puisse être séparé des gaz de produit reformé. L'entrée d'anode de la pile à combustible à oxyde solide est connectée de manière opérationnelle à l'appareil de séparation d'hydrogène de sorte que l'hydrogène puisse être alimenté en provenance de l'appareil de séparation d'hydrogène comme combustible vers la pile à combustible à oxyde solide.
EP08862643A 2007-12-17 2008-12-15 Système à base de pile à combustible de génération de puissance électrique Withdrawn EP2220712A1 (fr)

Applications Claiming Priority (2)

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US1428507P 2007-12-17 2007-12-17
PCT/US2008/086755 WO2009079426A1 (fr) 2007-12-17 2008-12-15 Système à base de pile à combustible de génération de puissance électrique

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CN102460808A (zh) * 2009-06-16 2012-05-16 国际壳牌研究有限公司 燃料电池系统及其操作方法
EP2740174B1 (fr) * 2011-08-03 2018-11-07 TVS Motor Company Limited Système de piles à combustible
CN105390717B (zh) * 2015-11-04 2017-08-25 佛山索弗克氢能源有限公司 固体氧化物燃料电池的输出功率调节方法

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GB9403198D0 (en) * 1994-02-19 1994-04-13 Rolls Royce Plc A solid oxide fuel cell stack
US20030054215A1 (en) * 2001-09-20 2003-03-20 Honeywell International, Inc. Compact integrated solid oxide fuel cell system
GB0221304D0 (en) * 2002-09-13 2002-10-23 Prototech As Co-production of hydrogen
US7285350B2 (en) * 2002-09-27 2007-10-23 Questair Technologies Inc. Enhanced solid oxide fuel cell systems
CN101905866A (zh) * 2003-02-24 2010-12-08 德士古发展公司 同时固定co2的柴油蒸汽重整
WO2007117406A2 (fr) * 2006-04-03 2007-10-18 Bloom Energy Corporation Système de pile à combustible et configuration de partie classique
US7883813B2 (en) * 2006-04-03 2011-02-08 Bloom Energy Corporation Fuel cell system ventilation scheme

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CN101946356A (zh) 2011-01-12
EP2220717A1 (fr) 2010-08-25
WO2009079427A1 (fr) 2009-06-25
WO2009079426A1 (fr) 2009-06-25
CN101946355A (zh) 2011-01-12
AU2008338501A1 (en) 2009-06-25
WO2009079427A9 (fr) 2010-09-02
AU2008338500A1 (en) 2009-06-25

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