ABSTRACT
Abstract
A method in which a high temperature electrochemical system, such as a solid oxide fuel cell system, generates hydrogen and optionally electricity in a fuel cell mode. At least a part of the generated hydrogen is separated and stored or provided to a hydrogen using device. A solid oxide regenerative fuel cell system stores carbon dioxide in a fuel cell mode. The system generates a methane fuel in an electrolysis mode from the stored carbon dioxide and water by using a Sabatier subsystem. Alternatively, the system generates a hydrogen fuel in an electrolysis mode from water alone.
Description
This application is a divisional application of U.S. application Ser. No. 10/446,704, filed May 29, 2003, which issued as U.S. Pat. No. 7,482,078 on Jan. 27, 2009, which claims the benefit of priority of U.S. provisional application 60/461,190 filed on Apr. 9, 2003, which are incorporated by reference in their entirety.
FIELD OF THE INVENTION
The present invention is directed generally to electrochemical systems and more particularly to co-production of electricity and hydrogen in a high temperature fuel cell system.
BACKGROUND OF THE INVENTION
A solid oxide fuel cell (SOFC) is an electrochemical device that converts chemical energy directly into electrical energy. A solid oxide regenerative fuel cell (SORFC) is an electrochemical device that converts electrical energy directly into chemical energy and subsequently reconverts chemical energy back to electrical energy. This device differs significantly from rechargeable batteries in that the chemicals are stored outside of the SORFC converter. The SORFC system has many building electrical energy storage applications that cannot be satisfied by batteries. For example, a SORFC system for building power generation is discussed in the Proceedings of the 2001 DOE Hydrogen Program Review NREL/CP-570-30535. A SORFC system which generates hydrogen in the electrolysis mode and which generates electricity in the fuel cell mode is described in Proceedings of the 2002 DOE Hydrogen Program Review NREL/CP-610-32405. This SORFC system may contain a separate electrolyzer unit which operates in the electrolysis mode and which is operatively connected to the fuel cell stack to generate hydrogen. However, these SORFC systems have certain environmental and economic drawbacks.
The SOFC and SORFC are high temperature electrochemical systems. Another high temperature electrochemical system is a molten carbonate fuel cell. Fuel cells often use hydrogen as fuel. For example, fuel cell powered vehicles would require hydrogen refueling stations for operation. However, distribution of hydrogen from centralized hydrogen producing plants to refuel vehicles is not currently economical. Furthermore, hydrogen production is fairly expensive.
BRIEF SUMMARY OF THE INVENTION
A preferred embodiment of the present invention provides a high temperature electrochemical system, comprising a high temperature fuel cell, a carbon containing fuel source, and a hydrogen separator which is adapted to separate at least a portion of hydrogen from a fuel side exhaust stream while the fuel cell operates in a fuel cell mode. The system also comprises a hydrogen storage/use subsystem operatively connected to the hydrogen separator which is adapted to store at least a portion of hydrogen received from the hydrogen separator or a hydrogen storage/use subsystem operatively connected to the hydrogen separator which is adapted to provide at least a portion of hydrogen received from the hydrogen separator to a hydrogen using device.
Another preferred embodiment of the present invention provides a solid oxide electrochemical system, comprising a solid oxide fuel cell, a carbon containing fuel source, and a hydrogen separator which is adapted to separate at least a portion of hydrogen from a fuel side exhaust stream while the fuel cell generates electricity and operates in the fuel cell mode. The system also comprises a hydrogen storage/use subsystem operatively connected to the hydrogen separator which is adapted to store at least a portion of hydrogen received from the hydrogen separator or a hydrogen storage/use subsystem operatively connected to the hydrogen separator which is adapted to provide at least a portion of hydrogen received from the hydrogen separator to a hydrogen using device.
Another preferred embodiment of the present invention provides a high temperature fuel cell system, comprising a first means for generating a fuel side exhaust stream from a carbon containing fuel inlet stream and an oxidizer inlet stream by oxygen ion conduction, a second means for separating at least a portion of the hydrogen from the fuel side exhaust stream during generation of electricity by the first means, and a third means for storing at least a portion of the separated hydrogen or a third means for providing at least a portion of the separated hydrogen to a hydrogen using device.
Another preferred embodiment of the present invention provides a method of producing hydrogen, comprising providing a carbon containing fuel and an oxidizer into a high temperature fuel cell, generating a fuel side exhaust stream from the fuel cell while the fuel and the oxidizer are provided into the fuel cell operating in a fuel cell mode, separating at least a portion of hydrogen from the fuel side exhaust stream during the fuel cell mode, and providing at least a portion of the separated hydrogen to a hydrogen storage vessel or to a hydrogen using device.
Another preferred embodiment of the present invention provides a method of co-producing hydrogen and electricity, comprising providing a carbon containing fuel and an oxidizer into a solid oxide fuel cell, generating electricity and a fuel side exhaust stream from the fuel cell while the fuel and the oxidizer are provided into the fuel cell, separating at least a portion of hydrogen from the fuel side exhaust stream during generation of electricity, and providing at least a portion of the separated hydrogen to a hydrogen storage vessel or to a hydrogen using device.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1A , 1 B, 1 C and 1 D are system schematics of systems according to preferred aspects of the first preferred embodiment.
FIG. 2 is a schematic of inputs and outputs from a system according to the second preferred embodiment.
FIG. 3 is a schematic cross section of a single SORFC operating in the electrolysis mode according to a preferred embodiment of the present invention.
FIG. 4 is a schematic cross section of a single SORFC operating in the fuel cell mode according to a preferred embodiment of the present invention.
FIG. 5 is a schematic side of view of a Sabatier reactor according to a preferred embodiment of the present invention.
FIGS. 6A and 6B are system schematics of the major fuel cell system components operating in the fuel cell mode, according to a preferred embodiment of the present invention.
FIG. 7 is a system schematic of the major fuel cell system components operating in the electrolysis mode, according to a preferred embodiment of the present invention.
FIGS. 8 and 9 are schematics of a system of an alternative embodiment of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The First Preferred Embodiment
The present inventors have realized that a suitably configured high temperature electrochemical system, such as a solid oxide electrochemical system, such as a SOFC or a SORFC system, or a molten carbonate fuel cell system, can be used to co-produce hydrogen and electricity in the fuel cell mode. Thus, while the prior art SORFC system can generate either electricity in the fuel cell mode or hydrogen in an electrolysis mode, the system of the first preferred embodiment of the present invention can co-produce both hydrogen and electricity (i.e., produce hydrogen and electricity together). The system of the first preferred embodiment generates a hydrogen rich exhaust stream using reforming reactions that occur within the fuel cell stack and/or in a reformer in thermal integration with the fuel cell stack. The amount of hydrogen produced can be controlled by the operator. The hydrogen rich stream is further conditioned if necessary and stored or used directly by the operator. Thus, the high temperature electrochemical systems produce purified hydrogen as a by-product of fuel reformation in the fuel cell mode. The electrochemical system may operate in the fuel cell mode, when no external electricity input is required, to generate diffusion of ions across an electrolyte of the system. In contrast, a reversible or regenerative electrochemical system operates in the electrolysis mode when external electricity is required to generate diffusion of ions across the electrolyte of the system.
It should be noted that the electrochemical system of the first embodiment does not necessarily co-produce or co-generate power or electricity for use outside the system. The system may be operated to primarily internally reform a carbon and hydrogen containing fuel into hydrogen with minimal power generation or without delivering or outputting power from the system at all. If desired, a small amount of power may be generated and used internally within the system, such as to keep the system at operating temperature and to power system components in addition to other parasitic loads in the system.
The system of the first preferred embodiment which produces hydrogen in the fuel cell mode may be any high temperature electrochemical system which produces sufficient heat to free bound hydrogen contained in a fuel gas provided into the system. For example, the system may be a solid oxide or a molten carbonate system. The solid oxide system, such as a SOFC or SORFC is preferred. The following description of the preferred aspects of the present invention describes SOFC or SORFC systems. However, it should be noted that other suitable electrochemical systems may also be used.
Thus, in a preferred aspect of the first embodiment of the present invention, the high temperature electrochemical system is a SOFC or a SORFC system which co-produces electricity and hydrogen in the fuel cell mode. A SOFC or SORFC system operates in the fuel cell mode when oxygen ions diffuse through an electrolyte of the fuel cells from the oxidizer side to the fuel side of the fuel cell containing the carbon and hydrogen containing gas stream. Thus, when the high temperature electrochemical system, such as a SOFC or SORFC system operates in the fuel cell mode to generate hydrogen, a separate electrolyzer unit operating in electrolysis mode and which is operatively connected to the fuel cell stack is not required for generation of hydrogen. Instead, the hydrogen is separated directly from the fuel cell stack fuel side exhaust gas stream without using additional electricity to operate a separate electrolyzer unit.
When an SORFC system is used rather than an SOFC system, the SORFC system can be connected to a primary source of electricity (e.g., grid power) and can accept electricity from the primary source when desirable or can deliver electricity to the primary source when desirable. Thus, when operating the SORFC system of the first preferred embodiment, the system operator does not have to sacrifice electricity production to produce hydrogen and vice versa. The SORFC system does not require a hot thermal mass which absorbs heat in the fuel cell mode and which releases heat in the electrolysis mode for operation or energy storage. However, a hot thermal mass may be used if desired. Furthermore, the system may use, but does not require a fuel reformer.
Furthermore, in a preferred aspect of the first embodiment, a relative amount of hydrogen and electricity produced can be freely controlled. All or a portion of the hydrogen in the fuel side exhaust stream may be recirculated into the fuel inlet stream to provide control of the amount of electricity and hydrogen being co-produced in the system, as will be described in more detail below. The hydrogen product can be further conditioned, if necessary, and stored or used directly in a variety of applications, such as transportation, power generation, cooling, hydrogenation reactions, or semiconductor manufacture, either in a pressurized or a near ambient state.
FIG. 1A illustrates an SOFC or SORFC electricity generation system 100 according to the first preferred embodiment. The system derives power from the oxidation of a carbon and hydrogen containing fuel, such as a hydrocarbon fuel, such as methane, natural gas which contains methane with hydrogen and other gases, propane or other biogas, or a mixture of a carbon fuel, such as carbon monoxide, oxygenated carbon containing gas, such as methanol, or other carbon containing gas with a hydrogen containing gas, such as water vapor, H 2 gas or their mixtures. For example, the mixture may comprise syngas derived from coal or natural gas reformation. Free hydrogen is carried in several of the system process flow streams. The carbon containing fuel is provided into the system from a fuel source, which may comprise a fuel inlet into the fuel cell stack, a fuel supply conduit and/or a fuel storage vessel.
The system illustrated in FIG. 1A contains a fuel preprocessor subsystem 104 , which may contain a heat exchanger and/or other fuel processing elements. In one preferred aspect of the present invention, the fuel preprocessor subsystem 104 converts a biogas, such as natural gas, to methane, and supplies methane into the fuel cell. The system 100 also contains an oxidizer inlet conduit 105 , which preferably contains an air or other oxidizer blower (schematically shown in FIG. 1 ), and fuel inlet 106 and outlet 109 conduits. The system also contains a stack of SOFCs or SORFCs 110 , which have a fuel inlet 107 and a fuel outlet 108 . The stack 110 preferably contains the fuel cells, separator plates, seals, gas conduits, heaters, thermal insulation, control electronics and various other suitable elements used in fuel cell stacks. If desired, the system may have an optional oxidizer exhaust or outlet 116 . Alternatively, the oxidizer outlet may be omitted to allow all oxygen to diffuse from the oxidizer inlet conduit 105 through the fuel cell electrolyte. The oxidizer inlet conduit 105 may also be used as an oxygen outlet when a SORFC is operated in the electrolysis mode. Water may be recirculated into the fuel inlet 107 from the fuel outlet 108 , as will be described in more detail with respect to FIGS. 6A and 6B .
The s
This application is a divisional application of U.S. application Ser. No. 10/446,704, filed May 29, 2003, which issued as U.S. Pat. No. 7,482,078 on Jan. 27, 2009, which claims the benefit of priority of U.S. provisional application 60/461,190 filed on Apr. 9, 2003, which are incorporated by reference in their entirety.
FIELD OF THE INVENTION
The present invention is directed generally to electrochemical systems and more particularly to co-production of electricity and hydrogen in a high temperature fuel cell system.
BACKGROUND OF THE INVENTION
A solid oxide fuel cell (SOFC) is an electrochemical device that converts chemical energy directly into electrical energy. A solid oxide regenerative fuel cell (SORFC) is an electrochemical device that converts electrical energy directly into chemical energy and subsequently reconverts chemical energy back to electrical energy. This device differs significantly from rechargeable batteries in that the chemicals are stored outside of the SORFC converter. The SORFC system has many building electrical energy storage applications that cannot be satisfied by batteries. For example, a SORFC system for building power generation is discussed in the Proceedings of the 2001 DOE Hydrogen Program Review NREL/CP-570-30535. A SORFC system which generates hydrogen in the electrolysis mode and which generates electricity in the fuel cell mode is described in Proceedings of the 2002 DOE Hydrogen Program Review NREL/CP-610-32405. This SORFC system may contain a separate electrolyzer unit which operates in the electrolysis mode and which is operatively connected to the fuel cell stack to generate hydrogen. However, these SORFC systems have certain environmental and economic drawbacks.
The SOFC and SORFC are high temperature electrochemical systems. Another high temperature electrochemical system is a molten carbonate fuel cell. Fuel cells often use hydrogen as fuel. For example, fuel cell powered vehicles would require hydrogen refueling stations for operation. However, distribution of hydrogen from centralized hydrogen producing plants to refuel vehicles is not currently economical. Furthermore, hydrogen production is fairly expensive.
BRIEF SUMMARY OF THE INVENTION
A preferred embodiment of the present invention provides a high temperature electrochemical system, comprising a high temperature fuel cell, a carbon containing fuel source, and a hydrogen separator which is adapted to separate at least a portion of hydrogen from a fuel side exhaust stream while the fuel cell operates in a fuel cell mode. The system also comprises a hydrogen storage/use subsystem operatively connected to the hydrogen separator which is adapted to store at least a portion of hydrogen received from the hydrogen separator or a hydrogen storage/use subsystem operatively connected to the hydrogen separator which is adapted to provide at least a portion of hydrogen received from the hydrogen separator to a hydrogen using device.
Another preferred embodiment of the present invention provides a solid oxide electrochemical system, comprising a solid oxide fuel cell, a carbon containing fuel source, and a hydrogen separator which is adapted to separate at least a portion of hydrogen from a fuel side exhaust stream while the fuel cell generates electricity and operates in the fuel cell mode. The system also comprises a hydrogen storage/use subsystem operatively connected to the hydrogen separator which is adapted to store at least a portion of hydrogen received from the hydrogen separator or a hydrogen storage/use subsystem operatively connected to the hydrogen separator which is adapted to provide at least a portion of hydrogen received from the hydrogen separator to a hydrogen using device.
Another preferred embodiment of the present invention provides a high temperature fuel cell system, comprising a first means for generating a fuel side exhaust stream from a carbon containing fuel inlet stream and an oxidizer inlet stream by oxygen ion conduction, a second means for separating at least a portion of the hydrogen from the fuel side exhaust stream during generation of electricity by the first means, and a third means for storing at least a portion of the separated hydrogen or a third means for providing at least a portion of the separated hydrogen to a hydrogen using device.
Another preferred embodiment of the present invention provides a method of producing hydrogen, comprising providing a carbon containing fuel and an oxidizer into a high temperature fuel cell, generating a fuel side exhaust stream from the fuel cell while the fuel and the oxidizer are provided into the fuel cell operating in a fuel cell mode, separating at least a portion of hydrogen from the fuel side exhaust stream during the fuel cell mode, and providing at least a portion of the separated hydrogen to a hydrogen storage vessel or to a hydrogen using device.
Another preferred embodiment of the present invention provides a method of co-producing hydrogen and electricity, comprising providing a carbon containing fuel and an oxidizer into a solid oxide fuel cell, generating electricity and a fuel side exhaust stream from the fuel cell while the fuel and the oxidizer are provided into the fuel cell, separating at least a portion of hydrogen from the fuel side exhaust stream during generation of electricity, and providing at least a portion of the separated hydrogen to a hydrogen storage vessel or to a hydrogen using device.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1A , 1 B, 1 C and 1 D are system schematics of systems according to preferred aspects of the first preferred embodiment.
FIG. 2 is a schematic of inputs and outputs from a system according to the second preferred embodiment.
FIG. 3 is a schematic cross section of a single SORFC operating in the electrolysis mode according to a preferred embodiment of the present invention.
FIG. 4 is a schematic cross section of a single SORFC operating in the fuel cell mode according to a preferred embodiment of the present invention.
FIG. 5 is a schematic side of view of a Sabatier reactor according to a preferred embodiment of the present invention.
FIGS. 6A and 6B are system schematics of the major fuel cell system components operating in the fuel cell mode, according to a preferred embodiment of the present invention.
FIG. 7 is a system schematic of the major fuel cell system components operating in the electrolysis mode, according to a preferred embodiment of the present invention.
FIGS. 8 and 9 are schematics of a system of an alternative embodiment of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The First Preferred Embodiment
The present inventors have realized that a suitably configured high temperature electrochemical system, such as a solid oxide electrochemical system, such as a SOFC or a SORFC system, or a molten carbonate fuel cell system, can be used to co-produce hydrogen and electricity in the fuel cell mode. Thus, while the prior art SORFC system can generate either electricity in the fuel cell mode or hydrogen in an electrolysis mode, the system of the first preferred embodiment of the present invention can co-produce both hydrogen and electricity (i.e., produce hydrogen and electricity together). The system of the first preferred embodiment generates a hydrogen rich exhaust stream using reforming reactions that occur within the fuel cell stack and/or in a reformer in thermal integration with the fuel cell stack. The amount of hydrogen produced can be controlled by the operator. The hydrogen rich stream is further conditioned if necessary and stored or used directly by the operator. Thus, the high temperature electrochemical systems produce purified hydrogen as a by-product of fuel reformation in the fuel cell mode. The electrochemical system may operate in the fuel cell mode, when no external electricity input is required, to generate diffusion of ions across an electrolyte of the system. In contrast, a reversible or regenerative electrochemical system operates in the electrolysis mode when external electricity is required to generate diffusion of ions across the electrolyte of the system.
It should be noted that the electrochemical system of the first embodiment does not necessarily co-produce or co-generate power or electricity for use outside the system. The system may be operated to primarily internally reform a carbon and hydrogen containing fuel into hydrogen with minimal power generation or without delivering or outputting power from the system at all. If desired, a small amount of power may be generated and used internally within the system, such as to keep the system at operating temperature and to power system components in addition to other parasitic loads in the system.
The system of the first preferred embodiment which produces hydrogen in the fuel cell mode may be any high temperature electrochemical system which produces sufficient heat to free bound hydrogen contained in a fuel gas provided into the system. For example, the system may be a solid oxide or a molten carbonate system. The solid oxide system, such as a SOFC or SORFC is preferred. The following description of the preferred aspects of the present invention describes SOFC or SORFC systems. However, it should be noted that other suitable electrochemical systems may also be used.
Thus, in a preferred aspect of the first embodiment of the present invention, the high temperature electrochemical system is a SOFC or a SORFC system which co-produces electricity and hydrogen in the fuel cell mode. A SOFC or SORFC system operates in the fuel cell mode when oxygen ions diffuse through an electrolyte of the fuel cells from the oxidizer side to the fuel side of the fuel cell containing the carbon and hydrogen containing gas stream. Thus, when the high temperature electrochemical system, such as a SOFC or SORFC system operates in the fuel cell mode to generate hydrogen, a separate electrolyzer unit operating in electrolysis mode and which is operatively connected to the fuel cell stack is not required for generation of hydrogen. Instead, the hydrogen is separated directly from the fuel cell stack fuel side exhaust gas stream without using additional electricity to operate a separate electrolyzer unit.
When an SORFC system is used rather than an SOFC system, the SORFC system can be connected to a primary source of electricity (e.g., grid power) and can accept electricity from the primary source when desirable or can deliver electricity to the primary source when desirable. Thus, when operating the SORFC system of the first preferred embodiment, the system operator does not have to sacrifice electricity production to produce hydrogen and vice versa. The SORFC system does not require a hot thermal mass which absorbs heat in the fuel cell mode and which releases heat in the electrolysis mode for operation or energy storage. However, a hot thermal mass may be used if desired. Furthermore, the system may use, but does not require a fuel reformer.
Furthermore, in a preferred aspect of the first embodiment, a relative amount of hydrogen and electricity produced can be freely controlled. All or a portion of the hydrogen in the fuel side exhaust stream may be recirculated into the fuel inlet stream to provide control of the amount of electricity and hydrogen being co-produced in the system, as will be described in more detail below. The hydrogen product can be further conditioned, if necessary, and stored or used directly in a variety of applications, such as transportation, power generation, cooling, hydrogenation reactions, or semiconductor manufacture, either in a pressurized or a near ambient state.
FIG. 1A illustrates an SOFC or SORFC electricity generation system 100 according to the first preferred embodiment. The system derives power from the oxidation of a carbon and hydrogen containing fuel, such as a hydrocarbon fuel, such as methane, natural gas which contains methane with hydrogen and other gases, propane or other biogas, or a mixture of a carbon fuel, such as carbon monoxide, oxygenated carbon containing gas, such as methanol, or other carbon containing gas with a hydrogen containing gas, such as water vapor, H 2 gas or their mixtures. For example, the mixture may comprise syngas derived from coal or natural gas reformation. Free hydrogen is carried in several of the system process flow streams. The carbon containing fuel is provided into the system from a fuel source, which may comprise a fuel inlet into the fuel cell stack, a fuel supply conduit and/or a fuel storage vessel.
The system illustrated in FIG. 1A contains a fuel preprocessor subsystem 104 , which may contain a heat exchanger and/or other fuel processing elements. In one preferred aspect of the present invention, the fuel preprocessor subsystem 104 converts a biogas, such as natural gas, to methane, and supplies methane into the fuel cell. The system 100 also contains an oxidizer inlet conduit 105 , which preferably contains an air or other oxidizer blower (schematically shown in FIG. 1 ), and fuel inlet 106 and outlet 109 conduits. The system also contains a stack of SOFCs or SORFCs 110 , which have a fuel inlet 107 and a fuel outlet 108 . The stack 110 preferably contains the fuel cells, separator plates, seals, gas conduits, heaters, thermal insulation, control electronics and various other suitable elements used in fuel cell stacks. If desired, the system may have an optional oxidizer exhaust or outlet 116 . Alternatively, the oxidizer outlet may be omitted to allow all oxygen to diffuse from the oxidizer inlet conduit 105 through the fuel cell electrolyte. The oxidizer inlet conduit 105 may also be used as an oxygen outlet when a SORFC is operated in the electrolysis mode. Water may be recirculated into the fuel inlet 107 from the fuel outlet 108 , as will be described in more detail with respect to FIGS. 6A and 6B .
The system 100 also contains at least one hydrogen separator 113 . The hydrogen separator 113 may comprise any device which can separate some or all hydrogen from a hydrogen containing gas stream. Preferably, the hydrogen separator is a device which can separate a desired or variable amount of hydrogen from a hydrogen gas containing stream, depending on user requirements. Alternatively, the hydrogen separator 113 may comprise a device which separates all or substantially all hydrogen from a hydrogen containing gas stream.
The hydrogen separator 113 may comprise one or more polymeric proton exchange membranes, ceramic proton exchange membranes, polymeric gas separation membranes, adsorption-based gas separation columns (such as pressure swing adsorption units), and flow diverting devices such as valves. The suitable device may be selected based on the state point of the gas stream (composition, temperature, and pressure), the desired product purity, available volume that depends on the specific generator design, and economic factors.
The system 100 also contains an optional hydrogen conditioner 114 . The hydrogen conditioner 114 may be any suitable device which can purify, dry, compress (i.e., a compressor), or otherwise change the state point of the hydrogen-rich gas stream provided from the hydrogen separator 113 . If desired, the hydrogen conditioner 114 may be omitted.
The system 100 also contains a hydrogen storage/ use subsystem 115 . This subsystem 115 may comprise a hydrogen storage vessel, such as a hydrogen storage tank, a hydrogen dispenser, such as a conduit which provides hydrogen or a hydrogen-rich stream to a device which uses hydrogen, or a hydrogen using device. For example, the subsystem 115 may comprise a conduit leading to a hydrogen using device or the hydrogen using device itself, used in transportation, power generation, cooling, hydrogenation reactions, or semiconductor manufacture.
For example, the system 100 may be located in a chemical or a semiconductor plant to provide primary or secondary (i.e., backup) power for the plant as well as hydrogen for use in hydrogenation (i.e., passivation of semiconductor device) or other chemical reactions which require hydrogen that are carried out in the plant.
Alternatively, the subsystem 115 may also comprise another fuel cell, such as an SOFC or SORFC or any other fuel cell, which uses hydrogen as a fuel. Thus, the hydrogen from the system 100 is provided as fuel to one or more additional fuel cells 115 . For example, the system 100 may be located in a stationary location, such as a building or an area outside or below a building and is used to provide power to the building. The additional fuel cells 115 may be located in vehicles located in a garage or a parking area adjacent to the stationary location. In this case, the carbon and hydrogen containing fuel is provided to the system 100 to generate electricity for the building and to generate hydrogen which is provided as fuel to the fuel cell 115 powered vehicles. The generated hydrogen may be stored temporarily in a storage vessel and then provided from the storage vessel to the vehicle fuel cells 115 on demand (analogous to a gas station) or the generated hydrogen may be provided directly from the system 100 to the vehicle fuel cells 115 .
In one preferred aspect of the present invention, the hydrogen separator 113 is used to separate and route hydrogen from the fuel side exhaust stream only into the subsystem 115 . In another preferred aspect of the present invention, the hydrogen separator 113 is used to separate hydrogen from the fuel side exhaust stream and to route all or a part of the hydrogen back into the fuel inlet 107 of the fuel cell stack 110 through conduit 112 , to route all or part of the hydrogen to the subsystem 115 and/or to route the hydrogen out with the tail gas.
Alternatively, two different hydrogen separators may be used to route the hydrogen to the conduit 112 and to the subsystem 115 , as shown in FIG. 6B and described in more detail below. Thus, the fuel side exhaust is separated by a valve or another device to two different hydrogen separators. The first hydrogen separator separates hydrogen from the first part of the fuel side exhaust and routes the hydrogen to conduit 112 to be recirculated into the inlet 107 . The second hydrogen separator separates hydrogen from the second part of the fuel side exhaust and routes the hydrogen to the subsystem 115 . Thus, the amount of hydrogen provided to conduit 112 and to subsystem 115 may be varied by controlling the amount of fuel side exhaust provided into each hydrogen separator.
Alternatively, only one hydrogen separator 113 is used. A valve or another device separates the hydrogen output from the separator into conduit 112 and into subsystem 115 . Thus, the valve or another such device determines the amount of hydrogen provided to conduit 112 and subsystem 115 . In both cases the valve or similar device may be controlled by an operator or controlled automatically by a computer based on predetermined data or on input parameters.
FIG. 1B illustrates a system 120 according to an alternative aspect of the first preferred embodiment. The system 120 is identical to the system 100 illustrated in FIG. 1A , except that the system 120 contains a fuel reformer 124 upstream of the fuel inlet 107 . Preferably, the fuel reformer is included in the system 120 instead of the fuel preprocessing subsystem 104 . However, if desired, the fuel reformer 124 may be used together with the fuel preprocessing subsystem 104 , such that the output of the subsystem 104 is provided into the reformer.
The fuel reformer 124 may be any suitable device which is capable of reforming a carbon and bound hydrogen containing fuel to form a carbon containing fuel and free hydrogen. For example, the fuel reformer 124 may be any suitable device which can reform a hydrocarbon gas into a gas mixture of free hydrogen and a carbon containing gas. For example, the fuel reformer 124 may reform a biogas, such as natural gas to form free hydrogen and carbon monoxide. The free hydrogen and carbon monoxide are then provided into the fuel inlet 107 of the fuel cell stack 110 . If desired, some or all free hydrogen may also be separated from the carbon containing gas by an additional hydrogen separator prior to entry into the fuel cell stack 110 and provided to the hydrogen storage/ use subsystem 115 .
In a preferred aspect of the first embodiment, the fuel reformer 124 is thermally integrated with the fuel cell stack 110 . The term âthermally integratedâ in this context means that the heat from the reaction in the fuel cell stack 110 drives the net endothermic fuel reformation in the fuel reformer 124 . The fuel reformer 124 may be thermally integrated with the fuel cell stack 110 by placing the reformer 124 and stack 110 in physical and thermal contact with each other, or by providing a thermal conduit or thermally conductive material which connects the stack 110 to the reformer 124 . While less preferred, a separate heater may also be used to heat the reformer 124 instead of or in addition to the heat provided from the stack 110 . If any hydrogen is recycled from the separator 113 back into the fuel cell stack 110 , then the hydrogen may be provided by the conduit 112 directly into the reformer 124 or into the fuel cell stack 110 inlet 107 .
FIG. 1C illustrates a system 130 according to an alternative aspect of the first preferred embodiment. The system 130 is identical to the system 100 illustrated in FIG. 1A , except that the system 130 contains a water- gas shift reactor 133 . The water- gas shift reactor 133 may be any suitable device which converts at least a portion of the water exiting the fuel cell stack 110 fuel outlet 108 into free hydrogen. For example, the reactor 133 may comprise a tube or conduit containing a catalyst which converts some or all of the carbon monoxide and water vapor in the tail gas exiting outlet 108 into carbon dioxide and hydrogen. The catalyst may be any suitable catalyst, such as a iron oxide or a chromium promoted iron oxide catalyst. The reactor 133 is preferably located between the outlet 108 and the hydrogen separator 113 (i.e., downstream of the outlet 108 and upstream of the separator 113 ).
The reactor 133 works in tandem with the separator 113 by increasing the amount of free hydrogen in the fuel side exhaust (i.e., tail gas) by converting some or all water present in the fuel side exhaust gas into hydrogen. The reactor 133 then provides hydrogen and carbon dioxide to the separator 113 . The separator 113 separates the hydrogen from the carbon dioxide. Thus, all or some of the water present in the fuel may be converted to hydrogen in the reactor 133 .
FIG. 1D illustrates a system 140 according to an alternative aspect of the first preferred embodiment. The system 140 is identical to the system 100 illustrated in FIG. 1A , except that the system 140 contains a water supply 144 . The water supply 144 may be any suitable liquid water and/or water vapor supply device, such as a water conduit or storage tank. The water supply is located upstream of the fuel inlet 107 to provide water into the fuel inlet 107 in addition to the fuel being provided to the inlet from the preprocessing subsystem 104 or the reformer 124 .
The water supply 144 is preferably, but not necessarily, used to provide water into the fuel inlet 107 when the fuel cell stack 110 is operated to generate hydrogen while generating little or no electricity in the fuel cell mode (i.e., no net electricity is produced in the fuel cell mode). The additional water is used to support fuel reforming as needed.
The elements of
systems
100 , 120 , 130 and 140 may be used in any suitable combination. For example, the reformer 124 , the reactor 133 and the water supply 144 may be used together in one system with or without the fuel preprocessing subsystem 104 . Furthermore, any two or three elements selected from the fuel preprocessing subsystem 104 , the reformer 124 , the reactor 133 and the water supply 144 may be used together in the same system.
The
systems
100 , 120 , 130 and 140 illustrated in FIGS. 1A-1D may have other embodiments and configurations, as desired. Other components, such as fuel side exhaust stream condensers, heat exchangers, heat-driven heat pumps, turbines, additional gas separation devices, may be added if desired, as described, for example, in U.S. application Ser. No. 10/300,021, filed on Nov. 20, 2002, to Matthias Gottmann, et al., incorporated herein by reference in its entirety.
A preferred method of operating the
systems
100 , 120 , 130 , 140 will now be described. The systems are preferably operated so that excess fuel is provided to the fuel cell stack 110 . Any suitable carbon containing and hydrogen containing fuel is provided into the fuel cell stack. The fuel may comprise a fuel such as a hydrocarbon fuel, such as methane, natural gas which contains methane with hydrogen and other gases, propane or other biogas.
If desired, hydrogen and/or water vapor may be added to the hydrocarbon fuel. Alternatively, the fuel may comprise 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 a water vapor or hydrogen gas, for example the mixture may comprise syngas derived from coal or natural gas reformation. The hydrogen and water vapor may be recycled from the fuel side exhaust gas stream or provided from hydrogen and water vapor conduits or storage vessels.
The reformation reactions occur within the fuel cell stack 110 and/or in the optional reformer 124 and result in the formation of free hydrogen in the fuel side exhaust gas stream. For example, if a hydrocarbon gas such as methane is used as a fuel, then the methane is reformed to form a mixture containing non-utilized hydrogen, carbon dioxide and water vapor in the fuel cell stack 110 . If natural gas is used as a fuel, then the natural gas may be converted to methane in the preprocessing subsystem 104 or it may be reformed directly to a non-hydrocarbon carbon containing gas such as carbon monoxide in the reformer 124 .
The following Table I summarizes one or more reactions that may occur within the fuel cell stack 110 when methane is supplied to the stack.
TABLE I
Steam-methane reforming
CH 4 + H 2 O -> CO + 3H 2
Water-gas shift
CO + H 2 O -> CO 2 + H 2
CO oxidation
CO + ½O 2 -> CO 2
Hydrogen oxidation
H 2 + ½O 2 -> H 2 O
Partial oxidation
CH 4 + ½O 2 -> CO + 2H 2
If a mixture of a hydrogen containing gas and a non-hydrocarbon carbon containing gas, such as carbon monoxide, is used as a fuel, then some of the carbon monoxide is converted to carbon dioxide in the fuel cell stack 110 and a gas mixture including carbon monoxide, carbon dioxide and unutilized hydrogen is provided from the fuel cell stack 110 . If the water- gas shift reactor 133 is included in the system, then it converts some of the carbon monoxide and water vapor in the fuel side exhaust gas stream to hydrogen and carbon dioxide.
Preferably, the fraction of hydrogen separated by the hydrogen separator 113 and the amount of total fuel provided to the fuel cell stack 110 for electricity and hydrogen production are variable and under the control of an operator operating a control unit of the system. An operator may be a human operator who controls the hydrogen separation and electricity production or a computer which automatically adjusts the amount of hydrogen separation and electricity production based on predetermined criteria, such as time, and/or based on received outside data or request, such as a demand for electricity by the power grid and/or a demand for hydrogen by the subsystem 115 . Controlling these two parameters allows the operator to specify largely independently the amount of hydrogen produced and the amount of electricity generated. The outside data or request may comprise one or more of electricity demand, hydrogen demand, electricity price and hydrogen price, which may be transmitted electronically to a computer system operator or visually or audibly to a human system operator.
In one extreme, when the user of the system needs electricity, but does not need additional hydrogen, then the operator can choose to have the hydrogen containing streams recirculated back into the fuel cell stack 110 by the separator 113 through conduit 112 while providing no hydrogen or a minimum amount of hydrogen to the subsystem 115 .
In another extreme, when the user of the system needs hydrogen, but does not need any electricity generated, the operator can choose to have the fuel cell stack 110 act primarily to internally reform the carbon containing fuel into hydrogen with minimal power generation and/or minimal or no external power output/delivery from the system. A small amount of power may be generated to keep the system at operating temperature and to power the hydrogen separ
CLAIMS
Claims ( 30 )
1. A method of producing hydrogen, comprising:
providing a carbon containing fuel and an oxidizer into a high temperature fuel cell;
generating a fuel side exhaust stream from the fuel cell while the fuel and the oxidizer are provided into the fuel cell operating in a fuel cell mode;
providing the fuel side exhaust stream to a hydrogen separator;
separating in the hydrogen separator at least a portion of hydrogen from a stream consisting of the fuel side exhaust stream during the fuel cell mode;
providing at least a first portion of the separated hydrogen from the hydrogen separator to a hydrogen storage vessel or to a hydrogen using device;
recycling at least a second portion of the separated hydrogen the hydrogen separator to the fuel cell; and
providing a remainder of the fuel side exhaust stream from the hydrogen separator as tail gas, and wherein the step of separating in the hydrogen separator at least the portion of hydrogen occurs prior to recycling a portion of the fuel side exhaust stream toward the fuel cell.
2. The method of claim 1 , further comprising generating electricity during the step of separating at least a portion of hydrogen.
3. The method of claim 2 , wherein the high temperature fuel cell comprises a molten carbonate fuel cell.
4. The method of claim 2 , wherein the high temperature fuel cell comprises a solid oxide fuel cell.
5. The method of claim 1 , wherein the high temperature fuel cell comprises a solid oxide fuel cell.
6. The method of claim 1 , further comprising conditioning the separated hydrogen and providing the conditioned hydrogen to the hydrogen storage vessel or to the hydrogen using device.
7. The method of claim 2 , further comprising controlling a variable amount of separated hydrogen based on predetermined criteria or based on received data.
8. The method of claim 7 , further comprising controlling a variable ratio of an amount of electricity generated to an amount of separated hydrogen.
9. The method of claim 8 , wherein 20 to 50% of the fuel provided into the fuel cell is utilized for hydrogen production.
10. The method of claim 7 , wherein the ratio is controlled by varying at least one of an amount of current drawn from the fuel cell and the amount of fuel being provided into the fuel cell.
11. The method of claim 1 , wherein the separated hydrogen is provided to a hydrogen storage vessel.
12. The method of claim 1 , wherein the separated hydrogen is provided to a hydrogen using device.
13. The method of claim 12 , wherein the hydrogen using device comprises a second fuel cell.
14. The method of claim 1 , further comprising recirculating a portion of the separated hydrogen into a fuel inlet gas stream.
15. The method of claim 14 , further comprising using a first hydrogen separator to recirculate a portion of the separated hydrogen into a fuel inlet gas stream and using a second hydrogen separator to provide the separated hydrogen to the hydrogen storage vessel or to the hydrogen using device.
16. The method of claim 1 , wherein the solid oxide fuel cell is a solid oxide regenerative fuel cell which acts as a power generator and a hydrocarbon fuel reformer in the fuel cell mode.
17. The method of claim 16 , further comprising:
providing carbon dioxide from the solid oxide regenerative fuel cell into a carbon dioxide storage vessel when the solid oxide regenerative fuel cell operates in a fuel cell mode;
providing the carbon dioxide from the carbon dioxide storage vessel and water from a water source into the solid oxide regenerative fuel cell and providing carbon monoxide and hydrogen from the solid oxide regenerative fuel cell into a Sabatier subsystem when the solid oxide regenerative fuel cell operates in an electrolysis mode;
generating methane and water vapor in the Sabatier subsystem from the received carbon monoxide and hydrogen; and
providing the methane into a methane storage vessel.
18. The method of claim 1 , wherein the fuel comprises a methane or a natural gas fuel.
19. The method of claim 1 , wherein the fuel comprises at least 50% non-hydrocarbon carbon containing fuel.
20. The method of claim 1 , further comprising converting a natural gas fuel into a methane fuel and providing the methane fuel into the fuel cell.
21. The method of claim 1 , further comprising reforming a carbon and bound hydrogen containing fuel to a carbon containing and free hydrogen containing fuel and providing the carbon containing and free hydrogen containing fuel into the fuel cell.
22. The method of claim 1 , further comprising converting at least a portion of water in the fuel side exhaust stream to hydrogen and providing at least a portion of the converted hydrogen to the hydrogen storage vessel or to the hydrogen using device.
23. The method of claim 1 , further comprising providing water together with the fuel into a fuel inlet of the fuel cell.
24. A method of producing hydrogen, comprising:
providing a carbon containing fuel and an oxidizer into a solid oxide fuel cell;
generating electricity and a fuel side exhaust stream from the fuel cell while the fuel and the oxidizer are provided into the fuel cell;
providing the fuel side exhaust stream to a hydrogen separator;
separating in the hydrogen separator at least a portion of hydrogen from a stream consisting of the fuel side exhaust stream during generation of electricity;
providing at least a first portion of the separated hydrogen from the hydrogen separator to a hydrogen storage vessel or to a hydrogen using device;
recycling at least a second portion of the separated hydrogen from the hydrogen separator to the fuel cell; and
providing a remainder of the fuel side exhaust stream from the hydrogen separator as tail gas, and wherein the step of separating in the hydrogen separator at least the portion of hydrogen occurs prior to recycling a portion of the fuel side exhaust stream toward the fuel cell.
25. The method of claim 24 , further comprising controlling a variable ratio of an amount of electricity generated to an amount of separated hydrogen based on predetermined criteria or based on received data.
26. The method of claim 24 , wherein the separated hydrogen is provided to a hydrogen storage vessel.
27. The method of claim 24 , wherein the separated hydrogen is provided to a hydrogen using device.
28. The method of claim 24 , further comprising recirculating a portion of the separated hydrogen into a fuel inlet gas stream.
29. The method of claim 24 , wherein the step of providing a carbon containing fuel comprises providing a hydrocarbon fuel into the fuel cell and reforming the hydrocarbon fuel in the fuel cell.
30. The method of claim 24 , wherein the step of providing a carbon containing fuel comprises:
providing a hydrocarbon fuel into a reformer which is thermally integrated with the fuel cell;
reforming the hydrocarbon fuel in the reformer; and
introducing the reformed fuel into the fuel cell.
US12/230,486
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